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Sample records for iron-porphyrin catalyzed reduction

  1. 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.

  2. Syntheses and CO2 reduction activities of π-expanded/extended iron porphyrin complexes.

    PubMed

    Okabe, Yuki; Lee, Sze Koon; Kondo, Mio; Masaoka, Shigeyuki

    2017-07-01

    The construction of molecular catalysts that are active toward CO2 reduction is of great significance for designing sustainable energy conversion systems. In this study, we aimed to develop catalysts for CO2 reduction by introducing aromatic substituents to the meso-positions of iron porphyrin complexes. Three novel iron porphyrin complexes with π-expanded substituents (5,10,15,20-tetrakis(pyren-1-yl)porphyrinato iron(III) chloride (Fe-Py)), π-extended substituents (5,10,15,20-tetrakis((1,1'-biphenyl)-4-yl)porphyrinato iron(III) chloride (Fe-PPh)) and π-expanded and extended substituents (5,10,15,20-tetrakis(4-(pyren-1-yl)phenyl)porphyrinato iron(III) chloride (Fe-PPy)) were successfully synthesized, and their physical properties were investigated by UV-vis absorption spectroscopy and electrochemical measurements under Ar in comparison with an iron complex with a basic framework, 5,10,15,20-tetrakis(phenyl)porphyrinato iron(III) chloride (Fe-Ph). Moreover, the catalytic activity of the complexes was studied by electrochemical measurements under CO2, and it is found that the complex with the π-expanded substituents exhibits the highest activity among these complexes.

  3. 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

    2015-12-07

    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.

  4. Medium effects are as important as catalyst design for selectivity in electrocatalytic oxygen reduction by iron-porphyrin complexes.

    PubMed

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

    2015-04-08

    Several substituted iron-porphyrin complexes were evaluated for oxygen reduction reaction (ORR) electrocatalysis in different homogeneous and heterogeneous media. The selectivity for four-electron reduction to H2O versus two-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 selectivity results from supported and soluble molecular ORR electrocatalysts must be interpreted with caution, as selectivity is a property not only of the catalyst, but also of the larger mesoscale environment beyond 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.

  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. Selective four electron reduction of O2 by an iron porphyrin electrocatalyst under fast and slow electron fluxes.

    PubMed

    Samanta, Subhra; Sengupta, Kushal; Mittra, Kaustuv; Bandyopadhyay, Sabyasachi; Dey, Abhishek

    2012-08-07

    An iron porphyrin catalyst with four electron donor groups is reported. The porphyrin ligand bears a distal hydrogen bonding pocket which inverts the normal axial ligand binding selectivity exhibited by porphyrins bearing sterically crowded distal structures. This catalyst specifically reduces O(2) by four electrons under both fast and slow electron fluxes at pH 7.

  7. Second sphere control of redox catalysis: selective reduction of O2 to O2- or H2O by an iron porphyrin catalyst.

    PubMed

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

    2013-02-04

    "Click" reaction has been utilized to synthesize porphyrin ligands possessing distal superstructures functionalized with ferrocenes, carboxylic acid esters, and phenols. Both structural and spectroscopic evidence indicate that hydrogen bonding interaction between the triazole residues resulting from the "click" reaction promotes axial ligand binding into the sterically demanding distal pocket in preference to the open proximal side. An iron porphyrin complex with four ferrocene groups is found to bind O(2) and quantitatively reduce it by one electron to O(2)(-) in apolar organic solvents. However the same complex electro-catalytically reduces O(2) by four electrons to H(2)O in aqueous medium under fast, moderate, and slow electron fluxes. This selectivity for O(2) reduction is governed by the reduction potential of the electron transfer site (i.e., ferrocene) which in turn is governed by the solvent. This catalyst mimics control of catalysis of an enzyme active site by a second sphere electron transfer residue which is often encountered in naturally occurring metallo-enzymes.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. Impact of iron porphyrin complexes when hydroprocessing algal HTL biocrude

    SciTech Connect

    Jarvis, Jacqueline M.; Sudasinghe, Nilusha M.; Albrecht, Karl O.; Schmidt, Andrew J.; Hallen, Richard T.; Anderson, Daniel B.; Billing, Justin M.; Schaub, Tanner M.

    2016-10-01

    We apply Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for direct characterization of iron-porphyrins in hydrothermal liquefaction (HTL) biocrude oils derived from two algae: Tetraselmis sp. and cyanobacteria. The ironporphyrin compounds are shown to cause catalyst bed plugging during hydroprocessing due to iron deposition. Inductively-coupled plasma optical emission spectrometry (ICPOES) was utilized for iron quantitation in the plugged catalyst beds formed through hydroprocessing of the two HTL biocrudes and identifies an enrichment of iron in the upper five centimeters of the catalyst bed for Tetraselmis sp. (Fe=100,728 ppm) and cyanobacteria (Fe=115,450 ppm). Direct infusion FT-ICR MS analysis of the two HTL biocrudes with optimized instrument conditions facilitates rapid screening and identification of iron-porphyrins without prior chromatographic separation. With FT-ICR MS we identify 138 unique iron-porphyrin compounds in the two HTL biocrudes that are structurally similar to metal-porphyrins (e.g. Ni and V) observed in petroleum. No ironporphyrins are observed in the cyanobacteria HTL biocrude after hydroprocessing, which indicates that iron-porphyrin structures in the HTL biocrude are degraded during hydroprocessing. Hydrodemetallization reactions that occur through hydroprocessing of HTL biocrudes could be responsible for the decomposition of iron-porphyrin structures leading to metal deposition in the catalyst bed that result in catalyst deactivation and bed plugging, and must be addressed for effective upgrading of algal HTL biocrudes.

  13. Hydrosulfide (HS−) Coordination in Iron Porphyrinates

    PubMed Central

    Pavlik, Jeffrey W.; Noll, Bruce C.; Oliver, Allen G.; Schulz, Charles E.; Scheidt, W. Robert

    2010-01-01

    Recent reports of potential physiological roles of hydrogen sulfide have prompted interest in heme-sulfide interactions. Heme-H2S and/or heme-HS− interactions could potentially occur during endogenous production, transport, signaling events, and catabolism of H2S. We have investigated the interaction of the hydrosulfide ion (HS−) with iron porphyrinates. UV-vis spectral studies show the formation of [Fe(Por)(SH)]−, [Fe(Por)(SH)2]2−, and the mixed ligand species [Fe(Por)(Im)(SH)]−. UV-vis binding studies of [Fe(OEP)] and [Fe(Tp-OMePP)] (OEP = octaethylporphyrinate, Tp-OMePP = tetra-p-methoxyphenylporphyrinate) with HS− allowed for calculation of formation constants and extinction coefficients of the mono- and bis-HS− complexes. We report the synthesis of the first HS− bound iron(II) porphyrin compounds, [Na(222)][Fe(OEP)(SH)]·0.5C6H6 and [Na(222)][Fe(Tp-OMePP)(SH)]·C6H5Cl (222 = kryptofix-222). Characterization by single-crystal X-ray analysis, mass spectrometry, and Mössbauer and IR spectroscopy are all consistent with that of known sulfur-bound high-spin iron(II) compounds. The Fe–S distances of 2.3929(5) and 2.3887(13) Å are longer than all reported values of [FeII(Por)(SR)]− species. An analysis of porphyrin non-planarity for these derivatives and for all five-coordinate high-spin iron(II) porphyrinate derivatives with an axial anion ligand is presented. In our hands, attempts to synthesize iron(III) HS− derivatives led to iron(II) species. PMID:20038134

  14. Mechanism of stereoselective epoxidation of alkenes by oxo-iron porphyrins

    SciTech Connect

    Joergensen, K.A.

    1987-02-04

    The structure of oxo-iron porphyrins and their stereoselective epoxidation properties of alkenes are analyzed from a theoretical point of view. It is found that the most stable structure of oxo-iron porphyrin is one in which oxygen is inserted into the iron-nitrogen bond. This structure is equivalent to some of the carbene analogues, and the bond lengths for Fe-O (1.9 A) and N-O (1.4 A) are in good agreement with those found in the nickel analogue of 6. The insertion of oxygen into the iron-nitrogen bond makes some of the d orbitals on iron available for interaction with the alkene; this type of complex is supported by recent experimental observations. The alkene can be coordinated in a perpendicular or parallel orientation at the iron atom (relative to the iron-oxygen bond), and the perpendicular orientation is found to be the most favorable. This binding of the alkene can then cause the stereoselective epoxidation properties, as the trans substituents will interact repulsively with the iron-porphyrin moiety. It is then suggested that the next step in the reaction mechanism is a slipping motion of the alkene toward the oxygen. This motion is controlled by a favorable interaction between the ..pi..* orbital of the alkene and the lone pair on the oxygen which is antisymmetric with respect to the iron-oxygen-nitrogen plane. Aspects of this type of mechanism in relation to the experimental results as well as other transition metal catalyzed epoxidation reactions are discussed.

  15. Dual-Functional Electrocatalyst Derived from Iron-Porphyrin-Encapsulated Metal-Organic Frameworks.

    PubMed

    Park, Jungwon; Lee, Hyunjoon; Bae, Young Eun; Park, Kyoung Chul; Ji, Hoon; Jeong, Nak Cheon; Lee, Min Hyung; Kwon, Oh Joong; Lee, Chang Yeon

    2017-08-30

    Active, stable electrocatalysts based on non-precious metals for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) are critical for the development of cost-effective, efficient renewable energy technologies. Here, Fe/Fe3C-embedded nitrogen-doped carbon was fabricated via pyrolysis of iron-porphyrin-encapsulated mesoporous metal-organic frameworks [PCN-333 (Fe), where "PCN" stands for "porous coordination network"] at 700 °C. The various characterization techniques confirmed that Fe- and Fe3C-containing Fe-N-C material (FeP-P333-700) was successfully prepared by pyrolysis of porphyrin-encapsulated PCN-333 (Fe). FeP-P333-700 exhibited superior electrocatalytic performance for the ORR and HER owing to the synergistic effect of Fe/Fe3C and Fe-N-C active sites.

  16. Iron porphyrins with a hydrogen bonding cavity: effect of weak interactions on their electronic structure and reactivity.

    PubMed

    Mittra, Kaustuv; Singha, Asmita; Dey, Abhishek

    2016-12-21

    The electronic structure and reactivity of iron porphyrin complexes bearing 2(nd) sphere hydrogen bonding residues have been investigated over the last few years. The presence of these weak interactions alters the spin ground state, and axial ligand bonding and provides a proton translocation pathway into the active site. Mechanistic investigations in organic as well as aqueous media demonstrate how controlled delivery of protons is fundamental in dictating the selectivity of a multi-electron multi-proton process like the reduction of dioxygen to water.

