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Sample records for iron-porphyrin catalyzed reduction

  1. O2 reduction reaction by biologically relevant anionic ligand bound iron porphyrin complexes.

    PubMed

    Samanta, Subhra; Das, Pradip Kumar; Chatterjee, Sudipta; Sengupta, Kushal; Mondal, Biswajit; Dey, Abhishek

    2013-11-18

    Iron porphyrin complex with a covalently attached thiolate ligand and another with a covalently attached phenolate ligand has been synthesized. The thiolate bound complex shows spectroscopic features characteristic of P450, including the hallmark absorption spectrum of the CO adduct. Electrocatalytic O2 reduction by this complex, which bears a terminal alkyne group, is investigated by both physiabsorbing on graphite surfaces (fast electron transfer rates) and covalent attachment to azide terminated self-assembled monolayer (physiologically relevant electron transfer rates) using the terminal alkyne group. Analysis of the steady state electrochemical kinetics reveals that this catalyst can selectively reduce O2 to H2O with a second-order k(cat.) ~10(7) M(-1 )s(-1) at pH 7. The analogous phenolate bound iron porphyrin complex reduces O2 with a second-order rate constant of 10(5) M(-1) s(-1) under the same conditions. The anionic ligand bound iron porphyrin complexes catalyze oxygen reduction reactions faster than any known synthetic heme porphyrin analogues. The kinetic parameters of O2 reduction of the synthetic thiolate bound complex, which is devoid of any second sphere effects present in protein active sites, provide fundamental insight into the role of the protein environment in tuning the reactivity of thiolate bound iron porphyrin containing metalloenzymes. PMID:24171513

  2. The secondary coordination sphere and axial ligand effects on oxygen reduction reaction by iron porphyrins: a DFT computational study.

    PubMed

    Ohta, Takehiro; Nagaraju, Perumandla; Liu, Jin-Gang; Ogura, Takashi; Naruta, Yoshinori

    2016-09-01

    Oxygen reduction reaction (ORR) catalyzed by a bio-inspired iron porphyrin bearing a hanging carboxylic acid group over the porphyrin ring, and a tethered axial imidazole ligand was studied by DFT calculations. BP86 free energy calculations of the redox potentials and pK a's of reaction components involved in the proton coupled electron transfer (PCET) reactions of the ferric-hydroxo and -superoxo complexes were performed based on Born-Haber thermodynamic cycle in conjunction with a continuum solvation model. The comparison was made with iron porphyrins that lack either in the hanging acid group or axial ligand, suggesting that H-bond interaction between the carboxylic acid and iron-bound hydroxo, aquo, superoxo, and peroxo ligands (de)stabilizes the Fe-O bonding, resulting in the increase in the reduction potential of the ferric complexes. The axial ligand interaction with the imidazole raises the affinity of the iron-bound superoxo and peroxo ligands for proton. In addition, a low-spin end-on ferric-hydroperoxo intermediate, a key precursor for O-O cleavage, can be stabilized in the presence of axial ligation. Thus, selective and efficient ORR of iron porphyrin can be achieved with the aid of the secondary coordination sphere and axial ligand interactions. PMID:27501847

  3. Direct observation of intermediates formed during steady-state electrocatalytic O2 reduction by iron porphyrins

    PubMed Central

    Sengupta, Kushal; Chatterjee, Sudipta; Samanta, Subhra; Dey, Abhishek

    2013-01-01

    Heme/porphyrin-based electrocatalysts (both synthetic and natural) have been known to catalyze electrochemical O2, H+, and CO2 reduction for more than five decades. So far, no direct spectroscopic investigations of intermediates formed on the electrodes during these processes have been reported; and this has limited detailed understanding of the mechanism of these catalysts, which is key to their development. Rotating disk electrochemistry coupled to resonance Raman spectroscopy is reported for iron porphyrin electrocatalysts that reduce O2 in buffered aqueous solutions. Unlike conventional single-turnover intermediate trapping experiments, these experiments probe the system while it is under steady state. A combination of oxidation and spin-state marker bands and metal ligand vibrations (identified using isotopically enriched substrates) allow in situ identification of O2-derived intermediates formed on the electrode surface. This approach, combining dynamic electrochemistry with resonance Raman spectroscopy, may be routinely used to investigate a plethora of metalloporphyrin complexes and heme enzymes used as electrocatalysts for small-molecule activation. PMID:23650367

  4. Electrocatalytic Dioxygen Reduction by Carbon Electrodes Noncovalently Modified with Iron Porphyrin Complexes: Enhancements from a Single Proton Relay.

    PubMed

    Sinha, Soumalya; Aaron, Michael S; Blagojevic, Jovan; Warren, Jeffrey J

    2015-12-01

    Oxygen reduction in acidic aqueous solution mediated by a series of asymmetric iron (III)-tetra(aryl)porphyrins adsorbed to basal- and edge- plane graphite electrodes is investigated. The asymmetric iron porphyrin systems bear phenyl groups at three meso positions and either a 2-pyridyl, a 2-benzoic acid, or a 2-hydroxyphenyl group at the remaining meso position. The presence of the three unmodified phenyl groups makes the compounds insoluble in water, enabling catalyst retention during electrochemical experiments. Resonance Raman data demonstrate that catalyst layers are maintained, but can undergo modification after prolonged catalysis in the presence of O2 . The introduction of a single proton relay group at the fourth meso position makes the asymmetric iron porphyrins markedly more robust catalysts; these molecules support higher sustained current densities than the parent iron tetraphenylporphyrin. Iron porphyrins bearing a 2-pyridyl group are the most active catalysts and operate at stable current densities ≥1 mA cm(-2) for over 5 h. Comparative analysis of the catalysts with different proton relays also is reported. PMID:26459272

  5. Medium Effects are as Important as Catalyst Design for Selectivity in Electrocatalytic Oxygen Reduction by Iron-porphyrin Complexes

    SciTech Connect

    Rigsby, Matthew L.; Wasylenko, Derek J.; Pegis, Michael L.; Mayer, James M.

    2015-04-08

    Several substituted iron porphyrin com-plexes were evaluated for oxygen reduction reaction (ORR) electrocatalysis in different homogeneous and heterogeneous media. The selectivity for 4-electron re-duction to H2O vs. 2-electron reduction to H2O2 varies substantially from one medium to another for a given catalyst. In many cases, the influence of the medium in which the catalyst is evaluated has a larger effect on the observed selectivity than the factors attributable to chemical modification of the catalyst. For instance, introduction of potential proton relays has variable effects depending on the catalyst medium. Thus, comparisons of ORR selectivity results need to be interpreted with caution, as the catalysis is a property not just of the catalyst, but also of the larger mesoscale environment be-yond the catalyst. Still, in all the direct pairwise comparisons in the same medium, the catalysts with potential proton relays have similar or better selectivity for the preferred 4e– path. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  6. Distant protonated pyridine groups in water-soluble iron porphyrin electrocatalysts promote selective oxygen reduction to water

    SciTech Connect

    Matson, Benjamin D.; Carver, Colin T.; Von Ruden, Amber L.; Yang, Jenny Y.; Raugei, Simone; Mayer, James M.

    2012-11-08

    Fe(III)-meso-tetra(pyridyl)porphines are selective electrocatalysts for the reduction of dioxygen to water in aqueous acidic solution. The 2-pyridyl derivatives, both the triflate and chloride salts, are more selective than the isomeric 4-pyridyl complexes. The improved selectivity of is ascribed to the inward-pointing pyridinium groups acting as intramolecular proton relays. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  7. Iron porphyrin polymer films: Materials for the modification of electrode surfaces and the detection of nitric oxide

    SciTech Connect

    McGuire, M.; Drew, S.M.

    1996-10-01

    We are currently investigating a new method for the detection and quantification of nitric oxide (NO) based on a carbon electrode chemically modified with an iron porphyrin polymer film. Commercially available vinyl-substituted iron porphyrin monomers can be polymerized directly onto electrode surfaces through a published electrochemical polymerization process. We are also developing a synthesis for a new vinyl-substituted monomer, iron 5,10,15-triphenyl-20-vinyl porphyrin chloride, in hopes of improving polymer film stability. The electrochemistry of NO is also being investigated at electrodes chemically modified with an iron porphyrin polymer film. We are studying the catalytic oxidation of iron porphyrin bound NO to nitrate by molecular oxygen. The reaction with molecular oxygen is preceded by a one electron reduction of the iron porphyrin-NO complex. If currents proportional to nitric oxide concentration can be measured, a new NO electrochemical sensor will be designed.

  8. Redox Reactions of Metalloporphyrins and their Role in Catalyzed Reduction of Carbon Dioxide

    SciTech Connect

    Neta, P.

    2002-09-01

    Pulse radiolysis and laser photolysis are used to study redox processes of metalloporphyrins and related complexes in order to evaluate these light absorbing molecules as sensitizers and intermediates in solar energy conversion schemes. The main thrust of the current studies is to investigate the role of reduced metalloporphyrins as intermediates in the catalyzed reduction of carbon dioxide. Studies involve cobalt and iron porphyrins, phthalocyanines, corroles, and corrins as homogeneous catalysts for reduction of carbon dioxide in solution. The main aim is to understand the mechanisms of these photochemical schemes in order to facilitate their potential utilization.

  9. Molecular catalysis of the oxygen reduction reaction by iron porphyrin catalysts tethered into Nafion layers: An electrochemical study in solution and a membrane-electrode-assembly study in fuel cells

    NASA Astrophysics Data System (ADS)

    He, Qinggang; Mugadza, Tawanda; Kang, Xiongwu; Zhu, Xiaobing; Chen, Shaowei; Kerr, John; Nyokong, Tebello

    2012-10-01

    This study was motivated by the need for improved understanding of the kinetics and transport phenomena in a homogeneous catalyst system for the oxygen reduction reaction (ORR). Direct interaction between the sulfonic groups of Nafion and an Fe(III) meso-tetra(N-methyl-4-pyridyl) porphine chloride (Fe(III)TMPyP) compound was observed using FTIR and in situ UV-Vis spectroelectrochemical characterizations. A positive shift of the half wave potential value (E1/2) for ORR on the iron porphyrin catalyst (Fe(III)TMPyP) was observed upon addition of a specific quantity of Nafion ionomer on a glassy carbon working electrode, indicating not only a faster charge transfer rate but also the role of protonation in the oxygen reduction reaction (ORR) process. A membrane electrode assembly (MEA) was made as a sandwich of a Pt-coated anode, a Nafion® 212 membrane, and a Fe(III)TMPyP + Nafion ionomer-coated cathode. This three-dimensional catalysis system has been demonstrated to be working in a H2/O2 proton exchange membrane (PEM) fuel cell test.

  10. 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

    SciTech Connect

    Klobukowski, Erik

    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

  11. Nickel-Catalyzed Reductive Couplings.

    PubMed

    Wang, Xuan; Dai, Yijing; Gong, Hegui

    2016-08-01

    The Ni-catalyzed reductive coupling of alkyl/aryl with other electrophiles has evolved to be an important protocol for the construction of C-C bonds. This chapter first emphasizes the recent progress on the Ni-catalyzed alkylation, arylation/vinylation, and acylation of alkyl electrophiles. A brief overview of CO2 fixation is also addressed. The chemoselectivity between the electrophiles and the reactivity of the alkyl substrates will be detailed on the basis of different Ni-catalyzed conditions and mechanistic perspective. The asymmetric formation of C(sp(3))-C(sp(2)) bonds arising from activated alkyl halides is next depicted followed by allylic carbonylation. Finally, the coupling of aryl halides with other C(sp(2))-electrophiles is detailed at the end of this chapter. PMID:27573395

  12. Catalytic and Biocatalytic Iron Porphyrin Carbene Formation: Effects of Binding Mode, Carbene Substituent, Porphyrin Substituent, and Protein Axial Ligand.

    PubMed

    Khade, Rahul L; Zhang, Yong

    2015-06-24

    Iron porphyrin carbenes (IPCs) are important intermediates in various chemical reactions catalyzed by iron porphyrins and engineered heme proteins, as well as in the metabolism of various xenobiotics by cytochrome P450. However, there are no prior theoretical reports to help understand their formation mechanisms and identify key information governing the binding mode, formation feasibility, and stability/reactivity. A systematic quantum chemical study was performed to investigate the effects of carbene substituent, porphyrin substituent, and axial ligand on IPC formation pathways. Results not only are consistent with available experimental data but also provide a number of unprecedented insights into electronic, steric, and H-bonding effects of various structural factors on IPC formation mechanisms. These results shall facilitate research on IPC and related systems for sustainable chemical catalysis and biocatalysis. PMID:26067900

  13. Hydroxylation of alkanes using sodium hypochlorite catalyzed by iron porphyrins

    SciTech Connect

    Sorokin, A.B.; Khenkin, A.M.

    1988-10-01

    This communication presents data about the oxidation of alkanes to alcohols with hypochlorite in the presence of Fe(III) phenylporphyrin derivatives in the system water-benzene. We used as catalysts the following compounds: tetraphenylporphyrin iron chloride, tetramesitylporphyrin iron chloride, tetra(2-fluorophenyl)porphyrin from chloride, and tetra (2-ntrophenyl)porphyrin iron chloride. The reaction products were analyzed by gas-liquid chromatography. The efficiency of the reaction was determined by the structure of the porphyrin used.

  14. Lactoperoxidase haem, an iron-porphyrin thiol.

    PubMed Central

    Nichol, A W; Angel, L A; Moon, T; Clezy, P S

    1987-01-01

    The haem prosthetic group of lactoperoxidase can be prepared from the enzyme in high yield by reductive cleavage with mercaptoethanol in 8 M-urea under mild conditions. The product yields porphyrins, after removal of iron, which show visible spectroscopic properties similar to protoporphyrin but are considerably more polar. In the presence of iodoacetamide, a different product is obtained by reductive cleavage. The proton n.m.r. and mass spectra of this compound indicate that the prosthetic group of the enzyme is the iron complex of 18-mercaptomethyl-2,7,12-trimethyl-3,8-divinylporphyrin-13,17-d ipropionic acid. It is proposed that the unusual strength of binding of the prosthetic group to the apoprotein is due to formation of a disulphide bond from a cysteine residue to the porphyrin thiol. PMID:3689341

  15. Palladium Catalyzed Reduction of Nitrobenzene.

    ERIC Educational Resources Information Center

    Mangravite, John A.

    1983-01-01

    Compares two palladium (Pd/C) reducing systems to iron/tin-hydrochloric acid (Fe/HCl and Sn/HCl) reductions and suggests an efficient, clean, and inexpensive procedures for the conversion of nitrobenzene to aniline. Includes laboratory procedures used and discussion of typical results obtained. (JN)

  16. First insight into catalytic activity of anionic iron porphyrins immobilized on exfoliated layered double hydroxides.

    PubMed

    Nakagaki, Shirley; Halma, Matilte; Bail, Alesandro; Arízaga, Gregório Guadalupe Carbajal; Wypych, Fernando

    2005-01-15

    Mg-Al layered double hydroxide (LDH) intercalated with glycinate anions was synthesized through co-precipitation and exfoliated in formamide and the single-layer suspension was reacted with aqueous iron porphyrin solutions (Fe(TDFSPP) and Fe(TCFSPP)). The obtained materials were characterized by X-ray powder diffraction, UV-vis, and electron paramagnetic resonance and investigated in the oxidation reaction of cyclooctene and cyclohexane using iodosylbenzene as oxidant. The iron porphyrin seems to be immobilized at the surface of the glycinate intercalated LDH. The catalytic activities obtained in heterogeneous media for iron porphyrin, Fe(TDFSPP), was superior to the results obtained under homogeneous conditions, but the opposite effect was observed on the Fe(TCFSPP), indicating that, instead of the structural similarity of both iron porphyrins (second-generation porphyrins), the immobilization of each one produced different catalysts. The best catalytic activity of the Fe(TDFSPP)/Gly-LDH, compared to Fe(TCFSPP)/Gly-LDH, can be explained by the easy access of the oxidant and the substrate to the catalytic sites in the former, probably located at the surface of the layered double hydroxide pillared with glycinate anions. A model for the immobilization and a mechanism for the oxidation reaction will be discussed. PMID:15571697

  17. Mechanisms of bacterially catalyzed reductive dehalogenation

    SciTech Connect

    Picardal, F.W.

    1992-12-31

    Nine bacteria were tested for the ability to dehalogenate tetrachloromethane (CT), tetrachloroethene (PCE), and 1, 1, 1-trichloroethane (TCA) under anaerobic conditions. Three bacteria were able to reductively dehalogenate CT. Dehalogenation ability was not readily linked to a common metabolism or changes in culture redox potential. None of the bacteria tested were able to dehalogenate PCE or TCA. One of the bacteria capable of dehalogenating CT, Shewanella putrefaciens, was chosen as a model organism to study mechanisms of bacterially catalyzed reductive dehalogenation. The effect of a variety of alternate electron acceptors on CT dehalogenation ability by S. putrefaciens was determined. oxygen and nitrogen oxides were inhibitory but Fe (III), trimethylamine oxide, and fumarate were not. A model of the electron transport chain of S. putrefaciens was developed to explain inhibition patterns. A period of microaerobic growth prior to CT exposure increased the ability of S. putrefaciens to dehalogenate CT. A microaerobic growth period also increased cytochrome concentrations. A relationship between cytochrome content and dehalogenation ability was developed from studies in which cytochrome concentrations in S. putrefaciens were manipulated by changing growth conditions. Stoichiometry studies using {sup 14}C-CT suggested that CT was first reduced to form a trichloromethyl radical. Reduction of the radical to produce chloroform and reaction of the radical with cellular biochemicals explained observed product distributions. Carbon dioxide or other fully dehalogenated products were not found.

  18. Computation Sheds Insight into Iron Porphyrin Carbenes' Electronic Structure, Formation, and N-H Insertion Reactivity.

    PubMed

    Sharon, Dina A; Mallick, Dibyendu; Wang, Binju; Shaik, Sason

    2016-08-01

    Iron porphyrin carbenes constitute a new frontier of species with considerable synthetic potential. Exquisitely engineered myoglobin and cytochrome P450 enzymes can generate these complexes and facilitate the transformations they mediate. The current work harnesses density functional theoretical methods to provide insight into the electronic structure, formation, and N-H insertion reactivity of an iron porphyrin carbene, [Fe(Por)(SCH3)(CHCO2Et)](-), a model of a complex believed to exist in an experimentally studied artificial metalloenzyme. The ground state electronic structure of the terminal form of this complex is an open-shell singlet, with two antiferromagnetically coupled electrons residing on the iron center and carbene ligand. As we shall reveal, the bonding properties of [Fe(Por)(SCH3)(CHCO2Et)](-) are remarkably analogous to those of ferric heme superoxide complexes. The carbene forms by dinitrogen loss from ethyl diazoacetate. This reaction occurs preferentially through an open-shell singlet transition state: iron donates electron density to weaken the C-N bond undergoing cleavage. Once formed, the iron porphyrin carbene accomplishes N-H insertion via nucleophilic attack. The resulting ylide then rearranges, using an internal carbonyl base, to form an enol that leads to the product. The findings rationalize experimentally observed reactivity trends reported in artificial metalloenzymes employing iron porphyrin carbenes. Furthermore, these results suggest a possible expansion of enzymatic substrate scope, to include aliphatic amines. Thus, this work, among the first several computational explorations of these species, contributes insights and predictions to the surging interest in iron porphyrin carbenes and their synthetic potential. PMID:27347808

  19. Titanium Catalyzed Perchlorate Reduction and Applications

    SciTech Connect

    Gu, Baohua; Bonnesen, Peter V; Sloop Jr, Frederick {Fred} V; Brown, Gilbert M

    2006-01-01

    This work provides a proof-of-principle demonstration that Ti(III)-catalyzed electrochemical techniques could potentially be used for reduction of ClO{sub 4}{sup -} in small waste streams, such as the regeneration of selective anion-exchange resins that are loaded with ClO{sub 4}{sup -}. The technique may not be directly applied for the treatment of large volumes of ClO{sub 4}{sup -}-contaminated water at relatively low concentrations because of its slow reaction kinetics and the use of chemical reagents. Further studies are needed to optimize the reaction conditions in order to achieve a complete reduction of ClO{sub 4}{sup -} and the regeneration of spent resin beds. Alternative complexing and reducing agents may be used to enhance the reaction completeness of sorbed ClO{sub 4}{sup -} in the resin and to overcome potential clogging of micropores within the resin beads resulting from the precipitation of TiO{sub 2}.

  20. Model studies in cytochrome P-450 mediated toxicity of halogenated compounds: radical processes involving iron porphyrins

    SciTech Connect

    Brault, D.

    1985-12-01

    Haloalkane toxicity originates from attack on biological targets by reactive intermediates derived from haloalkane metabolism by a hemoprotein, cytochrome P-450. Carbon-centered radicals and their peroxylderivatives are most likely involved. The reactions of iron porphyrin - a model for cytochrome P-450 - with various carbon-centered and peroxyl radicals generated by pulse radiolysis are examined. Competition between iron porphyrin and unsaturated fatty acids for attack by peroxyl radicals is pointed out. These kinetic data are used to derive a model for toxicity of haloalkanes with particular attention to carbon tetrachloride and halothane. The importance of local oxygen concentration and structural arrangement of fatty acids around cytochrome P-450 is emphasized. 56 references.

  1. Current Issues in Molecular Catalysis Illustrated by Iron Porphyrins as Catalysts of the CO2-to-CO Electrochemical Conversion.

    PubMed

    Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel

    2015-12-15

    Recent attention aroused by the reduction of carbon dioxide has as main objective the production of useful products, the "solar fuels", in which solar energy would be stored. One route to this goal is the design of photochemical schemes that would operate this conversion using directly sun light energy. An indirect approach consists in first converting sunlight energy into electricity then using it to reduce CO2 electrochemically. Conversion of carbon dioxide into carbon monoxide is thus a key step through the classical dihydrogen-reductive Fischer-Tropsch chemistry. Direct and catalytic electrochemical CO2 reduction already aroused active interest during the 1980-1990 period. The new wave of interest for these matters that has been growing since 2012 is in direct conjunction with modern energy issues. Among molecular catalysts, electrogenerated Fe(0) porphyrins have proved to be particularly efficient and robust. Recent progress in this field has closely associated the search of more and more efficient catalysts in the iron porphyrin family with an unprecedentedly rigorous deciphering of mechanisms. Accordingly, the coupling of proton transfer with electron transfer and breaking of one of the two C-O bonds of CO2 have been the subjects of relentless scrutiny and mechanistic analysis with systematic investigation of the degree of concertedness of these three events. Catalysis of the electrochemical CO2-to-CO conversion has thus been a good testing ground for the mechanism diagnostic strategies and the all concerted reactivity model proposed then. The role of added Brönsted acids, both as H-bond providers and proton donors, has been elucidated. These efforts have been a preliminary to the inclusion of the acid functionalities within the catalyst molecule, giving rise to considerable increase of the catalytic efficiency. The design of more and more efficient catalysts made it necessary to propose "catalytic Tafel plots" relating the turnover frequency to the

  2. Oxo-rhenium catalyzed reductive coupling and deoxygenation of alcohols.

    PubMed

    Kasner, Gabrielle R; Boucher-Jacobs, Camille; Michael McClain, J; Nicholas, Kenneth M

    2016-06-01

    Representative benzylic, allylic and α-keto alcohols are deoxygenated to alkanes and/or reductively coupled to alkane dimers by reaction with PPh3 catalyzed by (PPh3)2ReIO2 (1). The newly discovered catalytic reductive coupling reaction is a rare C-C bond-forming transformation of alcohols. PMID:27174412

  3. Cu(II) - Catalyzed Hydrazine Reduction of Ferrous Nitrate

    SciTech Connect

    Karraker, D.G.

    2001-10-15

    This report discusses the results of a study of catalyzed hydrazine reduction of ferrous nitrate. It is apparent that there is a substantial reaction between hydrazine and nitrate ion (or nitric acid) to produce HN3 during both the reduction of Fe(III) and during storage at room temperature.

  4. The Accuracy of Geometries for Iron Porphyrin Complexes from Density Functional Theory

    NASA Astrophysics Data System (ADS)

    Rydberg, Patrik; Olsen, Lars

    2009-08-01

    Iron porphyrin complexes are cofactors in many important proteins such as cytochromes P450, hemoglobin, heme peroxidases, etc. Many computational studies on these systems have been done over the past decade. In this study, the performance of some of the most commonly used density functional theory functionals is evaluated with regard to how they reproduce experimental structures. Seven different functionals (BP86, PBE, PBE0, TPSS, TPSSH, B3LYP, and B97-D) are used to study eight different iron porphyrin complexes. The results show that the TPSSH, PBE0, and TPSS functionals give the best results (absolute bond distance deviations of 0.015-0.016 Å), but the geometries are well-reproduced by all functionals except B3LYP. We also test four different basis sets of double-ζ quality, and we find that a combination of double-ζ basis set of Schäfer et al. on the iron atom and the 6-31G* basis set on the other atoms performs best. Finally, we remove the porphyrin side chains and increase the basis set size systematically to see if this affects the results. We show that basis sets larger than double-ζ quality are not necessary to get accurate geometries, and nonaromatic side chains do not affect the geometries.

  5. Nickel-Catalyzed Reductive Amidation of Unactivated Alkyl Bromides.

    PubMed

    Serrano, Eloisa; Martin, Ruben

    2016-09-01

    A user-friendly, nickel-catalyzed reductive amidation of unactivated primary, secondary, and tertiary alkyl bromides with isocyanates is described. This catalytic strategy offers an efficient synthesis of a wide range of aliphatic amides under mild conditions and with an excellent chemoselectivity profile while avoiding the use of stoichiometric and sensitive organometallic reagents. PMID:27357076

  6. Catalyzed reduction of nitrate in aqueous solutions

    SciTech Connect

    Haas, P.A.

    1994-08-01

    Sodium nitrate and other nitrate salts in wastes is a major source of difficulty for permanent disposal. Reduction of nitrate using aluminum metal has been demonstrated, but NH{sub 3}, hydrazine, or organic compounds containing oxygen would be advantageous for reduction of nitrate in sodium nitrate solutions. Objective of this seed money study was to determine minimum conditions for reduction. Proposed procedure was batchwise heating of aqueous solutions in closed vessels with monitoring of temperatures and pressures. A simple, convenient apparatus and procedure were demonstrated for observing formation of gaseous products and collecting samples for analyses. The test conditions were 250{degree}C and 1000 psi max. Any useful reduction of sodium nitrate to sodium hydroxide as the primary product was not found. The nitrate present at pHs < 4 as HNO{sub 3} or NH{sub 4}NO{sub 3} is easily decomposed, and the effect of nitromethane at these low pHs was confirmed. When acetic acid or formic acid was added, 21 to 56% of the nitrate in sodium nitrate solutions was reduced by methanol or formaldehyde. With hydrazine and acetic acid, 73 % of the nitrate was decomposed to convert NaNO{sub 3} to sodium acetate. With hydrazine and formic acid, 36% of the nitrate was decomposed. If these products are more acceptable for final disposal than sodium nitrate, the reagents are cheap and the conversion conditions would be practical for easy use. Ammonium acetate or formate salts did not significantly reduce nitrate in sodium nitrate solutions.

  7. Iridium-Catalyzed Reductive Nitro-Mannich Cyclization

    PubMed Central

    Gregory, Alex W; Chambers, Alan; Hawkins, Alison; Jakubec, Pavol; Dixon, Darren J

    2015-01-01

    A new chemoselective reductive nitro-Mannich cyclization reaction sequence of nitroalkyl-tethered lactams has been developed. Relying on the rapid and chemoselective iridium(I)-catalyzed reduction of lactams to the corresponding enamine, subsequent nitro-Mannich cyclization of tethered nitroalkyl functionality provides direct access to important alkaloid natural-product-like structures in yields up to 81 % and in diastereoselectivities that are typically good to excellent. An in-depth understanding of the reaction mechanism has been gained through NMR studies and characterization of reaction intermediates. The new methodology has been applied to the total synthesis of (±)-epi-epiquinamide in four steps. PMID:25399919

  8. CO2 reduction catalyzed by mercaptopteridine on glassy carbon.

    PubMed

    Xiang, Dongmei; Magana, Donny; Dyer, R Brian

    2014-10-01

    The catalytic reduction of CO2 is of great current interest because of its role in climate change and the energy cycle. We report a pterin electrocatalyst, 6,7-dimethyl-4-hydroxy-2-mercaptopteridine (PTE), that catalyzes the reduction of CO2 and formic acid on a glassy carbon electrode. Pterins are natural cofactors for a wide range of enzymes, functioning as redox mediators and C1 carriers, but they have not been exploited as electrocatalysts. Bulk electrolysis of a saturated CO2 solution in the presence of the PTE catalyst produces methanol, as confirmed by gas chromatography and (13)C NMR spectroscopy, with a Faradaic efficiency of 10-23%. FTIR spectroelectrochemistry detected a progression of two-electron reduction products during bulk electrolysis, including formate, aqueous formaldehyde, and methanol. A transient intermediate was also detected by FTIR and tentatively assigned as a PTE carbamate. The results demonstrate that PTE catalyzes the reduction of CO2 at low overpotential and without the involvement of any metal. PMID:25259884

  9. Iron porphyrinate Fe(TPPS) reduces brain cell damage in rats intrastriatally lesioned by quinolinate.

    PubMed

    González-Cortés, Carolina; Salinas-Lara, Citlaltepetl; Gómez-López, Marcos Artemio; Tena-Suck, Martha Lilia; Pérez-De La Cruz, Verónica; Rembao-Bojórquez, Daniel; Pedraza-Chaverrí, José; Gómez-Ruiz, Celedonio; Galván-Arzate, Sonia; Ali, Syed F; Santamaría, Abel

    2008-01-01

    It has been recently demonstrated that the reactive nitrogen species (RNS) peroxynitrite (ONOO(-)) is involved in the neurotoxic pattern produced by quinolinic acid in the rat brain [V. Pérez-De La Cruz, C. González-Cortés, S. Galván-Arzate, O.N. Medina-Campos, F. Pérez-Severiano, S.F. Ali, J. Pedraza-Chaverrí, A. Santamaría, Excitotoxic brain damage involves early peroxynitrite formation in a model of Huntington's disease in rats: protective role of iron porphyrinate 5,10,15,20-tetrakis (4-sulfonatophenyl)porphyrinate iron (III), Neuroscience 135 (2005) 463-474.]. The aim of this work was to investigate whether ONOO(-) can also be responsible for morphological alterations and inflammatory events in the same paradigm. For this purpose, we evaluated the effect of a pre-treatment with the iron porphyrinate Fe(TPPS), a well-known ONOO(-) decomposition catalyst (10 mg/kg, i.p., 120 min before lesion), on the quinolinate-induced striatal cell damage and immunoreactivities to glial-fibrilar acidic protein (GFAP), interleukin 6 (IL-6) and inducible nitric oxide synthase (iNOS), one and seven days after the intrastriatal infusion of quinolinate (240 nmol/microl) to rats. The striatal tissue from animals lesioned by quinolinate showed a significant degree of damage and enhanced immunoreactivities to GFAP, IL-6 and iNOS, both at 1 and 7 days post-lesion. Pre-treatment of rats with Fe(TPPS) significantly attenuated or prevented all these markers at both post-lesion times tested, except for GFAP immunoreactivity at 7 days post-lesion and iNOS immunoreactivity at 1 day post-lesion. Altogether, our results suggest that ONOO(-) is actively participating in triggering inflammatory events and morphological alterations in the toxic model produced by quinolinate, since the use of agents affecting its formation, such as Fe(TPPS), are effective experimental tools to reduce the brain lesions associated to excitotoxic and oxidative damage. PMID:18579343

  10. Anisotropic Iron Motion in Nitrosyl Iron Porphyrinates: Natural and Synthetic Hemes

    PubMed Central

    2015-01-01

    The vibrational spectra of two five-coordinate nitrosyl iron porphyrinates, [Fe(OEP)(NO)] (OEP = dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin) and [Fe(DPIX)(NO)] (DPIX = deuteroporphyrin IX), have been studied by oriented single-crystal nuclear resonance vibrational spectroscopy. Single crystals (both are in the triclinic crystal system) were oriented to give vibrational spectra perpendicular to the porphyrin plane. Additionally, two orthogonal in-plane measurements that were also either perpendicular or parallel to the projection of the FeNO plane onto the porphyrin plane yield the complete set of vibrations with iron motion. In addition to cleanly enabling the assignment of the FeNO bending and stretching modes, the measurements reveal that the two in-plane spectra from the parallel and perpendicular in-plane directions for both compounds have substantial differences. The assignment of these in-plane vibrations were aided by density functional theory predictions. The differences in the two in-plane directions result from the strongly bonded axial NO ligand. The direction of the in-plane iron motion is thus found to be largely parallel and perpendicular to the projection of the FeNO plane on the porphyrin plane. These axial ligand effects on the in-plane iron motion are related to the strength of the axial ligand-to-iron bond. PMID:24528178

  11. Cathodic oxygen reduction catalyzed by bacteria in microbial fuel cells.

    PubMed

    Rabaey, Korneel; Read, Suzanne T; Clauwaert, Peter; Freguia, Stefano; Bond, Philip L; Blackall, Linda L; Keller, Jurg

    2008-05-01

    Microbial fuel cells (MFCs) have the potential to combine wastewater treatment efficiency with energetic efficiency. One of the major impediments to MFC implementation is the operation of the cathode compartment, as it employs environmentally unfriendly catalysts such as platinum. As recently shown, bacteria can facilitate sustainable and cost-effective cathode catalysis for nitrate and also oxygen. Here we describe a carbon cathode open to the air, on which attached bacteria catalyzed oxygen reduction. The bacteria present were able to reduce oxygen as the ultimate electron acceptor using electrons provided by the solid-phase cathode. Current densities of up to 2.2 A m(-2) cathode projected surface were obtained (0.303+/-0.017 W m(-2), 15 W m(-3) total reactor volume). The cathodic microbial community was dominated by Sphingobacterium, Acinetobacter and Acidovorax sp., according to 16S rRNA gene clone library analysis. Isolates of Sphingobacterium sp. and Acinetobacter sp. were obtained using H(2)/O(2) mixtures. Some of the pure culture isolates obtained from the cathode showed an increase in the power output of up to three-fold compared to a non-inoculated control, that is, from 0.015+/-0.001 to 0.049+/-0.025 W m(-2) cathode projected surface. The strong decrease in activation losses indicates that bacteria function as true catalysts for oxygen reduction. Owing to the high overpotential for non-catalyzed reduction, oxygen is only to a limited extent competitive toward the electron donor, that is, the cathode. Further research to refine the operational parameters and increase the current density by modifying the electrode surface and elucidating the bacterial metabolism is warranted. PMID:18288216

  12. Nickel-Catalyzed Reductive Cross-Coupling of Aryl Bromides with Alkyl Bromides: Et3N as the Terminal Reductant.

    PubMed

    Duan, Zhengli; Li, Wu; Lei, Aiwen

    2016-08-19

    Reductive cross-coupling has emerged as a direct method for the construction of carbon-carbon bonds. Most cobalt-, nickel-, and palladium-catalyzed reductive cross-coupling reactions to date are limited to stoichiometric Mn(0) or Zn(0) as the reductant. One nickel-catalyzed cross-coupling paradigm using Et3N as the terminal reductant is reported. By using this photoredox catalysis and nickel catalysis approach, a direct Csp(2)-Csp(3) reductive cross-coupling of aryl bromides with alkyl bromides is achieved under mild conditions without stoichiometric metal reductants. PMID:27472556

  13. A Convenient Palladium-Catalyzed Reductive Carbonylation of Aryl Iodides with Dual Role of Formic Acid.

    PubMed

    Qi, Xinxin; Li, Chong-Liang; Wu, Xiao-Feng

    2016-04-18

    Palladium-catalyzed reductive carbonylation of aryl halides represents a straightforward pathway for the synthesis of aromatic aldehydes. The known reductive carbonylation procedures either require CO gas or complexed compounds as CO sources. In this communication, we developed a palladium-catalyzed reductive carbonylation of aryl iodides with formic acid as the formyl source. As a convenient, practical, and environmental friendly methodology, no additional silane or H2 was required. A variety of aromatic aldehydes were isolated in moderate to excellent yields under mild reaction conditions. Notably, this is the first procedure on using formic acid as the formyl source. PMID:26934464

  14. Regeneration of anion exchange resins by catalyzed electrochemical reduction

    DOEpatents

    Gu, Baohua; Brown, Gilbert M.