  17. 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)

  18. 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)

  19. Detection of iron-porphyrin proteins with a biochemiluminescent method in search of extraterrestrial life.

    PubMed

    Sotnikov, G G

    1970-01-01

    Iron-porphyrin proteins (catalase, peroxidase, hemoglobin, cytochrome C) represent an important group of redoxenzymes which have vitally important functions in micro-organisms. A biochemiluminescent method was employed for the detection of iron-porphyrin proteins. The reaction of luminol oxidation with H2O2 is accompanied by chemiluminescence. The rate of hydrogen peroxide decomposition increased 10(5)-10(7) -fold in the presence of the above enzymes as compared with ferrous (or ferric) ions. Possible application of this reaction for the detection of iron-porphyrin proteins of microbial origin was studied. Other authors have suggested this reaction for the detection of extraterrestrial life. Kinetics of the above reaction in the presence of iron-porphyrin proteins were shown to differ both in amplitude and duration of the signal from the pattern observed in the presence of non-hemin catalysts. The reaction pattern in the presence of mixed-soil populations is similar to those observed with pure bacterial cultures and individual iron-porphyrin proteins. Photometric tests revealed that among preparations studied the addition of 0.01% lysozyme was the most effective in destroying cell walls in microbial populations. However, removal of cell walls is not a necessary prerequisite for the detection of iron porphyrin since, for effective luminol oxidation with H2O2 the medium should be kept at pH 12.0. Pretreatment of microbial suspensions with ultrasound increased 2-fold the total signal due to iron porphyrins. The above method gives a reproducible signal indicating the presence of iron porphyrins when sterile nutrient media were innoculated with desert soil samples (Repeteck, Kara-Kum) and incubated for 13 hr. The device was able to detect the presence of no less than 10(5) - 10(6) cells per ml. The addition of limonite (Fe2O3 X nH2O) does not result in the appearance of an appreciable signal in the luminol + H2O2 system.

  20. Probing Framework-Restricted Metal Axial Ligation and Spin State Patterns in a Post-Synthetically Reduced Iron-Porphyrin-Based Metal-Organic Framework.

    PubMed

    Kucheryavy, Pavel; Lahanas, Nicole; Velasco, Ever; Sun, Cheng-Jun; Lockard, Jenny V

    2016-04-07

    An iron-porphyrin-based metal organic framework PCN-222(Fe) is investigated upon postsynthetic reduction with piperidine. Fe K-edge X-ray absorption and Kβ mainline emission spectroscopy measurements reveal the local coordination geometry, oxidation, and spin state changes experienced by the Fe sites upon reaction with this axially coordinating reducing agent. Analysis and fitting of these data confirm the binding pattern predicted by a space-filling model of the structurally constrained pore environments. These results are further supported by UV-vis diffuse reflectance, IR, and resonance Raman spectroscopy data.

  1. 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

    2016-08-03

    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.

  2. Mechanisms of bacterially catalyzed reductive dehalogenation

    SciTech Connect

    Picardal, Flynn William

    1992-01-01

    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 14C-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.

  3. Heterogeneous biomimetic catalysis using iron porphyrin for cyclohexane oxidation promoted by chitosan

    NASA Astrophysics Data System (ADS)

    Huang, Guan; Liu, Yao; Cai, Jing Li; Chen, Xiang Feng; Zhao, Shu Kai; Guo, Yong An; Wei, Su Juan; Li, Xu

    2017-04-01

    This study investigates how ligands modulate metalloporphyrin activity with the goal of producing a practical biomimetic catalyst for use in the chemical industry. We immobilized iron porphyrinate [iron-tetrakis-(4-sulfonatophenyl)-porphyrin; Fe(III) (TPPS)] on powdered chitosan (pd-CTS) to form an immobilized catalyst Fe(III) (TPPS)/pd-CTS, which was characterized using modern spectroscopic techniques and used for catalytic oxidation of cyclohexane with O2. Amino coordination to iron porphyrin in Fe(III) (TPPS)/pd-CTS altered the electron cloud density around the iron cation, probably by reducing the activation energy of Fe(III) (TPPS) and raising the reactivity of the iron ion catalytic center, thereby improving the catalytic efficiency. One milligram of Fe(III) (TPPS) catalyst can be reused three times for the oxidation reaction to yield an average of 22.9 mol% of cyclohexanone and cyclohexanol.

  4. 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

  5. Detection of alkylperoxo and ferryl, (Fe sup IV = O) sup 2+ , intermediates during the reaction of tert-butyl hydroperoxide with iron porphyrins in toluene solution

    SciTech Connect

    Arasasingham, R.D.; Cornman, C.R.; Balch, A.L. )

    1989-11-27

    PFe{sup II} and PFe{sup III}OH (P is a porphyrin dianion) catalyze the decomposition of tert-butyl hydroperoxide in toluene solution without appreciable attack on the porphyrin ligand. {sup 1}H NMR spectroscopic studies at low temperature ({minus}70{degree}C) give evidence for the formation of a high-spin, five-coordinate intermediate, PFe{sup III}OOC(CH{sub 3}){sub 3}. Organic products formed from this reaction are tert-butyl alcohol, di-tert-butyl peroxide, benzaldehyde, acetone, and benzyl-tert-butyl peroxide, which arise largely from a radical chain process initiated by the iron porphyrin but continuing without its intervention.

  6. Physicochemical peculiarities of iron porphyrin-containing electrodes in catalase- and peroxidase-type biomimetic sensors

    NASA Astrophysics Data System (ADS)

    Sardarly, N. A.; Nagiev, T. M.

    2009-08-01

    New catalase- and peroxidase-type iron porphyrin biomimetic electrodes have been developed for determining ultralow concentrations of H2O2 and C2H5OH in aqueous solutions. Their physicochemical features have been studied. A mechanism of catalase and peroxidase reactions was suggested. Biomimetic electrodes did not lose their activity for a long time under the action of the oxidant, intermediates, and the final products of the decomposition of H2O2. Potentiometric biomimetic sensors of catalase and peroxidase types have been designed and studied.

  7. 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.

  8. 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.

  9. 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.

  10. Copper-catalyzed asymmetric reduction of 3,3-diarylacrylonitriles.

    PubMed

    Lee, Daehyung; Yang, Youngmin; Yun, Jaesook

    2007-07-05

    CuH-catalyzed enantioselective conjugate reduction of 3,3-diaryl-substituted acrylonitriles is described. A range of 3-aryl-3-pyridylacrylonitriles were reduced with high levels of enantioselectivity under optimal conditions employing a copper/Josiphos complex in the presence of polymethylhydrosiloxane (PMHS).

  11. Methodological CASPT2 study of the valence excited states of an iron-porphyrin complex.

    PubMed

    Ben Amor, Nadia; Soupart, Adrien; Heitz, Marie-Catherine

    2017-02-01

    The singlet valence excited states of an iron-porphyrin-pyrazine-carbonyl complex are investigated up to the Soret band (about 3 eV) using multi-state complete active space with perturbation at the second order (MS-CASPT2). This complex is a model for the active site of carboxy-hemoglobin/myoglobin. The spectrum of the excited states is rather dense, comprising states of different nature: d→π* transitions, d→d states, π→π* excitations of the porphyrin, and doubly excited states involving simultaneous intra-porphyrin π→π* and d→d transitions. Specific features of the MS-CASPT2 method are investigated. The effect of varying the number of roots in the state average calculation is quantified as well as the consequence of targeted modifications of the active space. The effect of inclusion of standard ionization potential-electron affinity (IPEA) shift in the perturbation treatment is also investigated.

  12. Aldose Reductase-catalyzed Reduction of Aldehyde Phospholipids

    PubMed Central

    Srivastava, Sanjay; Spite, Matthew; Trent, John O.; West, Matthew B.; Ahmed, Yonis; Bhatnagar, Aruni

    2012-01-01

    SUMMARY Oxidation of unsaturated phospholipids results in the generation of aldehyde side chains that remain esterified to the phospholipid backbone. Such “core” aldehydes elicit immune responses and promote inflammation. However, the biochemical mechanisms by which phospholipid aldehydes are metabolized or detoxified are not well understood. In the studies reported here, we examined whether aldose reductase (AR), which reduces hydrophobic aldehydes, metabolizes phospholipid aldehydes. Incubation with AR led to the reduction of 5-oxovaleroyl, 7-oxo-5-heptenoyl, 5-hydroxy-6-oxo-caproyl, and 5-hydroxy-8-oxo-6-octenoyl phospholipids generated upon oxidation of 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine (PAPC). The enzyme also catalyzed the reduction of phospholipid aldehydes generated from the oxidation of 1-alkyl, and 1-alkenyl analogs of PAPC, and 1-palmitoyl-2-arachidonoyl phosphatidic acid or phosphoglycerol. Aldose reductase catalyzed the reduction of chemically synthesized 1-palmitoyl-2-(5-oxovaleroyl)-sn-glycero-3-phosphatidylcholine (POVPC) with a Km of 10 μM. Addition of POVPC to the culture medium led to incorporation and reduction of the aldehyde in COS-7 and THP-1 cells. Reduction of POVPC in these cells was prevented by the AR inhibitors sorbinil and tolrestat and was increased in COS-7 cells overexpressing AR. Together, these observations suggest that AR may be a significant participant in the metabolism of several structurally diverse phospholipid aldehydes. This metabolism may be a critical regulator of the pro-inflammatory and immunogenic effects of oxidized phospholipids. PMID:15465833

  13. Effect of amino acid ligands on the structure of iron porphyrins and their ability to bind oxygen.

    PubMed

    Berryman, Victoria E J; Baker, Matthew G; Boyd, Russell J

    2014-06-26

    Density functional theory is used to study a series of model iron porphyrins in the gas phase. In the first part of this study, three range-separated hybrid density functionals developed by Chai and Head-Gordon were assessed; ωB97, ωB97X, and ωB97XD. The effects of including full Hartree-Fock exchange at long-range and dispersion corrections are reported with respect to the geometries and binding energies of oxygen to the iron porphyrin systems. The functionals all correctly predict the quintet ground state for the deoxy-iron porphyrins, where typically hybrid functionals fail and predict a triplet ground state. Including dispersion in ωB97XD is shown to give the best results for the O2 binding energy and geometrical parameters. The second part of the study employs ωB97XD to study iron porphine systems with different amino acids in the axial position. Geometrical parameters are reported and compared to experimental data, where available. Binding energies of the systems with oxygen are also reported and discussed.

  14. 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.

  15. The axial ligand effect of oxo-iron porphyrin catalysts. How does chloride compare to thiolate?

    PubMed

    de Visser, Sam P

    2006-03-01

    We have performed density functional theory calculations on an oxo-iron porphyrin catalyst with chloride as an axial ligand and tested its reactivity toward propene. The reactions proceed via multistate reactivity on competing doublet and quartet spin surfaces. Close-lying epoxidation and hydroxylation mechanisms are identified, whereby in the gas phase the epoxidation reaction is dominant, while in environments with a large dielectric constant the hydroxylation pathways become competitive. By contrast to reactions with thiolate as an axial ligand all low-lying pathways have small ring-closure and rebound barriers, so it is expected that side products and rearrangements will be unlikely with Fe=O(porphyrin)Cl, whereas with Fe=O(porphyrin)SH some side products were predicted. The major differences in the electronic configurations of Fe=O(porphyrin)Cl and Fe=O(porphyrin)SH are due to strong mixing of thiolate orbitals with iron 3d orbitals, a mixing which is much less with chloride as an axial ligand. Predictions of the reactivity of ethylbenzene-h (12) versus ethylbenzene-d (12) are made.