    2002-01-01

    Anion exchange resins sorbed with perchlorate may be regenerated by a combination of chemical reduction of perchlorate to chloride using a reducing agent and an electrochemical reduction of the oxidized reducing agent. Transitional metals including Ti, Re, and V are preferred chemical reagents for the reduction of perchlorate to chloride. Complexing agents such as oxalate are used to prevent the precipitation of the oxidized Ti(IV) species, and ethyl alcohol may be added to accelerate the reduction kinetics of perchlorate. The regeneration may be performed by continuously recycling the regenerating solution through the resin bed and an electrochemical cell so that the secondary waste generation is minimized.

  15. Nickel(0)-catalyzed intramolecular reductive coupling of alkenes and aldehydes or ketones with hydrosilanes.

    PubMed

    Hayashi, Yukari; Hoshimoto, Yoichi; Kumar, Ravindra; Ohashi, Masato; Ogoshi, Sensuke

    2016-05-01

    A nickel(0)-catalyzed reductive coupling of aldehydes and simple alkenes with hydrosilanes has been developed. A variety of silyl-protected 1-indanol derivatives were prepared in a highly diastereoselective manner (up to >99 : 1 dr) by employing a combination of nickel(0)/N-heterocyclic carbene and triethylsilane. The present system was also applied to a reductive coupling with ketones. Preliminary results of a nickel(0)-catalyzed asymmetric three-component coupling reaction of an aldehyde, an alkene, and triethylsilane are also shown. PMID:27077829

  16. Local Pathways in Coherent Electron Transport through Iron Porphyrin Complexes: A Challenge for First-Principles Transport Calculations

    SciTech Connect

    Herrmann, C.; Solomon, G.C.; Ratner, Mark A.

    2010-12-09

    We investigate the coherent electron transport properties of a selection of iron porphyrin complexes in their low-spin and high-spin states, binding the system to metallic electrodes with three different substitution patterns. We use a study of the local transmission through the complexes and their molecular orbitals to show the role of the various components of the molecular structure in mediating electron transport. While there are energies where the metal center and the axial ligands participate in transport, in the off-resonant energy range, these components simply form a scaffold, and the transport is dominated by transmission through the porphyrin macrocyle alone. This is still true when going from the low-spin to the high-spin state, except that now, an additional iron-centered MO contributes to transport in the formerly off-resonant region. It is found that while the choice of the exchange-correlation functional can strongly influence the quantitative results, our qualitative conclusions hold irrespective of the functional employed.

  17. Carbon dioxide reduction to methane and coupling with acetylene to form propylene catalyzed by remodeled nitrogenase

    PubMed Central

    Yang, Zhi-Yong; Moure, Vivian R.; Dean, Dennis R.; Seefeldt, Lance C.

    2012-01-01

    A doubly substituted form of the nitrogenase MoFe protein (α-70Val→Ala, α-195His→Gln) has the capacity to catalyze the reduction of carbon dioxide (CO2) to yield methane (CH4). Under optimized conditions, 1 nmol of the substituted MoFe protein catalyzes the formation of 21 nmol of CH4 within 20 min. The catalytic rate depends on the partial pressure of CO2 (or concentration of HCO3−) and the electron flux through nitrogenase. The doubly substituted MoFe protein also has the capacity to catalyze the unprecedented formation of propylene (H2C = CH-CH3) through the reductive coupling of CO2 and acetylene (HC≡CH). In light of these observations, we suggest that an emerging understanding of the mechanistic features of nitrogenase could be relevant to the design of synthetic catalysts for CO2 sequestration and formation of olefins. PMID:23150564

  18. Humic substances as a mediator for microbially catalyzed metal reduction

    USGS Publications Warehouse

    Lovley, D.R.; Fraga, J.L.; Blunt-Harris, E. L.; Hayes, L.A.; Phillips, E.J.P.; Coates, J.D.

    1998-01-01

    The potential for humic substances to serve as a terminal electron acceptor in microbial respiration and to function as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides was investigated. The Fe(III)-reducing microorganism Geobacter metallireducens conserved energy to support growth from electron transport to humics as evidenced by continued oxidation of acetate to carbon dioxide after as many as nine transfers in a medium with acetate as the electron donor and soil humic acids as the electron acceptor. Growth of G. metallireducens with poorly crystalline Fe(III) oxide as the electron acceptor was greatly stimulated by the addition of as little as 100 ??M of the humics analog, anthraquinone-2,6-disulfonate. Other quinones investigated, including lawsone, menadione, and anthraquinone-2-sulfonate, also stimulated Fe(III) oxide reduction. A wide phylogenetic diversity of microorganisms capable of Fe(III) reduction were also able to transfer electrons to humics. Microorganisms which can not reduce Fe(III) could not reduce humics. Humics stimulated the reduction of structural Fe(III) in clay and the crystalline Fe(III) forms, goethite and hematite. These results demonstrate that electron shuttling between Fe(III)-reducing microorganisms and Fe(III) via humics not only accelerates the microbial reduction of poorly crystalline Fe(III) oxide, but also can facilitate the reduction of Fe(III) forms that are not typically reduced by microorganisms in the absence of humics. Addition of humic substances to enhance electron shuttling between Fe(III)-reducing microorganisms and Fe(III) oxides may be a useful strategy to stimulate the remediation of soils and sediments contaminated with organic or metal pollutants.

  19. Oxygen reduction on a graphite paste and a catalyst loaded graphite paste electrode

    SciTech Connect

    DiMarco, D.M.

    1980-03-01

    Oxygen reduction was studied in basic solution at a graphite paste electrode (GPE). The GPE was used as the disk of a rotating ring disk electrode (RRDE) and experiments were done using the voltage scan technique. The enhancements afforded by catalysts applied to the GPE were also studied. Oxygen reduction on a GPE was shown to be a two-electron process resulting in the formation of peroxide. The Tafel slope (plotted as potential versus log(i/sub l/ x i/(i/sub l/ - i))) was 180 mV. The presence of gold, silver, or platinum on the GPE shifted the oxygen reduction wave approximately 800 mV in the anodic direction. Comparison of the data on a metal catalyzed GPE to the solid metal electrode showed that the former electrode produced a greater fraction of peroxide as product than did the latter. Silver and gold catalyzed GPEs gave Tagel slopes of about 120 mV. The intermediate catalysis of iron and cobalt porphyrin was also examined. While the cobalt porphyrin catalyzed oxygen reduction at a more anodic potential than the iron porphyrin, the latter appeared more active in reacting the peroxide formed as the product of the disk reaction.

  20. Molybdenum Nitrogenase Catalyzes the Reduction and Coupling of CO to Form Hydrocarbons*♦

    PubMed Central

    Yang, Zhi-Yong; Dean, Dennis R.; Seefeldt, Lance C.

    2011-01-01

    The molybdenum-dependent nitrogenase catalyzes the multi-electron reduction of protons and N2 to yield H2 and 2NH3. It also catalyzes the reduction of a number of non-physiological doubly and triply bonded small molecules (e.g. C2H2, N2O). Carbon monoxide (CO) is not reduced by the wild-type molybdenum nitrogenase but instead inhibits the reduction of all substrates catalyzed by nitrogenase except protons. Here, we report that when the nitrogenase MoFe protein α-Val70 residue is substituted by alanine or glycine, the resulting variant proteins will catalyze the reduction and coupling of CO to form methane (CH4), ethane (C2H6), ethylene (C2H4), propene (C3H6), and propane (C3H8). The rates and ratios of hydrocarbon production from CO can be adjusted by changing the flux of electrons through nitrogenase, by substitution of other amino acids located near the FeMo-cofactor, or by changing the partial pressure of CO. Increasing the partial pressure of CO shifted the product ratio in favor of the longer chain alkanes and alkenes. The implications of these findings in understanding the nitrogenase mechanism and the relationship to Fischer-Tropsch production of hydrocarbons from CO are discussed. PMID:21454640

  1. Glutathione-supported arsenate reduction coupled to arsenolysis catalyzed by ornithine carbamoyl transferase

    SciTech Connect

    Nemeti, Balazs; Gregus, Zoltan

    2009-09-01

    Three cytosolic phosphorolytic/arsenolytic enzymes, (purine nucleoside phosphorylase [PNP], glycogen phosphorylase, glyceraldehyde-3-phosphate dehydrogenase) have been shown to mediate reduction of arsenate (AsV) to the more toxic arsenite (AsIII) in a thiol-dependent manner. With unknown mechanism, hepatic mitochondria also reduce AsV. Mitochondria possess ornithine carbamoyl transferase (OCT), which catalyzes phosphorolytic or arsenolytic citrulline cleavage; therefore, we examined if mitochondrial OCT facilitated AsV reduction in presence of glutathione. Isolated rat liver mitochondria were incubated with AsV, and AsIII formed was quantified. Glutathione-supplemented permeabilized or solubilized mitochondria reduced AsV. Citrulline (substrate for OCT-catalyzed arsenolysis) increased AsV reduction. The citrulline-stimulated AsV reduction was abolished by ornithine (OCT substrate inhibiting citrulline cleavage), phosphate (OCT substrate competing with AsV), and the OCT inhibitor norvaline or PALO, indicating that AsV reduction is coupled to OCT-catalyzed arsenolysis of citrulline. Corroborating this conclusion, purified bacterial OCT mediated AsV reduction in presence of citrulline and glutathione with similar responsiveness to these agents. In contrast, AsIII formation by intact mitochondria was unaffected by PALO and slightly stimulated by citrulline, ornithine, and norvaline, suggesting minimal role for OCT in AsV reduction in intact mitochondria. In addition to OCT, mitochondrial PNP can also mediate AsIII formation; however, its role in AsV reduction appears severely limited by purine nucleoside supply. Collectively, mitochondrial and bacterial OCT promote glutathione-dependent AsV reduction with coupled arsenolysis of citrulline, supporting the hypothesis that AsV reduction is mediated by phosphorolytic/arsenolytic enzymes. Nevertheless, because citrulline cleavage is disfavored physiologically, OCT may have little role in AsV reduction in vivo.

  2. Oxygen reduction catalyzed by gold nanoclusters supported on carbon nanosheets

    NASA Astrophysics Data System (ADS)

    Wang, Qiannan; Wang, Likai; Tang, Zhenghua; Wang, Fucai; Yan, Wei; Yang, Hongyu; Zhou, Weijia; Li, Ligui; Kang, Xiongwu; Chen, Shaowei

    2016-03-01

    Nanocomposites based on p-mercaptobenzoic acid-functionalized gold nanoclusters, Au102(p-MBA)44, and porous carbon nanosheets have been fabricated and employed as highly efficient electrocatalysts for oxygen reduction reaction (ORR). Au102(p-MBA)44 clusters were synthesized via a wet chemical approach, and loaded onto carbon nanosheets. Pyrolysis at elevated temperatures led to effective removal of the thiolate ligands and the formation of uniform nanoparticles supported on the carbon scaffolds. The nanocomposite structures were characterized by using a wide range of experimental techniques such as transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, UV-visible absorption spectroscopy, thermogravimetric analysis and BET nitrogen adsorption/desorption. Electrochemical studies showed that the composites demonstrated apparent ORR activity in alkaline media, and the sample with a 30% Au mass loading was identified as the best catalyst among the series, with a performance comparable to that of commercial Pt/C, but superior to those of Au102 nanoclusters and carbon nanosheets alone, within the context of onset potential, kinetic current density, and durability. The results suggest an effective approach to the preparation of high-performance ORR catalysts based on gold nanoclusters supported on carbon nanosheets.Nanocomposites based on p-mercaptobenzoic acid-functionalized gold nanoclusters, Au102(p-MBA)44, and porous carbon nanosheets have been fabricated and employed as highly efficient electrocatalysts for oxygen reduction reaction (ORR). Au102(p-MBA)44 clusters were synthesized via a wet chemical approach, and loaded onto carbon nanosheets. Pyrolysis at elevated temperatures led to effective removal of the thiolate ligands and the formation of uniform nanoparticles supported on the carbon scaffolds. The nanocomposite structures were characterized by using a wide range of experimental techniques such as

  3. Oxygen reduction catalyzed by gold nanoclusters supported on carbon nanosheets.

    PubMed

    Wang, Qiannan; Wang, Likai; Tang, Zhenghua; Wang, Fucai; Yan, Wei; Yang, Hongyu; Zhou, Weijia; Li, Ligui; Kang, Xiongwu; Chen, Shaowei

    2016-03-28

    Nanocomposites based on p-mercaptobenzoic acid-functionalized gold nanoclusters, Au102(p-MBA)44, and porous carbon nanosheets have been fabricated and employed as highly efficient electrocatalysts for oxygen reduction reaction (ORR). Au102(p-MBA)44 clusters were synthesized via a wet chemical approach, and loaded onto carbon nanosheets. Pyrolysis at elevated temperatures led to effective removal of the thiolate ligands and the formation of uniform nanoparticles supported on the carbon scaffolds. The nanocomposite structures were characterized by using a wide range of experimental techniques such as transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, UV-visible absorption spectroscopy, thermogravimetric analysis and BET nitrogen adsorption/desorption. Electrochemical studies showed that the composites demonstrated apparent ORR activity in alkaline media, and the sample with a 30% Au mass loading was identified as the best catalyst among the series, with a performance comparable to that of commercial Pt/C, but superior to those of Au102 nanoclusters and carbon nanosheets alone, within the context of onset potential, kinetic current density, and durability. The results suggest an effective approach to the preparation of high-performance ORR catalysts based on gold nanoclusters supported on carbon nanosheets. PMID:26940367

  4. Metal-Catalyzed β-Functionalization of Michael Acceptors through Reductive Radical Addition Reactions.

    PubMed

    Streuff, Jan; Gansäuer, Andreas

    2015-11-23

    Transition-metal-catalyzed radical reactions are becoming increasingly important in modern organic chemistry. They offer fascinating and unconventional ways for connecting molecular fragments that are often complementary to traditional methods. In particular, reductive radical additions to α,β-unsaturated compounds have recently gained substantial attention as a result of their broad applicability in organic synthesis. This Minireview critically discusses the recent landmark achievements in this field in context with earlier reports that laid the foundation for today's developments. PMID:26471460

  5. Nickel-Catalyzed Asymmetric Reductive Cross-Coupling Between Vinyl and Benzyl Electrophiles

    PubMed Central

    2015-01-01

    A Ni-catalyzed asymmetric reductive cross-coupling between vinyl bromides and benzyl chlorides has been developed. This method provides direct access to enantioenriched products bearing aryl-substituted tertiary allylic stereogenic centers from simple, stable starting materials. A broad substrate scope is achieved under mild reaction conditions that preclude the pregeneration of organometallic reagents and the regioselectivity issues commonly associated with asymmetric allylic arylation. PMID:25245492

  6. Copper-Catalyzed Reductive N-Alkylation of Amides with N-Tosylhydrazones Derived from Ketones.

    PubMed

    Xu, Peng; Qi, Fu-Ling; Han, Fu-She; Wang, Yan-Hua

    2016-07-20

    A CuI-catalyzed reductive coupling of ketone-derived N-tosylhydrazones with amides is presented. Under the optimized conditions, an array of N-tosylhydrazones derived from aryl-alkyl and diaryl ketones could couple effectively with a wide variety of (hetero)aryl as well as aliphatic amides to afford the N-alkylated amides in high yields. The method represents the very few examples for reliably accessing secondary and tertiary amides through a reductive N-alkylation protocol. PMID:27346856

  7. Lewis Base Activation of Silyl Acetals: Iridium-Catalyzed Reductive Horner-Wadsworth-Emmons Olefination.

    PubMed

    Dakarapu, Udaya Sree; Bokka, Apparao; Asgari, Parham; Trog, Gabriela; Hua, Yuanda; Nguyen, Hiep H; Rahman, Nawal; Jeon, Junha

    2015-12-01

    A Lewis base promoted deprotonative pronucleophile addition to silyl acetals has been developed and applied to the iridium-catalyzed reductive Horner-Wadsworth-Emmons (HWE) olefination of esters and the chemoselective reduction of the resulting enoates. Lewis base activation of silyl acetals generates putative pentacoordinate silicate acetals, which fragment into aldehydes, silanes, and alkoxides in situ. Subsequent deprotonative metalation of phosphonate esters followed by HWE with aldehydes furnishes enoates. This operationally convenient, mechanistically unique protocol converts the traditionally challenging aryl, alkenyl, and alkynyl esters to homologated enoates at room temperature within a single vessel. PMID:26566189

  8. Azotobacter vinelandii vanadium nitrogenase: formaldehyde is a product of catalyzed HCN reduction, and excess ammonia arises directly from catalyzed azide reduction.

    PubMed

    Fisher, Karl; Dilworth, Michael J; Newton, William E

    2006-04-01

    The Mo-nitrogenase-catalyzed reduction of both cyanide and azide results in the production of excess NH3, which is an amount of NH3 over and above that expected to be formed from the well-recognized reactions. Several suggestions about the possible sources of excess NH3 have been made, but previous attempts to characterize these reactions have met with either limited (or no) success or controversy. Because V-nitrogenase has a propensity to release partially reduced intermediates, e.g., N2H4 during N2 reduction, it was selected to probe the reduction of cyanide and azide. Sensitive assay procedures were developed and employed to monitor the production of either HCHO or CH3OH (its further two-electron-reduced product) from HCN. Like Mo-nitrogenase, V-nitrogenase suffered electron-flux inhibition by CN- (but was much less sensitive than Mo-nitrogenase), but unlike the case for Mo-nitrogenase, MgATP hydrolysis was also inhibited by CN-. V-Nitrogenase also released more of the four-electron-reduced intermediate, CH3NH2, than did Mo-nitrogenase. At high NaCN concentrations, V-nitrogenase directed a significant percentage of electron flux into excess NH3, and under these conditions, substantial amounts of HCHO, but no CH3OH, were detected for the first time. With azide, in contrast to the case for Mo-nitrogenase, both total electron flux and MgATP hydrolysis with V-nitrogenase were inhibited. V-Nitrogenase, unlike Mo-nitrogenase, showed no preference between the two-electron reduction to N2-plus-NH3 and the six-electron reduction to N2H4-plus-NH3. V-Nitrogenase formed more excess NH3, but reduction of the N2 produced by the two-electron reduction of N3(-) was not its source. Rather, it was formed directly by the eight-electron reduction of N3(-). Unlike Mo-nitrogenase, CO could not completely eliminate either cyanide or azide reduction by V-nitrogenase. CO did, however, eliminate the inhibition of both electron flux and MgATP hydrolysis by CN-, but not that caused by

  9. A lithium-air fuel cell using copper to catalyze oxygen-reduction based on copper-corrosion mechanism.

    PubMed

    Wang, Yonggang; Zhou, Haoshen

    2010-09-14

    The copper-catalyzed O(2) reduction in aqueous electrolyte and the Li-anode in organic electrolyte were united together by a ceramic Li-ions exchange film to form a lithium-air fuel cell. The achieved results demonstrate the cycle between Cu and Cu(2)O can be used to catalyze O(2) electrochemical reduction based on the copper-corrosion mechanism. PMID:20668776

  10. Studies on the electrochemical reduction of oxygen catalyzed by reduced graphene sheets in neutral media

    NASA Astrophysics Data System (ADS)

    Wu, Jiajia; Wang, Yi; Zhang, Dun; Hou, Baorong

    Reduced graphene sheets (RGSs) were prepared via chemical reduction of graphite oxide and their morphology was characterized by atomic force microscopy. The electrochemical reduction of oxygen (O 2) with RGSs was studied by cyclic, rotating disk electrode, and rotating ring-disk electrode voltammetry using the RGSs-modified glassy carbon (RGSs/GC) electrode in 3.5% NaCl solution. The results show that O 2 reduction undergoes three steps at the RGSs/GC electrode: electrochemical reduction of O 2 to H 2O 2 mediated by quinone-like groups on the RGSs surface, a direct 2-electron reduction of O 2, and reduction of the H 2O 2 produced to H 2O. The modification of RGSs results in an obvious positive shift of the peak potential and a larger current density. The kinetics study shows that the number of electrons transferred for O 2 reduction can reach to 3.0 at potentials of the first reduction step, indicating RGSs can effectively catalyze the disproportionation of H 2O 2. Such catalytic activity of RGSs enables a 4-electron reduction of O 2 at a relatively low overpotential in neutral media. RGSs are a potential electrode material for microbial fuel cells.

  11. Inhibitory effect of water on the oxygen reduction catalyzed by cobalt(II) tetraphenylporphyrin.

    PubMed

    Trojánek, Antonín; Langmaier, Jan; Kvapilová, Hana; Záliš, Stanislav; Samec, Zdeněk

    2014-03-20

    Stopped-flow kinetic measurements, UV-vis spectroscopy, rotating disk voltammetry, and quantum chemical calculations are used to clarify the role of water in the homogeneous two-electron reduction of O2 to H2O2 in 1,2-dichloroethane (DCE) using ferrocene (Fc) as an electron donor, tetrakis(pentafluorophenyl)boric acid (HTB) as a proton donor, and [5,10,15,20-tetraphenyl-21H,23H-porphine]cobalt(II) (Co(II)TTP) as a catalyst. Kinetic analysis suggests that the reaction is controlled by the intramolecular proton coupled electron transfer to the O2 molecule coordinated to the metal center producing the O2H(•) radical. This rate-determining step is common to both the O2 reduction by Fc catalyzed by Co(II)TPP and the O2 reduction by Co(II)TPP itself. Experimental data point to the competitive coordination of water to the metal center leading to a strong inhibition of the catalytic reaction. In agreement with this finding, quantum chemical calculations indicate that water is bound to the metal center much more strongly than triplet O2. A similar effect is demonstrated also for the O2 reduction catalyzed by the porphyrin free base (H2TPP), though its rate is lower by 2 orders of magnitude. PMID:24564521

  12. Kinetics of tetrachloroethylene-reductive dechlorination catalyzed by vitamin B{sub 12}

    SciTech Connect

    Burris, D.R.; Deng, B.; Buck, L.E.; Hatfield, K.

    1998-09-01

    Reductive dechlorination kinetics of tetrachloroethylene (PCE) to ethylene catalyzed by vitamin B{sub 12} using Ti[III] citrate as the bulk reductant was examined in a vapor-water batch system. A kinetic model incorporating substrate-B{sub 12} electron-transfer complex formation and subsequent product release was developed. The model also accounted for the primary reductive dechlorination pathways (hydrogenolysis and reductive {beta} elimination) and vapor/water-phase partitioning. Reaction rate constants were sequentially determined by fitting the model to experimental kinetic data while moving upward through consecutive reaction pathways. The release of product from the complex was found to be second order with respect to substrate concentration for both PCE and acetylene; all other substrates appeared to release by first order. Reductive {beta} elimination was found to be a significant reaction pathway for trichloroethylene (TCE), and chloroacetylene was observed as a reactive intermediate. Acetylene production appears to be primarily due to the reduction of chloroacetylene derived from TCE. The reduction of cis-dichloroethylene (cis-DCE), the primary DCE isomer formed, was extremely slow, leading to a significant buildup of cis-DCE. The kinetics of acetylene and vinyl chloride reduction appeared to be limited by the formation of relatively stable substrate-B{sub 12} complexes. The relatively simple model examined appears to adequately represent the main features of the experimental data.

  13. Cytochromes P450 Catalyze the Reduction of α,β-Unsaturated Aldehydes

    PubMed Central

    Amunom, Immaculate; Dieter, Laura J.; Tamasi, Viola; Cai, Jan; Conklin, Daniel J.; Srivastava, Sanjay; Martin, Martha V.; Guengerich, F. Peter; Prough, Russell A.

    2011-01-01

    The metabolism of α,β-unsaturated aldehydes, e.g. 4-hydroxynonenal, involves oxidation to carboxylic acids, reduction to alcohols, and glutathionylation to eventually form mercapturide conjugates. Recently we demonstrated that P450s can oxidize aldehydes to carboxylic acids, a reaction previously thought to involve aldehyde dehydrogenase. When recombinant cytochrome P450 3A4 was incubated with 4-hydroxynonenal, O2, and NADPH, several products were produced, including 1,4-dihydroxynonene (DHN), 4-hydroxy-2-nonenoic acid (HNA), and an unknown metabolite. Several P450s catalyzed the reduction reaction in the order (human) P450 2B6 ≅ P450 3A4 > P450 1A2 > P450 2J2 > (mouse) P450 2c29. Other P450s did not catalyze the reduction reaction (human P450 2E1 & rabbit P450 2B4). Metabolism by isolated rat hepatocytes showed that HNA formation was inhibited by cyanamide, while DHN formation was not affected. Troleandomycin increased HNA production 1.6-fold while inhibiting DHN formation, suggesting that P450 3A11 is a major enzyme involved in rat hepatic clearance of 4-HNE. A fluorescent assay was developed using 9-anthracenealdehyde to measure both reactions. Feeding mice diet containing t-butylated hydroxyanisole increased the level of both activities with hepatic microsomal fractions, but not proportionally. Miconazole (0.5 mM) was a potent inhibitor of these microsomal reduction reactions, while phenytoin and α-naphthoflavone (both at 0.5 mM) were partial inhibitors, suggesting the role of multiple P450 enzymes. The oxidative metabolism of these aldehydes was inhibited >90% in an Ar or CO atmosphere, while the reductive reactions were not greatly affected. These results suggest that P450s are significant catalysts of reduction of α,β-unsaturated aldehydes in liver. PMID:21766881

  14. Simultaneous reduction of particulate matter and NO(x) emissions using 4-way catalyzed filtration systems.

    PubMed

    Swanson, Jacob J; Watts, Winthrop F; Newman, Robert A; Ziebarth, Robin R; Kittelson, David B

    2013-05-01

    The next generation of diesel emission control devices includes 4-way catalyzed filtration systems (4WCFS) consisting of both NOx and diesel particulate matter (DPM) control. A methodology was developed to simultaneously evaluate the NOx and DPM control performance of miniature 4WCFS made from acicular mullite, an advanced ceramic material (ACM), that were challenged with diesel exhaust. The impact of catalyst loading and substrate porosity on catalytic performance of the NOx trap was evaluated. Simultaneously with NOx measurements, the real-time solid particle filtration performance of catalyst-coated standard and high porosity filters was determined for steady-state and regenerative conditions. The use of high porosity ACM 4-way catalyzed filtration systems reduced NOx by 99% and solid and total particulate matter by 95% when averaged over 10 regeneration cycles. A "regeneration cycle" refers to an oxidizing ("lean") exhaust condition followed by a reducing ("rich") exhaust condition resulting in NOx storage and NOx reduction (i.e., trap "regeneration"), respectively. Standard porosity ACM 4-way catalyzed filtration systems reduced NOx by 60-75% and exhibited 99.9% filtration efficiency. The rich/lean cycling used to regenerate the filter had almost no impact on solid particle filtration efficiency but impacted NOx control. Cycling resulted in the formation of very low concentrations of semivolatile nucleation mode particles for some 4WCFS formulations. Overall, 4WCFS show promise for significantly reducing diesel emissions into the atmosphere in a single control device. PMID:23550802

  15. Asymmetric reduction of prochiral ketones to chiral alcohols catalyzed by plants tissue.

    PubMed

    Yang, Zhong-Hua; Zeng, Rong; Yang, Gai; Wang, Yu; Li, Li-Zhen; Lv, Zao-Sheng; Yao, Man; Lai, Bin

    2008-09-01

    As an important organic compound, chiral alcohols are the key chiral building blocks to many single enantiomer pharmaceuticals. Asymmetric reduction of the corresponding prochiral ketones to produce the chiral alcohols by biocatalysis is one of the most promising routes. Asymmetric reduction of different kinds of non-natural prochiral ketones catalyzed by various plants tissue was studied in this work. Acetophenone, 4'-chloroacetophenone and ethyl 4-chloroacetoacetate were chosen as the model substrates for simple ketone, halogen-containing aromatic ketone and beta-ketoesters, respectively. Apple (Malus pumila), carrot (Daucus carota), cucumber (Cucumis sativus), onion (Allium cepa), potato (Soanum tuberosum), radish (Raphanus sativus) and sweet potato (Ipomoea batatas) were chosen as the biocatalysts. It was found that these kinds of prochiral ketoness could be reduced by these plants tissue with high enantioselectivity. Both R- and S-form configuration chiral alcohols could be obtained. The e.e. and chemical yield could reach about 98 and 80% respectively for acetophenone and 4'-chloroacetophenone reduction reaction with favorable plant tissue. And the e.e. and yield for ethyl 4-chloroacetoacetate reduction reaction was about 91 and 45% respectively. PMID:18548304

  16. Dimer Involvement and Origin of Crossover in Nickel-Catalyzed Aldehyde–Alkyne Reductive Couplings

    PubMed Central

    2015-01-01

    The mechanism of nickel(0)-catalyzed reductive coupling of aldehydes and alkynes has been studied. Extensive double-labeling crossover studies have been conducted. While previous studies illustrated that phosphine- and N-heterocyclic carbene-derived catalysts exhibited differing behavior, the origin of these effects has now been evaluated in detail. Many variables, including ligand class, sterics of the ligand and alkyne, temperature, and ring size being formed in intramolecular versions, all influence the extent of crossover observed. A computational evaluation of these effects suggests that dimerization of a key metallacyclic intermediate provides the origin of crossover. Protocols that proceed with crossover are typically less efficient than those without crossover given the thermodynamic stability and low reactivity of the dimeric metallacycles involved in crossover pathways. PMID:25401337

  17. Palladium(0)/NHC-Catalyzed Reductive Heck Reaction of Enones: A Detailed Mechanistic Study.

    PubMed

    Raoufmoghaddam, Saeed; Mannathan, Subramaniyan; Minnaard, Adriaan J; de Vries, Johannes G; Reek, Joost N H

    2015-12-14

    We have studied the mechanism of the palladium-catalyzed reductive Heck reaction of para-substituted enones with 4-iodoanisole by using N,N-diisopropylethylamine (DIPEA) as the reductant. Kinetic studies and in situ spectroscopic analysis have provided a detailed insight into the reaction. Progress kinetic analysis demonstrated that neither catalyst decomposition nor product inhibition occurred during the catalysis. The reaction is first order in the palladium and aryl iodide, and zero order in the activated alkene, N-heterocyclic carbene (NHC) ligand, and DIPEA. The experiments with deuterated solvent ([D7]DMF) and deuterated base ([D15]Et3N) supported the role of the amine as a reductant in the reaction. The palladium complex [Pd(0)(NHC)(1)] has been identified as the resting state. The kinetic experiments by stopped-flow UV/Vis also revealed that the presence of the second substrate, benzylideneacetone 1, slows down the oxidative addition of 4-iodoanisole through its competing coordination to the palladium center. The kinetic and mechanistic studies indicated that the oxidative addition of the aryl iodide is the rate-determining step. Various scenarios for the oxidative addition step have been analyzed by using DFT calculations (bp86/def2-TZVP) that supported the inhibiting effect of substrate 1 by formation of resting state [Pd(0)(NHC)(1)] species at the cost of further increase in the energy barrier of the oxidative addition step. PMID:26561034

  18. Oxyl and hydroxyl radical transfer in mitochondrial amidoxime reducing component-catalyzed nitrite reduction.

    PubMed

    Yang, Jing; Giles, Logan J; Ruppelt, Christian; Mendel, Ralf R; Bittner, Florian; Kirk, Martin L

    2015-04-29

    A combination of electron paramagnetic resonance (EPR) spectroscopy and computational approaches has provided insight into the nature of the reaction coordinate for the one-electron reduction of nitrite by the mitochondrial amidoxime reducing component (mARC) enzyme. The results show that a paramagnetic Mo(V) species is generated when reduced enzyme is exposed to nitrite, and an analysis of the resulting EPR hyperfine parameters confirms that mARC is remarkably similar to the low-pH form of sulfite oxidase. Two mechanisms for nitrite reduction have been considered. The first shows a modest reaction barrier of 14 kcal/mol for the formation of ·NO from unprotonated nitrite substrate. In marked contrast, protonation of the substrate oxygen proximal to Mo in the Mo(IV)-O-N-O substrate-bound species results in barrierless conversion to products. A fragment orbital analysis reveals a high degree of Mo-O(H)-N-O covalency that provides a π-orbital pathway for one-electron transfer to the substrate and defines orbital constraints on the Mo-substrate geometry for productive catalysis in mARC and other pyranopterin molybdenum enzymes that catalyze this one-electron transformation. PMID:25897643

  19. Practical carbon-carbon bond formation from olefins through nickel-catalyzed reductive olefin hydrocarbonation.

    PubMed

    Lu, Xi; Xiao, Bin; Zhang, Zhenqi; Gong, Tianjun; Su, Wei; Yi, Jun; Fu, Yao; Liu, Lei

    2016-01-01

    New carbon-carbon bond formation reactions expand our horizon of retrosynthetic analysis for the synthesis of complex organic molecules. Although many methods are now available for the formation of C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds via transition metal-catalyzed cross-coupling of alkyl organometallic reagents, direct use of readily available olefins in a formal fashion of hydrocarbonation to make C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds remains to be developed. Here we report the discovery of a general process for the intermolecular reductive coupling of unactivated olefins with alkyl or aryl electrophiles under the promotion of a simple nickel catalyst system. This new reaction presents a conceptually unique and practical strategy for the construction of C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds without using any organometallic reagent. The reductive olefin hydrocarbonation also exhibits excellent compatibility with varieties of synthetically important functional groups and therefore, provides a straightforward approach for modification of complex organic molecules containing olefin groups. PMID:27033405

  20. Practical carbon–carbon bond formation from olefins through nickel-catalyzed reductive olefin hydrocarbonation

    PubMed Central

    Lu, Xi; Xiao, Bin; Zhang, Zhenqi; Gong, Tianjun; Su, Wei; Yi, Jun; Fu, Yao; Liu, Lei

    2016-01-01

    New carbon–carbon bond formation reactions expand our horizon of retrosynthetic analysis for the synthesis of complex organic molecules. Although many methods are now available for the formation of C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds via transition metal-catalyzed cross-coupling of alkyl organometallic reagents, direct use of readily available olefins in a formal fashion of hydrocarbonation to make C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds remains to be developed. Here we report the discovery of a general process for the intermolecular reductive coupling of unactivated olefins with alkyl or aryl electrophiles under the promotion of a simple nickel catalyst system. This new reaction presents a conceptually unique and practical strategy for the construction of C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds without using any organometallic reagent. The reductive olefin hydrocarbonation also exhibits excellent compatibility with varieties of synthetically important functional groups and therefore, provides a straightforward approach for modification of complex organic molecules containing olefin groups. PMID:27033405

  1. Unification of reaction pathway and kinetic scheme for N2 reduction catalyzed by nitrogenase

    PubMed Central

    Lukoyanov, Dmitriy; Yang, Zhi-Yong; Barney, Brett M.; Dean, Dennis R.; Seefeldt, Lance C.; Hoffman, Brian M.