  16. Iridium-catalyzed reductive nitro-Mannich cyclization.

    PubMed

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

    2015-01-02

    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Human carbonyl reductase catalyzes reduction of 4-oxonon-2-enal.

    PubMed

    Doorn, Jonathan A; Maser, Edmund; Blum, Andreas; Claffey, David J; Petersen, Dennis R

    2004-10-19

    4-Oxonon-2-enal (4ONE) was demonstrated to be a product of lipid peroxidation, and previous studies found that it was highly reactive toward DNA and protein. The present study sought to determine whether carbonyl reductase (CR) catalyzes reduction of 4ONE, representing a potential pathway for metabolism of the lipid peroxidation product. Recombinant CR was cloned from a human liver cDNA library, expressed in Escherichia coli, and purified by metal chelate chromatography. Both 4ONE and its glutathione conjugate were found to be substrates for CR, and kinetic parameters were calculated. TLC analysis of reaction products revealed the presence of three compounds, two of which were identified as 4-hydroxynon-2-enal (4HNE) and 1-hydroxynon-2-en-4-one (1HNO). GC/MS analysis confirmed 4HNE and 1HNO and identified the unknown reaction product as 4-oxononanal (4ONA). Analysis of oxime derivatives of the reaction products via LC/MS confirmed the unknown as 4ONA. The time course for CR-mediated, NADPH-dependent 4ONE reduction and appearance of 4HNE and 1HNO was determined using HPLC, demonstrating 4HNE to be a major product and 1HNO and 4ONA to be minor products. Simulated structures of 4ONE in the active site of CR/NADPH calculated via docking experiments predict the ketone positioned as primary hydride acceptor. Results of the present study demonstrate that 4ONE is a substrate for CR/NADPH and the enzyme may represent a pathway for biotransformation of the lipid. Furthermore, these findings reveal that CR catalyzes hydride transfer selectively to the ketone but also to the aldehyde and C=C of 4ONE, resulting in 4HNE, 1HNO, and 4ONA, respectively.

  18. Assistance of the iron porphyrin ligands to the binding interaction between the Fe center and small molecules in solution.

    PubMed

    Xiao, Jie; Golnak, Ronny; Atak, Kaan; Pflüger, Mika; Pohl, Marvin; Suljoti, Edlira; Winter, Bernd; Aziz, Emad F

    2014-08-07

    Solute-solvent electronic structure interactions of iron porphyrin at very low concentration in dichloromethane (CH2Cl2) liquid solution are reported. Two iron porphyrin complexes are investigated here-iron octaethylporphyrin chloride (FeOEP-Cl) and iron tetraphenylporphyrin chloride (FeTPP-Cl)-using X-ray absorption and emission spectroscopy at the Fe L2,3 edge, and spectra are interpreted with the help of density functional theory/restricted open-shell configuration interaction singles (DFT/ROCIS) calculations. It is argued that the Fe center of FeOEP-Cl is more capable of binding small solvent molecules, exemplified here for Cl2CH2, than FeTPP-Cl in solution. The proposed binding mechanism is through the assistance of the dipole interaction between the porphyrin-ligand system and the solvent molecule, in a situation where the ligand structure and arrangement maximize the binding interactions. Our studies demonstrate that even small ligands, depending on their structure and arrangement, can have considerable effects on porphyrin's metal center chemistry in liquid solution.

  19. Interaction of nitrogen bases with iron-porphyrin nitrito complexes Fe(Por)(ONO) in sublimed solids.

    PubMed

    Kurtikyan, Tigran S; Hovhannisyan, Astghik A; Gulyan, Gurgen M; Ford, Peter C

    2007-08-20

    The reactions of the nitrogen Lewis bases (B) 1-methylimidazole (1-MeIm), pyridine (Py), and NH3 as gases with sublimed layers containing the 5-coordinate nitrito iron(III)-porphyrinato complexes Fe(Por)(eta1-ONO) (1) are described (Por = meso-tetraphenyl-porphyrinato or meso-tetra-p-tolyl-porphyrinato dianions). In situ FTIR and optical spectra are used to characterize the formation of the 6-coordinate nitro complexes formed by the reaction of 1 with B = 1-MeIm, Py, or NH3. These represent the first examples of 6-coordinate amino-nitro complexes with sterically unprotected iron-porphyrins. The interaction of ammonia with Fe(Por)(ONO) at 140 K initially led to the nitrito species Fe(Por)(NH3)(eta1-ONO), and this species isomerized to the nitro complexes Fe(Por)(NH3)(eta1-NO2) upon warming to 180 K. When the latter were warmed to room temperature under intense pumping, the initial nitrito complexes Fe(Por)(eta1-ONO) were restored. Assignments of vibrational frequencies for the coordinated nitro group in 6-coordinate iron-porphyrin complexes are given and confirmed using 15N-labeled nitrogen dioxide to identify characteristic infrared bands. For M(Por)(B)(NO2) complexes (M = Fe or Co), an inverse correlation between the net charge transfer from the axial ligand B to the nitro group and the value of Deltanu = nua(NO2) - nus(NO2) is proposed. These observations are discussed in the context of growing interest in potential physiological roles of nitrite ion reactions with ferro- and ferri-heme proteins.

  20. Chemoselective, Enzymatic C-H Bond Amination Catalyzed by a Cytochrome P450 Containing an Ir(Me)-PIX Cofactor.

    PubMed

    Dydio, Paweł; Key, Hanna M; Hayashi, Hiroki; Clark, Douglas S; Hartwig, John F

    2017-02-08

    Cytochrome P450 enzymes have been engineered to catalyze abiological C-H bond amination reactions, but the yields of these reactions have been limited by low chemoselectivity for the amination of C-H bonds over competing reduction of the azide substrate to a sulfonamide. Here we report that P450s derived from a thermophilic organism and containing an iridium porphyrin cofactor (Ir(Me)-PIX) in place of the heme catalyze enantioselective intramolecular C-H bond amination reactions of sulfonyl azides. These reactions occur with chemoselectivity for insertion of the nitrene units into C-H bonds over reduction of the azides to the sulfonamides that is higher and with substrate scope that is broader than those of enzymes containing iron porphyrins. The products from C-H amination are formed in up to 98% yield and ∼300 TON. In one case, the enantiomeric excess reaches 95:5 er, and the reactions can occur with divergent site selectivity. The chemoselectivity for C-H bond amination is greater than 20:1 in all cases. Variants of the Ir(Me)-PIX CYP119 displaying these properties were identified rapidly by evaluating CYP119 mutants containing Ir(Me)-PIX in cell lysates, rather than as purified enzymes. This study sets the stage to discover suitable enzymes to catalyze challenging C-H amination reactions.

  1. Iodide-catalyzed reductions: development of a synthesis of phenylacetic acids.

    PubMed

    Milne, Jacqueline E; Storz, Thomas; Colyer, John T; Thiel, Oliver R; Dilmeghani Seran, Mina; Larsen, Robert D; Murry, Jerry A

    2011-11-18

    A new convenient and scalable synthesis of phenylacetic acids has been developed via the iodide catalyzed reduction of mandelic acids. The procedure relies on in situ generation of hydroiodic acid from catalytic sodium iodide, employing phosphorus acid as the stoichiometric reductant.

  2. 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.

  3. Iron porphyrin-modified PVDF membrane as a biomimetic material and its effectiveness on nitric oxide binding

    NASA Astrophysics Data System (ADS)

    Can, Faruk; Demirci, Osman Cahit; Dumoulin, Fabienne; Erhan, Elif; Arslan, Leyla Colakerol; Ergenekon, Pınar

    2017-10-01

    Nitric oxide (NO) is a reactive gas well-known as an air pollutant causing severe environmental problems. NO is also an important signaling molecule having a strong affinity towards heme proteins in the body. Taking this specialty as a model, a biomimetic membrane was developed by modification of the membrane surface with iron-porphyrin which depicts very similar structure to heme proteins. In this study, PVDF membrane was coated with synthesized (4-carboxyphenyl)-10,15,20-triphenyl-porphyrin iron(III) chloride (FeCTPP) to promote NO fixation on the surface. The coated membrane was characterized in terms of ATR-IR spectra, contact angle measurement, chemical composition, and morphological structure. Contact angle of original PVDF first decreased sharply after plasma treatment and surface polymerization steps but after incorporation of FeCTPP, the surface acquired its hydrophobicity again. NO binding capability of modified membrane surface was evaluated on the basis of X-ray Photoelectron. Upon exposure to NO gas, a chemical shift of Fe+3 and appearance of new N peak was observed due to the electron transfer from NO ligand to Fe ion with the attachment of nitrosyl group to FeCTPP. This modification brings the functionality to the membrane for being used in biological systems such as membrane bioreactor material in biological NO removal technology.

  4. Enantioselective imine reduction catalyzed by imine reductases and artificial metalloenzymes.

    PubMed

    Gamenara, Daniela; Domínguez de María, Pablo

    2014-05-21

    Adding value to organic synthesis. Novel imine reductases enable the enantioselective reduction of imines to afford optically active amines. Likewise, novel bioinspired artificial metalloenzymes can perform the same reaction as well. Emerging proof-of-concepts are herein discussed.

  5. Reductive dechlorination of tetrachloroethylene (PCE) catalyzed by cyanocobalamin

    SciTech Connect

    Habeck, B.D.; Sublette, K.L.

    1995-12-31

    A biomimetic system has been developed for the reductive dechlorination of tetrachloroethylene (PCE). PCE was dechlorinated to trichloroethylene (TCE) and 1,2-dichloroethylene (DCE) in the presence of dithiothreitol or Ti (III) citrate and catalytic amounts of cyanocobalamin in both homogeneous reaction mixtures and packed bed reactor systems. In packed bed reactors with Ti (III) citrate as the reductant, PCE (0.18 mM) conversion averaged 55% at residence times of 1.75 and 3.5 h. The product distribution was 94% TCE and 6% DCE at the lower residence time. DCE formation increased to 45% at the higher residence time. No reduction of PCE was observed in the absence of cyanocobalamin. This system may be useful as a means of pretreatment of halogenated aliphatic hydrocarbons in advance of biological treatment.

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

    PubMed

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

    2012-11-27

    A doubly substituted form of the nitrogenase MoFe protein (α-70(Val)(→Ala), α-195(His→Gln)) has the capacity to catalyze the reduction of carbon dioxide (CO(2)) to yield methane (CH(4)). Under optimized conditions, 1 nmol of the substituted MoFe protein catalyzes the formation of 21 nmol of CH(4) within 20 min. The catalytic rate depends on the partial pressure of CO(2) (or concentration of HCO(3)(-)) and the electron flux through nitrogenase. The doubly substituted MoFe protein also has the capacity to catalyze the unprecedented formation of propylene (H(2)C = CH-CH(3)) through the reductive coupling of CO(2) 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 CO(2) sequestration and formation of olefins.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. Enantioselective Brønsted acid catalyzed transfer hydrogenation: organocatalytic reduction of imines.

    PubMed

    Rueping, Magnus; Sugiono, Erli; Azap, Cengiz; Theissmann, Thomas; Bolte, Michael

    2005-08-18

    The first enantioselective Brønsted acid catalyzed reduction of imines has been developed. This new organocatalytic transfer hydrogenation of ketimines with Hantzsch dihydropyridine as the hydrogen source offers a mild method to various chiral amines with high enantioselectivity. The stereochemistry of the chiral amines can be rationalized by a stereochemical model derived from an X-ray crystal structure of a chiral BINOL phosphate catalyst. [reaction: see text

  12. Proton-coupled oxygen reduction at liquid-liquid interfaces catalyzed by cobalt porphine.

    PubMed

    Hatay, Imren; Su, Bin; Li, Fei; Méndez, Manuel Alejandro; Khoury, Tony; Gros, Claude P; Barbe, Jean-Michel; Ersoz, Mustafa; Samec, Zdenek; Girault, Hubert H

    2009-09-23

    Cobalt porphine (CoP) dissolved in the organic phase of a biphasic system is used to catalyze O(2) reduction by an electron donor, ferrocene (Fc). Using voltammetry at the interface between two immiscible electrolyte solutions (ITIES), it is possible to drive this catalytic reduction at the interface as a function of the applied potential difference, where aqueous protons and organic electron donors combine to reduce O(2). The current signal observed corresponds to a proton-coupled electron transfer (PCET) reaction, as no current and no reaction can be observed in the absence of either the aqueous acid, CoP, Fc, or O(2).

  13. Ruthenium Catalyzed Reductive Coupling of Paraformaldehyde to Trifluoromethyl Allenes: CF3-Bearing All-Carbon Quaternary Centers

    PubMed Central

    Sam, Brannon; Montgomery, T. Patrick; Krische, Michael J.

    2013-01-01

    Trifluoromethyl substituted allenes engage in ruthenium catalyzed reductive couplings with paraformaldehyde to form products of hydrohydroxymethylation as single regioisomers. This method enables generation of CF3-bearing all-carbon quaternary stereocenters. PMID:23841678

  14. 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.

  15. Role of reductants in CuZSM-5 catalyzed NOx reduction

    SciTech Connect

    Bhore, N.A.; Dwyer, F.G.; Marler, D.O.; McWilliams, J.P.

    1993-12-31

    The implementation of clean burn engines is limited by technology to efficiently remove nitrogen oxides from the net oxidizing exhaust composition. High NO{sub x} conversions require the preferential reaction of reductants (hydrogen, carbon monoxide, olefins and paraffins) with nitrogen oxides over that of combustion. This study examines the role of these reactions over CuZM-5 catalyst in a simulated lean burn engine exhaust. By careful addition of a known amount of individual reductant over fresh and aged catalysts, the authors find that propylene is the primary-reductant for NO{sub x} conversion; hydrogen and carbon monoxide are not. For stoichiometric-burn engines, carbon monoxide and hydrogen are known to be primary reductants on three-way catalysts. Other light olefins such as isobutylene and ethylene are also effective in NO{sub x} reduction. Paraffins are much less effective. The efficacy of olefin reductant decreases on aging.

  16. 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

    2013-05-07

    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.

  17. 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

  18. Cytochromes P450 catalyze the reduction of α,β-unsaturated aldehydes.

    PubMed

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

    2011-08-15

    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, O(2), 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 and 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 a 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 the reduction of α,β-unsaturated aldehydes in the liver.

  19. Reduction of nitric oxide catalyzed by hydroxylamine oxidoreductase from an anammox bacterium.

    PubMed

    Irisa, Tatsuya; Hira, Daisuke; Furukawa, Kenji; Fujii, Takao

    2014-12-01

    The hydroxylamine oxidoreductase (HAO) from the anammox bacterium, Candidatus Kuenenia stuttgartiensis has been reported to catalyze the oxidation of hydroxylamine (NH2OH) to nitric oxide (NO) by using bovine cytochrome c as an oxidant. In contrast, we investigated whether the HAO from anammox bacterium strain KSU-1 could catalyze the reduction of NO with reduced benzyl viologen (BVred) and the NO-releasing reagent, NOC 7. The reduction proceeded, resulting in the formation of NH2OH as a product. The oxidation rate of BVred was proportional to the concentration of BVred itself for a short period in each experiment, a situation that was termed quasi-steady state. The analyses of the states at various concentrations of HAO allowed us to determine the rate constant for the catalytic reaction, (2.85 ± 0.19) × 10(5) M(-1) s(-1), governing NO reduction by BVred and HAO, which was comparable to that reported for the HAO from the ammonium oxidizer, Nitrosomonas with reduced methyl viologen. These results suggest that the anammox HAO functions to adjust anammox by inter-conversion of NO and NH2OH depending on the redox potential of the physiological electron transfer protein in anammox bacteria. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  20. Enantioselective Synthesis of β-Arylamines via Chiral Phosphoric Acid-Catalyzed Asymmetric Reductive Amination.

    PubMed

    Kim, Kyung-Hee; Lee, Chun-Young; Cheon, Cheol-Hong

    2015-06-19

    A new method for the synthesis of chiral β-aryl amines via chiral phosphoric acid-catalyzed enantioselective reductive amination of benzyl methyl ketone derivatives with Hantzsch ester was developed. Various chiral β-aryl amines were obtained in high yields and with good to high enantioselectivities. This transformation is applicable to gram-scale reactions, and the catalyst loading can be reduced to 1 mol % without sacrificing any catalytic efficacy. Furthermore, the resulting β-aryl amine was successfully converted into a tetrahydroisoquinoline compound without any loss of enantioselectivity.

  1. Resonance Raman, electron paramagnetic resonance, and density functional theory calculations of a phenolate-bound iron porphyrin complex: electrostatic versus covalent contribution to bonding.

    PubMed

    Das, Pradip Kumar; Dey, Abhishek

    2014-07-21

    Resonance Raman (rR), electron paramagnetic resonance (EPR), and density functional theory (DFT) calculations of a phenolate-bound iron porphyrin complex are reported. The complex is found to exist in a five-coordinate high-spin state in a noncoordinating solvent and in a six-coordinate low-spin state in a coordinating solvent. The vibrations originating from the iron phenolate-bound chromophores reproduced those reported for heme tyrosine active sites in nature. The EPR parameters and iron-pyrrole (Fe-Npyr) vibrations of phenolate, thiolate, and imidazole ligated iron porphyrin complexes indicate that the phenolate axial ligand acts as a π anisotropic ligand, which is more covalent than a neutral imidazole ligand but less covalent than a thiolate axial ligand. While the Fe(III/II) potential of the phenolate compound in a noncoordinating solvent is 500 mV more negative than that of the imidazole-bound complex, it is also 110 mV more negative than that of the thiolate-bound complex. DFT calculations reproduce the geometry and vibrational frequencies and show that while both phenolate and thiolate axial ligands bear π and σ interaction with the ferric center, the former is significantly less covalent than the thiolate. The higher covalency of the thiolate ligand is responsible for the lower Fe-Npyr vibration and higher V/λ (from EPR) of the thiolate-bound complexes relative to those of the phenolate-bound complex, whereas the greater electrostatic stabilization of the Fe(III)-OPh bond is responsible for lowering the Fe(III/II) E° of the phenolate-bound complex relative to that of the thiolate-bound complex in a medium having a reasonable dielectric constant.

  2. Computational studies of face-to-face porphyrin catalyzed reduction of dioxygen.

    SciTech Connect

    Ingersoll, David T.; Muller, Richard Partain, Dr.

    2004-08-01

    We are investigating the use of face-to-face porphyrin (FTF) materials as potential oxygen reduction catalysts in fuel cells. The FTF materials were popularized by Anson and Collman, and have the interesting property that varying the spacing between the porphyrin rings changes the chemistry they catalyze from a two-electron reduction of oxygen to a four-electron reduction of oxygen. Our goal is to understand how changes in the structure of the FTF materials lead to either two-electron or four-electron reductions. This understand of the FTF catalysis is important because of the potential use of these materials as fuel cell electrocatalysts. Furthermore, the laccase family of enzymes, which has been proposed as an electrocatalytic enzyme in biofuel cell applications, also has family members that display either two-electron or four electron reduction of oxygen, and we believe that an understanding of the structure-function relationships in the FTF materials may lead to an understanding of the behavior of laccase and other enzymes. We will report the results of B3LYP density functional theory studies with implicit solvent models of the reduction of oxygen in several members of the cobalt FTF family.

  3. Oxygen reduction catalyzed by a fluorinated tetraphenylporphyrin free base at liquid/liquid interfaces.

    PubMed

    Hatay, Imren; Su, Bin; Méndez, Manuel A; Corminboeuf, Clémence; Khoury, Tony; Gros, Claude P; Bourdillon, Mélanie; Meyer, Michel; Barbe, Jean-Michel; Ersoz, Mustafa; Zális, Stanislav; Samec, Zdenek; Girault, Hubert H

    2010-10-06

    The diprotonated form of a fluorinated free base porphyrin, namely 5-(p-aminophenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (H(2)FAP), can catalyze the reduction of oxygen by a weak electron donor, namely ferrocene (Fc). At a water/1,2-dichloroethane interface, the interfacial formation of H(4)FAP(2+) is observed by UV-vis spectroscopy and ion-transfer voltammetry, due to the double protonation of H(2)FAP at the imino nitrogen atoms in the tetrapyrrole ring. H(4)FAP(2+) is shown to bind oxygen, and the complex in the organic phase can easily be reduced by Fc to produce hydrogen peroxide as studied by two-phase reactions with the Galvani potential difference between the two phases being controlled by the partition of a common ion. Spectrophotometric measurements performed in 1,2-dichloroethane solutions clearly evidence that reduction of oxygen by Fc catalyzed by H(4)FAP(2+) only occurs in the presence of the tetrakis(pentafluorophenyl)borate (TB(-)) counteranion in the organic phase. Finally, ab initio computations support the catalytic activation of H(4)FAP(2+) on oxygen.

  4. Reduction of xylose to xylitol catalyzed by glucose-fructose oxidoreductase from Zymomonas mobilis.

    PubMed

    Zhang, Xiaomei; Chen, Guanjun; Liu, Weifeng

    2009-04-01

    Genetic improvements of Zymomonas mobilis for pentose utilization have a huge potential in fuel ethanol production. The production of xylitol and the resulting growth inhibition by xylitol phosphate have been considered to be one of the important factors affecting the rates and yields from xylose metabolism by the recombinant Z. mobilis, but the mechanism of xylitol formation is largely unknown. Here, we reported that glucose-fructose oxidoreductase (GFOR), a periplasmic enzyme responsible for sorbitol production, catalyzed the reduction of xylose to xylitol in vitro, operating via a ping-pong mechanism similar to that in the formation of sorbitol. However, the specific activity of GFOR for sorbitol was higher than that for xylitol (68.39 vs. 1.102 micromol min(-1) mg(-1)), and an apparent substrate-induced positive cooperativity occurred during the catalyzed formation of xylitol, with the Hill coefficient being about 2. While a change of the potential acid-base catalyst Tyr269 to Phe almost completely abolished the activity toward xylose as well as fructose, mutant S116D, which has been shown to lose tight cofactor binding, displayed an even slower catalytic process against xylose.