    2012-01-01

    Nitrogenase catalyzes the reduction of N2 and protons to yield two NH3 and one H2. Substrate binding occurs at a complex organo-metallocluster called FeMo-cofactor (FeMo-co). Each catalytic cycle involves the sequential delivery of eight electrons/protons to this cluster, and this process has been framed within a kinetic scheme developed by Lowe and Thorneley. Rapid freezing of a modified nitrogenase under turnover conditions using diazene, methyldiazene (HN = N-CH3), or hydrazine as substrate recently was shown to trap a common intermediate, designated I. It was further concluded that the two N-atoms of N2 are hydrogenated alternately (“Alternating” (A) pathway). In the present work, Q-band CW EPR and 95Mo ESEEM spectroscopy reveal such samples also contain a common intermediate with FeMo-co in an integer-spin state having a ground-state “non-Kramers” doublet. This species, designated H, has been characterized by ESEEM spectroscopy using a combination of 14,15N isotopologs plus 1,2H isotopologs of methyldiazene. It is concluded that: H has NH2 bound to FeMo-co and corresponds to the penultimate intermediate of N2 hydrogenation, the state formed after the accumulation of seven electrons/protons and the release of the first NH3; I corresponds to the final intermediate in N2 reduction, the state formed after accumulation of eight electrons/protons, with NH3 still bound to FeMo-co prior to release and regeneration of resting-state FeMo-co. A proposed unification of the Lowe-Thorneley kinetic model with the “prompt” alternating reaction pathway represents a draft mechanism for N2 reduction by nitrogenase. PMID:22460797

  2. Kinetics of homogeneous and surface-catalyzed mercury(II) reduction by iron(II)

    USGS Publications Warehouse

    Amirbahman, Aria; Kent, Douglas B.; Curtis, Gary P.; Marvin-DiPasquale, Mark C.

    2013-01-01

    Production of elemental mercury, Hg(0), via Hg(II) reduction is an important pathway that should be considered when studying Hg fate in environment. We conducted a kinetic study of abiotic homogeneous and surface-catalyzed Hg(0) production by Fe(II) under dark anoxic conditions. Hg(0) production rate, from initial 50 pM Hg(II) concentration, increased with increasing pH (5.5–8.1) and aqueous Fe(II) concentration (0.1–1 mM). The homogeneous rate was best described by the expression, rhom = khom [FeOH+] [Hg(OH)2]; khom = 7.19 × 10+3 L (mol min)−1. Compared to the homogeneous case, goethite (α-FeOOH) and hematite (α-Fe2O3) increased and γ-alumina (γ-Al2O3) decreased the Hg(0) production rate. Heterogeneous Hg(0) production rates were well described by a model incorporating equilibrium Fe(II) adsorption, rate-limited Hg(II) reduction by dissolved and adsorbed Fe(II), and rate-limited Hg(II) adsorption. Equilibrium Fe(II) adsorption was described using a surface complexation model calibrated with previously published experimental data. The Hg(0) production rate was well described by the expression rhet = khet [>SOFe(II)] [Hg(OH)2], where >SOFe(II) is the total adsorbed Fe(II) concentration; khet values were 5.36 × 10+3, 4.69 × 10+3, and 1.08 × 10+2 L (mol min)−1 for hematite, goethite, and γ-alumina, respectively. Hg(0) production coupled to reduction by Fe(II) may be an important process to consider in ecosystem Hg studies.

  3. Computational Characterization of Redox Non-Innocence in Cobalt-Bis(Diaryldithiolene)-Catalyzed Proton Reduction.

    PubMed

    Panetier, Julien A; Letko, Christopher S; Tilley, T Don; Head-Gordon, Martin

    2016-01-12

    Localized orbital bonding analysis (LOBA) was employed to probe the oxidation state in cobalt-bis(diaryldithiolene)-catalyzed proton reduction in nonaqueous media. LOBA calculations provide both the oxidation state and chemically intuitive views of bonding in cobalt-bis(diaryldithiolene) species and therefore allow characterization of the role of the redox non-innocent dithiolene ligand. LOBA results show that the reduction of the monoanion species [1Br](-) is metal-centered and gives a cobalt(II) ion species, [1Br](2-), coordinated to two dianionic ene-1,2-dithiolates. This electronic configuration is in agreement with the solution magnetic moment observed for the analogous salt [1F](2-) (μeff = 2.39 μB). Protonation of [1Br](2-) yields the cobalt(III)-hydride [1Br(CoH)](-) species in which the Co-H bond is computed to be highly covalent (Löwdin populations close to 0.50 on cobalt and hydrogen atoms). Further reduction of [1Br(CoH)](-) forms a more basic cobalt(II)-H intermediate [1Br(CoH)](2-) (S = 0) from which protonation at sulfur gives a S-H bond syn to the Co-H bond. Formation of a cobalt-dihydrogen [1Br(CoH2)](-) intermediate is calculated to occur via a homocoupling (H(•) + H(•) → H2) step with a free energy of activation of 5.9 kcal/mol in solution (via C-PCM approach). PMID:26598074

  4. Effect of mass transfer on the oxygen reduction reaction catalyzed by platinum dendrimer encapsulated nanoparticles

    PubMed Central

    Dumitrescu, Ioana; Crooks, Richard M.

    2012-01-01

    Here we report on the effect of the mass transfer rate (kt) on the oxygen reduction reaction (ORR) catalyzed by Pt dendrimer-encapsulated nanoparticles (DENs) comprised of 147 and 55 atoms (Pt147 and Pt55). The experiments were carried out using a dual-electrode microelectrochemical device, which enables the study of the ORR under high kt conditions with simultaneous detection of H2O2. At low kt (0.02 to 0.12 cm s-1) the effective number of electrons involved in ORR, neff, is 3.7 for Pt147 and 3.4 for Pt55. As kt is increased, the mass-transfer-limited current for the ORR becomes significantly lower than the value predicted by the Levich equation for a 4-electron process regardless of catalyst size. However, the percentage of H2O2 detected remains constant, such that neff barely changes over the entire kt range explored (0.02 cm s-1). This suggests that mass transfer does not affect neff, which has implications for the mechanism of the ORR on Pt nanoparticles. Interestingly, there is a significant difference in neff for the two sizes of Pt DENs (neff = 3.7 and 3.5 for Pt147 and Pt55, respectively) that cannot be assigned to mass transfer effects and that we therefore attribute to a particle size effect. PMID:22665772

  5. Nickel-Catalyzed Reductive Conjugate Addition to Enones Via Allylnickel Intermediates

    PubMed Central

    Shrestha, Ruja; Dorn, Stephanie C. M.; Weix, Daniel J.

    2013-01-01

    An alternative method to copper-catalyzed conjugate addition followed by enolate silylation for the synthesis of β-di-substituted silyl enol ether products (R1(R2)HCCH=C(OSiR43)R3) is presented. This method uses haloarenes instead of nucleophilic aryl reagents. Nickel ligated to either neocuproine or bipyridine couples an α,β-unsaturated ketone or aldehyde (R2HC=CHC(O)R3) with an organic halide (R1-X) in the presence of a trialkylchlorosilane reagent (Cl-SiR43). Reactions are assembled on the bench-top and tolerate a variety of functional groups (aldehyde, ketone, nitrile, sulfone, pentafluorosulfur, and N-aryltrifluoroacetamide), electron-rich iodoarenes, and electron-poor haloarenes. Mechanistic studies have confirmed the first example of a catalytic reductive conjugate addition of organic halides that proceeds via an allylnickel intermediate. Selectivity is attributed to: 1) rapid, selective reaction of LNi0 with chlorotriethylsilane and enone in the presence of other organic electrophiles, and 2) minimization of enone dimerization by ligand steric effects. PMID:23270480

  6. The heme-copper oxidases of Thermus thermophilus catalyze the reduction of nitric oxide: Evolutionary implications

    PubMed Central

    Giuffrè, Alessandro; Stubauer, Gottfried; Sarti, Paolo; Brunori, Maurizio; Zumft, Walter G.; Buse, Gerhard; Soulimane, Tewfik

    1999-01-01

    We show that the heme-copper terminal oxidases of Thermus thermophilus (called ba3 and caa3) are able to catalyze the reduction of nitric oxide (NO) to nitrous oxide (N2O) under reducing anaerobic conditions. The rate of NO consumption and N2O production were found to be linearly dependent on enzyme concentration, and activity was abolished by enzyme denaturation. Thus, contrary to the eukaryotic enzyme, both T. thermophilus oxidases display a NO reductase activity (3.0 ± 0.7 mol NO/mol ba3 × min and 32 ± 8 mol NO/mol caa3 × min at [NO] ≈ 50 μM and 20°C) that, though considerably lower than that of bona fide NO reductases (300–4,500 mol NO/mol enzyme × min), is definitely significant. We also show that for ba3 oxidase, NO reduction is associated to oxidation of cytochrome b at a rate compatible with turnover, suggesting a mechanism consistent with the stoichiometry of the overall reaction. We propose that the NO reductase activity of T. thermophilus oxidases may depend on a peculiar CuB+ coordination, which may be revealed by the forthcoming three-dimensional structure. These findings support the hypothesis of a common phylogeny of aerobic respiration and bacterial denitrification, which was proposed on the basis of structural similarities between the Pseudomonas stutzeri NO reductase and the cbb3 terminal oxidases. Our findings represent functional evidence in support of this hypothesis. PMID:10611279

  7. Mechanistic Basis for Regioselection and Regiodivergence in Nickel-Catalyzed Reductive Couplings

    PubMed Central

    Jackson, Evan P.; Malik, Hasnain A.; Sormunen, Grant J.; Baxter, Ryan D.; Liu, Peng; Wang, Hengbin; Shareef, Abdur-Rafay; Montgomery, John

    2015-01-01

    CONSPECTUS The control of regiochemistry is a considerable challenge in the development of a wide array of catalytic processes. Simple π-components such as alkenes, alkynes, 1,3-dienes, and allenes are among the many classes of substrates that present complexities in regioselective catalysis. Considering an internal alkyne as a representative example, when steric and electronic differences between the two substituents are minimal, differentiating among the two termini of the alkyne presents a great challenge. In cases where the differences between the alkyne substituents are substantial, overcoming those biases to access the regioisomer opposite that favored by substrate biases often presents an even greater challenge. Nickel-catalyzed reductive couplings of unsymmetrical π-components make up a group of reactions where control of regiochemistry presents a challenging but important objective. In the course of our studies of aldehyde-alkyne reductive couplings, complementary solutions to challenges in regiocontrol have been developed. Through careful selection of the ligand and reductant, as well as the more subtle reaction variables such as temperature and concentration, effective protocols have been established that allow highly selective access to either regiosiomer of the the allylic alcohol products using a wide range of unsymmetrical alkynes. Computational studies and an evaluation of reaction kinetics have provided an understanding of the origin of the regioselectivity control. Throughout the various procedures described, the development of ligand-substrate interactions play a key role, and the overall kinetic descriptions were found to differ between protocols. Rational alteration of the rate-determining step plays a key role in the regiochemistry reversal strategy, and in one instance, the two possible regioisomeric outcomes in a single reaction were found to operate by different kinetic descriptions. With this mechanistic information in hand, the

  8. Hydroxymethylation beyond Carbonylation: Enantioselective Iridium-Catalyzed Reductive Coupling of Formaldehyde with Allylic Acetates via Enantiotopic π-Facial Discrimination.

    PubMed

    Garza, Victoria J; Krische, Michael J

    2016-03-23

    Chiral iridium complexes modified by SEGPHOS catalyze the 2-propanol-mediated reductive coupling of branched allylic acetates 1a-1o with formaldehyde to form primary homoallylic alcohols 2a-2o with excellent control of regio- and enantioselectivity. These processes, which rely on enantiotopic π-facial discrimination of σ-allyliridium intermediates, represent the first examples of enantioselective formaldehyde C-C coupling beyond aldol addition. PMID:26958737

  9. Effect of mass transfer on the oxygen reduction reaction catalyzed by platinum dendrimer encapsulated nanoparticles.

    PubMed

    Dumitrescu, Ioana; Crooks, Richard M

    2012-07-17

    Here we report on the effect of the mass transfer rate (k(t)) on the oxygen reduction reaction (ORR) catalyzed by Pt dendrimer-encapsulated nanoparticles (DENs) comprised of 147 and 55 atoms (Pt(147) and Pt(55)). The experiments were carried out using a dual-electrode microelectrochemical device, which enables the study of the ORR under high k(t) conditions with simultaneous detection of H(2)O(2). At low k(t) (0.02 to 0.12 cm s(-1)) the effective number of electrons involved in ORR, n(eff), is 3.7 for Pt(147) and 3.4 for Pt(55). As k(t) is increased, the mass-transfer-limited current for the ORR becomes significantly lower than the value predicted by the Levich equation for a 4-electron process regardless of catalyst size. However, the percentage of H(2)O(2) detected remains constant, such that n(eff) barely changes over the entire k(t) range explored (0.02 cm s(-1)). This suggests that mass transfer does not affect n(eff), which has implications for the mechanism of the ORR on Pt nanoparticles. Interestingly, there is a significant difference in n(eff) for the two sizes of Pt DENs (n(eff) = 3.7 and 3.5 for Pt(147) and Pt(55), respectively) that cannot be assigned to mass transfer effects and that we therefore attribute to a particle size effect. PMID:22665772

  10. Optimizing Metalloporphyrin-Catalyzed Reduction Reactions for In Situ Remediation of DOE Contaminants

    SciTech Connect

    Schlautman, Mark A.

    2013-07-14

    Past activities have resulted in a legacy of contaminated soil and groundwater at Department of Energy facilities nationwide. Uranium and chromium are among the most frequently encountered and highest-priority metal and radionuclide contaminants at DOE installations. Abiotic chemical reduction of uranium and chromium at contaminated DOE sites can be beneficial because the reduced metal species are less soluble in water, less mobile in the environment, and less toxic to humans and ecosystems. Although direct biological reduction has been reported for U(VI) and Cr(VI) in laboratory studies and at some field sites, the reactions can sometimes be slow or even inhibited due to unfavorable environmental conditions. One promising approach for the in-situ remediation of DOE contaminants is to develop electron shuttle catalysts that can be delivered precisely to the specific subsurface locations where contaminants reside. Previous research has shown that reduction of oxidized organic and inorganic contaminants often can be catalyzed by electron shuttle systems. Metalloporphyrins and their derivatives are well known electron shuttles for many biogeochemical systems, and thus were selected to study their catalytic capabilities for the reduction of chromium and uranium in the presence of reducing agents. Zero valent iron (ZVI) was chosen as the primary electron donor in most experimental systems. Research proceeded in three phases and the key findings of each phase are reported here. Phase I examined Cr(VI) reduction and utilized micro- and nano-sized ZVI as the electron donors. Electron shuttle catalysts tested were cobalt- and iron-containing metalloporphyrins and Vitamin B12. To aid in the recycle and reuse of the nano-sized ZVI and soluble catalysts, sol-gels and calcium-alginate gel beads were tested as immobilization/support matrices. Although the nano-sized ZVI could be incorporated within the alginate gel beads, preliminary attempts to trap it in sol-gels were not

  11. Rh-Catalyzed reductive Mannich-type reaction and its application towards the synthesis of (±)-ezetimibe

    PubMed Central

    Isoda, Motoyuki; Sato, Kazuyuki; Kunugi, Yurika; Tokonishi, Satsuki; Tarui, Atsushi; Minami, Hideki

    2016-01-01

    Summary An effective synthesis for syn-β-lactams was achieved using a Rh-catalyzed reductive Mannich-type reaction. A rhodium–hydride complex (Rh–H) derived from diethylzinc (Et2Zn) and a Rh catalyst was used for the 1,4-reduction of an α,β-unsaturated ester to give a Reformatsky-type reagent, which in turn, reacted with an imine to give the syn-β-lactam. Additionally, the reaction was applied to the synthesis of (±)-ezetimibe, a potent β-lactamic cholesterol absorption inhibitor. PMID:27559413

  12. Synthesis of ethers by GaBr3 -catalyzed reduction of carboxylic acid esters and lactones by siloxanes.

    PubMed

    Biermann, Ursula; Metzger, Jürgen O

    2014-02-01

    Ethers were synthesized by reduction of the respective esters catalyzed by gallium bromide (GaBr3 ) and using siloxanes, preferentially 1,1,3,3-tetramethyldisiloxane, as reductant. Methyl oleate, triglycerides, that is, tributyrine and glyceryl triundec-10-enoate as well as γ- and δ-lactones were converted into the respective ethers in high to moderate yields. γ-Lactones were reduced with high selectivity in the presence of a methyl ester functionality. The reduction has been carried out at room temperature or moderately elevated temperature of up to 60 °C using stoichiometric amounts of the reductant and 0.005-0.01 equiv of GaBr3 as catalyst per ester functionality without any solvent added. After a reaction time of 1-4 h the conversion of the substrate was 100 %. The product was separated from polymeric siloxanes formed as coupled product by simple distillation. PMID:24488681

  13. Ph(i-PrO)SiH2: An Exceptional Reductant for Metal-Catalyzed Hydrogen Atom Transfers.

    PubMed

    Obradors, Carla; Martinez, Ruben M; Shenvi, Ryan A

    2016-04-13

    We report the discovery of an outstanding reductant for metal-catalyzed radical hydrofunctionalization reactions. Observations of unexpected silane solvolysis distributions in the HAT-initiated hydrogenation of alkenes reveal that phenylsilane is not the kinetically preferred reductant in many of these transformations. Instead, isopropoxy(phenyl)silane forms under the reaction conditions, suggesting that alcohols function as important silane ligands to promote the formation of metal hydrides. Study of its reactivity showed that isopropoxy(phenyl)silane is an exceptionally efficient stoichiometric reductant, and it is now possible to significantly decrease catalyst loadings, lower reaction temperatures, broaden functional group tolerance, and use diverse, aprotic solvents in iron- and manganese-catalyzed hydrofunctionalizations. As representative examples, we have improved the yields and rates of alkene reduction, hydration, hydroamination, and conjugate addition. Discovery of this broadly applicable, chemoselective, and solvent-versatile reagent should allow an easier interface with existing radical reactions. Finally, isotope-labeling experiments rule out the alternative hypothesis of hydrogen atom transfer from a redox-active β-diketonate ligand in the HAT step. Instead, initial HAT from a metal hydride to directly generate a carbon-centered radical appears to be the most reasonable hypothesis. PMID:26984323

  14. Palladium-Catalyzed Ullmann Cross-Coupling/Tandem Reductive Cyclization Route to Key Members of the Uleine Alkaloid Family.

    PubMed

    Tang, Fei; Banwell, Martin G; Willis, Anthony C

    2016-04-01

    The trisubstituted cyclohexenone 12, generated through a palladium-catalyzed Ullmann cross-coupling reaction between o-iodonitrobenzene and a 4,5-trans-disubstituted 2-iodo-2-cyclohexen-1-one, engaged in a tandem reductive cyclization process upon exposure to hydrogen gas in the presence of Raney cobalt. As a result, the 1,5-methanoazocino[4,3-b]indole 13 was obtained and this could be readily elaborated to the racemic modifications of the alkaloids uleine, dasycarpidone, noruleine, and nordasycarpidone (1-4, respectively). PMID:26914482

  15. Enantioselective Reduction of Ketones and Imines Catalyzed by (CN-Box)Re(V)-Oxo Complexes

    PubMed Central

    Nolin, Kristine A.; Ahn, Richard W.; Kobayashi, Yusuke; Kennedy-Smith, Joshua J.

    2012-01-01

    The development and application of chiral, non-racemic Re(V)-oxo complexes to the enantioselective reduction of prochiral ketones is described. In addition to the enantioselective reduction of prochiral ketones, we report the application of these complexes to (1) a tandem Meyer-Schuster rearrangement/reduction to access enantioenriched allylic alcohols and (2) the enantioselective reduction of imines. PMID:20623567

  16. Iron catalyzed reduction of chromate by dissimilatory iron-reducing bacteria.

    SciTech Connect

    Wielinga, B.W.; M.M. Mizuba; C.M. Hansel; S. Fendorf

    2001-02-01

    The toxicity and mobility of chromium can be diminished through its reduction from the hexavalent state to the trivalent form. Here we demonstrate a microbially mediated pathway for chromate reduction. Iron reducing bacteria, ubiquitous organisms within soils and sediments, stimulate chromate reduction by generating ferrous iron--a facile reductant of hexavalent chromium. Subsequent to reduction, Cr(III) then precipitates as a chromium hydroxide.

  17. Nanoparticle-catalyzed reductive bleaching for fabricating turn-off and enzyme-free amplified colorimetric bioassays.

    PubMed

    Li, Wei; Qiang, Weibing; Li, Jie; Li, Hui; Dong, Yifan; Zhao, Yaju; Xu, Danke

    2014-01-15

    Nanoparticle-catalyzed reductive bleaching reactions of colored substrates are emerging as a class of novel indicator reactions for fabricating enzyme-free amplified colorimetric biosensing (turn-off mode), which are exactly opposite to the commonly used oxidative coloring processes of colorless substrates in traditional enzyme-catalyzed amplified colorimetric bioassays (turn-on mode). In this work, a simple theoretical analysis shows that the sensitivity of this colorimetric bioassay can be improved by increasing the amplification factor (kcatΔt), or enhancing the binding affinity between analyte and receptor (Kd), or selecting the colored substrates with high extinction coefficients (ε). Based on this novel strategy, we have developed a turn-off and cost-effective amplified colorimetric thrombin aptasensor. This aptasensor made full use of sandwich binding of two affinity aptamers for increased specificity, magnetic particles for easy separation and enrichment, and gold nanoparticle (AuNP)-catalyzed reductive bleaching reaction to generate the amplified colorimetric signal. With 4-nitrophenol (4-NP) as the non-dye colored substrate, colorimetric bioassay of thrombin was achieved by the endpoint method with a detection limit of 91pM. In particular, when using methylene blue (MB) as the substrate, for the first time, a more convenient and efficient kinetic-based colorimetric thrombin bioassay was achieved without the steps of acidification termination and magnetic removal of particles, with a low detection limit of 10pM, which was superior to the majority of the existing colorimetric thrombin aptasensors. The proposed colorimetric protocol is expected to hold great promise in field analysis and point-of-care applications. PMID:23962710

  18. Excitotoxic brain damage involves early peroxynitrite formation in a model of Huntington's disease in rats: protective role of iron porphyrinate 5,10,15,20-tetrakis (4-sulfonatophenyl)porphyrinate iron (III).

    PubMed

    Pérez-De La Cruz, V; González-Cortés, C; Galván-Arzate, S; Medina-Campos, O N; Pérez-Severiano, F; Ali, S F; Pedraza-Chaverrí, J; Santamaría, A

    2005-01-01

    Oxidative/nitrosative stress is involved in NMDA receptor-mediated excitotoxic brain damage produced by the glutamate analog quinolinic acid. The purpose of this work was to study a possible role of peroxynitrite, a reactive oxygen/nitrogen species, in the course of excitotoxic events evoked by quinolinic acid in the brain. The effects of Fe(TPPS) (5,10,15,20-tetrakis (4-sulfonatophenyl)porphyrinate iron (III)), an iron porphyrinate and putative peroxynitrite decomposition catalyst, were tested on lipid peroxidation and mitochondrial function in brain synaptic vesicles exposed to quinolinic acid, as well as on peroxynitrite formation, nitric oxide synthase and superoxide dismutase activities, lipid peroxidation, caspase-3-like activation, DNA fragmentation, and GABA levels in striatal tissue from rats lesioned by quinolinic acid. Circling behavior was also evaluated. Increasing concentrations of Fe(TPPS) reduced lipid peroxidation and mitochondrial dysfunction induced by quinolinic acid (100 microM) in synaptic vesicles in a concentration-dependent manner (10-800 microM). In addition, Fe(TPPS) (10 mg/kg, i.p.) administered 2 h before the striatal lesions, prevented the formation of peroxynitrite, the increased nitric oxide synthase activity, the decreased superoxide dismutase activity and the increased lipid peroxidation induced by quinolinic acid (240 nmol/microl) 120 min after the toxin infusion. Enhanced caspase-3-like activity and DNA fragmentation were also reduced by the porphyrinate 24 h after the injection of the excitotoxin. Circling behavior from quinolinic acid-treated rats was abolished by Fe(TPPS) six days after quinolinic acid injection, while the striatal levels of GABA, measured one day later, were partially recovered. The protective effects that Fe(TPPS) exerted on quinolinic acid-induced lipid peroxidation and mitochondrial dysfunction in synaptic vesicles suggest a primary action of the porphyrinate as an antioxidant molecule. In vivo findings

  19. Borane-Catalyzed Reductive α-Silylation of Conjugated Esters and Amides Leaving Carbonyl Groups Intact.

    PubMed

    Kim, Youngchan; Chang, Sukbok

    2016-01-01

    Described herein is the development of the B(C6F5)3-catalyzed hydrosilylation of α,β-unsaturated esters and amides to afford synthetically valuable α-silyl carbonyl products. The α-silylation occurs chemoselectively, thus leaving the labile carbonyl groups intact. The reaction features a broad scope of both acyclic and cyclic substrates, and the synthetic utility of the obtained α-silyl carbonyl products is also demonstrated. Mechanistic studies revealed two operative steps: fast 1,4-hydrosilylation of conjugated carbonyls and then slow silyl group migration of a silyl ether intermediate. PMID:26549843

  20. Durability Improvement of Pt/RGO Catalysts for PEMFC by Low-Temperature Self-Catalyzed Reduction.

    PubMed

    Sun, Kang Gyu; Chung, Jin Suk; Hur, Seung Hyun

    2015-12-01

    Pt/C catalyst used for polymer electrolyte membrane fuel cells (PEMFCs) displays excellent initial performance, but it does not last long because of the lack of durability. In this study, a Pt/reduced graphene oxide (RGO) catalyst was synthesized by the polyol method using ethylene glycol (EG) as the reducing agent, and then low-temperature hydrogen bubbling (LTHB) treatment was introduced to enhance the durability of the Pt/RGO catalyst. The cyclic voltammetry (CV), oxygen reduction reaction (ORR) analysis, and transmittance electron microscopy (TEM) results suggested that the loss of the oxygen functional groups, because of the hydrogen spillover and self-catalyzed dehydration reaction during LTHB, reduced the carbon corrosion and Pt agglomeration and thus enhanced the durability of the electrocatalyst. PMID:26061443

  1. Highly enantioselective reductive cyclization of acetylenic aldehydes via rhodium catalyzed asymmetric hydrogenation.

    PubMed

    Rhee, Jong Uk; Krische, Michael J

    2006-08-23

    Catalytic hydrogenation of acetylenic aldehydes 1a-12a using chirally modified cationic rhodium catalysts enables highly enantioselective reductive cyclization to afford cyclic allylic alcohols 1b-12b. Using an achiral hydrogenation catalyst, the chiral racemic acetylenic aldehydes 13a-15a engage in highly syn-diastereoselective reductive cyclizations to afford cyclic allylic alcohols 13b-15b. Ozonolysis of cyclization products 7b and 9b allows access to optically enriched alpha-hydroxy ketones 7c and 9c. Reductive cyclization of enyne 7a under a deuterium atmosphere provides the monodeuterated product deuterio-7b, consistent with a catalytic mechanism involving alkyne-carbonyl oxidative coupling followed by hydrogenolytic cleavage of the resulting oxametallacycle. These hydrogen-mediated transformations represent the first examples of the enantioselective reductive cyclization of acetylenic aldehydes. PMID:16910650

  2. Enantioselective CuH-Catalyzed Reductive Coupling of Aryl Alkenes and Activated Carboxylic Acids.

    PubMed

    Bandar, Jeffrey S; Ascic, Erhad; Buchwald, Stephen L

    2016-05-11

    A new method for the enantioselective reductive coupling of aryl alkenes with activated carboxylic acid derivatives via copper hydride catalysis is described. Dual catalytic cycles are proposed, with a relatively fast enantioselective hydroacylation cycle followed by a slower diastereoselective ketone reduction cycle. Symmetrical aryl carboxyclic anhydrides provide access to enantioenriched α-substituted ketones or alcohols with excellent stereoselectivity and functional group tolerance. PMID:27121395

  3. Kinetic modeling of inherent mineral catalyzed NO reduction by biomass char.

    PubMed

    Wu, X Y; Song, Q; Zhao, H B; Zhang, Z H; Yao, Q

    2014-04-01

    The evolution of rice straw char reactivity during reaction with NO was examined in differential reactor at 900 and 1000 °C. Original and acid-washed rice straw chars were used. Surface area and mineral content of char samples with different conversion were analyzed. The reactivity of the acid-washed char increased until conversion Xchar = 20%, remained constant, and then decreased continuously to zero. The reactivity of the original char decreased continuously to zero throughout the reaction, with a faster decrease at 1000 °C. Mineral transformation during original char reaction was obvious. Concentration of acid-soluble K decreased about 56% and 90% at 900 and 1000 °C. Ca and Mg released little to gas phase, but reacted with SiO2 in a small amount. The evolution of the acid-washed char reactivity correlated well with the development of surface area and was well predicted by random pore model. The reactivity of the original char depended not only on the development of surface area, but also on transformation of inherent minerals, mainly K. A two-reaction model was built which well predicted inherent K transformation. A modified random pore model was developed, which successfully simulated inherent mineral catalyzed char-NO reaction. PMID:24588459

  4. Electrochemical reduction of CO2 to formate catalyzed by electroplated tin coating on copper foam

    NASA Astrophysics Data System (ADS)

    Wang, Yan; Zhou, Jing; Lv, Weixin; Fang, Hailin; Wang, Wei

    2016-01-01

    Sn/f-Cu electrode has been prepared by electrodeposition Sn on a Cu foam substrate in aqueous plating solution, which has been used as the cathode for electrochemical reduction of carbon dioxide (CO2) in aqueous KHCO3 solution. Here, we have explored the effects of the deposition time and the electrolysis potential on the Faradaic efficiency for producing formate. The results demonstrate that maximum Faradaic efficiency of 83.5% is obtained at -1.8 V vs. Ag/AgCl when the Sn/f-Cu electrode is prepared by electrodeposition for 35 min. The Sn/f-Cu electrode exhibits excellent catalytic activity for CO2 reduction compared with the Cu foam electrode and the Sn plate electrode. The average current density and the production rate of formate for the Sn/f-Cu electrode are more than twice those for the Sn plate electrode during electrochemical reduction of CO2.

  5. Supported gold nanoparticles catalyzed cis-selective semihydrogenation of alkynes using ammonium formate as the reductant.

    PubMed

    Liang, Shengzong; Hammond, Gerald B; Xu, Bo

    2016-05-21

    TiO2 supported gold nanoparticles with low loading (0.5 mol%) are able to semihydrogenate non-fluorinated and gem-difluorinated alkynes to cis-alkenes with high selectivity, using cost-effective and easy-to-handle ammonium formate as the reductant. No over-reduction was observed. The good recyclability of Au/TiO2 allows for "green" semireduction of alkynes. A difluorinated pyran and α,β-unsaturated δ-lactone were easily prepared from the obtained gem-difluoro alkene building blocks. PMID:27063707

  6. Nickel-Catalyzed Cross-Electrophile Coupling with Organic Reductants in Non-Amide Solvents.

    PubMed

    Anka-Lufford, Lukiana L; Huihui, Kierra M M; Gower, Nicholas J; Ackerman, Laura K G; Weix, Daniel J

    2016-08-01

    Cross-electrophile coupling of aryl halides with alkyl halides has thus far been primarily conducted with stoichiometric metallic reductants in amide solvents. This report demonstrates that the use of tetrakis(dimethylamino)ethylene (TDAE) as an organic reductant enables the use of non-amide solvents, such as acetonitrile or propylene oxide, for the coupling of benzyl chlorides and alkyl iodides with aryl halides. Furthermore, these conditions work for several electron-poor heterocycles that are easily reduced by manganese. Finally, we demonstrate that TDAE addition can be used as a control element to 'hold' a reaction without diminishing yield or catalyst activity. PMID:27273457

  7. Ruthenium-catalyzed reductive methylation of imines using carbon dioxide and molecular hydrogen.

    PubMed

    Beydoun, Kassem; Ghattas, Ghazi; Thenert, Katharina; Klankermayer, Jürgen; Leitner, Walter

    2014-10-01

    The use of the well-defined [Ru(triphos)(tmm)] catalyst, CO2 as C1 source, and H2 as reducing agent enabled the reductive methylation of isolated imines, as well as the direct coupling of amines with aldehydes and the subsequent reductive methylation of the in situ formed imines. The method, which afforded the corresponding N-methyl amines in very good to excellent yields, was also used for the preparation of the antifungal agent butenafine in one step with no apparent waste, thus increasing the atom efficiency of its synthesis. PMID:25146346

  8. Platinum-catalyzed reduction of amides with hydrosilanes bearing dual Si-H groups: a theoretical study of the reaction mechanism.

    PubMed

    Nakatani, Naoki; Hasegawa, Jun-ya; Sunada, Yusuke; Nagashima, Hideo

    2015-11-28

    A platinum-catalyzed amide reduction through hydrosilylation with 1,2-bis(dimethylsilyl)benzene (BDSB) was investigated on a theoretical basis. While the platinum-catalyzed hydrosilylation of alkenes is well known, that of carbonyl groups rarely occurs. The only exception involves the use of bifunctional hydrosilanes having dual, closely located Si-H groups, which accelerate the hydrosilylation of carbonyl groups, leading to successful reduction of amides to amines under mild conditions. In the present study, we determined through density functional theory calculations that the platinum-catalyzed hydrosilylation of the C=O bond proceeds via a Pt(IV)-disilyl-dihydride intermediate with an associated activation energy of 29.6 kcal mol(-1). Although it was believed that the hydrosilylation of carbonyl groups does not occur via the classical Chalk-Harrod cycle, the computational results support a mechanism involving the insertion of the amide C=O bond into a Pt-H bond. This insertion readily occurs because a Pt-H bond in the Pt(IV)-disilyl-dihydride intermediate is highly activated due to the strong σ-donating interaction of the silyl groups. The modified Chalk-Harrod mechanism that occurs preferentially in rhodium-catalyzed hydrosilylation as well as the ionic outer sphere mechanism associated with iridium-catalyzed amide reduction were both safely ruled out as mechanisms for this platinum-catalyzed amide reduction, because of the unexpectedly large activation barrier (>40 kcal mol(-1)) for the Si-O bond formation. PMID:26497866

  9. Strategic use of nickel(0)-catalyzed enyne-epoxide reductive coupling towards the synthesis of (−)-cyatha-3,12-diene

    PubMed Central

    Sparling, Brian A.; Simpson, Graham L.; Jamison, Timothy F.

    2009-01-01

    Various situations are explored in which the nickel(0)-catalyzed enyne-epoxide reductive coupling was utilized to access key intermediates towards the total synthesis of (−)-cyatha-3,12-diene (1). Enantioenriched 3,5-dien-1-ols with a variety of functionality were obtained in a straightforward manner from easily accessible 1,3-enynes and terminal epoxides. PMID:20161213

  10. Mild and selective Et2Zn-catalyzed reduction of tertiary amides under hydrosilylation conditions.

    PubMed

    Kovalenko, Oleksandr O; Volkov, Alexey; Adolfsson, Hans

    2015-02-01

    Diethylzinc (Et2Zn) can be used as an efficient and chemoselective catalyst for the reduction of tertiary amides under mild reaction conditions employing cost-effective polymeric silane (PMHS) as the hydride source. Crucial for the catalytic activity was the addition of a substoichiometric amount of lithium chloride to the reaction mixture. A series of amides containing different additional functional groups were reduced to their corresponding amines, and the products were isolated in good-to-excellent yields. PMID:25587664

  11. Nickel-catalyzed reductive arylation of activated alkynes with aryl iodides

    PubMed Central

    Dorn, Stephanie C. M.; Olsen, Andrew K; Kelemen, Rachel E.; Shrestha, Ruja; Weix, Daniel J.