  5. Ni-catalyzed reductive homocoupling of unactivated alkyl bromides at room temperature and its synthetic application.

    PubMed

    Peng, Yu; Luo, Long; Yan, Chang-Song; Zhang, Jian-Jian; Wang, Ya-Wen

    2013-11-01

    A room-temperature Ni-catalyzed reductive approach to homocoupling of unactivated primary, secondary, and tertiary alkyl bromides is described. The catalytic system can be easily generated from air-stable and cheap materials and demonstrates broad functional group tolerance, thus allowing facile access to useful dimeric triterpene and lignan-like molecules. Moreover, the dimerization of tertiary bromide 6 efficiently establishes sterically hindered vicinal quaternary carbons (C3a and C3a'), which is a key linkage of intriguing bispyrrolo[2,3-b]indoline alkaloids, thereby enabling us to complete the total syntheses of racemic chimonanthine (9) and folicanthine (10). In addition, this dimerization method can be expanded to the highly stereoselective synthesis of bisperhydrofuro[2,3-b]furan (5a) and the dimeric spiroketal 5b, signifying the involvement of possible radical species.

  6. A highly efficient buckypaper-based electrode material for mediatorless laccase-catalyzed dioxygen reduction.

    PubMed

    Hussein, L; Rubenwolf, S; von Stetten, F; Urban, G; Zengerle, R; Krueger, M; Kerzenmacher, S

    2011-06-15

    The redox enzyme laccase from Trametes versicolor efficiently catalyzes the oxygen reduction reaction (ORR) in mediatorless biofuel cell cathodes when adsorbed onto multi-walled carbon nanotubes (MWCNTs). In this work we demonstrate that the fabrication of MWCNTs in form of buckypaper (BP) results in an excellent electrode material for laccase-catalyzed cathodes. BPs are mechanically stable, self-entangling mats with high dispersion of MWCNTs resulting in easy to handle homogeneous layers with highly mesoporous structures and excellent electrical conductivities. All biocathodes have been electrochemically investigated in oxygen-saturated buffer at pH 5 by galvanostatic polarization and potentiodynamic linear sweep voltammetry. Both methods confirm an efficient direct interaction of laccase with BP with a high open circuit potential of 0.882 V vs. normal hydrogen electrode (NHE). The high oxygen reduction performance leads to high current densities of 422±71 μA cm(-2) at a typical cathode potential of 0.744 V vs. NHE. When the current density is normalized to the mass of the electrode material (mass activity), the BP-based film electrodes exhibit a 68-fold higher current density at 0.744 V vs. NHE than electrodes fabricated from the same MWCNTs in a non-dispersed agglomerated form as packed electrodes. This clearly shows that MWCNTs can act more efficiently as cathode when prepared in form of BP. This can be attributed to reduced diffusional mass transfer limitations and enhanced electrical conductivity. BP is thus a very promising material for the construction of mediatorless laccase cathodes for ORR in biofuel cells. In addition we demonstrated that these electrodes exhibit a high tolerance towards glucose, the most common bioanode fuel. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. Ability of different biomaterials to enantioselectively catalyze oxidation and reduction reactions.

    PubMed

    Nagaoka, Hiroyuki

    2004-01-01

    We studied the ability of different biomaterials to enantioselectively catalyze oxidation or reduction reactions with the help of substrate rac-1-m or p-ArCH(OH)Me and the 1-o-ArC(O)Me derivatives. Apoenzyme (NAD(P)(+)-dependent secondary alcohol dehydrogenase(NAD(P)-E)) and cofactor (NAD(P)(+)) were activated by preincubating immobilized aqueous plant leaf (e.g., young wheat leaves), cereal tissue (wheat bran), vegetable (e.g., carrot), and seaweed (e.g., wakame seaweed) solutions, and the NAD(P)-E oxidized only (R)-isomers highly enantioselectively. Thus, greater than 99% ee(s) of (S)-isomers (1m-5m and 1p-5p) can be obtained from corresponding rac-1-m or p-ArCH(OH)Me. Further, immobilized chlorella cells and immobilized baker's yeast can reduce highly stereoselectively; greater than 99% ee(s) of (S)-isomers (1o-5o) can be obtained from corresponding 1-o-ArC(O)Me. Specific use of each isomer ((S)-6 and (R)-6) with greater than 99% ee(s) of racemic-1-2-NpCH(OH)Me becomes possible through selective use of NAD(P)-E eluted from artemisia vulgaris indica leaves and young wheat leaves. We suggest that the pH of the reaction media can determine not only the direction of NAD(P)-E, toward enantioselectively catalyzed oxidation (pH > 7.0) or reduction reaction (pH < 7.0), but also the regioselective reactivity of NAD(P)-E to the substrate o- (pH < 7.0), m-, and p-substituted groups (pH > 7.0). Thus, in comparison to current biocatalysts, several biomaterials can serve as asymmetric reagent bases, providing easily obtained, low-cost natural catalysts with stereoselectivity, regioselectivity, and substrate specificity that work under mild conditions for asymmetric synthesis of organic compounds.

  8. Capacity of reductants and chelators to prevent lipid oxidation catalyzed by fish hemoglobin.

    PubMed

    Maestre, Rodrigo; Pazos, Manuel; Iglesias, Jacobo; Medina, Isabel

    2009-10-14

    The efficiency of different reductants (reduced glutathione, ascorbic acid, and catalase) and metal chelators [ethylenediaminetetraacetic acid (EDTA), citric acid, sodium tripolyphosphate (STPP), and adenosine-5'-triphosphate (ATP)] to inhibit lipid oxidation promoted by fish hemoglobin was investigated. The inhibitory activity on hemoglobin-catalyzed lipid oxidation was also evaluated for grape oligomeric catechins (proanthocyanidins), which have both reducing and chelating properties. The antioxidant activity was studied in two different lipid oxidation models, liposomes and washed minced fish muscle. Grape proanthocyanidins were found to be significantly more effective than other reductants to prevent hemoglobin-mediated lipid oxidation in both liposomes and washed fish muscle. Reduced glutathione was also efficient to retard lipid oxidation at the same molarity in washed fish muscle, whereas catalase and ascorbic acid showed a lower antioxidant activity. Metal chelators were less active than reductants, and consequently, the former were necessarily evaluated at much higher concentration than grape proanthocyanidins and reducing compounds. STPP was found to be the iron chelator with the strongest efficiency to delay hemoglobin-mediated lipid oxidation followed by EDTA. Citric acid and ATP were ineffective in retarding lipid oxidation in both systems. Grape proanthocyanidins provided the most extensive protection to preserve hemoglobin at ferrous state in washed fish muscle. Our results draw attention to the greater capacity of reducing compounds to prevent fish hemoglobin-mediated lipid oxidation in comparison with iron chelators, suggesting that the free radical scavenging and/or reduction of ferrylHb species are crucial actions to avoid the pro-oxidant capacity of fish hemoglobin.

  9. Asymmetric reduction of α-amino ketones with a KBH4 solution catalyzed by chiral Lewis acids.

    PubMed

    He, Peng; Zheng, Haifeng; Liu, Xiaohua; Lian, Xiangjin; Lin, Lili; Feng, Xiaoming

    2014-10-13

    An efficient enantioselective reduction of α-amino ketones with potassium borohydride solution catalyzed by chiral N,N'-dioxide-metal complex catalysts was accomplished under mild reaction conditions for the first time. It provided a simple, convenient, and practical approaches for obtaining synthetically important chiral β-amino alcohols in good to excellent yields (up to 98%) and enantioselectivities (up to 97% ee).

  10. 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

  11. Vitamin A as an enzyme that catalyzes the reduction of MTT to formazan by vitamin C.

    PubMed

    Chakrabarti, R; Kundu, S; Kumar, S; Chakrabarti, R

    2000-09-18

    The tetrazolium salt 3(4,5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) is reduced to formazan by the succinate dehydrogenase system of active mitochondria, and hence, specifically used to assay for the viable cells, such as measurement of cell proliferation, cytotoxicity, and cell number. However, in the present study we have shown that some component specifically present in M199 but not in RPMI 1640 media can reduce MTT to formazan in the absence of a living system. Further study revealed that ascorbic acid reduced MTT to formazan, which was profoundly increased by a very small amount of retinol, whereas retinol alone had no effect. Oxidation of ascorbic acid by H(2)O(2) destroyed its ability to reduce MTT. The rate of MTT reduction was directly proportional to the concentration of MTT in the absence of retinol, but approached a zero-order state beyond a certain concentration of MTT in the presence of retinol. Furthermore, retinol remained unchanged after the completion of the reaction. Taken together, these results showed that retinol acts as a reductase that catalyzes the reduction of MTT to formazan using ascorbic acid as the cosubstrate (electron donor).

  12. 3D origami electrochemical device for sensitive Pb(2+) testing based on DNA functionalized iron-porphyrinic metal-organic framework.

    PubMed

    Wang, Xiu; Yang, Chunlei; Zhu, Shaojun; Yan, Mei; Ge, Shenguang; Yu, Jinghua

    2017-01-15

    A highly sensitive electrochemical (EC) biosensor combined with a 3D origami device for detection of Pb(2+)was developed based on novel Au nanoparticles modified paper working electrode (Au-PWE) as sensor platform and DNA functionalized iron-porphyrinic metal-organic framework ((Fe-P)n-MOF-Au-GR) hybrids as signal probes. In the presence of Pb(2+), GR could be specifically cleaved at the ribonucleotide (rA) site, which produced the short (Fe-P)n-MOF-linked oligonucleotide fragment to hybridize with hairpin DNA immobilized on the surface of Au-PWE. Because of the mimic peroxidase property of (Fe-P)n-MOF, enzymatically amplified electrochemical signal was obtained to offer the sensitive detection of Pb(2+). In addition, benefiting from the Pb(2+) dependent GR, the proposed assay could selectively detect Pb(2+) in the presence of other metal ions. This method showed a good linear relationship between the current response and the Pb(2+) concentration ranging from 0.03 to 1000nmolL(-1) with a detection limit of 0.02nmolL(-1). The Au-PWE based electrochemical sensor along with the (Fe-P)n-MOF-Au-GR probe exhibited the advantages of low-cost, simple fabrication, high sensitivity and selectivity, providing potential application of real-time Pb(2+) detection both in environmental and biological samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Frontispiece: asymmetric reduction of α-amino ketones with a KBH4 solution catalyzed by Chiral Lewis acids.