    2015-01-01

    The direct, regioselective, and stereoselective arylation of activated alkynes with aryl iodides using a nickel catalyst and manganese reductant is described. The reaction conditions are mild (40 °C in MeOH, no acid or base) and an intermediate organomanganese reagent is unlikely. Functional groups tolerated include halides and pseudohalides, free and protected anilines, and a benzyl alcohol. Other activated alkynes including an amide and a ketone also reacted to form arylated products in good yields. PMID:26028781

  12. Reductive metabolism of oxymatrine is catalyzed by microsomal CYP3A4

    PubMed Central

    Liu, Wenqin; Shi, Jian; Zhu, Lijun; Dong, Lingna; Luo, Feifei; Zhao, Min; Wang, Ying; Hu, Ming; Lu, Linlin; Liu, Zhongqiu

    2015-01-01

    Oxymatrine (OMT) is a pharmacologically active primary quinolizidine alkaloid with various beneficial and toxic effects. It is confirmed that, after oral administration, OMT could be transformed to the more toxic metabolite matrine (MT), and this process may be through the reduction reaction, but the study on the characteristics of this transformation is limited. The aim of this study was to investigate the characteristics of this transformation of OMT in the human liver microsomes (HLMs) and human intestinal microsomes (HIMs) and the cytochrome P450 (CYP) isoforms involved in this transformation. The current studies demonstrated that OMT could be metabolized to MT rapidly in HLMs and HIMs and CYP3A4 greatly contributed to this transformation. All HLMs, HIMs, and CYP3A4 isoform mediated reduction reaction followed typical biphasic kinetic model, and Km, Vmax, and CL were significant higher in HLMs than those in HIMs. Importantly, different oxygen contents could significantly affect the metabolism of OMT, and with the oxygen content decreased, the formation of metabolite was increased, suggesting this transformation was very likely a reduction reaction. Results of this in vitro study elucidated the metabolic pathways and characteristics of metabolism of OMT to MT and would provide a theoretical basis and guidance for the safe application of OMT. PMID:26586934

  13. Gold nanoparticle-catalyzed reduction in a model system: Quantitative determination of reactive heterogeneity of a supported nanoparticle surface

    SciTech Connect

    Nigra, Michael M.; Arslan, Ilke; Katz, Alexander

    2012-11-01

    Kinetic poisoning experiments employing organic ligands were conducted using a gold nanoparticle–catalyzed reaction consisting of the reduction of resazurin to resorufin. The kinetic contributions of three distinct types of sites along with the number density of each of these site types during reaction were determined. The calculated number densities of each of the three types of sites, hypothesized to be corners, edges, and terraces, correlates well with atomic-resolution micrographs of the supported gold nanoparticles, obtained using aberration-corrected transmission electron microscopy and with predictions based on geometric models of idealized gold nanoparticles. The most active sites comprising 1% of the surface atoms exhibit at least 30% of the total activity of the catalyst for resazurin reduction. The selective mechanical blocking of surface sites on nanoparticles, particularly undercoordinated sites, paves the way for novel approaches utilizing organic ligands to quantify the activity of different active sites and control catalysis on metal surfaces. This work was supported in part by the Laboratory Directed Research and Development program at the Pacific Northwest National Laboratory (PNNL). The aberration-corrected electron microscopy was performed in the William R. Wiley Environmental Molecular Sciences Laboratory, a U.S. Department of Energy (DOE) national scientific user facility located at PNNL and funded by BER. PNNL is operated by Battelle for the U.S. DOE under contract DE-AC05-76RL01830.

  14. An Inner-Sphere Mechanism for Molecular Oxygen Reduction Catalyzed by Copper Amine Oxidases

    PubMed Central

    Mukherjee, Arnab; Smirnov, Valeriy V.; Lanci, Michael P.; Brown, Doreen E.; Shepard, Eric M.; Dooley, David M.; Roth, Justine P.

    2008-01-01

    Copper and topaquinone (TPQ) containing amine oxidases utilize O2 for the metabolism of biogenic amines while concomitantly generating H2O2 for use by the cell. The mechanism of O2 reduction has been the subject of long-standing debate due to the obscuring influence of a proton-coupled electron transfer between the tyrosine-derived TPQ and copper, a rapidly established equilibrium precluding assignment of the enzyme in its reactive form. Here we show that substrate-reduced pea seedling amine oxidase (PSAO) exists predominantly in the CuI, TPQ semiquinone state. A new mechanistic proposal for O2 reduction is advanced on the basis of thermodynamic considerations together with kinetic studies (at varying pH, temperature and viscosity), the identification of steady-state intermediates and the analysis of competitive oxygen kinetic isotope effects: 18O KIEs, [kcat/KM(16,16O2)]/[kcat/KM(16,18O2)]. The 18O KIE = 1.0136 ± 0.0013 at pH 7.2 is independent of temperature from 5 to 47°C and insignificantly changed to 1.0122 ± 0.0020 upon raising the pH to 9, thus indicating the absence of kinetic complexity. Using density functional methods, the effect is found to be precisely in the range expected for reversible O2 binding to CuI to afford a superoxide, [CuII(η1-O2)−I]+, intermediate. Electron transfer from the TPQ semiquinone follows in the first irreversible step to form a peroxide, CuII(η1-O2)−II, intermediate driving the reduction of O2. The similar 18O KIEs reported for copper amine oxidases from other sources raise the possibility that all enzymes react by related inner-sphere mechanisms although additional experiments are needed to test this proposal. PMID:18582059

  15. A General, Practical Triethylborane-Catalyzed Reduction of Carbonyl Functions to Alcohols.

    PubMed

    Peng, Dongjie; Zhang, Mintao; Huang, Zheng

    2015-10-12

    A combination of the abundant and low-cost triethylborane and sodium alkoxide generates a highly efficient catalyst for reduction of esters, as well as ketones and aldehydes, to alcohols using an inexpensive hydrosilane under mild conditions. The catalyst system exhibits excellent chemoselectivity and a high level of functional group tolerance. Mechanistic studies revealed a resting state of sodium triethylalkoxylborate that is the product of the reaction of BEt3 with sodium alkoxide. This borate species reacts with hydrosilane to form NaBEt3 H, which rapidly reduces esters. PMID:26332613

  16. Ruthenium catalyzed C-C bond formation via transfer hydrogenation: branch-selective reductive coupling of allenes to paraformaldehyde and higher aldehydes.

    PubMed

    Ngai, Ming-Yu; Skucas, Eduardas; Krische, Michael J

    2008-07-01

    Under the conditions of ruthenium-catalyzed transfer hydrogenation employing 2-propanol as the terminal reductant, 1,1-disubstituted allenes 1a- h engage in reductive coupling to paraformaldehyde to furnish homoallylic alcohols 2a- h. Under identical transfer hydrogenation conditions, 1,1-disubstituted allenes engage in reductive coupling to aldehydes 3a- f to furnish homoallylic alcohols 4a- n. In all cases, reductive coupling occurs with branched regioselectivity to deliver homoallylic alcohols bearing all-carbon quaternary centers. PMID:18533665

  17. Secondary alcohol dehydrogenase catalyzes the reduction of exogenous acetone to 2-propanol in Trichomonas vaginalis.

    PubMed

    Sutak, Robert; Hrdy, Ivan; Dolezal, Pavel; Cabala, Radomir; Sedinová, Miroslava; Lewin, Joern; Harant, Karel; Müller, Miklos; Tachezy, Jan

    2012-08-01

    Secondary alcohols such as 2-propanol are readily produced by various anaerobic bacteria that possess secondary alcohol dehydrogenase (S-ADH), although production of 2-propanol is rare in eukaryotes. Specific bacterial-type S-ADH has been identified in a few unicellular eukaryotes, but its function is not known and the production of secondary alcohols has not been studied. We purified and characterized S-ADH from the human pathogen Trichomonas vaginalis. The kinetic properties and thermostability of T. vaginalis S-ADH were comparable with bacterial orthologues. The substantial activity of S-ADH in the parasite's cytosol was surprising, because only low amounts of ethanol and trace amounts of secondary alcohols were detected as metabolic end products. However, S-ADH provided the parasite with a high capacity to scavenge and reduce external acetone to 2-propanol. To maintain redox balance, the demand for reducing power to metabolize external acetone was compensated for by decreased cytosolic reduction of pyruvate to lactate and by hydrogenosomal metabolism of pyruvate. We speculate that hydrogen might be utilized to maintain cytosolic reducing power. The high activity of Tv-S-ADH together with the ability of T. vaginalis to modulate the metabolic fluxes indicate efficacious metabolic responsiveness that could be advantageous for rapid adaptation of the parasite to changes in the host environment. PMID:22686835

  18. ANME-2D Archaea Catalyze Methane Oxidation in Deep Subsurface Sediments Independent of Nitrate Reduction

    NASA Astrophysics Data System (ADS)

    Hernsdorf, A. W.; Amano, Y.; Suzuki, Y.; Ise, K.; Thomas, B. C.; Banfield, J. F.

    2015-12-01

    -reducing/oxidizing archaeon Ferroglobus placidus. Thus, we suggest that ANME2-D may couple methane oxidation to reduction of ferric iron minerals in the sediment and may be generally important as a link between the iron and methane cycles in deep subsurface environments. Such information has important implications for modeling the global carbon cycle.

  19. The Study of NADPH-Dependent Flavoenzyme-Catalyzed Reduction of Benzo[1,2-c]1,2,5-oxadiazole N-Oxides (Benzofuroxans)

    PubMed Central

    Šarlauskas, Jonas; Misevičienė, Lina; Marozienė, Audronė; Karvelis, Laimonas; Stankevičiūtė, Jonita; Krikštopaitis, Kastis; Čėnas, Narimantas; Yantsevich, Aleksey; Laurynėnas, Audrius; Anusevičius, Žilvinas

    2014-01-01

    The enzymatic reactivity of a series of benzo[1,2-c]1,2,5-oxadiazole N-oxides (benzofuroxans; BFXs) towards mammalian single-electron transferring NADPH:cytochrome P-450 reductase (P-450R) and two-electron (hydride) transferring NAD(P)H:quinone oxidoreductase (NQO1) was examined in this work. Since the =N+ (→O)O− moiety of furoxan fragments of BFXs bears some similarity to the aromatic nitro-group, the reactivity of BFXs was compared to that of nitro-aromatic compounds (NACs) whose reduction mechanisms by these and other related flavoenzymes have been extensively investigated. The reduction of BFXs by both P-450R and NQO1 was accompanied by O2 uptake, which was much lower than the NADPH oxidation rate; except for annelated BFXs, whose reduction was followed by the production of peroxide. In order to analyze the possible quantitative structure-activity relationships (QSARs) of the enzymatic reactivity of the compounds, their electron-accepting potency and other reactivity indices were assessed by quantum mechanical methods. In P-450R-catalyzed reactions, both BFXs and NACs showed the same reactivity dependence on their electron-accepting potency which might be consistent with an “outer sphere” electron transfer mechanism. In NQO1-catalyzed two-electron (hydride) transferring reactions, BFXs acted as more efficient substrates than NACs, and the reduction efficacy of BFXs by NQO1 was in general higher than by single-electron transferring P-450R. In NQO1-catalyzed reactions, QSARs obtained showed that the reduction efficacy of BFXs, as well as that of NACs, was determined by their electron-accepting potency and could be influenced by their binding mode in the active center of NQO1 and by their global softness as their electronic characteristic. The reductive conversion of benzofuroxan by both flavoenzymes yielded the same reduction product of benzofuroxan, 2,3-diaminophenazine, with the formation of o-benzoquinone dioxime as a putative primary reductive

  20. Synthesis of tertiary arylamines: Lewis acid-catalyzed direct reductive N-alkylation of secondary amines with ketones through an alternative pathway.

    PubMed

    Nayal, Onkar S; Thakur, Maheshwar S; Bhatt, Vinod; Kumar, Manoranjan; Kumar, Neeraj; Singh, Bikram; Sharma, Upendra

    2016-08-11

    We report herein a highly efficient, tin(ii)/PMHS catalyzed reductive N-alkylation of arylamines with ketones affording tertiary arylamines. A very wide substrate scope was observed for the current catalytic method as all six permutations of ketones/aldehydes/heterocyclic carbonyls and primary/secondary/heterocyclic amines were well tolerated, enabling access to secondary, tertiary and heterocyclic amines. The method is also convenient for the synthesis of N-substituted isoindolinones and phthalazinones via a tandem amination-amidation sequence. Mechanistic investigations revealed a carbocationic pathway instead of an ordinary direct reductive amination pathway. PMID:27363507

  1. A new approach to carbon-carbon bond formation: Development of aerobic Pd-catalyzed reductive coupling reactions of organometallic reagents and styrenes

    PubMed Central

    Gligorich, Keith M.; Iwai, Yasumasa; Cummings, Sarah A.; Sigman, Matthew S.

    2009-01-01

    Alkenes are attractive starting materials for organic synthesis and the development of new selective functionalization reactions are desired. Previously, our laboratory discovered a unique Pd-catalyzed hydroalkoxylation reaction of styrenes containing a phenol. Based upon deuterium labeling experiments, a mechanism involving an aerobic alcohol oxidation coupled to alkene functionalization was proposed. These results inspired the development of a new Pd-catalyzed reductive coupling reaction of alkenes and organometallic reagents that generates a new carbon-carbon bond. Optimization of the conditions for the coupling of both organostannanes and organoboronic esters is described and the initial scope of the transformation is presented. Additionally, several mechanistic experiments are outlined and support the rationale for the development of the reaction based upon coupling alcohol oxidation to alkene functionalization. PMID:20161306

  2. Intra- and Intermolecular Nickel-Catalyzed Reductive Cross-Electrophile Coupling Reactions of Benzylic Esters with Aryl Halides.

    PubMed

    Konev, Mikhail O; Hanna, Luke E; Jarvo, Elizabeth R

    2016-06-01

    Nickel-catalyzed cross-electrophile coupling reactions of benzylic esters and aryl halides have been developed. Both inter- and intramolecular variants proceed under mild reaction conditions. A range of heterocycles and functional groups are tolerated under the reaction conditions. Additionally, the first example of a stereospecific cross-electrophile coupling of a secondary benzylic ester is described. PMID:27099968

  3. Consecutive Cycloaddition/S(N)Ar/Reduction/Cyclization/Oxidation Sequences: A Copper-Catalyzed Multicomponent Synthesis of Fused N-Heterocycles.

    PubMed

    Jia, Feng-Cheng; Xu, Cheng; Zhou, Zhi-Wen; Cai, Qun; Li, Deng-Kui; Wu, An-Xin

    2015-06-01

    A highly efficient multicomponent domino protocol has been developed for the synthesis of 5-phenyl-[1,2,3]triazolo[1,5-c]quinazolines from simple and readily available (E)-1-bromo-2-(2-nitrovinyl)benzenes, aldehydes, and sodium azide. This elegant domino process involved consecutive [3 + 2] cycloaddition, copper-catalyzed S(N)Ar, reduction, cyclization, and oxidation sequences. Notably, sodium azide acted as a dual nitrogen source in the construction of this novel fused N-heterocycle. PMID:25996444

  4. Novel enzymatic activity of cell free extract from thermophilic Geobacillus sp. UZO 3 catalyzes reductive cleavage of diaryl ether bonds of 2,7-dichlorodibenzo-p-dioxin.

    PubMed

    Suzuki, Yuzoh; Nakamura, Masaya; Otsuka, Yuichiro; Suzuki, Nao; Ohyama, Keisuke; Kawakami, Takeshi; Sato, Kanna; Kajita, Shinya; Hishiyama, Shojiro; Fujii, Takeo; Takahashi, Atsushi; Katayama, Yoshihiro

    2011-04-01

    We characterized the ability of the cell free extract from polychlorinated dibenzo-p-dioxins degrading bacterium Geobacillus sp. UZO 3 to reduce even highly chlorinated dibenzo-p-dioxins such as octachlorodibenzo-p-dioxins in incineration fly ash. The degradation of 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) as a model dioxin catalyzed by the cell free extract from this strain implicates that the ether bonds of 2,7-DCDD molecule undergo reductive cleavage, since 4',5-dichloro-2-hydroxydiphenyl ether and 4-chlorophenol were detected as intermediate products of 2,7-DCDD degradation. PMID:21435685

  5. Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid.

    PubMed

    Brown, Katherine A; Harris, Derek F; Wilker, Molly B; Rasmussen, Andrew; Khadka, Nimesh; Hamby, Hayden; Keable, Stephen; Dukovic, Gordana; Peters, John W; Seefeldt, Lance C; King, Paul W

    2016-04-22

    The splitting of dinitrogen (N2) and reduction to ammonia (NH3) is a kinetically complex and energetically challenging multistep reaction. In the Haber-Bosch process, N2 reduction is accomplished at high temperature and pressure, whereas N2 fixation by the enzyme nitrogenase occurs under ambient conditions using chemical energy from adenosine 5'-triphosphate (ATP) hydrolysis. We show that cadmium sulfide (CdS) nanocrystals can be used to photosensitize the nitrogenase molybdenum-iron (MoFe) protein, where light harvesting replaces ATP hydrolysis to drive the enzymatic reduction of N2 into NH3 The turnover rate was 75 per minute, 63% of the ATP-coupled reaction rate for the nitrogenase complex under optimal conditions. Inhibitors of nitrogenase (i.e., acetylene, carbon monoxide, and dihydrogen) suppressed N2 reduction. The CdS:MoFe protein biohybrids provide a photochemical model for achieving light-driven N2 reduction to NH3. PMID:27102481

  6. Nickel-Catalyzed Reductive Cross-Coupling of Benzyl Chlorides with Aryl Chlorides/Fluorides: A One-Pot Synthesis of Diarylmethanes.

    PubMed

    Zhang, Jie; Lu, Gusheng; Xu, Jin; Sun, Hongmei; Shen, Qi

    2016-06-17

    The first nickel-catalyzed, magnesium-mediated reductive cross-coupling between benzyl chlorides and aryl chlorides or fluorides is reported. A variety of diarylmethanes can be prepared in good to excellent yields in a one-pot manner using easy-to-access mixed PPh3/NHC Ni(II) complexes of Ni(PPh3)(NHC)Br2 (NHC = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, IPr, 1a; 1,3-di-tert-butylimidazol-2-ylidene, ItBu, 1b) as catalyst precursors. Activation of polychloroarenes or chemoselective cross-coupling based on the difference in catalytic activity between 1a and 1b is used to construct oligo-diarylmethane motifs. PMID:27268781

  7. Extending the Scope of the B(C6 F5 )3 -Catalyzed C=N Bond Reduction: Hydrogenation of Oxime Ethers and Hydrazones.

    PubMed

    Mohr, Jens; Porwal, Digvijay; Chatterjee, Indranil; Oestreich, Martin

    2015-12-01

    The B(C6 F5 )3 -catalyzed hydrogenation is applied to aldoxime triisopropylsilyl ethers and hydrazones bearing an easily removable phthaloyl protective group. The CN reduction of aldehyde-derived substrates (oxime ethers and hydrazones) is enabled by using 1,4-dioxane as the solvent known to participate as the Lewis-basic component in FLP-type heterolytic dihydrogen splitting. More basic ketone-derived hydrazones act as Lewis bases themselves in the FLP-type dihydrogen activation and are therefore successfully hydrogenated in nondonating toluene. The difference in reactivity between aldehyde- and ketone-derived substrates is also reflected in the required catalyst loading and dihydrogen pressure. PMID:26489785

  8. Characterization of a transient intermediate formed in the liver alcohol dehydrogenase catalyzed reduction of 3-hydroxy-4-nitrobenzaldehyde

    SciTech Connect

    MacGibbon, A.K.H.; Koerber, S.C.; Pease, K.; Dunn, M.F.

    1987-06-02

    The compounds 3-hydroxy-4-nitrobenzaldehyde and 3-hydroxy-4-nitrobenzyl alcohol are introduced as new chromophoric substrates for probing the catalytic mechanism of horse liver alcohol dehydrogenase (LADH). Ionization of the phenolic hydroxyl group shifts the spectrum of the aldehyde from 360 to 433 nm (pK/sub a/ = 6.0), whereas the spectrum of the alcohol shifts from 350 to 417 nm (pK/sub a/ = 6.9). Rapid-scanning, stopped-flow (RSSF) studies at alkaline pH show that the LADH-catalyzed interconversion of these compounds occurs via the formation of an enzyme-bound intermediate with a blue-shifted spectrum. When reaction is limited to a single turnover of enzyme sites, the formation and decay of the intermediate when aldehyde reacts with enzyme-bound reduced nicotinamide adenine dinucleotide E(NADH) are characterized by two relaxations. Detailed stopped-flow kinetic studies were carried out to investigate the disappearance of aldehyde and NADH, the formation and decay of the intermediate, the displacement of Auramine O by substrate, and /sup 2/H kinetic isotope effects. It was found that (1) NADH oxidation takes place at the rate of the slower relaxation (2) when NADD is substituted for NADH, lambda/sub s/ is subject to a small primary isotope effect; and (3) the events that occur in lambda/sub s/ precede lambda/sub f/. These findings identify the intermediate as a ternary complex containing bound oxidized nicotinamide adenine dinucleotide (NAD/sup +/) and some form of 3-hydroxy-4-nitrobenzyl alcohol. The authors conclude that the LADH substrate site can be divided into two subsites: a highly polar, electropositive subsite in the vicinity of the active-site zinc and, just a few angstroms away, a rather nonpolar region.

  9. Oxygen reduction reaction catalyzed by platinum nanonetwork prepared by template free one step synthesis for polymer electrolyte membrane fuel cells

    SciTech Connect

    Narayanamoorthy, B.; Kumar, B.V.V.S. Pavan; Eswaramoorthy, M.; Balaji, S.

    2014-07-01

    Highlights: • Supportless Pt nanonetwork (Pt NN) synthesized by novel template free one step method as per our earlier reported procedure. • Electrocatalytic activity of Pt NN studied taking oxygen reduction reaction in acid medium. • Kinetic and thermodynamic parameters were deduced under hydrodynamic conditions. • ORR mechanistic pathway was proposed based on kinetic rate constants. • ADT analysis found enhanced stability (5000 cycles) for Pt NN than Pt NN/VC and reported Pt/C. - Abstract: The reduction reaction of molecular oxygen (ORR) was investigated using supportless Pt nanonetwork (Pt NN) electrocatalyst in sulfuric acid medium. Pt NN was prepared by template free borohydride reduction. The transmission electron microscope images revealed a network like nano-architecture having an average cluster size of 30 nm. The electrochemical characterization of supportless and Vulcan carbon supported Pt NN (Pt NN/VC) was carried out using rotating disc and ring disc electrodes at various temperatures. Kinetic and thermodynamic parameters were estimated under hydrodynamic conditions and compared with Pt NN/VC and reported Pt/C catalysts. The accelerated durability test revealed that supportless Pt NN is quite stable for 5000 potential cycles with 22% reduction in electrochemical surface area (ECSA). While the initial limiting current density has in fact increased by 11.6%, whereas Pt NN/VC suffered nearly 55% loss in ECSA and 13% loss in limiting current density confirming an enhanced stability of supportless Pt NN morphology for ORR compared to conventional Pt/C ORR catalysts in acid medium.

  10. A General and Selective Rhodium-Catalyzed Reduction of Amides, N-Acyl Amino Esters, and Dipeptides Using Phenylsilane.

    PubMed

    Das, Shoubhik; Li, Yuehui; Lu, Liang-Qiu; Junge, Kathrin; Beller, Matthias

    2016-05-17

    This article describes a selective reduction of functionalized amides, including N-acyl amino esters and dipeptides, to the corresponding amines using simple [Rh(acac)(cod)]. The catalyst shows excellent chemoselectivity in the presence of different sensitive functional moieties. PMID:26991132

  11. Selenium catalyzed Fe(III)-EDTA reduction by Na2SO3: a reaction-controlled phase transfer catalysis.

    PubMed

    Xiang, Kaisong; Liu, Hui; Yang, Bentao; Zhang, Cong; Yang, Shu; Liu, Zhilou; Liu, Cao; Xie, Xiaofeng; Chai, Liyuan; Min, Xiaobo

    2016-04-01

    Fe(II)-EDTA, a typical chelated iron, is able to coordinate with nitric oxide (NO) which accelerates the rates and kinetics of the absorption of flue gas. However, Fe(II)-EDTA can be easily oxidized to Fe(III)-EDTA which is unable to absorb NO. Therefore, the regeneration of fresh Fe(II)-EDTA, which actually is the reduction of Fe(III)-EDTA to Fe(II)-EDTA, becomes a crucial step in the denitrification process. To enhance the reduction rate of Fe(III)-EDTA, selenium was introduced into the SO3 (2-)/Fe(III)-EDTA system as catalyst for the first time. By comparison, the reduction rate was enhanced by four times after adding selenium even at room temperature (25 °C). Encouragingly, elemental Se could precipitate out when SO3 (2-) was consumed up by oxidation to achieve self-separation. A catalysis mechanism was proposed with the aid of ultraviolet-visible (UV-Vis) spectroscopy, Tyndall scattering, horizontal attenuated total reflection Fourier transform infrared (HATR-FTIR) spectroscopy, and X-ray diffraction (XRD). In the catalysis process, the interconversion between SeSO3 (2-) and nascent Se formed a catalysis circle for Fe(III)-EDTA reduction in SO3 (2-) circumstance. PMID:26888642

  12. Electrochemiluminescent quenching of quantum dots for ultrasensitive immunoassay through oxygen reduction catalyzed by nitrogen-doped graphene-supported hemin.

    PubMed

    Deng, Shengyuan; Lei, Jianping; Huang, Yin; Cheng, Yan; Ju, Huangxian

    2013-06-01

    A hemin functionalized graphene sheet was prepared via the noncovalent assembly of hemin on nitrogen-doped graphene. The graphene sheet could act as an oxygen reduction catalyst to produce sensitive electrochemiluminescent (ECL) quenching of quantum dots (QDs) due to the annihilation of dissolved oxygen, the ECL coreactant, by its electrocatalytic reduction. With the use of the catalyst with high loading of hemin as a signal tag of the secondary antibody, a novel ultrasensitive immunoassay method for biomarker detection was proposed. In an air-saturated pH 8.0 buffer, the immunosensor constructed by a stepwise immobilization of bidentate-chelated CdTe QDs and capture antibody showed an intensive cathodic ECL irradiation, which could be scavenged upon the formation of the catalyst-bound sandwich immunocomplex. With the use of the carcinoembryonic antigen as a model analyte, the immunoassay method showed a linear range from 0.1 pg mL(-1) to 10 ng mL(-1) and a detection limit of 24 fg mL(-1). The immunosensor exhibited good stability, acceptable fabrication reproducibility, and practicability. The electrocatalytic reduction-based ECL quenching strategy provided a powerful avenue for the design of the ultrasensitive detection method, showing great promise for clinical application. PMID:23659573

  13. Pd-Catalyzed oxidative isomerization of propargylic acetates: highly efficient access to α-acetoxyenones via alkenyl Csp(2)-O bond-forming reductive elimination from Pd(IV).

    PubMed

    Li, Jun; Yang, Wenjie; Yan, Fachao; Liu, Qing; Wang, Ping; Li, Yueyun; Zhao, Yi; Dong, Yunhui; Liu, Hui

    2016-08-23

    A Pd(ii)/(iv)-catalyzed oxidative isomerization of propargylic acetates developed for the synthesis of polysubstituted alkenyl acetates is described. The reductive elimination of alkenyl Csp(2)-OAc bonds from Pd(IV) intermediates is achieved. Mechanistic studies indicate that the reaction mechanism consists of trans acetoxypalladation of a triple bond, isomerization, oxidative addition with PhI(OAc)2 and alkenyl C-OAc bond reductive elimination. PMID:27500292

  14. Two-Electron Carbon Dioxide Reduction Catalyzed by Rhenium(I) Bis(imino)acenaphthene Carbonyl Complexes

    PubMed Central

    Portenkirchner, Engelbert; Kianfar, Elham; Sariciftci, Niyazi Serdar; Knör, Günther

    2014-01-01

    Rhenium(I) carbonyl complexes carrying substituted bis(arylimino)acenaphthene ligands (BIAN-R) have been tested as potential catalysts for the two-electron reduction of carbon dioxide. Cyclic voltammetric studies as well as controlled potential electrolysis experiments were performed using CO2-saturated solutions of the complexes in acetonitrile and acetonitrile–water mixtures. Faradaic efficiencies of more than 30 % have been determined for the electrocatalytic production of CO. The effects of ligand substitution patterns and water content of the reaction medium on the catalytic performance of the new catalysts are discussed. PMID:24737649

  15. Molybdenum Reduction to Molybdenum Blue in Serratia sp. Strain DRY5 Is Catalyzed by a Novel Molybdenum-Reducing Enzyme

    PubMed Central

    Shukor, M. Y.; Halmi, M. I. E.; Rahman, M. F. A.; Shamaan, N. A.; Syed, M. A.

    2014-01-01

    The first purification of the Mo-reducing enzyme from Serratia sp. strain DRY5 that is responsible for molybdenum reduction to molybdenum blue in the bacterium is reported. The monomeric enzyme has an apparent molecular weight of 105 kDalton. The isoelectric point of this enzyme was 7.55. The enzyme has an optimum pH of 6.0 and maximum activity between 25 and 35°C. The Mo-reducing enzyme was extremely sensitive to temperatures above 50°C (between 54 and 70°C). A plot of initial rates against substrate concentrations at 15 mM 12-MP registered a Vmax for NADH at 12.0 nmole Mo blue/min/mg protein. The apparent Km for NADH was 0.79 mM. At 5 mM NADH, the apparent Vmax and apparent Km values for 12-MP of 12.05 nmole/min/mg protein and 3.87 mM, respectively, were obtained. The catalytic efficiency (kcat/Km) of the Mo-reducing enzyme was 5.47 M−1 s−1. The purification of this enzyme could probably help to solve the phenomenon of molybdenum reduction to molybdenum blue first reported in 1896 and would be useful for the understanding of the underlying mechanism in molybdenum bioremediation involving bioreduction. PMID:24724104

  16. Reduction of the explosive 2,4,6-trinitrophenylmethylnitramine (tetryl) catalyzed by oxygen sensitive nitro reductase enzymes

    SciTech Connect

    Shah, M.M.; Spain, J.C.

    1995-12-01

    Reduction of nitroaromatic compounds by nitroreductase enzymes generally leads to the formation of the corresponding amines. However, we recently found that the incubation of the explosive 2,4,6-trinitrophenylmethylnitramine (tetryl) with ferredoxin-NADP oxidoreductase, an oxygen sensitive nitroreductase from spinach in the presence of NADPH led to the elimination of the nitramine nitro group from tetryl and the formation of N-methylpicramide (NMP). Other oxygen sensitive nitroreductase enzymes including glutathione reductase, xanthine oxidase, and cytochrome c reductase were also able to release nitrite from tetryl. Nitrite was not eliminated from tetryl by an oxygen insensitive nitrobenzene reductase. For every mole of tetryl reduced, one mole each of nitrite and NMP were produced. The rate of nitrite elimination was inhibited under aerobic conditions. Subsequent oxygen uptake studies suggested that under aerobic conditions, molecular oxygen was reduced by FNR and tetryl served as the redox mediator. Our results suggest that under aerobic conditions; tetryl is reduced to the nitroanion radical by the enzyme and this radical is involved in the reduction of molecular oxygen.

  17. Molybdenum reduction to molybdenum blue in Serratia sp. Strain DRY5 is catalyzed by a novel molybdenum-reducing enzyme.

    PubMed

    Shukor, M Y; Halmi, M I E; Rahman, M F A; Shamaan, N A; Syed, M A

    2014-01-01

    The first purification of the Mo-reducing enzyme from Serratia sp. strain DRY5 that is responsible for molybdenum reduction to molybdenum blue in the bacterium is reported. The monomeric enzyme has an apparent molecular weight of 105 kDalton. The isoelectric point of this enzyme was 7.55. The enzyme has an optimum pH of 6.0 and maximum activity between 25 and 35°C. The Mo-reducing enzyme was extremely sensitive to temperatures above 50°C (between 54 and 70°C). A plot of initial rates against substrate concentrations at 15 mM 12-MP registered a V max for NADH at 12.0 nmole Mo blue/min/mg protein. The apparent K m for NADH was 0.79 mM. At 5 mM NADH, the apparent V max and apparent K m values for 12-MP of 12.05 nmole/min/mg protein and 3.87 mM, respectively, were obtained. The catalytic efficiency (k cat/K m ) of the Mo-reducing enzyme was 5.47 M(-1) s(-1). The purification of this enzyme could probably help to solve the phenomenon of molybdenum reduction to molybdenum blue first reported in 1896 and would be useful for the understanding of the underlying mechanism in molybdenum bioremediation involving bioreduction. PMID:24724104

  18. Lewis Acid-Induced Change from Four- to Two-Electron Reduction of Dioxygen Catalyzed by Copper Complexes Using Scandium Triflate

    PubMed Central

    Kakuda, Saya; Rolle, Clarence; Ohkubo, Kei; Siegler, Maxime A.; Karlin, Kenneth D.; Fukuzumi, Shunichi

    2015-01-01

    Mononuclear copper complexes, [(tmpa)CuII(CH3CN)](ClO4)2 (1, tmpa = tris(2-pyridylmethyl)amine) and [(BzQ)CuII(H2O)2](ClO4)2 (2, BzQ = bis(2-quinolinylmethyl)benzylamine)], act as efficient catalysts for the selective two-electron reduction of O2 by ferrocene derivatives in the presence of scandium triflate (Sc(OTf)3), in acetone, whereas 1 catalyzes the four-electron reduction of O2 by the same reductant in the presence of Brønsted acids such as triflic acid. Following formation of the peroxo-bridged dicopper(II) complex [(tmpa)CuII(O2)CuII(tmpa)]2+, the two-electron reduced product of O2 with Sc3+ is observed to be scandium peroxide ([Sc3+(O22−)]+). In the presence of three equiv of hexamethylphosphoric triamide (HMPA), [Sc3+(O22−)]+ was oxidized by [Fe(bpy)3]3+ (bpy = 2,2′-bipyridine) to the known superoxide species [(HMPA)3Sc3+(O2•−)]2+ as detected by EPR spectroscopy. A kinetic study revealed that the rate-determining step of the catalytic cycle for the two-electron reduction of O2 with 1 is electron transfer from Fc* to 1 to give a cuprous complex which is highly reactive toward O2, whereas the rate-determining step with 2 is changed to the reaction of the cuprous complex with O2 following electron transfer from ferrocene derivatives to 2. The explanation for the change in catalytic O2-reaction stoichiometry from four-electron with Brønsted acids to two-electron reduction in the presence of Sc3+ and also for the change in the rate-determining step is clarified based on a kinetics interrogation of the overall catalytic cycle as well as each step of the catalytic cycle with study of the observed effects of Sc3+ on copper-oxygen intermediates. PMID:25659416

  19. Kinetic analysis of the reduction of 4-nitrophenol catalyzed by Au/Pd nanoalloys immobilized in spherical polyelectrolyte brushes.

    PubMed

    Gu, Sasa; Lu, Yan; Kaiser, Julian; Albrecht, Martin; Ballauff, Matthias

    2015-11-14

    We present a detailed study of the catalytic activity of Au/Pd nanoalloys with Au : Pd molar ratio 75 : 25 synthesized using spherical polyelectrolyte brushes (SPB) as carrier system. The reduction of 4-nitrophenol (Nip) by sodium borohydride (BH4(-)) has been used as a model reaction. This reaction proceeds in two steps: 4-nitrophenol is first reduced to 4-hydroxylaminophenol which in a second step is reduced to the final product 4-aminophenol. Both steps of the reaction proceed on the surface of the nanoparticles (Langmuir-Hinshelwood-mechanism). We use this model to analyze the experimental data obtained by catalysis with the Au/Pd-nanoalloys. Good agreements between theory and experiments were found up to 30% conversion of Nip. The kinetic parameters were compared with the data derived from neat Au and Pd nanoparticles immobilized in the same SPB carrier system. The addition of 25% molar ratio of Pd to the nanoalloys increases the reaction rate of the first step nearly 10 times compared with that of SPB-Au and 60 times compared with that of SPB-Pd. Analysis of the nanoalloy by high-resolution transmission electron microscopy suggests that the surface defects of the nanoalloys play an important role for the enhanced catalytic activity. PMID:25790094

  20. Acidithrix ferrooxidans gen. nov., sp. nov.; a filamentous and obligately heterotrophic, acidophilic member of the Actinobacteria that catalyzes dissimilatory oxido-reduction of iron.

    PubMed

    Jones, Rose M; Johnson, D Barrie

    2015-01-01

    A novel acidophilic member of the phylum Actinobacteria was isolated from an acidic stream draining an abandoned copper mine in north Wales. The isolate (PY-F3) was demonstrated to be a heterotroph that catalyzed the oxidation of ferrous iron (but not of sulfur or hydrogen) under aerobic conditions, and the reduction of ferric iron under micro-aerobic and anaerobic conditions. PY-F3 formed long entangled filaments of cells (>50 μm long) during active growth phases, though these degenerated into smaller fragments and single cells in late stationary phase. Although isolate PY-F3 was not observed to grow below pH 2.0 and 10 °C, harvested biomass was found to oxidize ferrous iron at relatively fast rates at pH 1.5 and 5 °C. Phylogenetic analysis, based on comparisons of 16S rRNA gene sequences, showed that isolate PY-F3 has 91-93% gene similarity to those of the four classified genera and species of acidophilic Actinobacteria, and therefore is a representative of a novel genus. The binomial Acidithrix ferrooxidans is proposed for this new species, with PY-F3 as the designated type strain (=DSM 28176(T), =JCM 19728(T)). PMID:25638020

  1. An efficient and practical synthesis of [2-11C]indole via superfast nucleophilic [11C]cyanation and RANEY® Nickel catalyzed reductive cyclization

    DOE PAGESBeta

    So Jeong Lee; Fowler, Joanna S.; Alexoff, David; Schueller, Michael; Kim, Dohyun; Nauth, Alexander; Weber, Carina; Kim, Sung Won; Hooker, Jacob M.; Ma, Ling; et al

    2015-09-21

    We developed a rapid method for the synthesis of carbon-11 radiolabeled indole using a sub-nanomolar quantity of no-carrier-added [11C]cyanide as radio-precursor. Based upon a reported synthesis of 2-(2-nitrophenyl)acetonitrile (2), a highly reactive substrate 2-nitrobenzyl bromide (1) was evaluated for nucleophilic [11C]cyanation. Additionally, related reaction conditions were explored with the goal of obtaining of highly reactive 2-(2-nitrophenyl)-[1-11C]acetonitrile ([11C]-2) while inhibiting its rapid conversion to 2,3-bis(2-nitrophenyl)-[1-11C]propanenitrile ([11C]-3). Next, a Raney Nickel catalyzed reductive cyclization method was utilized for synthesizing the desired [2-11C]indole with hydrazinium monoformate as the active reducing agent. Extensive and iterative screening of basicity, temperature and stoichiometry was required tomore » overcome the large stoichiometry bias that favored 2-nitrobenzylbromide (1) over [11C]cyanide, which both caused further alkylation of the desired nitrile and poisoned the Raney Nickel catalyst. The result is an efficient two-step, streamlined method to reliably synthesize [2-11C]indole with an entire radiochemical yield of 21 ± 2.2% (n = 5, ranging from 18 – 24%). The radiochemical purity of the final product was > 98% and specific activity was 176 ± 24.8 GBq/μmol (n = 5, ranging from 141 – 204 GBq/μmol). The total radiosynthesis time including product purification by semi-preparative HPLC was 50 – 55 min from end of cyclotron bombardment.« less

  2. An efficient and practical synthesis of [2-11C]indole via superfast nucleophilic [11C]cyanation and RANEY® Nickel catalyzed reductive cyclization

    SciTech Connect

    So Jeong Lee; Fowler, Joanna S.; Alexoff, David; Schueller, Michael; Kim, Dohyun; Nauth, Alexander; Weber, Carina; Kim, Sung Won; Hooker, Jacob M.; Ma, Ling; Qu, Wenchao

    2015-09-21

    We developed a rapid method for the synthesis of carbon-11 radiolabeled indole using a sub-nanomolar quantity of no-carrier-added [11C]cyanide as radio-precursor. Based upon a reported synthesis of 2-(2-nitrophenyl)acetonitrile (2), a highly reactive substrate 2-nitrobenzyl bromide (1) was evaluated for nucleophilic [11C]cyanation. Additionally, related reaction conditions were explored with the goal of obtaining of highly reactive 2-(2-nitrophenyl)-[1-11C]acetonitrile ([11C]-2) while inhibiting its rapid conversion to 2,3-bis(2-nitrophenyl)-[1-11C]propanenitrile ([11C]-3). Next, a Raney Nickel catalyzed reductive cyclization method was utilized for synthesizing the desired [2-11C]indole with hydrazinium monoformate as the active reducing agent. Extensive and iterative screening of basicity, temperature and stoichiometry was required to overcome the large stoichiometry bias that favored 2-nitrobenzylbromide (1) over [11C]cyanide, which both caused further alkylation of the desired nitrile and poisoned the Raney Nickel catalyst. The result is an efficient two-step, streamlined method to reliably synthesize [2-11C]indole with an entire radiochemical yield of 21 ± 2.2% (n = 5, ranging from 18 – 24%). The radiochemical purity of the final product was > 98% and specific activity was 176 ± 24.8 GBq/μmol (n = 5, ranging from 141 – 204 GBq/μmol). The total radiosynthesis time including product purification by semi-preparative HPLC was 50 – 55 min from end of cyclotron bombardment.

  3. The 1.5-Å Structure of XplA-heme, an Unusual Cytochrome P450 Heme Domain That Catalyzes Reductive Biotransformation of Royal Demolition Explosive*

    PubMed Central

    Sabbadin, Federico; Jackson, Rosamond; Haider, Kamran; Tampi, Girish; Turkenburg, Johan P.; Hart, Sam; Bruce, Neil C.; Grogan, Gideon

    2009-01-01

    XplA is a cytochrome P450 of unique structural organization, consisting of a heme- domain that is C-terminally fused to its native flavodoxin redox partner. XplA, along with flavodoxin reductase XplB, has been shown to catalyze the breakdown of the nitramine explosive and pollutant hexahydro-1,3,5-trinitro-1,3,5-triazine (royal demolition explosive) by reductive denitration. The structure of the heme domain of XplA (XplA-heme) has been solved in two crystal forms: as a dimer in space group P21 to a resolution of 1.9 Å and as a monomer in space group P21212 to a resolution of 1.5 Å, with the ligand imidazole bound at the heme iron. Although it shares the overall fold of cytochromes P450 of known structure, XplA-heme is unusual in that the kinked I-helix that traverses the distal face of the heme is broken by Met-394 and Ala-395 in place of the well conserved Asp/Glu plus Thr/Ser, important in oxidative P450s for the scission of the dioxygen bond prior to substrate oxygenation. The heme environment of XplA-heme is hydrophobic, featuring a cluster of three methionines above the heme, including Met-394. Imidazole was observed bound to the heme iron and is in close proximity to the side chain of Gln-438, which is situated over the distal face of the heme. Imidazole is also hydrogen-bonded to a water molecule that sits in place of the threonine side-chain hydroxyl exemplified by Thr-252 in Cyt-P450cam. Both Gln-438 → Ala and Ala-395 → Thr mutants of XplA-heme displayed markedly reduced activity compared with the wild type for royal demolition explosive degradation when combined with surrogate electron donors. PMID:19692330

  4. Electrocatalytic O2 reduction reaction by synthetic analogues of cytochrome P450 and myoglobin: in-situ resonance Raman and dynamic electrochemistry investigations.

    PubMed

    Chatterjee, Sudipta; Sengupta, Kushal; Samanta, Subhra; Das, Pradip Kumar; Dey, Abhishek

    2013-09-01

    Bioinspired electrodes have been constructed by physiabsorption of two air stable iron porphyrin complexes, one bearing an imidazole coordination and the other bearing a thiolate coordination. To control the electron transfer (ET) rate to these O2 reducing electrocatalysts, the complexes were immobilized on edge plane graphite electrode and alkyl thiol self-assembled monolayer (SAM) modified Au electrodes with varying chain lengths of the thiols. Catalyst immobilized SAM modified surfaces were characterized using surface enhanced resonance Raman spectroscopy (SERRS), and their electrocatalytic O2 reduction properties were investigated using rotating ring disc electrochemistry (RRDE). While the imidazole bound complex showed increase in partially reduced oxygen species (PROS) on decreasing ET rate, the thiolate bound complex showed the opposite trend, that is, the value of PROS reduced on decreasing the ET rate. SERRS coupled to rotating disc electrochemistry (SERRS-RDE) technique helps gain insight into the O2 reduction mechanism. The results obtained indicate that while the imidazole bound iron porphyrin complex reduces O2 through an inner sphere mechanism using a high-spin (HS) Fe(II) species, the thiolate ligated complex shows an inner sphere as well as outer sphere mechanism using a HS Fe(II) and low-spin (LS) Fe(II) species, respectively. The PROS formation by a HS Fe(II) species of this thiolate bound complex increases with decreasing ET rates while that of a LS Fe(II) species decreases with decreasing ET rates. PMID:23961832

  5. Characterization of a fatty acyl-CoA reductase from Marinobacter aquaeolei VT8: a bacterial enzyme catalyzing the reduction of fatty acyl-CoA to fatty alcohol.

    PubMed

    Willis, Robert M; Wahlen, Bradley D; Seefeldt, Lance C; Barney, Brett M

    2011-12-01

    Fatty alcohols are of interest as a renewable feedstock to replace petroleum compounds used as fuels, in cosmetics, and in pharmaceuticals. One biological approach to the production of fatty alcohols involves the sequential action of two bacterial enzymes: (i) reduction of a fatty acyl-CoA to the corresponding fatty aldehyde catalyzed by a fatty acyl-CoA reductase, followed by (ii) reduction of the fatty aldehyde to the corresponding fatty alcohol catalyzed by a fatty aldehyde reductase. Here, we identify, purify, and characterize a novel bacterial enzyme from Marinobacter aquaeolei VT8 that catalyzes the reduction of fatty acyl-CoA by four electrons to the corresponding fatty alcohol, eliminating the need for a separate fatty aldehyde reductase. The enzyme is shown to reduce fatty acyl-CoAs ranging from C8:0 to C20:4 to the corresponding fatty alcohols, with the highest rate found for palmitoyl-CoA (C16:0). The dependence of the rate of reduction of palmitoyl-CoA on substrate concentration was cooperative, with an apparent K(m) ~ 4 μM, V(max) ~ 200 nmol NADP(+) min(-1) (mg protein)(-1), and n ~ 3. The enzyme also reduced a range of fatty aldehydes with decanal having the highest activity. The substrate cis-11-hexadecenal was reduced in a cooperative manner with an apparent K(m) of ~50 μM, V(max) of ~8 μmol NADP(+) min(-1) (mg protein)(-1), and n ~ 2. PMID:22035211

  6. Mechanistic studies of alkene epoxidation catalyzed by nickel(II) cyclam complexes. /sup 18/O labeling and substituent effects

    SciTech Connect

    Kinneary, J.F.; Albert, J.S.; Burrows, C.J.

    1988-08-31

    The oxidations of cyclohexene and various aryl-substituted alkenes are catalyzed by the cyclam (1,4,8,11-tetraazacyclotetradecane) complex of Ni(NO/sub 3/)/sub 2/ with iodosylbenzene as terminal oxidant. Epoxides are the major products; however, small amounts of ring-opened products, over-oxidation to ketones or aldehydes, and allylic oxidation of cyclohexene are also observed. E olefins are more reactive than the corresponding Z olefins in contrast to the results of iron porphyrin catalysis, and kinetic studies of para-substituted styrenes indicate that the reaction is facilitated by electron-donating substituents. Labeling studies with PhI/sup 18/O confirm that the epoxide oxygen is derived from PhIO while allylic oxidation and over-oxidation products involve both PhIO and exogenous sources of oxygen. A pericyclic mechanism for the formation of PhCHO is proposed along with the intermediacy of a high-valent nickel-oxo complex as the active oxidant. These results are discussed in light related transition-metal/PhIO oxidation mechanisms.

  7. Silane-controlled diastereoselectivity in the tris(pentafluorophenyl)borane-catalyzed reduction of alpha-diketones to silyl-protected 1,2-Diols.

    PubMed

    Skjel, Miranda K; Houghton, Adrian Y; Kirby, Andrea E; Harrison, Daniel J; McDonald, Robert; Rosenberg, Lisa

    2010-01-15

    B(C(6)F(5))(3)-catalyzed bis(hydrosilylation) of alpha-diketones can give high diastereomeric excess of either meso/anti (small silanes and disilane reagents) or dl/syn (bulky silanes) silyl-protected 1,2-diols. This easily tuned diastereoselectivity is rationalized based on the classic Felkin-Anh model applied to a mechanism relying on Si-H abstraction by the electrophilic borane reagent. PMID:20014769

  8. A general and efficient approach to aryl thiols: CuI-catalyzed coupling of aryl iodides with sulfur and subsequent reduction.

    PubMed

    Jiang, Yongwen; Qin, Yuxia; Xie, Siwei; Zhang, Xiaojing; Dong, Jinhua; Ma, Dawei

    2009-11-19

    A CuI-catalyzed coupling reaction of aryl iodides and sulfur powder takes place in the presence of K(2)CO(3) at 90 degrees C. The coupling mixture is directly treated with NaBH(4) or triphenylphosphine to afford aryl thiols in good to excellent yields. A wide range of substituted aryl thiols that bear methoxy, hydroxyl, carboxylate, amido, keto, bromo, and fluoro groups can be assembled through this procedure. PMID:19835369

  9. O2 and H2O2 transformation steps for the oxygen reduction reaction catalyzed by graphitic nitrogen-doped carbon nanotubes in acidic electrolyte from first principles calculations.

    PubMed

    Li, Yuhang; Zhong, Guoyu; Yu, Hao; Wang, Hongjuan; Peng, Feng

    2015-09-14

    It is highly challenging but extremely desirable to develop carbon catalysts with high oxygen reduction reaction (ORR) activity and stability in acidic medium for commercial application. In this paper, based on density functional theory (DFT) calculations with long range interaction correction and solvation effects, the elementary transformations of all the probable intermediates in the ORR and the hydrogen peroxide reduction reaction (HPRR) over graphitic nitrogen-doped carbon nanotubes (NCNTs) in acidic medium were evaluated, and it was found that all the rate determining steps are related to the bonding hydroxyl group because of the strong interaction between the hydroxyl group and carbon. Thus, it is hard for the direct four-electron ORR and the two-electron HPRR to proceed. Together with hydrogen peroxide disproportionation (HPD), a mixed mechanism for the ORR in acidic electrolyte was proposed, where the two-electron and three-electron ORRs and HPD dominate the electrode reaction. The experimental result for the ORR catalyzed by NCNTs in acidic electrolyte also well illustrated the rationality of the theoretical calculations. This study not only gives new insights into the effect of graphitic nitrogen doping on the ORR catalyzed by carbon, but also provides a guide to design carbon catalysts with high ORR activity in acidic electrolyte. PMID:26234475

  10. Alkyne–Aldehyde Reductive C–C Coupling through Ruthenium-Catalyzed Transfer Hydrogenation: Direct Regio- and Stereoselective Carbonyl Vinylation to Form Trisubstituted Allylic Alcohols in the Absence of Premetallated Reagents

    PubMed Central

    Leung, Joyce C.; Patman, Ryan L.; Sam, Brannon

    2011-01-01

    Nonsymmetric 1,2-disubstituted alkynes engage in reductive coupling to a variety of aldehydes under the conditions of ruthenium-catalyzed transfer hydrogenation by employing formic acid as the terminal reductant and delivering the products of carbonyl vinylation with good to excellent levels of regioselectivity and with complete control of olefin stereochemistry. As revealed in an assessment of the ruthenium counterion, iodide plays an essential role in directing the regioselectivity of C–C bond formation. Isotopic labeling studies corroborate reversible catalytic propargyl C–H oxidative addition in advance of the C–C coupling, and demonstrate that the C–C coupling products do not experience reversible dehydrogenation by way of enone intermediates. This transfer hydrogenation protocol enables carbonyl vinylation in the absence of stoichiometric metallic reagents. PMID:21953608

  11. Alkyne-aldehyde reductive C-C coupling through ruthenium-catalyzed transfer hydrogenation: direct regio- and stereoselective carbonyl vinylation to form trisubstituted allylic alcohols in the absence of premetallated reagents.

    PubMed

    Leung, Joyce C; Patman, Ryan L; Sam, Brannon; Krische, Michael J

    2011-10-24

    Nonsymmetric 1,2-disubstituted alkynes engage in reductive coupling to a variety of aldehydes under the conditions of ruthenium-catalyzed transfer hydrogenation by employing formic acid as the terminal reductant and delivering the products of carbonyl vinylation with good to excellent levels of regioselectivity and with complete control of olefin stereochemistry. As revealed in an assessment of the ruthenium counterion, iodide plays an essential role in directing the regioselectivity of C-C bond formation. Isotopic labeling studies corroborate reversible catalytic propargyl C-H oxidative addition in advance of the C-C coupling, and demonstrate that the C-C coupling products do not experience reversible dehydrogenation by way of enone intermediates. This transfer hydrogenation protocol enables carbonyl vinylation in the absence of stoichiometric metallic reagents. PMID:21953608

  12. Metal-catalyzed electroless etching and nanoimprinting silicon nanowire-based solar cells: Silicon nanowire defect reduction and efficiency enhancement by two-step H2 annealing

    NASA Astrophysics Data System (ADS)

    Jevasuwan, Wipakorn; Nakajima, Kiyomi; Sugimoto, Yoshimasa; Fukata, Naoki

    2016-06-01

    The effects of H2 annealing on material properties including defects of silicon nanowire (SiNW) surface and Si film layer for solar cell application were investigated. Single-junction solar cells consisting of n-SiNWs and chemical vapor deposition grown p-Si matrix were demonstrated using two-step H2 annealing. n-SiNWs formed by two different methods of metal-catalyzed electroless etching and nanoimprinting followed by the Bosch process were compared. Two-step H2 annealing at 900 °C for 10 min after both n-SiNW formations and subsequent p-Si matrix deposition effectively improved SiNW surface and p-Si crystallinity, resulting in higher solar cell efficiency.

  13. Surface-Plasmon-Enhanced Photodriven CO2 Reduction Catalyzed by Metal-Organic-Framework-Derived Iron Nanoparticles Encapsulated by Ultrathin Carbon Layers.

    PubMed

    Zhang, Huabin; Wang, Tao; Wang, Junjie; Liu, Huimin; Dao, Thang Duy; Li, Mu; Liu, Guigao; Meng, Xianguang; Chang, Kun; Shi, Li; Nagao, Tadaaki; Ye, Jinhua

    2016-05-01

    Highly efficient utilization of solar light with an excellent reduction capacity is achieved for plasmonic Fe@C nanostructures. By carbon layer coating, the optimized catalyst exhibits enhanced selectivity and stability applied to the solar-driven reduction of CO2 into CO. The surface-plasmon effect of iron particles is proposed to excite CO2 molecules, and thereby facilitates the final reaction activity. PMID:27001900

  14. Chemo- and Enantioselective Addition and β-Hydrogen Transfer Reduction of Carbonyl Compounds with Diethylzinc Reagent in One Pot Catalyzed by a Single Chiral Organometallic Catalyst.

    PubMed

    Huang, Huayin; Zong, Hua; Bian, Guangling; Song, Ling

    2015-12-18

    Using a single chiral phosphoramide-Zn(II) complex as the catalyst, the asymmetric β-H transfer reduction of aromatic α-trifluoromethyl ketones and enantioselective addition of aromatic aldehydes with Et2Zn in one pot were successfully realized, affording the corresponding additive products of secondary alcohols in high yields (up to 99%) with excellent enantioselectivities (up to 98% ee) and the reduction products of α-trifluoromethyl alcohols in good to excellent yields with up to 77% ee. PMID:26579727

  15. Reduction in (pro-)inflammatory responses of lung cells exposed in vitro to diesel exhaust treated with a non-catalyzed diesel particle filter

    NASA Astrophysics Data System (ADS)

    Steiner, Sandro; Czerwinski, Jan; Comte, Pierre; Müller, Loretta L.; Heeb, Norbert V.; Mayer, Andreas; Petri-Fink, Alke; Rothen-Rutishauser, Barbara

    2013-12-01

    Increasingly stringent regulation of particulate matter emissions from diesel vehicles has led to the widespread use of diesel particle filters (DPFs), the effect of which on exhaust toxicity is so far poorly understood. We exposed a cellular model of the human respiratory epithelium at the air-liquid interface to non-catalyzed wall-flow DPF-filtered diesel exhaust and compared the resulting biological responses to the ones observed upon exposure to unfiltered exhaust. Filtered diesel exhaust acted highly oxidative, even though to a lesser extent than unfiltered exhaust (quantification of total reduced glutathione), and both exhaust types triggered comparable responses to oxidative stress (measurement of heme-oxygenase 1 (HMOX1) and superoxide-dismutase (SOD1) gene expression). Further, diesel exhaust filtration significantly reduced pro-inflammatory responses (measurement of tumor necrosis factor (TNF) and interleukin-8 (IL-8) gene expression and quantification of the secretion of their gene products TNF-α and IL-8). Because inflammatory processes are central to the onset of adverse respiratory health effects caused by diesel exhaust inhalation, our results imply that DPFs may make a valuable contribution to the detoxification of diesel vehicle emissions. The induction of significant oxidative stress by filtered diesel exhaust however, also implies that the non-particulate exhaust components also need to be considered for lung cell risk assessment.

  16. Catalyzed Ceramic Burner Material

    SciTech Connect

    Barnes, Amy S., Dr.

    2012-06-29

    period in accomplishing these objectives. Our work in the area of Pd-based, methane oxidation catalysts has led to the development of highly active catalysts with relatively low loadings of Pd metal using proprietary coating methods. The thermal stability of these Pd-based catalysts were characterized using SEM and BET analyses, further demonstrating that certain catalyst supports offer enhanced stability toward both PdO decomposition and/or thermal sintering/growth of Pd particles. When applied to commercially available fiber mesh substrates (both metallic and ceramic) and tested in an open-air burner, these catalyst-support chemistries showed modest improvements in the NOx emissions and radiant output compared to uncatalyzed substrates. More significant, though, was the performance of the catalyst-support chemistries on novel media substrates. These substrates were developed to overcome the limitations that are present with commercially available substrate designs and increase the gas-catalyst contact time. When catalyzed, these substrates demonstrated a 65-75% reduction in NOx emissions across the firing range when tested in an open air burner. In testing in a residential boiler, this translated into NOx emissions of <15 ppm over the 15-150 kBtu/hr firing range.

  17. Electrochemical reduction of oxygen and hydrogen peroxide catalyzed by a surface copper(II)-2,4,6-tris(2-piridil)-1,3,5-triazine complex adsorbed on a graphite electrode

    NASA Astrophysics Data System (ADS)

    Dias, Vera L. N.; Fernandes, Elizabeth N.; da Silva, Leila M. S.; Marques, Edmar P.; Zhang, Jiujun; Marques, Aldaléa L. Brandes

    A graphite electrode irreversibly adsorbed by 2,4,6-tris(2-piridil)-1,3,5-triazine (abbreviated as TPT) was examined by cyclic voltammetry. The adsorbed TPT exhibited two irreversible reduction waves in the potential range of -0.7 and -1.0 V (versus SCE). Upon strong adsorption, TPT can serve as a coordination ligand for copper ions to form a surface complex. Its three adjacent nitrogen positions provide strong affinity to the metal ions and bond copper(II) to an electrode surface. A 1:1 coordination between Cu(II) or Cu(I) and the TPT ligand to form [Cu(II)(TPT)] 2+ or [Cu(I)(TPT)] + is the predominant process, evidenced by spectrophotometry, surface cyclic voltammetry, and coordinated structural feasibility of Cu(II)/Cu(I)-TPT complexes. The predominant copper(II)-TPT surface complex shows a reversible redox wave, which is identified as one-electron process of [Cu(II)(TPT)] 2+ ↔ [Cu(I)(TPT)] +. The electrode adsorbed by [Cu(II)(TPT)] 2+ complex showed electrocatalytic activity towards oxygen and/or hydrogen peroxide reductions. The catalyzed reduction of oxygen and hydrogen peroxide were identified as four-electron and two-electron process to form water. It is suggested that the possible electrocatalytic reductions were due to an inner-sphere mechanism, which involved a coordination between substrate (O 2 or H 2O 2) and [Cu(I)(TPT)] +. The reduction kinetics were also investigated by a rotating disk electrode method.

  18. Safe and Selective Nitro Group Reductions Catalyzed by Sustainable and Recyclable Fe/ppm Pd Nanoparticles in Water at Room Temperature.

    PubMed

    Feng, Jie; Handa, Sachin; Gallou, Fabrice; Lipshutz, Bruce H

    2016-07-25

    As a result of a unique synergy between ligand-free Fe/ppm Pd nanoparticles and PEG-containing designer surfactants, a facile and selective reduction of nitro-containing aromatics and heteroaromatics can be effected in water at room temperature in the presence of NaBH4 . This new nanotechnology involves low catalyst loadings, is highly chemoselective, and tolerates a wide variety of functional groups. The process, which includes recycling of the entire aqueous medium, offers a general, environmentally responsible, and notably safe approach to highly valued reductions of nitro-containing compounds. PMID:27305385

  19. Ice crystals growth driving assembly of porous nitrogen-doped graphene for catalyzing oxygen reduction probed by in situ fluorescence electrochemistry

    PubMed Central

    Wang, Jiong; Wang, Huai-Song; Wang, Kang; Wang, Feng-Bin; Xia, Xing-Hua

    2014-01-01

    In recent years, doped carbonaceous materials as alternative catalysts for oxygen reduction reaction (ORR) have received considerable attention due to the low cost and high CO tolerance capability. Different theoretical studies have suggested that oxygen is reduced in a rapid sequence intermediated by diverse oxygen-containing reactive intermediates (ORI). However, due to the short lifetimes of the possible ORI, direct experimental evidence is very difficult to be obtained. Here, we report the synthesis of an ultralight and porous nitrogen-doped graphene (NG) by annealing graphite oxide (GO)-melamine scaffold shaped in ice template. The resultant NG exhibits excellent electrocatalytic activity toward 4e-reduction of oxygen with the onset potential as low as −0.05 V vs. Ag/AgCl in alkaline media. Using this material as model study, sensitive in situ fluorescence spectroelectrochemistry is applied to demonstrate the presence the reactive ORI. The global ORR pathway is unraveled as stepwise electron transfer involving hydroxyl radical as the important intermediate via both inner- and outer-sphere process. This result would likely provide a new insight into the further understanding of ORR mechanism on those intrinsic carbonaceous materials. PMID:25335571

  20. Ag@Au concave cuboctahedra: A unique probe for monitoring Au-catalyzed reduction and oxidation reactions by surface-enhanced Raman spectroscopy

    DOE PAGESBeta

    Zhang, Jiawei; Winget, Sarah A.; Wu, Yiren; Su, Dong; Sun, Xiaojun; Xie, Zhao -Xiong; Qin, Dong

    2016-01-26

    In this paper, we report a facile synthesis of Ag@Au concave cuboctahedra by titrating aqueous HAuCl4 into a suspension of Ag cuboctahedra in the presence of ascorbic acid (AA), NaOH, and poly(vinylpyrrolidone) (PVP) at room temperature. Initially, the Au atoms derived from the reduction of Au3+ by AA are conformally deposited on the entire surface of a Ag cuboctahedron. Upon the formation of a complete Au shell, however, the subsequently formed Au atoms are preferentially deposited onto the Au{100} facets, resulting in the formation of a Ag@Au cuboctahedron with concave structures at the sites of {111} facets. The concave cuboctahedramore » embrace excellent SERS activity that is more than 70-fold stronger than that of the original Ag cuboctahedra at an excitation wavelength of 785 nm. The concave cuboctahedra also exhibit remarkable stability in the presence of an oxidant such as H2O2 because of the protection by a complete Au shell. These two unique attributes enable in-situ SERS monitoring of the reduction of 4-nitrothiophenol (4-NTP) to 4-aminothiophenol (4-ATP) by NaBH4 through a 4,4'-dimercaptoazobenzene (trans-DMAB) intermediate and the subsequent oxidation of 4-ATP back to trans-DMAB upon the introduction of H2O2.« less

  1. Surface-enhanced Raman scattering studies of the reduction of p-nitroaniline catalyzed by a nanonized Ag porous-glass hybrid composite.

    PubMed

    Huang, Genin Gary; Sou, Nga-Lai; Hung, Mei-Jou

    2016-09-01

    Nanonized noble metal composites have been known for their excellent catalytic properties. However, the mechanism and intermediates formed on the surfaces of nanocatalysts during catalysis are speculated with mostly insufficient evidence. In this study, to obtain further understanding of the roles of noble metal nanocatalysts in a catalytic reaction, surface-enhanced Raman scattering (SERS) was used to monitor the surfaces of silver (Ag) nanocatalysts. Furthermore, UV-Vis spectrometry was used to trace the concentration variations of reactants and products in bulk solutions, thereby correlating the variations of the Ag nanocatalyst surfaces with those in the bulk solutions. Nanonized Ag porous-glass hybrid composites were prepared by reducing naked Ag nanoparticles on porous-glass filter plates and were used as catalysts for nitroanilines reduction. The complete process was monitored using SERS and UV-Vis spectrometry simultaneously. The results indicated that the reactant and product molecules adsorbed on the Ag nanocatalysts can reach equilibrium, and the equilibrium is affected by the reaction conditions, including reducing agent concentration, pH of the reaction system, and temperature. In addition, the reduction of reactants in the bulk solutions is also related to the behavior of Ag nanocatalyst surfaces. Furthermore, Ag nanocatalysts can act as electron relays even if their surfaces are occupied by reactants and products. Analyzing the collected SERS and UV-Vis spectra can provide a new insight into Ag nanoparticle catalysis, and the role of Ag nanocatalysts can be further comprehended. PMID:27179295

  2. Ice crystals growth driving assembly of porous nitrogen-doped graphene for catalyzing oxygen reduction probed by in situ fluorescence electrochemistry

    NASA Astrophysics Data System (ADS)

    Wang, Jiong; Wang, Huai-Song; Wang, Kang; Wang, Feng-Bin; Xia, Xing-Hua

    2014-10-01

    In recent years, doped carbonaceous materials as alternative catalysts for oxygen reduction reaction (ORR) have received considerable attention due to the low cost and high CO tolerance capability. Different theoretical studies have suggested that oxygen is reduced in a rapid sequence intermediated by diverse oxygen-containing reactive intermediates (ORI). However, due to the short lifetimes of the possible ORI, direct experimental evidence is very difficult to be obtained. Here, we report the synthesis of an ultralight and porous nitrogen-doped graphene (NG) by annealing graphite oxide (GO)-melamine scaffold shaped in ice template. The resultant NG exhibits excellent electrocatalytic activity toward 4e-reduction of oxygen with the onset potential as low as -0.05 V vs. Ag/AgCl in alkaline media. Using this material as model study, sensitive in situ fluorescence spectroelectrochemistry is applied to demonstrate the presence the reactive ORI. The global ORR pathway is unraveled as stepwise electron transfer involving hydroxyl radical as the important intermediate via both inner- and outer-sphere process. This result would likely provide a new insight into the further understanding of ORR mechanism on those intrinsic carbonaceous materials.

  3. Eco-friendly synthesis of silver and gold nanoparticles with enhanced bactericidal activity and study of silver catalyzed reduction of 4-nitrophenol

    NASA Astrophysics Data System (ADS)

    Naraginti, Saraschandra; Sivakumar, A.

    2014-07-01

    The present study reports a simple and robust method for synthesis of silver and gold nanoparticles using Coleus forskohlii root extract as reducing and stabilizing agent. Stable silver nanoparticles (AgNPs) and gold nanopoarticles (AuNPs) were formed on treatment of an aqueous silver nitrate (AgNO3) and chloroauric acid (HAuCl4) solutions with the root extract. The nanoparticles obtained were characterized by UV-Visible spectroscopy, Transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FT-IR). UV-Vis and TEM analysis indicate that with higher quantities of root extract, the interaction is enhanced leading to size reduction of spherical metal nanoparticles. XRD confirms face-centered cubic phase and the diffraction peaks can be attributed to (1 1 1), (2 0 0), (2 2 2) and (3 1 1) planes for these nanoparticles. These synthesized Ag and Au nanoparticles were found to exhibit excellent bactericidal activity against clinically isolated selected pathogens such as Escherichia coli (E. coli), Pseudomonas aeruginosa (P. aeruginosa) and Staphylococcus aureus (S. aureus). The synthesized AgNPs were also found to function as an efficient green catalyst in the reduction of anthropogenic pollutant 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by sodium borohydride, which was apparent from the periodical color change from bright yellow to colorless, after the addition of AgNPs.

  4. Surface-enhanced Raman scattering studies of the reduction of p-nitroaniline catalyzed by a nanonized Ag porous-glass hybrid composite

    NASA Astrophysics Data System (ADS)

    Huang, Genin Gary; Sou, Nga-Lai; Hung, Mei-Jou

    2016-09-01

    Nanonized noble metal composites have been known for their excellent catalytic properties. However, the mechanism and intermediates formed on the surfaces of nanocatalysts during catalysis are speculated with mostly insufficient evidence. In this study, to obtain further understanding of the roles of noble metal nanocatalysts in a catalytic reaction, surface-enhanced Raman scattering (SERS) was used to monitor the surfaces of silver (Ag) nanocatalysts. Furthermore, UV-Vis spectrometry was used to trace the concentration variations of reactants and products in bulk solutions, thereby correlating the variations of the Ag nanocatalyst surfaces with those in the bulk solutions. Nanonized Ag porous-glass hybrid composites were prepared by reducing naked Ag nanoparticles on porous-glass filter plates and were used as catalysts for nitroanilines reduction. The complete process was monitored using SERS and UV-Vis spectrometry simultaneously. The results indicated that the reactant and product molecules adsorbed on the Ag nanocatalysts can reach equilibrium, and the equilibrium is affected by the reaction conditions, including reducing agent concentration, pH of the reaction system, and temperature. In addition, the reduction of reactants in the bulk solutions is also related to the behavior of Ag nanocatalyst surfaces. Furthermore, Ag nanocatalysts can act as electron relays even if their surfaces are occupied by reactants and products. Analyzing the collected SERS and UV-Vis spectra can provide a new insight into Ag nanoparticle catalysis, and the role of Ag nanocatalysts can be further comprehended.

  5. Monodisperse core/shell Ni/FePt nanoparticles and their con-version to Ni/Pt to catalyze oxygen reduction

    SciTech Connect

    Zhang, Sen; Hao, Yizhou; Su, Dong; Doan-Nguyen, Vicky V. T.; Wu, Yaoting; Li, Jing; Sun, Shouheng; Murray, Christopher B.

    2014-10-28

    We report a size-controllable synthesis of monodisperse core/shell Ni/FePt nanoparticles (NPs) via a seed-mediated growth and their subsequent conversion to Ni/Pt NPs. Preventing surface oxidation of the Ni seeds is essential for the growth of uniform FePt shells. These Ni/FePt NPs have a thin (≈ 1 nm) FePt shell, and can be converted to Ni/Pt by acetic acid wash to yield active catalysts for oxygen reduction reaction (ORR). Tuning the core size allow for optimization of their electrocatalytic activity. The specific activity and mass activity of 4.2 nm/0.8 nm core/shell Ni/FePt reach 1.95 mA/cm² and 490 mA/mgPt at 0.9 V (vs. reversible hydrogen electrode, RHE), which are much higher than those of benchmark commercial Pt catalyst (0.34 mA/cm² and 92 mA/mgPt at 0.9 V). Our studies provide a robust approach to monodisperse core/shell NPs with non-precious metal core, making it possible to develop advanced NP catalysts with ultralow Pt content for ORR and many other heterogeneous reactions.

  6. Monodisperse core/shell Ni/FePt nanoparticles and their con-version to Ni/Pt to catalyze oxygen reduction

    DOE PAGESBeta

    Zhang, Sen; Hao, Yizhou; Su, Dong; Doan-Nguyen, Vicky V. T.; Wu, Yaoting; Li, Jing; Sun, Shouheng; Murray, Christopher B.