    PubMed

    He, Peng; Zheng, Haifeng; Liu, Xiaohua; Lian, Xiangjin; Lin, Lili; Feng, Xiaoming

    2014-10-13

    Asymmetric Alkali Metal Borohydride Reduction Alkali metal borohydrides are mild, inexpensive, highly selective, and environmentally friendly reducing agents in organic chemistry. In their Communication on page 13482 ff., X. Feng et al. demonstrate an efficient enantioselective reduction of both secondary and primary α-amino ketones with potassium borohydride solution catalyzed by chiral N,N'-dioxide-metal complex catalysts. The catalytic system features a convenient operation and tolerance to water, without the need for basic additives.

  14. 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.

  15. Reduction of CO2 to methanol catalyzed by a biomimetic organo-hydride produced from pyridine.

    PubMed

    Lim, Chern-Hooi; Holder, Aaron M; Hynes, James T; Musgrave, Charles B

    2014-11-12

    We use quantum chemical calculations to elucidate a viable mechanism for pyridine-catalyzed reduction of CO2 to methanol involving homogeneous catalytic steps. The first phase of the catalytic cycle involves generation of the key catalytic agent, 1,2-dihydropyridine (PyH2). First, pyridine (Py) undergoes a H(+) transfer (PT) to form pyridinium (PyH(+)), followed by an e(-) transfer (ET) to produce pyridinium radical (PyH(0)). Examples of systems to effect this ET to populate PyH(+)'s LUMO (E(0)(calc) ∼ -1.3 V vs SCE) to form the solution phase PyH(0) via highly reducing electrons include the photoelectrochemical p-GaP system (E(CBM) ∼ -1.5 V vs SCE at pH 5) and the photochemical [Ru(phen)3](2+)/ascorbate system. We predict that PyH(0) undergoes further PT-ET steps to form the key closed-shell, dearomatized (PyH2) species (with the PT capable of being assisted by a negatively biased cathode). Our proposed sequential PT-ET-PT-ET mechanism for transforming Py into PyH2 is analogous to that described in the formation of related dihydropyridines. Because it is driven by its proclivity to regain aromaticity, PyH2 is a potent recyclable organo-hydride donor that mimics important aspects of the role of NADPH in the formation of C-H bonds in the photosynthetic CO2 reduction process. In particular, in the second phase of the catalytic cycle, which involves three separate reduction steps, we predict that the PyH2/Py redox couple is kinetically and thermodynamically competent in catalytically effecting hydride and proton transfers (the latter often mediated by a proton relay chain) to CO2 and its two succeeding intermediates, namely, formic acid and formaldehyde, to ultimately form CH3OH. The hydride and proton transfers for the first of these reduction steps, the homogeneous reduction of CO2, are sequential in nature (in which the formate to formic acid protonation can be assisted by a negatively biased cathode). In contrast, these transfers are coupled in each of the two

  16. 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

  17. Concerted dismutation of chlorite ion: water-soluble iron-porphyrins as first generation model complexes for chlorite dismutase.

    PubMed

    Zdilla, Michael J; Lee, Amanda Q; Abu-Omar, Mahdi M

    2009-03-02

    Three iron-5,10,15,20-tetraarylporphyrins (Fe(Por-Ar4), Ar = 2,3,5,6-tetrafluro-N,N,N-trimethylanilinium (1), N,N,N-trimethylanilinium (2), and p-sulfonatophenyl (3)) have been investigated as catalysts for the dismutation of chlorite (ClO2-). Degradation of ClO2- by these catalysts occurs by two concurrent pathways. One leads to formation of chlorate (ClO3-) and chloride (Cl-), which is determined to be catalyzed by O=FeIV(Por) (Compound II) based on stopped-flow absorption spectroscopy, competition with 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonicacid), 18O-labeling studies, and kinetics. The second pathway is a concerted dismutation of chlorite to dioxygen (O2) and chloride. On the basis of isotope labeling studies using a residual gas analyzer, the mechanism is determined to be formation of O=FeIV(Por)*+ (Compound I) from oxygen atom transfer, and subsequent rebound with the resulting hypochlorite ion (ClO-) to give dioxygen and chloride. While the chlorate production pathway is dominant for catalysts 2 and 3, the O2-producing pathway is significant for catalyst 1. In addition to chlorite dismutation, complex 1 catalyzes hypochlorite disproportionation to chloride and dioxygen quantitatively.

  18. 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

  19. 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.

  20. Chiral Phosphoric Acid-Catalyzed Enantioselective Reductive Amination of 2-Pyridyl Ketones: Construction of Structurally Chiral Pyridine-Based Ligands.

    PubMed

    Abudu Rexit, Abulikemu; Luo, Shiwei; Mailikezati, Maihemuti

    2016-11-18

    A chiral phosphoric acid-catalyzed one-pot enantioselective reductive amination of 2-pyridyl ketones was realized to provide chiral pyridine-based ligands in excellent yields with high enantioselectivities (up to 98% yield, 94% ee). Computational studies on the key intermediate imine and transition state of the hydride transfer process revealed that the nitrogen atom of the pyridyl ring might be an important factor to significantly promote both the reaction activity and enantioselectivity.

  1. Molybdenum-Catalyzed Synthesis of Nitrogenated Polyheterocycles from Nitroarenes and Glycols with Reuse of Waste Reduction Byproduct.

    PubMed

    Rubio-Presa, Rubén; Pedrosa, Marı A R; Fernández-Rodríguez, Manuel A; Arnáiz, Francisco J; Sanz, Roberto

    2017-10-06

    A novel domino reduction/imine formation/intramolecular cyclization/oxidation for the efficient synthesis of pyrrolo(indolo)[1,2-a]quinoxalines and pyrrolo(indolo)[3,2-c]-quinolines from readily available nitrobenzenes and glycols is reported. The process utilizes the carbonyl byproduct of the initial dioxomolybdenum(VI)-catalyzed reduction of nitroaromatics with glycols as a reagent for the imine generation. This method represents the first sustainable domino reaction for the preparation of biologically relevant heterocycles that internally incorporates the waste formed in the first step to the final product.

  2. 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

  3. Z-Selective Olefin Synthesis via Iron-Catalyzed Reductive Coupling of Alkyl Halides with Terminal Arylalkynes

    PubMed Central

    2015-01-01

    Selective catalytic synthesis of Z-olefins has been challenging. Here we describe a method to produce 1,2-disubstituted olefins in high Z selectivity via reductive cross-coupling of alkyl halides with terminal arylalkynes. The method employs inexpensive and nontoxic catalyst (iron(II) bromide) and reductant (zinc). The substrate scope encompasses primary, secondary, and tertiary alkyl halides, and the reaction tolerates a large number of functional groups. The utility of the method is demonstrated in the synthesis of several pharmaceutically relevant molecules. Mechanistic study suggests that the reaction proceeds through an iron-catalyzed anti-selective carbozincation pathway. PMID:25831473

  4. Metal Nanoparticle-Catalyzed Reduction Using Borohydride in Aqueous Media: A Kinetic Analysis of the Surface Reaction by Microfluidic SERS.

    PubMed

    Xie, Wei; Grzeschik, Roland; Schlücker, Sebastian

    2016-10-24

    Hydrides are widely used in reduction reactions. In protic solvents, their hydrolysis generates molecular hydrogen as a second reducing agent. The competition between these two parallel reduction pathways has been overlooked so far since both typically yield the same product. We investigated the platinum-catalyzed reduction of 4-nitrothiophenol to 4-aminothiophenol in aqueous sodium borohydride solution as a prominent model reaction, by using label-free SERS monitoring in a microfluidic reactor. Kinetic analysis revealed a strong pH dependence. Surprisingly, only at pH>13 the reduction is driven exclusively by sodium borohydride. This study demonstrates the potential of microfluidics-based kinetic SERS monitoring of heterogeneous catalysis in colloidal suspension. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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.

  6. Effects of Ca2+ and sulfhydryl reductant on the polymerization of soybean glycinin catalyzed by mammalian and microbial transglutaminases.

    PubMed

    Zhang, Guoyan; Matsumura, Yasuki; Matsumoto, Shinya; Hayashi, Yukako; Mori, Tomohiko

    2003-01-01

    Two types of transglutaminases (TGases), Ca(2+)-dependent TGase derived from guinea pig liver (GTGase) and Ca(2+)-independent TGase derived from a variant of Streptoverticillium mobaraense (MTGase), were used to study the cross-linking of soybean 11S globulin (glycinin). The effects of sulfhydryl reductant (dithiothreitol, DTT) and Ca(2+) on the conformation and TGase-catalyzed polymerization of glycinin were investigated. The conformational change of glycinin was probed by spectral methods. The degree of cross-linking and the polymer (aggregate) formation were analyzed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and dynamic light scattering, respectively. Addition of DTT stimulated the TGase-catalyzed cross-linking reactions without destroying the secondary and tertiary structure of glycinin but did not influence the polymer or aggregate formation. It was found that Ca(2+) caused the formation of larger size polymers at lower concentrations, while it suppressed the polymerization at higher concentrations. In addition, the cross-linking behaviors of glycinin were shown to be different between MTGase- and GTGase-catalyzed systems.

  7. Synthesis of trans-disubstituted alkenes by cobalt-catalyzed reductive coupling of terminal alkynes with activated alkenes.

    PubMed

    Mannathan, Subramaniyan; Cheng, Chien-Hong

    2012-09-10

    A cobalt-catalyzed reductive coupling of terminal alkynes, RC≡CH, with activated alkenes, R'CH=CH(2), in the presence of zinc and water to give functionalized trans-disubstituted alkenes, RCH=CHCH(2)CH(2)R', is described. A variety of aromatic terminal alkynes underwent reductive coupling with activated alkenes including enones, acrylates, acrylonitrile, and vinyl sulfones in the presence of a CoCl(2)/P(OMe)(3)/Zn catalyst system to afford 1,2-trans-disubstituted alkenes with high regio- and stereoselectivity. Similarly, aliphatic terminal alkynes also efficiently participated in the coupling reaction with acrylates, enones, and vinyl sulfone, in the presence of the CoCl(2)/P(OPh)(3)/Zn system providing a mixture of 1,2-trans- and 1,1-disubstituted functionalized terminal alkene products in high yields. The scope of the reaction was also extended by the coupling of 1,3-enynes and acetylene gas with alkenes. Furthermore, a phosphine-free cobalt-catalyzed reductive coupling of terminal alkynes with enones, affording 1,2-trans-disubstituted alkenes as the major products in a high regioisomeric ratio, is demonstrated. In the reactions, less expensive and air-stable cobalt complexes, a mild reducing agent (Zn) and a simple hydrogen source (water) were used. A possible reaction mechanism involving a cobaltacyclopentene as the key intermediate is proposed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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

  9. 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).

  10. Single-Molecule Imaging of Iron-Phthalocyanine-Catalyzed Oxygen Reduction Reaction by in Situ Scanning Tunneling Microscopy.

    PubMed

    Gu, Jing-Ying; Cai, Zhen-Feng; Wang, Dong; Wan, Li-Jun

    2016-09-27

    We report herein an in situ electrochemical scanning tunneling microscopy (ECSTM) investigation of iron-phthalocyanine (FePc)-catalyzed oxygen reduction reaction (ORR). A highly ordered FePc adlayer is revealed on a Au(111) electrode. The center ions in the FePc adlayer show uniform high contrast in an oxygen-saturated electrolyte, which is attributed to the formation of an FePc-O2 complex. In situ STM results reveal the sharp contrast change upon shifting the electrode potential to trigger the ORR. Theoretical simulation has supplied further evidence for the contrast difference of the adsorbed FePc species.