    2014-10-28

    We report a size-controllable synthesis of monodisperse core/shell Ni/FePt nanoparticles (NPs) via a seed-mediated growth and their subsequent conversion to Ni/Pt NPs. Preventing surface oxidation of the Ni seeds is essential for the growth of uniform FePt shells. These Ni/FePt NPs have a thin (≈ 1 nm) FePt shell, and can be converted to Ni/Pt by acetic acid wash to yield active catalysts for oxygen reduction reaction (ORR). Tuning the core size allow for optimization of their electrocatalytic activity. The specific activity and mass activity of 4.2 nm/0.8 nm core/shell Ni/FePt reach 1.95 mA/cm² and 490 mA/mgPt at 0.9 Vmore » (vs. reversible hydrogen electrode, RHE), which are much higher than those of benchmark commercial Pt catalyst (0.34 mA/cm² and 92 mA/mgPt at 0.9 V). Our studies provide a robust approach to monodisperse core/shell NPs with non-precious metal core, making it possible to develop advanced NP catalysts with ultralow Pt content for ORR and many other heterogeneous reactions.« less

  7. Hollow-shell-structured nanospheres: a recoverable heterogeneous catalyst for rhodium-catalyzed tandem reduction/lactonization of ethyl 2-acylarylcarboxylates to chiral phthalides.

    PubMed

    Liu, Rui; Jin, Ronghua; An, Juzeng; Zhao, Qiankun; Cheng, Tanyu; Liu, Guohua

    2014-05-01

    Chiral organorhodium-functionalized hollow-shell-structured nanospheres were prepared by immobilization of a chiral N-sulfonylated diamine-based organorhodium complex within an ethylene-bridged organosilicate shell. Structural analysis and characterization reveal its well-defined single-site rhodium active center, and transmission electron microscopy images reveal a uniform dispersion of hollow-shell-structured nanospheres. As a heterogenous catalyst, it exhibits excellent catalytic activity and enantioselectivity in synthesis of chiral phthalides by a tandem reduction/lactonization of ethyl 2-acylarylcarboxylates in aqueous medium. The high catalytic performance is attributed to the synergistic effect of the high hydrophobicity and the confined chiral organorhodium catalytic nature. The organorhodium-functionalized nanospheres could be conveniently recovered and reused at least 10 times without loss of catalytic activity. This feature makes it an attractive catalyst in environmentally friendly organic reactions. The results of this study offer a new approach to immobilize chiral organometal functionalities within the hollow-shell-structured nanospheres to prepare materials with high activity in heterogeneous asymmetric catalysis. PMID:24623451

  8. High-performance of bare and Ti-doped α-MnO2 nanoparticles in catalyzing the Oxygen Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Pargoletti, E.; Cappelletti, G.; Minguzzi, A.; Rondinini, S.; Leoni, M.; Marelli, M.; Vertova, A.

    2016-09-01

    Nanostructured MnO2 has unique electrocatalytic properties towards the Oxygen Reduction Reaction (ORR, the main cathodic reaction in metal-air devices), representing an excellent alternative to the expensive platinum. Herein, we report the hydrothermal synthesis of bare and 5% Ti-doped α-MnO2 nanoparticles using two different oxidizing agents, namely ammonium persulfate for MH_N samples and potassium permanganate for MH_K ones. The physico-chemical characterizations show that oxidant cations induce different structural, morphological and surface properties of the final powders. Hence, correlations between the different α-MnO2 characteristics and their electrocatalytic performances towards the ORR are drawn, highlighting the diverse effect even on the kinetic point of view. The ORR activity in alkaline media is examined by means of Staircase - Linear Sweep Voltammetry (S-LSV), using Gas Diffusion Electrode (GDE) as the air-cathode. The presence of these nanoparticles in the GDEs leads to a significant shift of the ORR onset potential (∼100 mV) towards less cathodic values, underlining the electrocatalytic efficiency of all the nanopowders. Furthermore, high exchange current densities (j0) are determined for GDEs with Ti-doped MnO2, comparable to the well-performing Pd45Pt5Sn50, and making it a promising material for the ORR.

  9. Identification and Environmental Distribution of dcpA, Which Encodes the Reductive Dehalogenase Catalyzing the Dichloroelimination of 1,2-Dichloropropane to Propene in Organohalide-Respiring Chloroflexi

    PubMed Central

    Padilla-Crespo, Elizabeth; Yan, Jun; Swift, Cynthia; Wagner, Darlene D.; Chourey, Karuna; Hettich, Robert L.; Ritalahti, Kirsti M.

    2014-01-01

    Dehalococcoides mccartyi strains KS and RC grow with 1,2-dichloropropane (1,2-D) as an electron acceptor in enrichment cultures derived from hydrocarbon-contaminated and pristine river sediments, respectively. Transcription, expression, enzymatic, and PCR analyses implicated the reductive dehalogenase gene dcpA in 1,2-D dichloroelimination to propene and inorganic chloride. Quantitative real-time PCR (qPCR) analyses demonstrated a D. mccartyi cell increase during growth with 1,2-D and suggested that both D. mccartyi strains carried a single dcpA gene copy per genome. D. mccartyi strain RC and strain KS produced 1.8 × 107 ± 0.1 × 107 and 1.4 × 107 ± 0.5 × 107 cells per μmol of propene formed, respectively. The dcpA gene was identified in 1,2-D-to-propene-dechlorinating microcosms established with sediment samples collected from different geographical locations in Europe and North and South America. Clone library analysis revealed two distinct dcpA phylogenetic clusters, both of which were captured by the dcpA gene-targeted qPCR assay, suggesting that the qPCR assay is useful for site assessment and bioremediation monitoring at 1,2-D-contaminated sites. PMID:24242248

  10. Homogeneous gold-catalyzed efficient oxidative dimerization of propargylic acetates.

    PubMed

    Cui, Li; Zhang, Guozhu; Zhang, Liming

    2009-07-15

    A highly efficient gold-catalyzed oxidative dimerization of propargylic acetates is developed. In this chemistry, Selectfluor oxidation of Au(I) to Au(III) is readily incorporated into Au-catalyzed tandem reactions of propargylic acetates, and transmetallation and reductive elimination on Au(III) intermediates are likely involved. PMID:19362834

  11. Reduction of nitroaromatic compounds mediated by Streptomyces sp. exudates.

    PubMed Central

    Glaus, M A; Heijman, C G; Schwarzenbach, R P; Zeyer, J

    1992-01-01

    Exudates from Streptomyces griseoflavus Tü 2484 effectively mediated electron transfer between hydrogen sulfide and various nitrobenzenes. In general, pseudo-first-order kinetics were observed, except for the initial phase of the reaction at higher pH values. Under fixed pH and Dh conditions, linear free energy relationships were found between the logarithms of the reaction rate constants and the one-electron reduction potentials of the nitroaromatic compounds. No competition was observed between various compounds. Comparison of the results of this study with the results of experiments conducted with model quinones and an iron porphyrin suggest that the secondary metabolites cinnaquinone and dicinnaquinone, excreted by strain Tü 2484 on the order of 100 mg/liter, are responsible for the catalytic activity of the exudate. Further support for this hypothesis comes from the facts that the catalytic activity of the exudate became prominent only after the growth phase of the microorganisms and that the mediating substances have a molecular weight of less than 3,000. PMID:1622270

  12. Muon Catalyzed Fusion

    NASA Technical Reports Server (NTRS)

    Armour, Edward A.G.

    2007-01-01

    Muon catalyzed fusion is a process in which a negatively charged muon combines with two nuclei of isotopes of hydrogen, e.g, a proton and a deuteron or a deuteron and a triton, to form a muonic molecular ion in which the binding is so tight that nuclear fusion occurs. The muon is normally released after fusion has taken place and so can catalyze further fusions. As the muon has a mean lifetime of 2.2 microseconds, this is the maximum period over which a muon can participate in this process. This article gives an outline of the history of muon catalyzed fusion from 1947, when it was first realised that such a process might occur, to the present day. It includes a description of the contribution that Drachrnan has made to the theory of muon catalyzed fusion and the influence this has had on the author's research.

  13. Hydrogen evolution catalyzed by cobaloximes.

    PubMed

    Dempsey, Jillian L; Brunschwig, Bruce S; Winkler, Jay R; Gray, Harry B

    2009-12-21

    Natural photosynthesis uses sunlight to drive the conversion of energy-poor molecules (H(2)O, CO(2)) to energy-rich ones (O(2), (CH(2)O)(n)). Scientists are working hard to develop efficient artificial photosynthetic systems toward the "Holy Grail" of solar-driven water splitting. High on the list of challenges is the discovery of molecules that efficiently catalyze the reduction of protons to H(2). In this Account, we report on one promising class of molecules: cobalt complexes with diglyoxime ligands (cobaloximes). Chemical, electrochemical, and photochemical methods all have been utilized to explore proton reduction catalysis by cobaloxime complexes. Reduction of a Co(II)-diglyoxime generates a Co(I) species that reacts with a proton source to produce a Co(III)-hydride. Then, in a homolytic pathway, two Co(III)-hydrides react in a bimolecular step to eliminate H(2). Alternatively, in a heterolytic pathway, protonation of the Co(III)-hydride produces H(2) and Co(III). A thermodynamic analysis of H(2) evolution pathways sheds new light on the barriers and driving forces of the elementary reaction steps involved in proton reduction by Co(I)-diglyoximes. In combination with experimental results, this analysis shows that the barriers to H(2) evolution along the heterolytic pathway are, in most cases, substantially greater than those of the homolytic route. In particular, a formidable barrier is associated with Co(III)-diglyoxime formation along the heterolytic pathway. Our investigations of cobaloxime-catalyzed H(2) evolution, coupled with the thermodynamic preference for a homolytic route, suggest that the rate-limiting step is associated with formation of the hydride. An efficient water splitting device may require the tethering of catalysts to an electrode surface in a fashion that does not inhibit association of Co(III)-hydrides. PMID:19928840

  14. Catalyzed sodium chlorate candles

    NASA Technical Reports Server (NTRS)

    Malich, C. W.; Wydeven, T.

    1972-01-01

    The catalytic effect of cobalt powder on chlorate decomposition has been confirmed. Catalysis is enhanced by oxidation of the metal during burning. Catalysts other than cobalt compounds should also be effective; the complete elimination of fuel has shown that the oxidation of cobalt during decomposition is not a vital factor in the improved performance of catalyzed candles.

  15. Tritium catalyzed deuterium tokamaks

    SciTech Connect

    Greenspan, E.; Miley, G.H.; Jung, J.; Gilligan, J.

    1984-04-01

    A preliminary assessment of the promise of the Tritium Catalyzed Deuterium (TCD) tokamak power reactors relative to that of deuterium-tritium (D-T) and catalyzed deuterium (Cat-D) tokamaks is undertaken. The TCD mode of operation is arrived at by converting the /sup 3/He from the D(D,n)/sup 3/He reaction into tritium, by neutron capture in the blanket; the tritium thus produced is fed into the plasma. There are three main parts to the assessment: blanket study, reactor design and economic analysis and an assessment of the prospects for improvements in the performance of TCD reactors (and in the promise of the TCD mode of operation, in general).

  16. Hydrogen Peroxide-Resistant CotA and YjqC of Bacillus altitudinis Spores Are a Promising Biocatalyst for Catalyzing Reduction of Sinapic Acid and Sinapine in Rapeseed Meal

    PubMed Central

    Zhang, Yanzhou; Li, Xunhang; Hao, Zhikui; Xi, Ruchun; Cai, Yujie; Liao, Xiangru

    2016-01-01

    For the more efficient detoxification of phenolic compounds, a promising avenue would be to develop a multi-enzyme biocatalyst comprising peroxidase, laccase and other oxidases. However, the development of this multi-enzyme biocatalyst is limited by the vulnerability of fungal laccases and peroxidases to hydrogen peroxide (H2O2)-induced inactivation. Therefore, H2O2-resistant peroxidase and laccase should be exploited. In this study, H2O2-stable CotA and YjqC were isolated from the outer coat of Bacillus altitudinis SYBC hb4 spores. In addition to the thermal and alkali stability of catalytic activity, CotA also exhibited a much higher H2O2 tolerance than fungal laccases from Trametes versicolor and Trametes trogii. YjqC is a sporulation-related manganese (Mn) catalase with striking peroxidase activity for sinapic acid (SA) and sinapine (SNP). In contrast to the typical heme-containing peroxidases, the peroxidase activity of YjqC was also highly resistant to inhibition by H2O2 and heat. CotA could also catalyze the oxidation of SA and SNP. CotA had a much higher affinity for SA than B. subtilis CotA. CotA and YjqC rendered from B. altitudinis spores had promising laccase and peroxidase activities for SA and SNP. Specifically, the B. altitudinis spores could be regarded as a multi-enzyme biocatalyst composed of CotA and YjqC. The B. altitudinis spores were efficient for catalyzing the degradation of SA and SNP in rapeseed meal. Moreover, efficiency of the spore-catalyzed degradation of SA and SNP was greatly improved by the presence of 15 mM H2O2. This effect was largely attributed to synergistic biocatalysis of the H2O2-resistant CotA and YjqC toward SA and SNP. PMID:27362423

  17. Trypsin-Catalyzed Deltamethrin Degradation

    PubMed Central

    Xiong, Chunrong; Fang, Fujin; Chen, Lin; Yang, Qinggui; He, Ji; Zhou, Dan; Shen, Bo; Ma, Lei; Sun, Yan; Zhang, Donghui; Zhu, Changliang

    2014-01-01

    To explore if trypsin could catalyze the degradation of non-protein molecule deltamethrin, we compared in vitro hydrolytic reactions of deltamethrin in the presence and absence of trypsin with ultraviolet-visible (UV/Vis) spectrophotometry and gas chromatography-mass spectrometry (GC/MS). In addition, acute oral toxicity of the degradation products was determined in Wistar rats. The results show that the absorption peak of deltamethrin is around 264 nm, while the absorption peaks of deltamethrin degradation products are around 250 nm and 296 nm. In our GC setting, the retention time of undegraded deltamethrin was 37.968 min, while those of deltamethrin degradation products were 15.289 min and 18.730 min. The LD50 of deltamethrin in Wistar rats is 55 mg/kg, while that of deltamethrin degradation products is 3358 mg/kg in female rats and 1045 mg/kg in male rates (61-fold and 19-fold reductions in toxicity), suggesting that trypsin could directly degrade deltamethrin, which significantly reduces the toxicity of deltamethrin. These results expand people's understanding of the functions of proteases and point to potential applications of trypsin as an attractive agent to control residual pesticides in the environment and on agricultural products. PMID:24594869

  18. Elucidating Oxygen Reduction Active Sites in Pyrolyzed Metal–Nitrogen Coordinated Non-Precious-Metal Electrocatalyst Systems

    PubMed Central

    2015-01-01

    Detailed understanding of the nature of the active centers in non-precious-metal-based electrocatalyst, and their role in oxygen reduction reaction (ORR) mechanistic pathways will have a profound effect on successful commercialization of emission-free energy devices such as fuel cells. Recently, using pyrolyzed model structures of iron porphyrins, we have demonstrated that a covalent integration of the Fe–Nx sites into π-conjugated carbon basal plane modifies electron donating/withdrawing capability of the carbonaceous ligand, consequently improving ORR activity. Here, we employ a combination of in situ X-ray spectroscopy and electrochemical methods to identify the various structural and functional forms of the active centers in non-heme Fe/N/C catalysts. Both methods corroboratively confirm the single site 2e– × 2e– mechanism in alkaline media on the primary Fe2+–N4 centers and the dual-site 2e– × 2e– mechanism in acid media with the significant role of the surface bound coexisting Fe/FexOy nanoparticles (NPs) as the secondary active sites. PMID:24817921

  19. Hydroxide-catalyzed bonding

    NASA Technical Reports Server (NTRS)

    Gwo, Dz-Hung (Inventor)

    2003-01-01

    A method of bonding substrates by hydroxide-catalyzed hydration/dehydration involves applying a bonding material to at least one surface to be bonded, and placing the at least one surface sufficiently close to another surface such that a bonding interface is formed between them. A bonding material of the invention comprises a source of hydroxide ions, and may optionally include a silicate component, a particulate filling material, and a property-modifying component. Bonding methods of the invention reliably and reproducibly provide bonds which are strong and precise, and which may be tailored according to a wide range of possible applications. Possible applications for bonding materials of the invention include: forming composite materials, coating substrates, forming laminate structures, assembly of precision optical components, and preparing objects of defined geometry and composition. Bonding materials and methods of preparing the same are also disclosed.

  20. Chiral Epoxides via Borane Reduction of 2-Haloketones Catalyzed By Spiroborate Ester: Application to the Synthesis of Optically Pure 1,2-Hydroxy Ethers and 1,2-Azido Alcohols

    PubMed Central

    Huang, Kun; Wang, Haiyang; Stepanenko, Viatcheslav; De Jesús, Melvin; Torruellas, Carilyn; Correa, Wildeliz; Ortiz-Marciales, Margarita

    2011-01-01

    An enantioselective borane-mediated reduction of a variety of 2-haloketones using 10% of spiroaminoborate ester 1 as catalyst is described. By a simple basic workup of 2-halohydrins, optically active epoxides are obtained in high yield and with excellent enantiopurity (up to 99% ee). Ring opening of oxiranes with phenoxides or sodium azide is investigated under different reaction conditions affording nonracemic 1,2-hydroxy ethers and 1,2-azido alcohols with excellent enantioselectivity (99% ee) and in good to high chemical yield. PMID:21294519

  1. NEW CORDIERITE DIESEL PARTICULATE FILTERS FOR CATALYZED AND NON-CATALYZED APPLICATIONS

    SciTech Connect

    Merkel, G; Cutler, W; Tao, T Chiffey, A; Phillips, P; Twigg, M; Walker, A

    2003-08-24

    Cordierite diesel particulate filters provide an economical approach to diesel emissions control. However, further reduction in the pressure drop of catalyzed and non-catalyzed cordierite filters is desirable. In order to derive a fundamental understanding of the relationship between clean and sootloaded pressure drop and the pore microstructure of the ceramic, and to optimize the microstructure for filter performance, cordierite filters have been fabricated spanning an extended range in porosity, pore size distribution, and pore connectivity. Analysis of the results has been applied to the development of several new cordierite diesel particulate filters that possess a unique combination of high filtration efficiency, high strength, and very low clean and soot-loaded pressure drop. Furthermore, catalyst systems have been developed that result in a minimal pressure drop increase of the catalyzed filter. Optimization of porosity and cell geometry has enabled fabrication o f filters with either high or low thermal mass appropriate to the regeneration strategy employed for a given engine management system.

  2. In situ measurements of microbially-catalyzed nitrification and nitrate reduction rates in an ephemeral drainage channel receiving water from coalbed natural gas discharge, Powder River Basin, Wyoming, USA

    USGS Publications Warehouse

    Harris, S.H.; Smith, R.L.

    2009-01-01

    Nitrification and nitrate reduction were examined in an ephemeral drainage channel receiving discharge from coalbed natural gas (CBNG) production wells in the Powder River Basin, Wyoming. CBNG co-produced water typically contains dissolved inorganic nitrogen (DIN), primarily as ammonium. In this study, a substantial portion of discharged ammonium was oxidized within 50??m of downstream transport, but speciation was markedly influenced by diel fluctuations in dissolved oxygen (> 300????M). After 300??m of transport, 60% of the initial DIN load had been removed. The effect of benthic nitrogen-cycling processes on stream water chemistry was assessed at 2 locations within the stream channel using acrylic chambers to conduct short-term (2-6??h), in-stream incubations. The highest ambient DIN removal rates (2103????mol N m- 2 h- 1) were found at a location where ammonium concentrations > 350????M. This occurred during light incubations when oxygen concentrations were highest. Nitrification was occurring at the site, however, net accumulation of nitrate and nitrite accounted for < 12% of the ammonium consumed, indicating that other ammonium-consuming processes were also occurring. In dark incubations, nitrite and nitrate consumption were dominant processes, while ammonium was produced rather than consumed. At a downstream location nitrification was not a factor and changes in DIN removal rates were controlled by nitrate reduction, diel fluctuations in oxygen concentration, and availability of electron donor. This study indicates that short-term adaptation of stream channel processes can be effective for removing CBNG DIN loads given sufficient travel distances, but the long-term potential for nitrogen remobilization and nitrogen saturation remain to be determined.

  3. Palladium-Catalyzed Arylation of Fluoroalkylamines

    PubMed Central

    Brusoe, Andrew T.; Hartwig, John F.

    2015-01-01

    We report the synthesis of fluorinated anilines by palladium-catalyzed coupling of fluoroalkylamines with aryl bromides and aryl chlorides. The products of these reactions are valuable because anilines typically require the presence of an electron-withdrawing substituent on nitrogen to suppress aerobic or metabolic oxidation, and the fluoroalkyl groups have steric properties and polarity distinct from those of more common electron-withdrawing amide and sulfonamide units. The fluoroalkylaniline products are unstable under typical conditions for C–N coupling reactions (heat and strong base). However, the reactions conducted with the weaker base KOPh, which has rarely been used in cross-coupling to form C–N bonds, occurred in high yield in the presence of a catalyst derived from commercially available AdBippyPhos and [Pd(allyl)Cl]2. Under these conditions, the reactions occur with low catalyst loadings (<0.50 mol % for most substrates) and tolerate the presence of various functional groups that react with the strong bases that are typically used in Pd-catalyzed C–N cross-coupling reactions of aryl halides. The resting state of the catalyst is the phenoxide complex, (BippyPhosPd(Ar)OPh); due to the electron-withdrawing property of the fluoroalkyl substituent, the turnover-limiting step of the reaction is reductive elimination to form the C–N bond. PMID:26065341

  4. Solvent-free lipase-catalyzed preparation of diacylglycerols.

    PubMed

    Weber, Nikolaus; Mukherjee, Kumar D

    2004-08-25

    Various methods have been applied for the enzymatic preparation of diacylglycerols that are used as dietary oils for weight reduction in obesity and related disorders. Interesterification of rapeseed oil triacylglycerols with commercial preparations of monoacylglycerols, such as Monomuls 90-O18, Mulgaprime 90, and Nutrisoft 55, catalyzed by immobilized lipase from Rhizomucor miehei (Lipozyme RM IM) in vacuo at 60 degrees C led to extensive (from 60 to 75%) formation of diacylglycerols. Esterification of rapeseed oil fatty acids with Nutrisoft, catalyzed by Lipozyme RM in vacuo at 60 degrees C, also led to extensive (from 60 to 70%) formation of diacylglycerols. Esterification of rapeseed oil fatty acids with glycerol in vacuo at 60 degrees C, catalyzed by Lipozyme RM and lipases from Thermomyces lanuginosus (Lipozyme TL IM) and Candida antarctica (lipase B, Novozym 435), also provided diacylglycerols, however, to a lower extent (40-45%). Glycerolysis of rapeseed oil triacylglycerols with glycerol in vacuo at 60 degrees C, catalyzed by Lipozyme TL and Novozym 435, led to diacylglycerols to the extent of reduction of its activity. The products of esterification of rapeseed oil fatty acids with Monomuls and glycerol yielded upon short-path vacuum distillation residues (diacylglycerol oils) containing 66-70% diacylglycerols. PMID:15315368

  5. Analysis of enzyme-catalyzed nucleotide modification by aldose reductase

    SciTech Connect

    Grimshaw, C.E.

    1987-05-01

    Homogeneous bovine kidney aldose reductase catalyzes two reactions in addition to the normal aldehyde-dependent oxidation of NADPH. First, adduct formation between the oxidized nucleotide and the oxidized substrate is observed during turnover due to initial formation of a reversible E:NADP/sup +/:R-CHO ternary complex, which subsequently reacts to give the covalent complex (E:NADP/sup +/-R-CHO). The reaction is enzyme-catalyzed with substantial enhancement of both the pseudo-first order rate constant and the overall K/sub eq/ relative to the reaction with free NADP/sup +/ in aqueous buffer. Analysis of the concentration dependence and time-course for reversible dead-end and covalent complex formation are described for several aldehyde and nucleotide substrates. Non-linear time courses for aldehyde reduction and substrate inhibition by the aldehyde substrate in initial velocity studies are completely accounted for by this mechanism, thereby eliminating a simple Dalziel-type explanation for the substrate activation by aldehyde which is also observed. Second, enzyme-catalyzed oxidation of NADPH occurs in the absence of aldehyde substrate with a rate equal to .03% of V/sub max/ for the normal reduction of glyceraldehyde. By 500 MHz /sup 1/H-NMR, the enzyme-catalyzed oxidation of (4-/sup 2/H)NADPH appears to be greater than 95% stereospecific. Spectroscopic evidence for a similar oxidation reaction is observed for the covalent E:NADP/sup +/-R-CHO adduct with glyceraldehyde, but not with glycolaldehyde.

  6. Towards alpha- or beta-D-C-glycosyl compounds by tin-catalyzed addition of glycosyl radicals to acrylonitrile and vinylphosphonate, and flexible reduction of tetra-O-acetyl-alpha-D-glucopyranosyl bromide with cyanoborohydride.

    PubMed

    Praly, Jean-Pierre; Ardakani, Azin Salek; Bruyère, Isabelle; Marie-Luce, Chrystelle; Bing Qin, Bing

    2002-10-01

    Photo-induced radical addition of acetylated alpha-D-glucopyranosyl bromide (1). to acrylonitrile or diethyl vinylphosphonate, in the presence of catalytic amounts of tri-n-butyltin chloride and sodium (or tetra-n-butylammonium) cyanoborohydride in excess, allowed efficient preparations of alpha-configurated nonononitrile and 2-(alpha-D-glucopyranosyl)-ethylphosphonate (79, 70% yields, respectively). These conditions led to 2-(alpha-D-manno-, and galactopyranosyl)-ethylphosphonates in 68 and 76% yields. Similarly, radical addition of acetylated 1-bromo-beta-D-glucopyranosyl chloride (2). to acrylonitrile or diethyl vinylphosphonate afforded mainly intermediate chlorides which, upon radical reduction with excess tri-n-butyltin hydride, afforded the corresponding beta anomers (40 and 38%, respectively) by sequential C-C and C-H bond formation. Stereocontrol relies on the alpha-stereoselective quenching of D-glycopyranos-1-yl radicals. We found also that UV light irradiation of 1 with excess NaBH(3)CN in tert-butanol afforded either 1,3,4,6-tetra-O-acetyl-2-deoxy-alpha-D-arabino-hexopyranose (65% after crystallization) or, when 10% mol thiophenol was added, 2,3,4,6-tetra-O-acetyl-1,5-anhydro-D-glucitol (79%). These are simple, tin-free, and easily controlled conditions, which compare well with known preparations of these reduced sugars. PMID:12423963

  7. Iodine-Catalyzed Polysaccharide Esterification

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A review is provided of the recent reports to use iodine-catalyzed esterification reaction to produce esters from polysaccharides. The process entails reaction of the polysaccharide with an acid anhydride in the presence of a catalytic level of iodine, and in the absence of additional solvents. T...

  8. Silanediol-Catalyzed Chromenone Functionalization.

    PubMed

    Hardman-Baldwin, Andrea M; Visco, Michael D; Wieting, Joshua M; Stern, Charlotte; Kondo, Shin-Ichi; Mattson, Anita E

    2016-08-01

    Promising levels of enantiocontrol are observed in the silanediol-catalyzed addition of silyl ketene acetals to benzopyrylium triflates. This rare example of enantioselective, intermolecular chromenone functionalization with carbonyl-containing nucleophiles has potential applications in the synthesis of bioactive chromanones and tetrahydroxanthones. PMID:27453257

  9. Performance of catalyzed hydrazine in field applications

    SciTech Connect

    Allgood, T.B.

    1987-01-01

    The performance of newly developed oxygen scavengers for boilers is often compared to sulfite and hydrazine. Catalyzed hydrazine out-performs hydrazine and might be preferred when catalyzed sulfite cannot be used. Data from a Midwest Utility confirms that, under field conditions, catalyzed hydrazine out-performance hydrazine and carbohydrazine when feedwater oxygen and iron levels were critical. Catalyzed hydrazine might be preferred when high performance and economics are the primary concerns.

  10. Selective Metal-Free Hydrosilylation of CO2 Catalyzed by Triphenylborane in Highly Polar, Aprotic Solvents.

    PubMed

    Mukherjee, Debabrata; Sauer, Daniel F; Zanardi, Alessandro; Okuda, Jun

    2016-06-01

    Triphenylborane (BPh3 ) in highly polar, aprotic solvents catalyzes hydrosilylation of CO2 effectively under mild conditions to provide silyl formates with high chemoselectivity (>95 %) and without over-reduction. This system also promotes reductive hydrosilylation of tertiary amides as well as dehydrogenative coupling of silane with alcohols. PMID:27028161

  11. Gold-Catalyzed Synthesis of Heterocycles

    NASA Astrophysics Data System (ADS)

    Arcadi, Antonio

    2014-04-01

    The following sections are included: * Introduction * Synthesis of Heterocycles via Gold-Catalyzed Heteroatom Addition to Unsaturated C-C Bonds * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cyclization of Polyunsaturated Compounds * Synthesis of Heterocyclic Compounds via α-Oxo Gold Carbenoid * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cycloaddition Reactions * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Activation of Carbonyl Groups and Alcohols * Synthesis of Heterocyclic Compounds through Gold-Mediated C-H Bond Functionalization * Gold-Catalyzed Domino Cyclization/Oxidative Coupling Reactions * Conclusions * References

  12. Thermodynamic limitations on microbially catalyzed reaction rates

    NASA Astrophysics Data System (ADS)

    LaRowe, Douglas E.; Dale, Andrew W.; Amend, Jan P.; Van Cappellen, Philippe

    2012-08-01

    Quantification of global biogeochemical cycles requires knowledge of the rates at which microorganisms catalyze chemical reactions. In order for models that describe these processes to capture global patterns of change, the underlying formulations in them must account for biogeochemical transformations over seasonal and millennial time scales in environments characterized by different energy levels. Building on existing models, a new thermodynamic limiting function is introduced. With only one adjustable parameter, this function that can be used to model microbial metabolism throughout the range of conditions in which organisms are known to be active. The formulation is based on a comparison of the amount of energy available from any redox reaction to the energy required to maintain a membrane potential, a proxy for the minimum amount of energy required by an active microorganism. This function does not require species- or metabolism-specific parameters, and can be used to model metabolisms that capture any amount of energy. The utility of this new thermodynamic rate limiting term is illustrated by applying it to three low-energy processes: fermentation, methanogenesis and sulfate reduction. The model predicts that the rate of fermentation will be reduced by half once the Gibbs energy of the catalyzed reaction reaches -12 kJ (mol e-)-1, and then slowing exponentially until the energy yield approaches zero. Similarly, the new model predicts that the low energy yield of methanogenesis, -4 to -0.5 kJ (mol e-)-1, for a partial pressure of H2 between 11 and 0.6 Pa decreases the reaction rate by 95-99%. Finally, the new function's utility is illustrated through its ability to accurately model sulfate concentration data in an anoxic marine sediment.

  13. Iridium-Catalyzed Hydrogen Transfer Reactions

    NASA Astrophysics Data System (ADS)

    Saidi, Ourida; Williams, Jonathan M. J.

    This chapter describes the application of iridium complexes to catalytic hydrogen transfer reactions. Transfer hydrogenation reactions provide an alternative to direct hydrogenation for the reduction of a range of substrates. A hydrogen donor, typically an alcohol or formic acid, can be used as the source of hydrogen for the reduction of carbonyl compounds, imines, and alkenes. Heteroaromatic compounds and even carbon dioxide have also been reduced by transfer hydrogenation reactions. In the reverse process, the oxidation of alcohols to carbonyl compounds can be achieved by iridium-catalyzed hydrogen transfer reactions, where a ketone or alkene is used as a suitable hydrogen acceptor. The reversible nature of many hydrogen transfer processes has been exploited for the racemization of alcohols, where temporary removal of hydrogen generates an achiral ketone intermediate. In addition, there is a growing body of work where temporary removal of hydrogen provides an opportunity for using alcohols as alkylating agents. In this chemistry, an iridium catalyst "borrows" hydrogen from an alcohol to give an aldehyde or ketone intermediate, which can be transformed into either an imine or alkene under the reaction conditions. Return of the hydrogen from the catalyst provides methodology for the formation of amines or C-C bonds where the only by-product is typically water.

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

    SciTech Connect

    Bicker, D.; Bonaventura, J.

    1988-06-14

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

  15. Mechanism of Boron-Catalyzed N-Alkylation of Amines with Carboxylic Acids.

    PubMed

    Zhang, Qi; Fu, Ming-Chen; Yu, Hai-Zhu; Fu, Yao

    2016-08-01

    Mechanistic study has been carried out on the B(C6F5)3-catalyzed amine alkylation with carboxylic acid. The reaction includes acid-amine condensation and amide reduction steps. In condensation step, the catalyst-free mechanism is found to be more favorable than the B(C6F5)3-catalyzed mechanism, because the automatic formation of the stable B(C6F5)3-amine complex deactivates the catalyst in the latter case. Meanwhile, the catalyst-free condensation is constituted by nucleophilic attack and the indirect H2O-elimination (with acid acting as proton shuttle) steps. After that, the amide reduction undergoes a Lewis acid (B(C6F5)3)-catalyzed mechanism rather than a Brønsted acid (B(C6F5)3-coordinated HCOOH)-catalyzed one. The B(C6F5)3)-catalyzed reduction includes twice silyl-hydride transfer steps, while the first silyl transfer is the rate-determining step of the overall alkylation catalytic cycle. The above condensation-reduction mechanism is supported by control experiments (on both temperature and substrates). Meanwhile, the predicted chemoselectivity is consistent with the predominant formation of the alkylation product (over disilyl acetal product). PMID:27441997

  16. Thermodynamics of Enzyme-Catalyzed Reactions Database

    National Institute of Standards and Technology Data Gateway

    SRD 74 Thermodynamics of Enzyme-Catalyzed Reactions Database (Web, free access)   The Thermodynamics of Enzyme-Catalyzed Reactions Database contains thermodynamic data on enzyme-catalyzed reactions that have been recently published in the Journal of Physical and Chemical Reference Data (JPCRD). For each reaction the following information is provided: the reference for the data, the reaction studied, the name of the enzyme used and its Enzyme Commission number, the method of measurement, the data and an evaluation thereof.

  17. Enzymatic reduction of protein-bound methionine sulfoxide.

    PubMed Central

    Brot, N; Weissbach, L; Werth, J; Weissbach, H

    1981-01-01

    An enzyme that catalyzes the reduction of methionine sulfoxide residues in ribosomal protein L12 has been partially purified from Escherichia coli extracts. Methionine sulfoxide present in oxidize [Met]enkephalin is also reduced by the purified enzyme. The enzyme is different from a previously reported E. coli enzyme that catalyzes the reduction of methionine sulfoxide to methionine [Ejiri, S. I., Weissbach, H. & Brot, N. (1980) Anal. Biochem. 102, 393--398]. Extracts of rat tissues, Euglena gracilis, Tetrahymena pyriformis, HeLa cells, and spinach also can catalyze the reduction of methionine sulfoxide residues in protein. PMID:7017726

  18. Iridium-Catalyzed Allylic Substitution

    NASA Astrophysics Data System (ADS)

    Hartwig, John F.; Pouy, Mark J.

    Iridium-catalyzed asymmetric allylic substitution has become a valuable method to prepare products from the addition of nucleophiles at the more substituted carbon of an allyl unit. The most active and selective catalysts contain a phosphoramidite ligand possessing at least one arylethyl substituent on the nitrogen atom of the ligand. In these systems, the active catalyst is generated by a base-induced cyclometalation at the methyl group of this substituent to generate an iridium metalacycle bound by the COD ligand of the [Ir(COD)Cl]2 precursor and one additional labile dative ligand. Such complexes catalyze the reactions of linear allylic esters with alkylamines, arylamines, phenols, alcohols, imides, carbamates, ammonia, enolates and enolate equivalents, as well as typical stabilized carbon nucleophiles generated from malonates and cyanoesters. Iridium catalysts for enantioselective allylic substitution have also been generated from phosphorus ligands with substituents bound by heteroatoms, and an account of the studies of such systems, along with a description of the development of iridium catalysts is included.

  19. Iodide effects in transition metal catalyzed reactions.

    PubMed

    Maitlis, Peter M; Haynes, Anthony; James, Brian R; Catellani, Marta; Chiusoli, Gian Paolo

    2004-11-01

    The unique properties of I(-) allow it to be involved in several different ways in reactions catalyzed by the late transition metals: in the oxidative addition, the migration, and the coupling/reductive elimination steps, as well as in substrate activation. Most steps are accelerated by I(-)(for example through an increased nucleophilicity of the metal center), but some are retarded, because a coordination site is blocked. The "soft" iodide ligand binds more strongly to soft metals (low oxidation state, electron rich, and polarizable) such as the later and heavier transition metals, than do the other halides, or N- and O-centered ligands. Hence in a catalytic cycle that includes the metal in a formally low oxidation state there will be less tendency for the metal to precipitate (and be removed from the cycle) in the presence of I(-) than most other ligands. Iodide is a good nucleophile and is also easily and reversibly oxidized to I(2). In addition, I(-) can play key roles in purely organic reactions that occur as part of a catalytic cycle. Thus to understand the function of iodide requires careful analysis, since two or sometimes more effects occur in different steps of one single cycle. Each of these topics is illustrated with examples of the influence of iodide from homogeneous catalytic reactions in the literature: methanol carbonylation to acetic acid and related reactions; CO hydrogenation; imine hydrogenation; and C-C and C-N coupling reactions. General features are summarised in the Conclusions. PMID:15510253

  20. Designing 'Totem' C2 -Symmetrical Iron Porphyrin Catalysts for Stereoselective Cyclopropanations.

    PubMed

    Carminati, Daniela Maria; Intrieri, Daniela; Caselli, Alessandro; Le Gac, Stéphane; Boitrel, Bernard; Toma, Lucio; Legnani, Laura; Gallo, Emma

    2016-09-12

    The catalytic activity of the iron(III) C2 chiral porphyrin Fe(2)(OMe) in alkene cyclopropanation is herein reported. The catalyst promoted the reaction of differently substituted styrenes with diazo derivatives with trans-diastereoselectivities and enantioselectivities up to 99:1 and 87 %, respectively. In addition, high TON and TOF values (up to 10 000 and 120 000 h(-1) , respectively) were observed indicating good activity and stability of the catalyst in optimized experimental conditions. The study of the cyclopropanation reaction revealed that the porphyrin skeleton is composed of two 'totem' parts which were independently responsible for the observed enantio- and diastereoselectivities. To further our research we also investigated the catalytic role of the methoxy axial ligand coordinated to the iron atom. The molecular structure of Fe(2)(OMe) was optimized by DFT calculations which were also employed to achieve a better understanding of the mechanistic details of the carbene transfer reaction. PMID:27555480

  1. Femtosecond relaxation of an iron porphyrin observed with polarization spectroscopy in a three-level system

    PubMed Central

    Andrews, John R.; Hochstrasser, Robin M.

    1980-01-01

    An experimental and theoretical study is presented of the nonlinear response of a dilute solution being pumped by two laser fields having different frequencies ω1 and ω2 that are both in resonance with electronic transitions of the solute. Experimental results were obtained for the dispersion of the third-order susceptibility ǀχ(3)(ω2)ǀ2 for a dilute solution of iron(III) tetraphenylporphyrin chloride in chloroform with a fixed intense field (ω1) resonant with the Qo transition and a tunable weaker field (ω2) resonant with the Soret transition. The observed Lorentzian dispersion is slightly narrower than the linear absorption spectrum. The theoretical model for the third-order polarization incorporates three levels coupled to two electromagnetic fields and a population reservoir. The equations of motion for the density operator were solved in third order for the appropriate Fourier component. The resulting dispersion curve depends on both total dephasing and population decay rates, thereby demonstrating a general method for the determination of subpicosecond relaxation processes in systems to which the model is applicable. Theoretical fits to the results for iron(III) tetraphenylporphyrin chloride imply that the Soret transition is essentially homogeneously broadened with a total dephasing width of 900 ± 200 cm-1, and it is argued that the population decay time in this case is approximately 3.5 fsec. The broad linear absorption spectrum of the Soret band is interpreted as resulting from intramolecular perturbations between the Soret and lower energy excited states of iron(III) tetraphenylporphyrin chloride. PMID:16592833

  2. Linkage Isomerization in Heme–NOx Compounds: Understanding NO, Nitrite, and Hyponitrite Interactions with Iron Porphyrins

    PubMed Central

    Xu, Nan; Yi, Jun

    2011-01-01

    Nitric oxide (NO) and its derivatives such as nitrite and hyponitrite are biologically important species of relevance to human health. Much of their physiological relevance stems from their interactions with the iron centers in heme proteins. The chemical reactivities displayed by the heme-NOx species (NOx = NO, nitrite, hyponitrite) are a function of the binding modes of the NOx ligands. Hence, an understanding of the types of binding modes extant in heme-NOx compounds is important if we are to unravel the inherent chemical properties of these NOx metabolites. In this Forum article, the experimentally characterized linkage isomers of heme-NOx models and proteins are presented and reviewed. Nitrosyl linkage isomers of synthetic Fe and Ru porphyrins have been generated by photolysis at low temperatures and characterized by spectroscopy and DFT calculations. Nitrite linkage isomers in synthetic metalloporphyrin derivatives have been generated from photolysis experiments and in low-temperature matrices. In the case of nitrite adducts of heme proteins, both N-binding and O-binding have been determined crystallographically, and the role of the distal Hbonding residue in myoglobin in directing the O-binding mode of nitrite has been explored using mutagenesis. To date, only one synthetic metalloporphyrin complex containing a hyponitrite ligand (displaying an O-binding mode) has been characterized by crystallography. This is contrasted with other hyponitrite binding modes experimentally determined for coordination compounds and computationally for NO reductase enzymes. Although linkage isomerism in heme-NOx derivatives is still in its infancy, opportunities now exist for a detailed exploration of the existence and stabilities of the metastable states in both heme models and heme proteins. PMID:20666385

  3. Linkage isomerization in heme-NOx compounds: understanding NO, nitrite, and hyponitrite interactions with iron porphyrins.

    PubMed

    Xu, Nan; Yi, Jun; Richter-Addo, George B

    2010-07-19

    Nitric oxide (NO) and its derivatives such as nitrite and hyponitrite are biologically important species of relevance to human health. Much of their physiological relevance stems from their interactions with the iron centers in heme proteins. The chemical reactivities displayed by the heme-NOx species (NOx = NO, nitrite, hyponitrite) are a function of the binding modes of the NOx ligands. Hence, an understanding of the types of binding modes extant in heme-NOx compounds is important if we are to unravel the inherent chemical properties of these NOx metabolites. In this Forum Article, the experimentally characterized linkage isomers of heme-NOx models and proteins are presented and reviewed. Nitrosyl linkage isomers of synthetic iron and ruthenium porphyrins have been generated by photolysis at low temperatures and characterized by spectroscopy and density functional theory calculations. Nitrite linkage isomers in synthetic metalloporphyrin derivatives have been generated from photolysis experiments and in low-temperature matrices. In the case of nitrite adducts of heme proteins, both N and O binding have been determined crystallographically, and the role of the distal H-bonding residue in myoglobin in directing the O-binding mode of nitrite has been explored using mutagenesis. To date, only one synthetic metalloporphyrin complex containing a hyponitrite ligand (displaying an O-binding mode) has been characterized by crystallography. This is contrasted with other hyponitrite binding modes experimentally determined for coordination compounds and computationally for NO reductase enzymes. Although linkage isomerism in heme-NOx derivatives is still in its infancy, opportunities now exist for a detailed exploration of the existence and stabilities of the metastable states in both heme models and heme proteins. PMID:20666385

  4. Gold-catalyzed naphthalene functionalization

    PubMed Central

    Rivilla, Iván

    2011-01-01

    Summary The complexes IPrMCl (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene, M = Cu, 1a; M = Au, 1b), in the presence of one equiv of NaBAr'4 (Ar' = 3,5-bis(trifluoromethyl)phenyl), catalyze the transfer of carbene groups: C(R)CO2Et (R = H, Me) from N2C(R)CO2Et to afford products that depend on the nature of the metal center. The copper-based catalyst yields exclusively a cycloheptatriene derivative from the Buchner reaction, whereas the gold analog affords a mixture of products derived either from the formal insertion of the carbene unit into the aromatic C–H bond or from its addition to a double bond. In addition, no byproducts derived from carbene coupling were observed. PMID:21647320

  5. Gold-catalyzed naphthalene functionalization.

    PubMed

    Pérez, Pedro J; Díaz-Requejo, M Mar; Rivilla, Iván

    2011-01-01

    The complexes IPrMCl (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene, M = Cu, 1a; M = Au, 1b), in the presence of one equiv of NaBAr'(4) (Ar' = 3,5-bis(trifluoromethyl)phenyl), catalyze the transfer of carbene groups: C(R)CO(2)Et (R = H, Me) from N(2)C(R)CO(2)Et to afford products that depend on the nature of the metal center. The copper-based catalyst yields exclusively a cycloheptatriene derivative from the Buchner reaction, whereas the gold analog affords a mixture of products derived either from the formal insertion of the carbene unit into the aromatic C-H bond or from its addition to a double bond. In addition, no byproducts derived from carbene coupling were observed. PMID:21647320

  6. Copper(I)-Catalyzed Allylic Substitutions with a Hydride Nucleophile.

    PubMed

    Nguyen, T N Thanh; Thiel, Niklas O; Pape, Felix; Teichert, Johannes F

    2016-05-20

    An easily accessible copper(I)/N-heterocyclic carbene (NHC) complex enables a regioselective hydride transfer to allylic bromides, an allylic reduction. The resulting aryl- and alkyl-substituted branched α-olefins, which are valuable building blocks for synthesis, are obtained in good yields and regioselectivity. A commercially available silane, (TMSO)2Si(Me)H, is employed as hydride source. This protocol offers a unified alternative to the established metal-catalyzed allylic substitutions with carbon nucleophiles, as no adaption of the catalyst to the nature of the nucleophile is required. PMID:27151495

  7. Nickel-Catalyzed Negishi Cross-Coupling of Bromodifluoroacetamides.

    PubMed

    Tarui, Atsushi; Shinohara, Saori; Sato, Kazuyuki; Omote, Masaaki; Ando, Akira

    2016-03-01

    A nickel-catalyzed Negishi coupling of bromodifluoroacetamides with arylzinc reagents has been developed. This reaction allows access to difluoromethylated aromatic compounds containing a variety of aryl groups and amide moieties. Furthermore, highly effective transformation of the functionalized difluoromethyl group (-CF2CONR(1)R(2)) was realized via microwave-assisted reduction under mild conditions. The notable features of this strategy are its generality and its use of a low-cost nickel catalyst and ligand; thus, this reaction provides a facile method for applications in drug discovery and development. PMID:26910536

  8. Copper-Catalyzed Azide–Alkyne Click Chemistry for Bioconjugation

    PubMed Central

    Presolski, Stanislav I.; Hong, Vu Phong; Finn, M.G.

    2012-01-01

    The copper-catalyzed azide-alkyne cycloaddition reaction is widely used for the connection of molecular entities of all sizes. A protocol is provided here for the process with biomolecules. Ascorbate is used as reducing agent to maintain the required cuprous oxidation state. Since these convenient conditions produce reactive oxygen species, five equivalents of a copper-binding ligand is used with respect to metal. The ligand both accelerates the reaction and serves as a sacrificial reductant, protecting the biomolecules from oxidation. A procedure is also described for testing the efficiency of the reaction under desired conditions for purposes of optimization, before expensive biological reagents are used. PMID:22844652

  9. Hydrophobic properties of polytetrafluoroethylene thin films fabricated at various catalyzer temperatures through catalytic chemical vapor deposition using a tungsten catalyzer.

    PubMed

    Cha, Jeong Ok; Yeo, Seung Jun; Pode, Ramchandra; Ahn, Jeung Sun

    2011-07-01

    Using the catalytic chemical vapor deposition (Cat-CVD) method, polytetrafluoroethylene (PTFE) thin films were fabricated on Si(100) substrates at various catalyzer temperatures, using a tungsten catalyzer, and Fourier transform infrared (FTIR) spectroscopy and X-ray photoemission spectroscopy (XPS) were used to confirm the fabrication of the films. An atomic-force microscope (AFM) and a scanning electron microscope (SEM) were employed to study the correlation between the wettability and surface morphology of the samples. It was found that the wettability of the PTFE thin films fabricated via Cat-CVD is strongly correlated with the sizes of the film surfaces' nanoprotrusions, and that superhydrophobic PTFE thin-film surfaces can be easily achieved by controlling the sizes of the nanoprotrusions through the catalyzer temperature. The comparison of the wettability values and surface morphologies of the films confirmed that nanoscale surface roughness enhances the hydrophobic properties of PTFE thin films. Further, the detailed analysis of the films' surface morphologies from their AFM images with the use of the Wenzel and Cassie models confirmed that the nanoscale surface roughness enhanced the hydrophobic property of the PTFE films. Further, the variations of the wettability of the PTFE thin films prepared via Cat-CVD are well explained by the Cassie model. It seems that the increase in the trapping air and the reduction of the liquid-solid contact area are responsible for the superhydrophobicity of the PTFE thin films prepared via Cat-CVD. PMID:22121615

  10. Antibody-mediated reduction of {alpha}-ketoamides

    DOEpatents

    Schultz, P.G.; Gallop, M.A.

    1998-06-09

    Monoclonal antibodies raised against a 4-nitrophenyl phosphonate hapten catalyze the stereospecific reduction of an {alpha}-ketoamide to the corresponding {alpha}-hydroxyamide in the presence of an appropriate reducing agent.

  11. Antibody-mediated reduction of .alpha.-ketoamides

    DOEpatents

    Schultz, Peter G.; Gallop, Mark A.

    1998-01-01

    Monoclonal antibodies raised against a 4-nitrophenyl phosphonate hapten catalyze the stereospecific reduction of an .alpha.-ketoamide to the corresponding .alpha.-hydroxyamide in the presence of an appropriate reducing agent.

  12. Rapid Construction of (-)-Paroxetine and (-)-Femoxetine via N-Heterocyclic Carbene Catalyzed Homoenolate Addition to Nitroalkenes.

    PubMed

    White, Nicholas A; Ozboya, Kerem E; Flanigan, Darrin M; Rovis, Tomislav

    2014-04-01

    A concise enantioselective synthesis of (-)-paroxetine (Paxil) and (-)-femoxetine has been achieved. Key to these syntheses is a N-heterocyclic carbene catalyzed homoenolate addition to a nitroalkene followed by in situ reduction of the nitro-group to rapidly access δ-lactams. PMID:25485210

  13. Rapid Construction of (-)-Paroxetine and (-)-Femoxetine via N-Heterocyclic Carbene Catalyzed Homoenolate Addition to Nitroalkenes

    PubMed Central

    White, Nicholas A.; Ozboya, Kerem E.; Flanigan, Darrin M.

    2014-01-01

    A concise enantioselective synthesis of (-)-paroxetine (Paxil) and (-)-femoxetine has been achieved. Key to these syntheses is a N-heterocyclic carbene catalyzed homoenolate addition to a nitroalkene followed by in situ reduction of the nitro-group to rapidly access δ-lactams. PMID:25485210

  14. Palladium-catalyzed directing group-assisted C8-triflation of naphthalenes.

    PubMed

    Yang, Zhi-Wei; Zhang, Qi; Jiang, Yuan-Ye; Li, Lei; Xiao, Bin; Fu, Yao

    2016-05-10

    The transition-metal-catalyzed direct triflation of naphthyl amides and naphthyl ketones has been accomplished for the first time. Benzophenone (BP) was found to be a suitable ligand for the cross-coupling reactions. Density functional theory (DFT) calculations revealed that excessive amounts of HOTf inhibit the reductive elimination of the C-F bond to realize the unusual reductive elimination of the C-OTf bond. PMID:27117543

  15. Isotope-labeling of the fibril binding compound FSB via a Pd-catalyzed double alkoxycarbonylation.

    PubMed

    Burhardt, Mia N; Taaning, Rolf; Nielsen, Niels Chr; Skrydstrup, Troels

    2012-06-15

    We have synthesized two isotopically labeled variants of the β-amyloid binding compound FSB possessing (13)C-labels on the two terminal aryl carboxylic acid moieties. One of these was also fully deuterated on the olefinic spacers. The (13)C-isotope labeling was achieved applying a Pd-catalyzed methoxycarbonylation of the corresponding aryl chlorides with externally (ex situ) generated (13)C-labeled CO. Application of the Shirakawa-Hayashi protocol for the Pd-catalyzed reduction of a dialkyne intermediate using D(2)O allowed for the selective deuterium labeling of the two trans-C,C double bonds of FSB. PMID:22612598

  16. Formation of C-C bonds via ruthenium-catalyzed transfer hydrogenation().

    PubMed

    Moran, Joseph; Krische, Michael J

    2012-01-01

    Ruthenium-catalyzed transfer hydrogenation of diverse π-unsaturated reactants in the presence of aldehydes provides products of carbonyl addition. Dehydrogenation of primary alcohols in the presence of the same π-unsaturated reactants provides identical products of carbonyl addition. In this way, carbonyl addition is achieved from the alcohol or aldehyde oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. In this account, the discovery of ruthenium-catalyzed C-C bond-forming transfer hydrogenations and the recent development of diastereo- and enantioselective variants are discussed. PMID:23430602

  17. Formation of C–C bonds via ruthenium-catalyzed transfer hydrogenation*

    PubMed Central

    Moran, Joseph; Krische, Michael J.

    2013-01-01

    Ruthenium-catalyzed transfer hydrogenation of diverse π-unsaturated reactants in the presence of aldehydes provides products of carbonyl addition. Dehydrogenation of primary alcohols in the presence of the same π-unsaturated reactants provides identical products of carbonyl addition. In this way, carbonyl addition is achieved from the alcohol or aldehyde oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. In this account, the discovery of ruthenium-catalyzed C–C bond-forming transfer hydrogenations and the recent development of diastereo- and enantioselective variants are discussed. PMID:23430602

  18. Nickel-Catalyzed Cross-Coupling of Photoredox-Generated Radicals: Uncovering a General Manifold for Stereoconvergence in Nickel-Catalyzed Cross-Couplings

    PubMed Central

    2016-01-01

    The cross-coupling of sp3-hybridized organoboron reagents via photoredox/nickel dual catalysis represents a new paradigm of reactivity for engaging alkylmetallic reagents in transition-metal-catalyzed processes. Reported here is an investigation into the mechanistic details of this important transformation using density functional theory. Calculations bring to light a new reaction pathway involving an alkylnickel(I) complex generated by addition of an alkyl radical to Ni(0) that is likely to operate simultaneously with the previously proposed mechanism. Analysis of the enantioselective variant of the transformation reveals an unexpected manifold for stereoinduction involving dynamic kinetic resolution (DKR) of a Ni(III) intermediate wherein the stereodetermining step is reductive elimination. Furthermore, calculations suggest that the DKR-based stereoinduction manifold may be responsible for stereoselectivity observed in numerous other stereoconvergent Ni-catalyzed cross-couplings and reductive couplings. PMID:25836634

  19. Cobalt-Catalyzed Annulation of Salicylaldehydes and Alkynes to Form Chromones and 4-Chromanones.

    PubMed

    Yang, Junfeng; Yoshikai, Naohiko

    2016-02-01

    A unique cobalt(I)-diphosphine catalytic system has been identified for the coupling of salicylaldehyde (SA) and an internal alkyne affording a dehydrogenative annulation product (chromone) or a reductive annulation product (4-chromanone) depending on the alkyne substituents. Distinct from related rhodium(I)- and rhodium(III)-catalyzed reactions of SA and alkynes, these annulation reactions feature aldehyde C-H oxidative addition of SA and subsequent hydrometalation of the C=O bond of another SA molecule as common key steps. The reductive annulation to 4-chromanones also involves the action of Zn as a stoichiometric reductant. In addition to these mechanistic features, the Co(I) catalysis described herein is complementary to the Rh(I) - and Rh(III) -catalyzed reactions of SA and internal alkynes, particularly in the context of chromone synthesis. PMID:26804050

  20. Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

    NASA Astrophysics Data System (ADS)

    Inamdar, A. I.; Im, Hyunsik; Jung, Woong; Kim, Hyungsang; Kim, Byungchul; Yu, Kook-Hyun; Kim, Jin-Sang; Hwang, Sung-Min

    2013-05-01

    The effect of different wt.% of ionic liquid "1,6-bis (trimethylammonium-1-yl) hexane tetrafluoroborate" in 0.5 M LiClO4+PC electrolyte on the supercapacitor properties of polyaniline (PANI) thin film are investigated. The PANI film is synthesized using electropolymerization of aniline in the presence of sulfuric acid. The electrochemical properties of the PANI thin film are studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) measurements. The optimum amount of the ionic liquid is found to be 2 wt.% which provides better ionic conductivity of the electrolyte. The highest specific capacitance of 259 F/g is obtained using the 2 wt.% electrolyte. This capacitance remains at up to 208 F/g (80% capacity retention) after 1000 charge-discharge cycles at a current density of 0.5 mA/g. The PANI film in the 2 wt.% ionic liquid catalyzed 0.5 M LiClO4+PC electrolyte shows small electrochemical resistance, better rate performance and higher cyclability. The increased ionic conductivity of the 2 wt.% ionic liquid catalyzed electrolyte causes a reduction in resistance at the electrode/electrolyte interface, which can be useful in electrochemically-preferred power devices for better applicability.

  1. Ni-Catalyzed Amination Reactions: An Overview.

    PubMed

    Marín, Mario; Rama, Raquel J; Nicasio, M Carmen

    2016-08-01

    Nitrogen-containing organic compounds are valuable in many fields of science and industry. The most reliable method for the construction of C(sp(2) )-N bonds is undoubtedly palladium-catalyzed amination. In spite of the great achievements made in this area, the use of expensive Pd-based catalysts constitutes an important limitation for large-scale applications. Since nickel is the least expensive and most abundant among the group 10 metals, the interest in Ni-based catalysts for processes typically catalyzed by palladium has grown considerably over the last few years. Herein, we revise the development of Ni-catalyzed amination reactions, emphasizing the most relevant and recent advances in the field. PMID:27265724

  2. Attractor explosions and catalyzed vacuum decay

    NASA Astrophysics Data System (ADS)

    Green, Daniel; Silverstein, Eva; Starr, David

    2006-07-01

    We present a mechanism for catalyzed vacuum bubble production obtained by combining moduli stabilization with a generalized attractor phenomenon in which moduli are sourced by compact objects. This leads straightforwardly to a class of examples in which the Hawking decay process for black holes unveils a bubble of a different vacuum from the ambient one, generalizing the new end point for Hawking evaporation discovered recently by Horowitz. Catalyzed vacuum bubble production can occur for both charged and uncharged bodies, including Schwarzschild black holes for which massive particles produced in the Hawking process can trigger vacuum decay. We briefly discuss applications of this process to the population and stability of metastable vacua.

  3. Iron catalyzed asymmetric oxyamination of olefins.

    PubMed

    Williamson, Kevin S; Yoon, Tehshik P

    2012-08-01

    The regioselective and enantioselective oxyamination of alkenes with N-sulfonyl oxaziridines is catalyzed by a novel iron(II) bis(oxazoline) complex. This process affords oxazolidine products that can be easily manipulated to yield highly enantioenriched free amino alcohols. The regioselectivity of this process is complementary to that obtained from the analogous copper(II)-catalyzed reaction. Thus, both regioisomers of enantioenriched 1,2-aminoalcohols can be obtained using oxaziridine-mediated oxyamination reactions, and the overall sense of regiochemistry can be controlled using the appropriate choice of inexpensive first-row transition metal catalyst. PMID:22793789

  4. Attractor Explosions and Catalyzed Vacuum Decay

    SciTech Connect

    Green, Daniel; Silverstein, Eva; Starr, David

    2006-05-05

    We present a mechanism for catalyzed vacuum bubble production obtained by combining moduli stabilization with a generalized attractor phenomenon in which moduli are sourced by compact objects. This leads straightforwardly to a class of examples in which the Hawking decay process for black holes unveils a bubble of a different vacuum from the ambient one, generalizing the new endpoint for Hawking evaporation discovered recently by Horowitz. Catalyzed vacuum bubble production can occur for both charged and uncharged bodies, including Schwarzschild black holes for which massive particles produced in the Hawking process can trigger vacuum decay. We briefly discuss applications of this process to the population and stability of metastable vacua.

  5. Peroxidase catalyzed polymerization of phenol

    SciTech Connect

    Vasudevan, P.T.; Li, L.O.

    1996-07-01

    The effect of horseradish peroxidase (HRP) and H{sub 2}O{sub 2} concentrations on the removal efficiency of phenol, defined as the percentage of phenol removed from solution as a function of time, has been investigated. When phenol and H{sub 2}O{sub 2} react with an approximately one-to-one stoichiometry, the phenol is almost completely precipitated within 10 min. The reaction is inhibited at higher concentrations of H{sub 2}O{sub 2}. The removal efficiency increases with an increase in the concentration of HRP, but an increase in the time of treatment cannot be used to offset the reduction in removal efficiency at low concentrations of the enzyme, because of inactivation of the enzyme. One molecule of HRP is needed to remove approximately 1100 molecules of phenol when the reaction is conducted at pH 8.0 and at ambient temperature. 9 refs., 5 figs.

  6. Iron catalyzed coal liquefaction process

    DOEpatents

    Garg, Diwakar; Givens, Edwin N.

    1983-01-01

    A process is described for the solvent refining of coal into a gas product, a liquid product and a normally solid dissolved product. Particulate coal and a unique co-catalyst system are suspended in a coal solvent and processed in a coal liquefaction reactor, preferably an ebullated bed reactor. The co-catalyst system comprises a combination of a stoichiometric excess of iron oxide and pyrite which reduce predominantly to active iron sulfide catalysts in the reaction zone. This catalyst system results in increased catalytic activity with attendant improved coal conversion and enhanced oil product distribution as well as reduced sulfide effluent. Iron oxide is used in a stoichiometric excess of that required to react with sulfur indigenous to the feed coal and that produced during reduction of the pyrite catalyst to iron sulfide.

  7. Olefin hydroaryloxylation catalyzed by pincer-iridium complexes.

    PubMed

    Haibach, Michael C; Guan, Changjian; Wang, David Y; Li, Bo; Lease, Nicholas; Steffens, Andrew M; Krogh-Jespersen, Karsten; Goldman, Alan S

    2013-10-01

    Aryl alkyl ethers, which are widely used throughout the chemical industry, are typically produced via the Williamson ether synthesis. Olefin hydroaryloxylation potentially offers a much more atom-economical alternative. Known acidic catalysts for hydroaryloxylation, however, afford very poor selectivity. We report the organometallic-catalyzed intermolecular hydroaryloxylation of unactivated olefins by iridium "pincer" complexes. These catalysts do not operate via the hidden Brønsted acid pathway common to previously developed transition-metal-based catalysts. The reaction is proposed to proceed via olefin insertion into an iridium-alkoxide bond, followed by rate-determining C-H reductive elimination to yield the ether product. The reaction is highly chemo- and regioselective and offers a new approach to the atom-economical synthesis of industrially important ethers and, potentially, a wide range of other oxygenates. PMID:24028199

  8. Quinone-Catalyzed Selective Oxidation of Organic Molecules.

    PubMed

    Wendlandt, Alison E; Stahl, Shannon S

    2015-12-01

    Quinones are common stoichiometric reagents in organic chemistry. Para-quinones with high reduction potentials, such as DDQ and chloranil, are widely used and typically promote hydride abstraction. In recent years, many catalytic applications of these methods have been achieved by using transition metals, electrochemistry, or O2 to regenerate the oxidized quinone in situ. Complementary studies have led to the development of a different class of quinones that resemble the ortho-quinone cofactors in copper amine oxidases and mediate the efficient and selective aerobic and/or electrochemical dehydrogenation of amines. The latter reactions typically proceed by electrophilic transamination and/or addition-elimination reaction mechanisms, rather than hydride abstraction pathways. The collective observations show that the quinone structure has a significant influence on the reaction mechanism and has important implications for the development of new quinone reagents and quinone-catalyzed transformations. PMID:26530485

  9. Rhodium-Catalyzed Regiodivergent Hydrothiolation of Allyl Amines and Imines.

    PubMed

    Kennemur, Jennifer L; Kortman, Gregory D; Hull, Kami L

    2016-09-14

    The regiodivergent Rh-catalyzed hydrothiolation of allyl amines and imines is presented. Bidentate phosphine ligands with larger natural bite angles (βn ≥ 99°), for example, DPEphos, dpph, or L1, promote a Markovnikov-selective hydrothiolation in up to 88% yield and >20:1 regioselectivity. Conversely, when smaller bite angle ligands (βn ≤ 86°), for example, dppbz or dppp, are employed, the anti-Markovnikov product is formed in up to 74% yield and >20:1 regioselectivity. Initial mechanistic investigations are performed and are consistent with an oxidative addition/olefin insertion/reductive elimination mechanism for each regioisomeric pathway. We hypothesize that the change in regioselectivity is an effect of diverging coordination spheres to favor either Rh-S or Rh-H insertion to form the branched or linear isomer, respectively. PMID:27547858

  10. Zeolite 5A Catalyzed Etherification of Diphenylmethanol

    ERIC Educational Resources Information Center

    Cooke, Jason; Henderson, Eric J.; Lightbody, Owen C.

    2009-01-01

    An experiment for the synthetic undergraduate laboratory is described in which zeolite 5A catalyzes the room temperature dehydration of diphenylmethanol, (C[subscript 6]H[subscript 5])[subscript 2]CHOH, producing 1,1,1',1'-tetraphenyldimethyl ether, (C[subscript 6]H[subscript 5])[subscript 2]CHOCH(C[subscript 6]H[subscript 5])[subscript 2]. The…

  11. Data, Leadership, and Catalyzing Culture Change

    ERIC Educational Resources Information Center

    Benson, R. Todd; Trower, Cathy A.

    2012-01-01

    It is crucial to understand today's tenure-track workers so that colleges and universities can continue to attract and retain a large subset of them by understanding and supporting their satisfaction and success at work. In this article, the authors talk about data, leadership, and catalyzing culture change. They discuss data use in the academy…

  12. Microorganisms detected by enzyme-catalyzed reaction

    NASA Technical Reports Server (NTRS)

    Vango, S. P.; Weetall, H. H.; Weliky, N.

    1966-01-01

    Enzymes detect the presence of microorganisms in soils. The enzyme lysozymi is used to release the enzyme catalase from the microorganisms in a soil sample. The catalase catalyzes the decomposition of added hydrogen peroxide to produce oxygen which is detected manometrically. The partial pressure of the oxygen serves as an index of the samples bacteria content.

  13. Palladium catalyzed hydrogenation of bio-oils and organic compounds

    DOEpatents

    Elliott, Douglas C.; Hu, Jianli; Hart, Todd R.; Neuenschwander, Gary G.

    2008-09-16

    The invention provides palladium-catalyzed hydrogenations of bio-oils and certain organic compounds. Experimental results have shown unexpected and superior results for palladium-catalyzed hydrogenations of organic compounds typically found in bio-oils.

  14. Palladium catalyzed hydrogenation of bio-oils and organic compounds

    DOEpatents

    Elliott, Douglas C [Kennewick, WA; Hu, Jianli [Richland, WA; Hart,; Todd, R [Kennewick, WA; Neuenschwander, Gary G [Burbank, WA

    2011-06-07

    The invention provides palladium-catalyzed hydrogenations of bio-oils and certain organic compounds. Experimental results have shown unexpected and superior results for palladium-catalyzed hydrogenations of organic compounds typically found in bio-oils.

  15. Iron-Catalyzed Regioselective Transfer Hydrogenative Couplings of Unactivated Aldehydes with Simple Alkenes.

    PubMed

    Zheng, Yan-Long; Liu, Yan-Yao; Wu, Yi-Mei; Wang, Yin-Xia; Lin, Yu-Tong; Ye, Mengchun

    2016-05-17

    An FeBr3 -catalyzed reductive coupling of various aldehydes with alkenes that proceeds through a direct hydride transfer pathway has been developed. With (i) PrOH as the hydrogen donor under mild conditions, previously challenging coupling reactions of unactivated alkyl and aryl aldehydes with simple alkenes, such as styrene derivatives and α-olefins, proceeded smoothly to furnish a diverse range of functionalized alcohols with complete linear regioselectivity. PMID:27072872

  16. A Stereoselective Synthesis of Digitoxin and Digitoxigen Monoand Bisdigitoxoside from Digitoxigenin via a Palladium Catalyzed Glycosylation

    PubMed Central

    Zhou, Maoquan; O’Doherty, George A.

    2008-01-01

    A convergent and stereocontrolled route to trisaccharide natural product digitoxin has been developed. The route is amenable to the preparation of both the digitoxigen mono-and bisdigitoxoside. This route featured the iterative application of the palladium catalyzed glycosylation reaction, reductive 1,3-transposition, diastereoselective dihydroxylation and regioselective protection. The natural product digitoxin was fashioned in 15 steps starting from digitoxigenin 2 and pyranone 8a or 18 steps from achiral acylfuran. PMID:16956221

  17. Enantioselective synthesis of α-aminosilanes by copper-catalyzed hydroamination of vinylsilanes.

    PubMed

    Niljianskul, Nootaree; Zhu, Shaolin; Buchwald, Stephen L

    2015-01-26

    The synthesis of α-aminosilanes by a highly enantio- and regioselective copper-catalyzed hydroamination of vinylsilanes is reported. The system employs Cu-DTBM-SEGPHOS as the catalyst, diethoxymethylsilane as the stoichiometric reductant, and O-benzoylhydroxylamines as the electrophilic nitrogen source. This hydroamination reaction is compatible with differentially substituted vinylsilanes, thus providing access to amino acid mimics and other valuable chiral organosilicon compounds. PMID:25475991

  18. Enantioselective Synthesis of α-Aminosilanes by Copper-Catalyzed Hydroamination of Vinylsilanes**

    PubMed Central

    Niljianskul, Nootaree; Zhu, Shaolin; Buchwald, Stephen L.

    2015-01-01

    The synthesis of α-aminosilanes by a highly enantio- and regioselective copper-catalyzed hydroamination of vinylsilanes is reported. The system employs Cu-DTBM-SEG-PHOS as the catalyst, diethoxymethylsilane as the stoichiometric reductant, and O-benzoylhydroxylamines as the electrophilic nitrogen source. This hydroamination reaction is compatible with differentially substituted vinylsilanes, thus providing access to amino acid mimics and other valuable chiral organosilicon compounds. PMID:25475991

  19. Heterogeneously-Catalyzed Conversion of Carbohydrates

    NASA Astrophysics Data System (ADS)

    Vigier, Karine De Oliveira; Jérôme, François

    Polyfunctionality of carbohydrates and their low solubility in conventional organic solvents make rather complex their conversion to higher value added chemicals. Therefore, innovative processes are now strongly needed in order to increase the selectivity of these reactions. Here, we report an overview of the different heterogeneously-catalyzed processes described in the literature. In particular, hydrolysis, dehydration, oxidation, esterification, and etherification of carbohydrates are presented. We shall discuss the main structural parameters that need to be controlled and that permit the conversion of carbohydrates to bioproducts with good selectivity. The conversion of monosaccharides and disaccharides over solid catalysts, as well as recent advances in the heterogeneously-catalyzed conversion of cellulose, will be presented.

  20. Cold fusion catalyzed by muons and electrons

    SciTech Connect

    Kulsrud, R.M.