  11. Carbon dioxide mediated stereoselective copper-catalyzed reductive coupling of alkynes and thiols.

    PubMed

    Riduan, Siti Nurhanna; Ying, Jackie Y; Zhang, Yugen

    2012-04-06

    A simple protocol for the stereoselective copper-catalyzed hydrothiolation of alkynes under a CO(2) atmosphere has been developed. The stereoselectivity is determined by the presence/absence of a CO(2) atmosphere. The reaction system is robust and utilizes inexpensive, readily available substrates. A cyclic alkene/carboxylate copper complex intermediate is proposed as the key step in determining the stereoselectivity, and an equivalent amount of water is found to play an active role as a proton donor.

  12. Diastereoselective B(C6F5)3-Catalyzed Reductive Carbocyclization of Unsaturated Carbohydrates.

    PubMed

    Bender, Trandon A; Dabrowski, Jennifer A; Zhong, Hongyu; Gagné, Michel R

    2016-08-19

    A B(C6F5)3-catalyzed method for the selective conversion of unsaturated carbohydrates to cyclopentanes and cyclopropanes is disclosed. Catalyst activation of tertiary silanes generates the ion pair [(C6F5)3B-H][ROSi2] whose components synergistically activate C-O bonds for diastereoselective C-C bond formation. Sila-THF cations are invoked as key intermediates facilitating carbocyclizations. Complex chiral synthons are thereby obtained in a single pot.

  13. Facile synthesis of fluoroalkenes by palladium-catalyzed reductive defluorination of allylic gem-difluorides.

    PubMed

    Narumi, Tetsuo; Tomita, Kenji; Inokuchi, Eriko; Kobayashi, Kazuya; Oishi, Shinya; Ohno, Hiroaki; Fujii, Nobutaka

    2007-08-16

    Chemo- and stereoselective synthesis of fluoroalkenes was achieved in excellent yields via Pd-catalyzed C-F bond activation. In this transformation, Et3N plays a crucial role to produce reactive hydride species such as Ph(EtO)SiH2 and Ph(EtO)2SiH by promoting dehydrogenative coupling. The reaction proceeds efficiently at 50 degrees C with a variety of substrates and is also useful for the synthesis of fluoroalkene peptidomimetics.

  14. 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

  15. Glucose as a clean and renewable reductant in the Pd-nanoparticle-catalyzed reductive homocoupling of bromo- and chloroarenes in water.

    PubMed

    Monopoli, Antonio; Calò, Vincenzo; Ciminale, Francesco; Cotugno, Pietro; Angelici, Carlo; Cioffi, Nicola; Nacci, Angelo

    2010-06-04

    An efficient and highly sustainable Ullmann-type homocoupling of bromo- and chloroarenes, including the more challenging electron-rich chloroarenes (e.g., 4-chloroanisole), catalyzed by in situ generated Pd colloids, is carried out in aqueous medium under relatively mild conditions (temperatures ranging from 40 to 90 degrees C). Glucose is used as a clean and renewable reductant, while tetrabutylammonium hydroxide (TBAOH) acts as base, surfactant, and phase-transfer agent, creating a favorable environment for the catalyst. Pd nanoparticle sizes, morphology, and chemical composition are ascertained by TEM and XPS analyses.

  16. Selective 4e-/4H+ O2 reduction by an iron(tetraferrocenyl)porphyrin complex: from proton transfer followed by electron transfer in organic solvent to proton coupled electron transfer in aqueous medium.

    PubMed

    Mittra, Kaustuv; Chatterjee, Sudipta; Samanta, Subhra; Dey, Abhishek

    2013-12-16

    An iron porphyrin catalyst bearing four ferrocenes and a hydrogen bonding distal pocket is found to catalyze 4e(-)/4H(+) oxygen reduction reaction (ORR) in organic solvent under homogeneous conditions in the presence of 2-3 equiv of Trifluoromethanesulphonic acid. Absorption spectroscopy, electron paramagnetic resonance (EPR), and resonance Raman data along with H2O2 assay indicate that one out of the four electrons necessary to reduce O2 to H2O is donated by the ferrous porphyrin while three are donated by the distal ferrocene residues. The same catalyst shows 4e(-)/4H(+) reduction of O2 in an aqueous medium, under heterogeneous conditions, over a wide range of pH. Both the selectivity and the rate of ORR are found to be pH independent in an aqueous medium. The ORR proceeds via a proton transfer followed by electron transfer (PET) step in an organic medium and while a 2e(-)/1H(+) proton coupled electron transfer (PCET) step determines the electrochemical potential of ORR in an aqueous medium.

  17. Boron-Catalyzed Silylative Reduction of Nitriles in Accessing Primary Amines and Imines.

    PubMed

    Gandhamsetty, Narasimhulu; Jeong, Jinseong; Park, Juhyeon; Park, Sehoon; Chang, Sukbok

    2015-07-17

    Silylative reduction of nitriles was studied under transition metal-free conditions by using B(C6F5)3 as a catalyst with hydrosilanes as a reductant. Alkyl and (hetero)aryl nitriles were efficiently converted to primary amines or imines under mild conditions. The choice of silanes was found to determine the selectivity: while a full reduction of nitriles was highly facile, the use of sterically bulky silanes allowed for the partial reduction leading to N-silylimines.

  18. Hydrogen transfer reduction of polyketones catalyzed by iridium complexes: a novel route towards more biocompatible materials.

    PubMed

    Milani, Barbara; Crottib, Corrado; Farnetti, Erica

    2008-09-14

    Transfer hydrogenation from 2-propanol to CO/4-methylstyrene and CO/styrene polyketones was catalyzed by [Ir(diene)(N-N)X] (N-N = nitrogen chelating ligand; X = halogen) in the presence of a basic cocatalyst. The reactions were performed using dioxane as cosolvent, in order to overcome problems due to low polyketone solubility. The polyalcohols were obtained in yields up to 95%, the conversions being markedly dependent on the nature of the ligands coordinated to iridium as well as on the experimental conditions.

  19. Mononuclear copper complex-catalyzed four-electron reduction of oxygen.

    PubMed

    Fukuzumi, Shunichi; Kotani, Hiroaki; Lucas, Heather R; Doi, Kaoru; Suenobu, Tomoyoshi; Peterson, Ryan L; Karlin, Kenneth D

    2010-05-26

    A mononuclear Cu(II) complex acts as an efficient catalyst for four-electron reduction of O(2) to H(2)O. Its reduction by a ferrocene derivative (Fc*) and reaction with O(2) leads to the formation of a peroxodicopper(II) complex; this is subsequently reduced by Fc* in the presence of protons to regenerate the Cu(II) complex.

  20. Cobalt-porphine catalyzed CO2 electro-reduction: a novel protonation mechanism.

    PubMed

    Yao, Cang Lang; Li, Jian Chen; Gao, Wang; Jiang, Qing

    2017-06-14

    The urgent need for artificially fixing CO2 calls for catalysts of high efficiency. The transition metal functionalized porphyrin (TMP) is one of the most important types of organic catalysts for CO2 reduction. However, the catalytic mechanisms of TMP in CO2 reduction still remain controversial. Starting from the previously neglected catalyst self-protonation model, we uncover a new CO2 reduction mechanism on cobalt-porphine, which involves an indirect proton transfer step occurring at the beginning of the reduction cycle. Based on this protonation mechanism, we demonstrate the different correlations between producing rate and pH for the formation of CO and methane, in good agreement with available experimental observations. Our results reveal how pH and potential affect the CO2 reduction process, providing important clues and insights for further optimization of TMP catalysts.

  1. Copper-catalyzed asymmetric conjugate reduction as a route to novel β-azaheterocyclic acid derivatives

    PubMed Central

    Rainka, Matthew P.; Aye, Yimon; Buchwald, Stephen L.

    2004-01-01

    A chiral copper-hydride catalyst for the asymmetric conjugate reduction of α,β-unsaturated carbonyl compounds has been used for the reduction of substrates containing β-nitrogen substituents. A new set of reaction conditions has allowed for a variety of β-azaheterocyclic acid derivatives to be synthesized in excellent yields and with high degrees of enantioselectivity. In addition, the effect that the nature of the nitrogen substituent has on the rate of the conjugate reduction reaction has been explored. PMID:15067136

  2. Pd(0)-Catalyzed PMHS reductions of aromatic acid chlorides to aldehydes.

    PubMed

    Lee, Kyoungsoo; Maleczka, Robert E

    2006-04-27

    [reaction: see text] Contrary to previous reports, polymethylhydrosiloxane (PMHS) under Pd(0) catalysis can efficiently reduce aryl acid chlorides to their corresponding aldehydes without requiring an additional reductant, provided the reactions are run in the presence of fluoride.

  3. 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.

  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. Fluoride-Catalyzed Methylation of Amines by Reductive Functionalization of CO2 with Hydrosilanes.

    PubMed

    Liu, Xiao-Fang; Ma, Ran; Qiao, Chang; Cao, Han; He, Liang-Nian

    2016-11-07

    An effective and inexpensive organocatalyst tetrabutylammonium fluoride (TBAF) was developed for the reductive functionalization of CO2 with amines to selectively afford formamides or methylamines by employing hydrosilanes. Hydrosilanes with different substituents show discriminatory reducing activity. Thus, the formation of formamides and further reduction products, that is, methylamines could be controlled by elegantly tuning hydrosilane types. Formamides were obtained exclusively under an atmospheric pressure of CO2 with triethoxysilane. Using phenylsilane as a reductant, methylamines were attained with up to 99 % yield at 50 °C coupled to a complete deoxygenation of CO2 . The crucial intermediate silyl formate in the formylation step was identified and thereby a tentative mechanism involving the fluoride-promoted hydride transfer from the hydrosilane to CO2 /formamide was proposed. Striking features of this metal-free protocol are formylation and methylation of amines by reductive functionalization of CO2 with hydrosilanes and mild reaction conditions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Electrochemical Reduction of CO 2 Catalyzed by Re(pyridine-oxazoline)(CO) 3 Cl Complexes

    DOE PAGES

    Nganga, John K.; Samanamu, Christian R.; Tanski, Joseph M.; ...