    1990-10-01

    Two alternative methods have been suggested to produce fusion power at low temperature. The first, muon catalyzed fusion or MCF, uses muons to spontaneously catalyze fusion through the muon mesomolecule formation. Unfortunately, this method fails to generate enough fusion energy to supply the muons, by a factor of about ten. The physics of MCF is discussed, and a possible approach to increasing the number of MCF fusions generated by each muon is mentioned. The second method, which has become known as Cold Fusion,'' involves catalysis by electrons in electrolytic cells. The physics of this process, if it exists, is more mysterious than MCF. However, it now appears to be an artifact, the claims for its reality resting largely on experimental errors occurring in rather delicate experiments. However, a very low level of such fusion claimed by Jones may be real. Experiments in cold fusion will also be discussed.

  1. Palladium-Catalyzed Environmentally Benign Acylation.

    PubMed

    Suchand, Basuli; Satyanarayana, Gedu

    2016-08-01

    Recent trends in research have gained an orientation toward developing efficient strategies using innocuous reagents. The earlier reported transition-metal-catalyzed carbonylations involved either toxic carbon monoxide (CO) gas as carbonylating agent or functional-group-assisted ortho sp(2) C-H activation (i.e., ortho acylation) or carbonylation by activation of the carbonyl group (i.e., via the formation of enamines). Contradicting these methods, here we describe an environmentally benign process, [Pd]-catalyzed direct carbonylation starting from simple and commercially available iodo arenes and aldehydes, for the synthesis of a wide variety of ketones. Moreover, this method comprises direct coupling of iodoarenes with aldehydes without activation of the carbonyl and also without directing group assistance. Significantly, the strategy was successfully applied to the synthesis n-butylphthalide and pitofenone. PMID:27377566

  2. Iron-catalyzed asymmetric haloamination reactions.

    PubMed

    Cai, Yunfei; Liu, Xiaohua; Zhou, Pengfei; Kuang, Yulong; Lin, Lili; Feng, Xiaoming

    2013-09-21

    The first iron(III)/N,N'-dioxide-catalyzed asymmetric haloamination of 3-alkylidene- and 3-arylidene-indolin-2-ones was developed, affording the corresponding chiral oxindole derivatives bearing vicinal haloamine substituents with excellent results (up to 99% yield, 99% ee, >19 : 1 dr). This iron catalyst also exhibits perfect enantioselectivity for chalcone derivatives. The cooperative activation of the substrate and the reagent in concert guarantees the high stereoselectivity. PMID:23903004

  3. Antiproton catalyzed microfission/fusion propulsion

    NASA Technical Reports Server (NTRS)

    Chiang, Pi-Ren; Lewis, Raymond A.; Smith, Gerald A.; Newton, Richard; Dailey, James; Werthman, W. Lance; Chakrabarti, Suman

    1994-01-01

    Inertial confinement fusion (ICF) utilizing an antiproton catalyzed hybrid fission/fusion target is discussed as a potential energy source for interplanetary propulsion. A proof-of-principle experiment underway at Phillips Laboratory, Kirtland AFB and antiproton trapping experiments at CERN, Geneva, Switzerland, are presented. The ICAN propulsion concept is described and results of performance analyses are reviewed. Future work to further define the ICAN concept is outlined.

  4. Nickel-Catalyzed Stereoselective Dicarbofunctionalization of Alkynes.

    PubMed

    Li, Zhaodong; García-Domínguez, Andrés; Nevado, Cristina

    2016-06-01

    A nickel-catalyzed three-component reaction involving terminal alkynes, boronic acids, and alkyl halides is presented herein. Trisubstituted alkenes can be obtained in a highly regio- and stereocontrolled manner by the simultaneous addition of both aryl and alkyl groups across the triple bond in a radical-mediated process. The reaction, devoid of air- and moisture-sensitive organometallic reagents and catalysts, is operationally simple and offers a broad scope and functional-group tolerance. PMID:27111115

  5. Mechanism of salicylate hydroxylase-catalyzed decarboxylation.

    PubMed

    Suzuki, K; Katagiri, M

    1981-02-13

    Salicylate hydroxylase (salicylate, NADH: oxygen oxidoreductase (1-hydroxylating, decarboxylating), EC 1.14.13.1) in Pseudomonas putida catalyzed hydroxylation of the substrate analogue, salicylaldehyde, to form catechol and formate with stoichiometric consumption of NADH and O2. Consequently, a study of primary product derived from the carboxyl group of the authentic substrate, salicylate, was undertaken. The experimental results revealed that CO2 not H2CO3, was produced first. PMID:7213760

  6. Antibody-Catalyzed Degradation of Cocaine

    NASA Astrophysics Data System (ADS)

    Landry, Donald W.; Zhao, Kang; Yang, Ginger X.-Q.; Glickman, Michael; Georgiadis, Taxiarchis M.

    1993-03-01

    Immunization with a phosphonate monoester transition-state analog of cocaine provided monoclonal antibodies capable of catalyzing the hydrolysis of the cocaine benzoyl ester group. An assay for the degradation of radiolabeled cocaine identified active enzymes. Benzoyl esterolysis yields ecgonine methyl ester and benzoic acid, fragments devoid of cocaine's stimulant activity. Passive immunization with such an artificial enzyme could provide a treatment for dependence by blunting reinforcement.

  7. Microwave-assisted FLP-catalyzed hydrogenations.

    PubMed

    Tussing, S; Paradies, J

    2016-03-30

    FLP-catalyzed hydrogenations of 15 substrates were compared using microwave irradiation and conventional heating. The direct comparison revealed that a rate acceleration of up to 2.5 was achieved in the presence of microwaves. This heating method is particularly promising for the hydrogenation of nitrogen-containing heterocycles. Acridine, quinines and especially 1-methyl indole were reduced very efficiently under mild conditions and only 4 bar hydrogen pressure in high yields. PMID:26580129

  8. Transition-Metal-Catalyzed Bioorthogonal Cycloaddition Reactions.

    PubMed

    Yang, Maiyun; Yang, Yi; Chen, Peng R

    2016-02-01

    In recent years, bioorthogonal reactions have emerged as a powerful toolbox for specific labeling and visualization of biomolecules, even within the highly complex and fragile living systems. Among them, copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction is one of the most widely studied and used biocompatible reactions. The cytotoxicity of Cu(I) ions has been greatly reduced due to the use of Cu(I) ligands, which enabled the CuAAC reaction to proceed on the cell surface, as well as within an intracellular environment. Meanwhile, other transition metals such as ruthenium, rhodium and silver are now under development as alternative sources for catalyzing bioorthogonal cycloadditions. In this review, we summarize the development of CuAAC reaction as a prominent bioorthogonal reaction, discuss various ligands used in reducing Cu(I) toxicity while promoting the reaction rate, and illustrate some of its important biological applications. The development of additional transition metals in catalyzing cycloaddition reactions will also be briefly introduced. PMID:27572985

  9. Palladium-catalyzed oxidative carbonylation reactions.

    PubMed

    Wu, Xiao-Feng; Neumann, Helfried; Beller, Matthias

    2013-02-01

    Palladium-catalyzed coupling reactions have become a powerful tool for advanced organic synthesis. This type of reaction is of significant value for the preparation of pharmaceuticals, agrochemicals, as well as advanced materials. Both, academic as well as industrial laboratories continuously investigate new applications of the different methodologies. Clearly, this area constitutes one of the major topics in homogeneous catalysis and organic synthesis. Among the different palladium-catalyzed coupling reactions, several carbonylations have been developed and widely used in organic syntheses and are even applied in the pharmaceutical industry on ton-scale. Furthermore, methodologies such as the carbonylative Suzuki and Sonogashira reactions allow for the preparation of interesting building blocks, which can be easily refined further on. Although carbonylative coupling reactions of aryl halides have been well established, palladium-catalyzed oxidative carbonylation reactions are also interesting. Compared with the reactions of aryl halides, oxidative carbonylation reactions offer an interesting pathway. The oxidative addition step could be potentially avoided in oxidative reactions, but only few reviews exist in this area. In this Minireview, we summarize the recent development in the oxidative carbonylation reactions. PMID:23307763

  10. Fe-catalyzed etching of graphene layers

    NASA Astrophysics Data System (ADS)

    Cheng, Guangjun; Calizo, Irene; Hight Walker, Angela; PML, NIST Team

    We investigate the Fe-catalyzed etching of graphene layers in forming gas. Fe thin films are deposited by sputtering onto mechanically exfoliated graphene, few-layer graphene (FLG), and graphite flakes on a Si/SiO2 substrate. When the sample is rapidly annealed in forming gas, particles are produced due to the dewetting of the Fe thin film and those particles catalyze the etching of graphene layers. Monolayer graphene and FLG regions are severely damaged and that the particles catalytically etch channels in graphite. No etching is observed on graphite for the Fe thin film annealed in nitrogen. The critical role of hydrogen indicates that this graphite etching process is catalyzed by Fe particles through the carbon hydrogenation reaction. By comparing with the etched monolayer and FLG observed for the Fe film annealed in nitrogen, our Raman spectroscopy measurements identify that, in forming gas, the catalytic etching of monolayer and FLG is through carbon hydrogenation. During this process, Fe particles are catalytically active in the dissociation of hydrogen into hydrogen atoms and in the production of hydrogenated amorphous carbon through hydrogen spillover.

  11. Homogeneous and heterogeneous photoredox-catalyzed hydroxymethylation of ketones and keto esters: catalyst screening, chemoselectivity and dilution effects.

    PubMed

    Griesbeck, Axel G; Reckenthäler, Melissa

    2014-01-01

    The homogeneous titanium- and dye-catalyzed as well as the heterogeneous semiconductor particle-catalyzed photohydroxymethylation of ketones by methanol were investigated in order to evaluate the most active photocatalyst system. Dialkoxytitanium dichlorides are the most efficient species for chemoselective hydroxymethylation of acetophenone as well as other aromatic and aliphatic ketones. Pinacol coupling is the dominant process for semiconductor catalysis and ketone reduction dominates the Ti(OiPr)4/methanol or isopropanol systems. Application of dilution effects on the TiO2 catalysis leads to an increase in hydroxymethylation at the expense of the pinacol coupling. PMID:24991265

  12. Imidazole catalyzes chlorination by unreactive primary chloramines

    PubMed Central

    Roemeling, Margo D.; Williams, Jared; Beckman, Joseph S.; Hurst, James K.

    2015-01-01

    Hypochlorous acid and simple chloramines (RNHCl) are stable biologically-derived chlorinating agents. In general, the chlorination potential of HOCl is much greater than that of RNHCl, allowing it to oxidize or chlorinate a much wider variety of reaction partners. However, in this study we demonstrate by kinetic analysis that the reactivity of RNHCl can be dramatically promoted by imidazole and histidyl model compounds via intermediary formation of the corresponding imidazole chloramines. Two biologically relevant reactions were investigated—loss of imidazole-catalyzed chlorinating capacity and phenolic ring chlorination using fluorescein and the tyrosine analog, 4-hydroxyphenylacetic acid (HPA). HOCl reacted stoichiometrically with imidazole, N-acetylhistidine (NAH), or imidazoleacetic acid to generate the corresponding imidazole chloramines which subsequently decomposed. Chloramine (NH2Cl) also underwent a markedly accelerated loss in chlorinating capacity when NAH was present, although in this case NAHCl did not accumulate, indicating that the catalytic intermediate must be highly reactive. Mixing HOCl with 1-methylimidazole (MeIm) led to very rapid loss in chlorinating capacity via formation of a highly reactive chlorinium ion (MeImCl+) intermediate; this behavior suggests that the reactive forms of the analogous imidazole chloramines are their conjugate acids, e.g., the imidazolechlorinium ion (HImCl+). HOCl-generated imidazole chloramine (ImCl) reacted rapidly with fluorescein in a specific acid-catalyzed second order reaction to give 3′-monochloro and 3′,5′-dichloro products. Equilibrium constants for the transchlorination reactions: HOCl + HIm = H2O + ImCl and NH2Cl + HIm = NH3 + ImCl were estimated from the dependence of the rate constants upon [HIm]/[HOCl] and literature data. Acid catalysis again suggests that the actual chlorinating agent is HImCl+; consistent with this interpretation, MeIm markedly catalyzed fluorescein chlorination by HOCl

  13. Imidazole catalyzes chlorination by unreactive primary chloramines.

    PubMed

    Roemeling, Margo D; Williams, Jared; Beckman, Joseph S; Hurst, James K

    2015-05-01

    Hypochlorous acid and simple chloramines (RNHCl) are stable biologically derived chlorinating agents. In general, the chlorination potential of HOCl is much greater than that of RNHCl, allowing it to oxidize or chlorinate a much wider variety of reaction partners. However, in this study we demonstrate by kinetic analysis that the reactivity of RNHCl can be dramatically promoted by imidazole and histidyl model compounds via intermediary formation of the corresponding imidazole chloramines. Two biologically relevant reactions were investigated--loss of imidazole-catalyzed chlorinating capacity and phenolic ring chlorination using fluorescein and the tyrosine analog, 4-hydroxyphenylacetic acid (HPA). HOCl reacted stoichiometrically with imidazole, N-acetylhistidine (NAH), or imidazoleacetic acid to generate the corresponding imidazole chloramines which subsequently decomposed. Chloramine (NH2Cl) also underwent a markedly accelerated loss in chlorinating capacity when NAH was present, although in this case N-α-acetylhistidine chloramine (NAHCl) did not accumulate, indicating that the catalytic intermediate must be highly reactive. Mixing HOCl with 1-methylimidazole (MeIm) led to very rapid loss in chlorinating capacity via formation of a highly reactive chlorinium ion (MeImCl(+)) intermediate; this behavior suggests that the reactive forms of the analogous imidazole chloramines are their conjugate acids, e.g., the imidazolechlorinium ion (HImCl(+)). HOCl-generated imidazole chloramine (ImCl) reacted rapidly with fluorescein in a specific acid-catalyzed second-order reaction to give 3'-monochloro and 3',5'-dichloro products. Equilibrium constants for the transchlorination reactions HOCl + HIm = H2O + ImCl and NH2Cl + HIm = NH3 + ImCl were estimated from the dependence of the rate constants on [HIm]/[HOCl] and literature data. Acid catalysis again suggests that the actual chlorinating agent is HImCl(+); consistent with this interpretation, MeIm markedly catalyzed

  14. Rhodium-Catalyzed Acyloxy Migration of Propargylic Esters in Cycloadditions, Inspiration from Recent “Gold Rush”

    PubMed Central

    Shu, Xing-Zhong; Shu, Dongxu; Schienebeck, Casi M.

    2012-01-01

    Transition metal-catalyzed acyloxy migration of propargylic esters offers versatile entries to allene and vinyl carbene intermediates for various fascinating subsequent transformations. Most π-acidic metals (e.g. gold and platinum) are capable of facilitating these acyloxy migration events. However, very few of these processes involve redox chemistry, which are well-known for most other transition metals such as rhodium. The coupling of acyloxy migration of propargylic esters with oxidative addition, migratory insertion, and reductive elimination may lead to ample new opportunities for the design of new reactions. This tutorial review summarizes recent developments in Rh-catalyzed 1,3- and 1,2-acyloxy migration of propargylic esters in a number of cycloaddition reactions. Related Au- and Pt-catalyzed cycloadditions involving acyloxy migration are also discussed. PMID:22895533

  15. A recyclable and reusable supported Cu(I) catalyzed azide-alkyne click polymerization

    NASA Astrophysics Data System (ADS)

    Wu, Haiqiang; Li, Hongkun; Kwok, Ryan T. K.; Zhao, Engui; Sun, Jing Zhi; Qin, Anjun; Tang, Ben Zhong

    2014-05-01

    The azide-alkyne click polymerization (AACP) has emerged as a powerful tool for the synthesis of functional polytriazoles. While, for the Cu(I)-catalyzed AACP, the removal of the catalytic Cu(I) species from the resulting polytriazoles is difficult, and the research on the recyclability and reusability of the catalyst remains intact. Herein, we reported the first example of using recyclable and reusable supported Cu(I) catalyst of CuI@A-21 for the AACP. CuI@A-21 could not only efficiently catalyze the AACP but also be reused for at least 4 cycles. Moreover, pronounced reduction of copper residues in the products was achieved. Apart from being a green and cost-effective polymer synthesis strategy, this method will also broaden the application of AACP in material and biological sciences and provide guidelines for other polymerizations with metal catalysts.

  16. A recyclable and reusable supported Cu(I) catalyzed azide-alkyne click polymerization

    PubMed Central

    Wu, Haiqiang; Li, Hongkun; Kwok, Ryan T. K.; Zhao, Engui; Sun, Jing Zhi; Qin, Anjun; Tang, Ben Zhong

    2014-01-01

    The azide–alkyne click polymerization (AACP) has emerged as a powerful tool for the synthesis of functional polytriazoles. While, for the Cu(I)-catalyzed AACP, the removal of the catalytic Cu(I) species from the resulting polytriazoles is difficult, and the research on the recyclability and reusability of the catalyst remains intact. Herein, we reported the first example of using recyclable and reusable supported Cu(I) catalyst of CuI@A-21 for the AACP. CuI@A-21 could not only efficiently catalyze the AACP but also be reused for at least 4 cycles. Moreover, pronounced reduction of copper residues in the products was achieved. Apart from being a green and cost-effective polymer synthesis strategy, this method will also broaden the application of AACP in material and biological sciences and provide guidelines for other polymerizations with metal catalysts. PMID:24875854

  17. Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

    PubMed

    Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

    2015-05-26

    The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect. PMID:25877865

  18. Mechanistic Insights into the Palladium-Catalyzed Aziridination of Aliphatic Amines by C-H Activation.

    PubMed

    Smalley, Adam P; Gaunt, Matthew J

    2015-08-26

    Detailed kinetic studies and computational investigations have been performed to elucidate the mechanism of a palladium-catalyzed C-H activation aziridination. A theoretical rate law has been derived that matches with experimental observations and has led to an improvement in the reaction conditions. Acetic acid was found to be beneficial in controlling the formation of an off-cycle intermediate, allowing a decrease in catalyst loading and improved yields. Density functional theory (DFT) studies were performed to examine the selectivities observed in the reaction. Evidence for electronic-controlled regioselectivity for the cyclopalladation step was obtained by a distortion-interaction analysis, whereas the aziridination product was justified through dissociation of acetic acid from the palladium(IV) intermediate preceding the product-forming reductive elimination step. The understanding of this reaction mechanism under the synthesis conditions should provide valuable assistance in the comprehension and design of palladium-catalyzed reactions on similar systems. PMID:26247373

  19. Asymmetric petasis reactions catalyzed by chiral biphenols.

    PubMed

    Lou, Sha; Schaus, Scott E

    2008-06-01

    Chiral biphenols catalyze the enantioselective Petasis reaction of alkenyl boronates, secondary amines, and ethyl glyoxylate. The reaction requires the use of 15 mol % of (S)-VAPOL as the catalyst, alkenyl boronates as nucleophiles, ethyl glyoxylate as the aldehyde component, and 3 A molecular sieves as an additive. The chiral alpha-amino ester products are obtained in good yields (71-92%) and high enantiomeric ratios (89:11-98:2). Mechanistic investigations indicate single ligand exchange of acyclic boronate with VAPOL and tetracoordinate boronate intermediates. PMID:18459782

  20. Cyanide-catalyzed cyclizations via aldimine coupling.

    PubMed

    Reich, B Jesse E; Justice, Aaron K; Beckstead, Brittany T; Reibenspies, Joseph H; Miller, Stephen A

    2004-02-20

    Aldimine coupling (AIC) is the nitrogen analogue of the benzoin condensation and has been applied to dialdimines, providing the first examples of cyclizations effected by cyanide-catalyzed AIC. Sodium cyanide promoted the facile, intramolecular cyclization of several dialdimines in N,N-dimethylformamide, methanol, or methylene chloride/water (phase-transfer conditions) yielding a variety of six-membered heterocycles. Under aerobic conditions, an oxidative cyclization occurs to provide the diimine heterocycle. Oligomerization was observed with rigid dialdimines for which cyclization was precluded. PMID:14961691

  1. Silver-catalyzed late-stage fluorination.

    PubMed

    Tang, Pingping; Furuya, Takeru; Ritter, Tobias

    2010-09-01

    Carbon-fluorine bond formation by transition metal catalysis is difficult, and only a few methods for the synthesis of aryl fluorides have been developed. All reported transition-metal-catalyzed fluorination reactions for the synthesis of functionalized arenes are based on palladium. Here we present silver catalysis for carbon-fluorine bond formation. Our report is the first example of the use of the transition metal silver to form carbon-heteroatom bonds by cross-coupling catalysis. The functional group tolerance and substrate scope presented here have not been demonstrated for any other fluorination reaction to date. PMID:20695434

  2. Catalyzed D-D stellarator reactor

    DOE PAGESBeta

    Sheffield, John; Spong, Donald A.

    2016-05-12

    The advantages of using the catalyzed deuterium-deuterium (D-D) approach for a fusion reactor—lower and less energetic neutron flux and no need for a tritium breeding blanket—have been evaluated in previous papers, giving examples of both tokamak and stellarator reactors. This paper presents an update for the stellarator example, taking account of more recent empirical transport scaling results and design studies of lower-aspect-ratio stellarators. We use a modified version of the Generic Magnetic Fusion Reactor model to cost a stellarator-type reactor. Recently, this model has been updated to reflect the improved science and technology base and costs in the magnetic fusionmore » program. Furthermore, it is shown that an interesting catalyzed D-D, stellarator power plant might be possible if the following parameters could be achieved: R/ ≈ 4, required improvement factor to ISS04 scaling, FR = 0.9 to 1.15, <β> ≈ 8.0% to 11.5%, Zeff ≈ 1.45 plus a relativistic temperature correction, fraction of fast ions lost ≈ 0.07, Bm ≈ 14 to 16 T, and R ≈ 18 to 24 m.« less

  3. Manganese Catalyzed C-H Halogenation.

    PubMed

    Liu, Wei; Groves, John T

    2015-06-16

    The remarkable aliphatic C-H hydroxylations catalyzed by the heme-containing enzyme, cytochrome P450, have attracted sustained attention for more than four decades. The effectiveness of P450 enzymes as highly selective biocatalysts for a wide range of oxygenation reactions of complex substrates has driven chemists to develop synthetic metalloporphyrin model compounds that mimic P450 reactivity. Among various known metalloporphyrins, manganese derivatives have received considerable attention since they have been shown to be versatile and powerful mediators for alkane hydroxylation and olefin epoxidation. Mechanistic studies have shown that the key intermediates of the manganese porphyrin-catalyzed oxygenation reactions include oxo- and dioxomanganese(V) species that transfer an oxygen atom to the substrate through a hydrogen abstraction/oxygen recombination pathway known as the oxygen rebound mechanism. Application of manganese porphyrins has been largely restricted to catalysis of oxygenation reactions until recently, however, due to ultrafast oxygen transfer rates. In this Account, we discuss recently developed carbon-halogen bond formation, including fluorination reactions catalyzed by manganese porphyrins and related salen species. We found that biphasic sodium hypochlorite/manganese porphyrin systems can efficiently and selectively convert even unactivated aliphatic C-H bonds to C-Cl bonds. An understanding of this novel reactivity derived from results obtained for the oxidation of the mechanistically diagnostic substrate and radical clock, norcarane. Significantly, the oxygen rebound rate in Mn-mediated hydroxylation is highly correlated with the nature of the trans-axial ligands bound to the manganese center (L-Mn(V)═O). Based on the ability of fluoride ion to decelerate the oxygen rebound step, we envisaged that a relatively long-lived substrate radical could be trapped by a Mn-F fluorine source, effecting carbon-fluorine bond formation. Indeed, this idea

  4. Iron-, Cobalt-, and Nickel-Catalyzed Asymmetric Transfer Hydrogenation and Asymmetric Hydrogenation of Ketones.

    PubMed

    Li, Yan-Yun; Yu, Shen-Luan; Shen, Wei-Yi; Gao, Jing-Xing

    2015-09-15

    Chiral alcohols are important building blocks in the pharmaceutical and fine chemical industries. The enantioselective reduction of prochiral ketones catalyzed by transition metal complexes, especially asymmetric transfer hydrogenation (ATH) and asymmetric hydrogenation (AH), is one of the most efficient and practical methods for producing chiral alcohols. In both academic laboratories and industrial operations, catalysts based on noble metals such as ruthenium, rhodium, and iridium dominated the asymmetric reduction of ketones. However, the limited availability, high price, and toxicity of these critical metals demand their replacement with abundant, nonprecious, and biocommon metals. In this respect, the reactions catalyzed by first-row transition metals, which are more abundant and benign, have attracted more and more attention. As one of the most abundant metals on earth, iron is inexpensive, environmentally benign, and of low toxicity, and as such it is a fascinating alternative to the precious metals for catalysis and sustainable chemical manufacturing. However, iron catalysts have been undeveloped compared to other transition metals. Compared with the examples of iron-catalyzed asymmetric reduction, cobalt- and nickel-catalyzed ATH and AH of ketones are even seldom reported. In early 2004, we reported the first ATH of ketones with catalysts generated in situ from iron cluster complex and chiral PNNP ligand. Since then, we have devoted ourselves to the development of ATH and AH of ketones with iron, cobalt, and nickel catalysts containing novel chiral aminophosphine ligands. In our study, the iron catalyst containing chiral aminophosphine ligands, which are expected to control the stereochemistry at the metal atom, restrict the number of possible diastereoisomers, and effectively transfer chiral information, are successful catalysts for enantioselective reduction of ketones. Among these novel chiral aminophosphine ligands, 22-membered macrocycle P2N4

  5. Mg-catalyzed autoclave synthesis of aligned silicon carbide nanostructures.

    PubMed

    Xi, Guangcheng; Liu, Yankuan; Liu, Xiaoyan; Wang, Xiaoqing; Qian, Yitai

    2006-07-27

    In this article, a novel magnesium-catalyzed co-reduction route was developed for the large-scale synthesis of aligned beta-SiC one-dimensional (1D) nanostructures at relative lower temperature (600 degrees C). By carefully controlling the reagent concentrations, we could synthesize beta-SiC rodlike and needlelike nanostructures. The possible growth mechanism of the as-synthesized beta-SiC 1D nanostructures has been investigated. The structure and morphology of the as-synthesized beta-SiC nanostructures are characterized using X-ray diffraction, Fourier transform infrared absorption, and scanning and transmission electron microscopes. Raman and photoluminescence properties are also investigated at room temperature. The as-synthesized beta-SiC nanostructures exhibit strong shape-dependent field emission properties. Corresponding to their shapes, the as-synthesized nanorods and nanoneedles display the turn-on fields of 12, 8.4, and 1.8 V/microm, respectively. PMID:16854116

  6. Ultrasound enhances lipase-catalyzed synthesis of poly (ethylene glutarate).

    PubMed

    Zhao, Xiaoman; Bansode, Sneha Ramrao; Ribeiro, Artur; Abreu, Ana S; Oliveira, César; Parpot, Pier; Gogate, P R; Rathod, V K; Cavaco-Paulo, Artur

    2016-07-01

    The present work explores the best conditions for the enzymatic synthesis of poly (ethylene glutarate) for the first time. The start-up materials are the liquids; diethyl glutarate and ethylene glycol diacetate, without the need of addition of extra solvent. The reactions are catalyzed by lipase B from Candida antarctica immobilized on glycidyl methacrylate-ter-divinylbenzene-ter-ethylene glycol dimethacrylate at 40°C during 18h in water bath with mechanical stirring or 1h in ultrasonic bath followed by 6h in vacuum in both the cases for evaporation of ethyl acetate. The application of ultrasound significantly intensified the polyesterification reaction with reduction of the processing time from 24h to 7h. The same degree of polymerization was obtained for the same enzyme loading in less time of reaction when using the ultrasound treatment. The degree of polymerization for long-term polyesterification was improved approximately 8-fold due to the presence of sonication during the reaction. The highest degree of polymerization achieved was 31, with a monomer conversion of 96.77%. The ultrasound treatment demonstrated to be an effective green approach to intensify the polyesterification reaction with enhanced initial kinetics and high degree of polymerization. PMID:26964978

  7. Molecular mechanisms of cobalt-catalyzed hydrogen evolution

    PubMed Central

    Marinescu, Smaranda C.; Winkler, Jay R.; Gray, Harry B.

    2012-01-01

    Several cobalt complexes catalyze the evolution of hydrogen from acidic solutions, both homogeneously and at electrodes. The detailed molecular mechanisms of these transformations remain unresolved, largely owing to the fact that key reactive intermediates have eluded detection. One method of stabilizing reactive intermediates involves minimizing the overall reaction free-energy change. Here, we report a new cobalt(I) complex that reacts with tosylic acid to evolve hydrogen with a driving force of just 30 meV/Co. Protonation of CoI produces a transient CoIII-H complex that was characterized by nuclear magnetic resonance spectroscopy. The CoIII-H intermediate decays by second-order kinetics with an inverse dependence on acid concentration. Analysis of the kinetics suggests that CoIII-H produces hydrogen by two competing pathways: a slower homolytic route involving two CoIII-H species and a dominant heterolytic channel in which a highly reactive CoII-H transient is generated by CoI reduction of CoIII-H. PMID:22949704

  8. Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab-initio Studies of Zero-Field Splittings

    SciTech Connect

    Stavretis, Shelby E.; Atanasov, Mihail; Podlesnyak, Andrey A.; Hunter, Seth C.; Neese, Frank; Xue, Zi-Ling

    2015-10-02

    Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H2TPP = tetraphenylporphyrin) are determined by inelastic neutron scattering (INS). The ZFS values are D = 4.49(9) cm–1 for tetragonal polycrystalline [Fe(TPP)F], and D = 8.8(2) cm–1, E = 0.1(2) cm–1 and D = 13.4(6) cm–1, E = 0.3(6) cm–1 for monoclinic polycrystalline [Fe(TPP)Br] and [Fe(TPP)I], respectively. Along with our recent report of the ZFS value of D = 6.33(8) cm–1 for tetragonal polycrystalline [Fe(TPP)Cl], these data provide a rare, complete determination of ZFS parameters in a metalloporphyrin halide series. The electronic structure of [Fe(TPP)X] (X = F, Cl, Br, I) has been studied by multireference ab initio methods: the complete active space self-consistent field (CASSCF) and the N-electron valence perturbation theory (NEVPT2) with the aim of exploring the origin of the large and positive zero-field splitting D of the 6A1 ground state. D was calculated from wave functions of the electronic multiplets spanned by the d5 configuration of Fe(III) along with spin–orbit coupling accounted for by quasi degenerate perturbation theory. Results reproduce trends of D from inelastic neutron scattering data increasing in the order from F, Cl, Br, to I. A mapping of energy eigenvalues and eigenfunctions of the S = 3/2 excited states on ligand field theory was used to characterize the σ- and π-antibonding effects decreasing from F to I. This is in agreement with similar results deduced from ab initio calculations on CrX63- complexes and also with the spectrochemical series showing a decrease of the ligand field in the same directions. A correlation is found between the increase of D and decrease of the π- and σ-antibonding energies eλX (λ = σ, π) in the series from X = F to I. Analysis of this correlation using second-order perturbation theory expressions in terms of angular overlap parameters rationalizes the experimentally deduced trend. Furthermore, D parameters from CASSCF and NEVPT2 results have been calibrated against those from the INS data, yielding a predictive power of these approaches. Methods to improve the quantitative agreement between ab initio calculated and experimental D and spectroscopic transitions for high-spin Fe(III) complexes are proposed.

  9. Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab-initio Studies of Zero-Field Splittings

    DOE PAGESBeta

    Stavretis, Shelby E.; Atanasov, Mihail; Podlesnyak, Andrey A.; Hunter, Seth C.; Neese, Frank; Xue, Zi-Ling

    2015-10-02

    Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H2TPP = tetraphenylporphyrin) are determined by inelastic neutron scattering (INS). The ZFS values are D = 4.49(9) cm–1 for tetragonal polycrystalline [Fe(TPP)F], and D = 8.8(2) cm–1, E = 0.1(2) cm–1 and D = 13.4(6) cm–1, E = 0.3(6) cm–1 for monoclinic polycrystalline [Fe(TPP)Br] and [Fe(TPP)I], respectively. Along with our recent report of the ZFS value of D = 6.33(8) cm–1 for tetragonal polycrystalline [Fe(TPP)Cl], these data provide a rare, complete determination of ZFS parameters in a metalloporphyrin halide series. The electronic structure of [Fe(TPP)X] (X =more » F, Cl, Br, I) has been studied by multireference ab initio methods: the complete active space self-consistent field (CASSCF) and the N-electron valence perturbation theory (NEVPT2) with the aim of exploring the origin of the large and positive zero-field splitting D of the 6A1 ground state. D was calculated from wave functions of the electronic multiplets spanned by the d5 configuration of Fe(III) along with spin–orbit coupling accounted for by quasi degenerate perturbation theory. Results reproduce trends of D from inelastic neutron scattering data increasing in the order from F, Cl, Br, to I. A mapping of energy eigenvalues and eigenfunctions of the S = 3/2 excited states on ligand field theory was used to characterize the σ- and π-antibonding effects decreasing from F to I. This is in agreement with similar results deduced from ab initio calculations on CrX63- complexes and also with the spectrochemical series showing a decrease of the ligand field in the same directions. A correlation is found between the increase of D and decrease of the π- and σ-antibonding energies eλX (λ = σ, π) in the series from X = F to I. Analysis of this correlation using second-order perturbation theory expressions in terms of angular overlap parameters rationalizes the experimentally deduced trend. Furthermore, D parameters from CASSCF and NEVPT2 results have been calibrated against those from the INS data, yielding a predictive power of these approaches. Methods to improve the quantitative agreement between ab initio calculated and experimental D and spectroscopic transitions for high-spin Fe(III) complexes are proposed.« less

  10. Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab Initio Studies of Zero-Field Splittings.

    PubMed

    Stavretis, Shelby E; Atanasov, Mihail; Podlesnyak, Andrey A; Hunter, Seth C; Neese, Frank; Xue, Zi-Ling

    2015-10-19

    Zero-field splitting (ZFS) parameters of nondeuterated metalloporphyrins [Fe(TPP)X] (X = F, Br, I; H₂TPP = tetraphenylporphyrin) have been directly determined by inelastic neutron scattering (INS). The ZFS values are D = 4.49(9) cm⁻¹ for tetragonal polycrystalline [Fe(TPP)F], and D = 8.8(2) cm⁻¹, E = 0.1(2) cm⁻¹ and D = 13.4(6) cm⁻¹, E = 0.3(6) cm⁻¹ for monoclinic polycrystalline [Fe(TPP)Br] and [Fe(TPP)I], respectively. Along with our recent report of the ZFS value of D = 6.33(8) cm⁻¹ for tetragonal polycrystalline [Fe(TPP)Cl], these data provide a rare, complete determination of ZFS parameters in a metalloporphyrin halide series. The electronic structure of [Fe(TPP)X] (X = F, Cl, Br, I) has been studied by multireference ab initio methods: the complete active space self-consistent field (CASSCF) and the N-electron valence perturbation theory (NEVPT2) with the aim of exploring the origin of the large and positive zero-field splitting D of the ⁶A₁ ground state. D was calculated from wave functions of the electronic multiplets spanned by the d⁵ configuration of Fe(III) along with spin–orbit coupling accounted for by quasi degenerate perturbation theory. Results reproduce trends of D from inelastic neutron scattering data increasing in the order from F, Cl, Br, to I. A mapping of energy eigenvalues and eigenfunctions of the S = 3/2 excited states on ligand field theory was used to characterize the σ- and π-antibonding effects decreasing from F to I. This is in agreement with similar results deduced from ab initio calculations on CrX₆³⁻ complexes and also with the spectrochemical series showing a decrease of the ligand field in the same directions. A correlation is found between the increase of D and decrease of the π- and σ-antibonding energies e(λ)(X) (λ = σ, π) in the series from X = F to I. Analysis of this correlation using second-order perturbation theory expressions in terms of angular overlap parameters rationalizes the experimentally deduced trend. D parameters from CASSCF and NEVPT2 results have been calibrated against those from the INS data, yielding a predictive power of these approaches. Methods to improve the quantitative agreement between ab initio calculated and experimental D and spectroscopic transitions for high-spin Fe(III) complexes are proposed. PMID:26428688