    2017-03-09

    In a series of rhenium tricarbonyl complexes coordinated by asymmetric diimine ligands containing a pyridine moiety bound to an oxazoline ring were synthesized, structurally and electrochemically characterized, and screened for CO2 reduction ability. We reported complexes are of the type Re(N-N)(CO)3Cl, with N-N = 2-(pyridin-2-yl)-4,5-dihydrooxazole (1), 5-methyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (2), and 5-phenyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (3). The electrocatalytic reduction of CO2 by these complexes was observed in a variety of solvents and proceeds more quickly in acetonitrile than in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The analysis of the catalytic cycle for electrochemical CO2 reduction by 1 in acetonitrile using density functional theory (DFT) supportsmore » the C–O bond cleavage step being the rate-determining step (RDS) (ΔG‡ = 27.2 kcal mol–1). Furthermore, the dependency of the turnover frequencies (TOFs) on the donor number (DN) of the solvent also supports that C–O bond cleavage is the rate-determining step. Moreover, the calculations using explicit solvent molecules indicate that the solvent dependence likely arises from a protonation-first mechanism. Unlike other complexes derived from fac-Re(bpy)(CO)3Cl (I; bpy = 2,2'-bipyridine), in which one of the pyridyl moieties in the bpy ligand is replaced by another imine, no catalytic enhancement occurs during the first reduction potential. Remarkably, catalysts 1 and 2 display relative turnover frequencies, (icat/ip)2, up to 7 times larger than that of I.« less

  7. 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

  8. 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

  9. Palladium-indium catalyzed reduction of N-nitrosodimethylamine: indium as a promoter metal.

    PubMed

    Davie, Matthew G; Shih, Kaimin; Pacheco, Federico A; Leckie, James O; Reinhard, Martin

    2008-04-15

    An emerging technology for the removal of N-nitrosodimethylamine (NDMA) from drinking and groundwater is reductive destruction using noble metal catalysts and hydrogen gas as a reducing agent. Bimetallic palladium-indium (Pd-In) supported on alumina combines the ability of Into activate NDMA with the hydrogen activating properties of Pd. This study examined the effect of In addition to a commercial 5% Pd by weight on gamma-Al2O3 catalyst on the efficacy of NDMA reduction. The pseudo-first-order rate constant increased proportionately to In loading from 0.057 h(-1) for 0% In to a maximum of 0.25 h(-1) for 1% In and then decreased with additional in loading. Data suggest that hydrogen activation occurred only on Pd surfaces and In activated NDMA 20 times more effectively than Pd on a mass basis. The rate-limiting factor was NDMA activation for In loadings below 1%. The decrease at higher loadings is interpreted as In blocking pore spaces and limiting access to Pd sites, suggesting monatomic hydrogen limitation. The only products detected were dimethylamine and ammonium with carbon and nitrogen balances in excess of 92%, consistent with a mechanism involving reductive N-N bond cleavage. Results from this study serve as a basis for optimizing bimetallic catalysts for treating NDMA contaminated waters.

  10. Asymmetric synthesis of tetrahydroquinolin-3-ols via CoCl2-catalyzed reductive cyclization of nitro cyclic sulfites with NaBH4.

    PubMed

    Jagdale, Arun R; Reddy, R Santhosh; Sudalai, Arumugam

    2009-02-19

    A new method for the construction of chiral 3-substituted tetrahydroquinoline derivatives based on asymmetric dihydroxylation and CoCl(2)-catalyzed reductive cyclization of nitro cyclic sulfites with NaBH(4) has been described with high optical purities. This method has been successfully applied in the formal synthesis of PNU 95666E and anachelin H chromophore.

  11. 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

  12. Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition.

    PubMed

    Nguyen, Khoa D; Park, Boyoung Y; Luong, Tom; Sato, Hiroki; Garza, Victoria J; Krische, Michael J

    2016-10-21

    α-Olefins are the most abundant petrochemical feedstock beyond alkanes, yet their use in commodity chemical manufacture is largely focused on polymerization and hydroformylation. The development of byproduct-free catalytic C-C bond-forming reactions that convert olefins to value-added products remains an important objective. Here, we review catalytic intermolecular reductive couplings of unactivated and activated olefin-derived nucleophiles with carbonyl partners. These processes represent an alternative to the longstanding use of stoichiometric organometallic reagents in carbonyl addition. Copyright © 2016, American Association for the Advancement of Science.

  13. Size-dependent production of radicals in catalyzed reduction of Eosin Y using gold nanorods

    NASA Astrophysics Data System (ADS)

    Weng, Guojun; Qi, Ying; Li, Jianjun; Zhao, Junwu

    2015-09-01

    Gold nanostructures have been widely used as catalysts for chemical processes, energy conversion, and pollution control. The size of gold nanocatalysts is thus paramount for their catalytic activity. In this paper, gold nanorods with different sizes were prepared by means of the improved seeding growth approach by adding aromatic additive. The sizes and aspect ratios of the obtained gold nanorods were calculated according to the TEM characterization. Then, we studied the catalytic activities of gold nanorods using a model reaction based on the reduction of Eosin Y by NaBH4. By monitoring the absorption intensities of the radicals induced by gold nanorods in real time, we observed the clear size-dependent activity in the conversion of EY2- to EY3-. The conversion efficiency indicated that the gold nanorods with the smallest size were catalytically the most active probably due to their high number of coordinatively unsaturated surface atoms. In addition, a compensation effect dominated by the surface area of nanorods was observed in this catalytic reduction, which could be primarily attributed to the configuration of Eosin Y absorbed onto the surfaces of gold nanorods.

  14. Improved oxygen reduction reaction catalyzed by Pt/Clay/Nafion nanocomposite for PEM fuel cells.

    PubMed

    Narayanamoorthy, B; Datta, K K R; Eswaramoorthy, M; Balaji, S

    2012-07-25

    A novel Pt nanoparticle (Pt NP) embedded aminoclay/Nafion (Pt/AC/N) nanocomposite catalyst film was prepared for oxygen reduction reaction by sol-gel method. The prepared nanocomposite films were surface characterized using XRD and TEM and thermal stability was studied by TGA. The prepared film has firmly bound Pt NP and could exhibit an improved electro-reduction activity compared to vulcan carbon/Nafion supported Pt NP (Pt/VC/N). Moreover, the Pt/AC/N film possessed good stability in the acidic environment. The limiting current density of the Pt/AC/N film with 35.4 μg/cm(2) of Pt loading was found to be 4.2 mA/cm(2), which is 30% higher than that of the Pt/VC/N. The maximum H2O2 intermediate formation was found to be ∼1.6% and the reaction found to follow a four electron transfer mechanism. Accelerated durability test for 2000 potential cycles showed that ca. 78% of initial limiting current was retained. The results are encouraging for possible use of the Pt/AC/N as the free-standing electrocatalyst layer for polymer electrolyte membrane fuel cells.

  15. Replacing conventional carbon nucleophiles with electrophiles: nickel-catalyzed reductive alkylation of aryl bromides and chlorides.

    PubMed

    Everson, Daniel A; Jones, Brittany A; Weix, Daniel J

    2012-04-11

    A general method is presented for the synthesis of alkylated arenes by the chemoselective combination of two electrophilic carbons. Under the optimized conditions, a variety of aryl and vinyl bromides are reductively coupled with alkyl bromides in high yields. Under similar conditions, activated aryl chlorides can also be coupled with bromoalkanes. The protocols are highly functional-group tolerant (-OH, -NHTs, -OAc, -OTs, -OTf, -COMe, -NHBoc, -NHCbz, -CN, -SO(2)Me), and the reactions are assembled on the benchtop with no special precautions to exclude air or moisture. The reaction displays different chemoselectivity than conventional cross-coupling reactions, such as the Suzuki-Miyaura, Stille, and Hiyama-Denmark reactions. Substrates bearing both an electrophilic and nucleophilic carbon result in selective coupling at the electrophilic carbon (R-X) and no reaction at the nucleophilic carbon (R-[M]) for organoboron (-Bpin), organotin (-SnMe(3)), and organosilicon (-SiMe(2)OH) containing organic halides (X-R-[M]). A Hammett study showed a linear correlation of σ and σ(-) parameters with the relative rate of reaction of substituted aryl bromides with bromoalkanes. The small ρ values for these correlations (1.2-1.7) indicate that oxidative addition of the bromoarene is not the turnover-frequency determining step. The rate of reaction has a positive dependence on the concentration of alkyl bromide and catalyst, no dependence upon the amount of zinc (reducing agent), and an inverse dependence upon aryl halide concentration. These results and studies with an organic reductant (TDAE) argue against the intermediacy of organozinc reagents. © 2012 American Chemical Society

  16. Replacing Conventional Carbon Nucleophiles with Electrophiles: Nickel-Catalyzed Reductive Alkylation of Aryl Bromides and Chlorides

    PubMed Central

    2012-01-01

    A general method is presented for the synthesis of alkylated arenes by the chemoselective combination of two electrophilic carbons. Under the optimized conditions, a variety of aryl and vinyl bromides are reductively coupled with alkyl bromides in high yields. Under similar conditions, activated aryl chlorides can also be coupled with bromoalkanes. The protocols are highly functional-group tolerant (−OH, −NHTs, −OAc, −OTs, −OTf, −COMe, −NHBoc, −NHCbz, −CN, −SO2Me), and the reactions are assembled on the benchtop with no special precautions to exclude air or moisture. The reaction displays different chemoselectivity than conventional cross-coupling reactions, such as the Suzuki–Miyaura, Stille, and Hiyama–Denmark reactions. Substrates bearing both an electrophilic and nucleophilic carbon result in selective coupling at the electrophilic carbon (R–X) and no reaction at the nucleophilic carbon (R–[M]) for organoboron (−Bpin), organotin (−SnMe3), and organosilicon (−SiMe2OH) containing organic halides (X–R–[M]). A Hammett study showed a linear correlation of σ and σ(−) parameters with the relative rate of reaction of substituted aryl bromides with bromoalkanes. The small ρ values for these correlations (1.2–1.7) indicate that oxidative addition of the bromoarene is not the turnover-frequency determining step. The rate of reaction has a positive dependence on the concentration of alkyl bromide and catalyst, no dependence upon the amount of zinc (reducing agent), and an inverse dependence upon aryl halide concentration. These results and studies with an organic reductant (TDAE) argue against the intermediacy of organozinc reagents. PMID:22463689

  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.

  18. Enzyme-catalyzed modification of PES surfaces: reduction in adsorption of BSA, dextrin and tannin.

    PubMed

    Nady, Norhan; Schroën, Karin; Franssen, Maurice C R; Fokkink, Remco; Mohy Eldin, Mohamed S; Zuilhof, Han; Boom, Remko M

    2012-07-15

    Poly(ethersulfone) (PES) can be modified in a flexible manner using mild, environmentally benign components such as 4-hydroxybenzoic acid and gallic acid, which can be attached to the surface via catalysis by the enzyme laccase. This leads to grafting of mostly linear polymeric chains (for 4-hydroxybenzoic acid, and for gallic acid at low concentration and short modification time) and of networks (for gallic acid at high concentration and long exposure time). The reaction is stopped at a specific time, and the modified surfaces are tested for adsorption of BSA, dextrin and tannin using in-situ reflectometry and AFM imaging. At short modification times, the adsorption of BSA, dextrin and tannin is significantly reduced. However, at longer modification times, the adsorption increases again for both substrates. As the contact angle on modified surfaces at short modification times is reduced (indicative of more hydrophilic surfaces), and keeps the same low values at longer modification times, hydrophilicity is not the only determining factor for the measured differences. At longer modification times, intra-layer reactivity will increase the amount of cross-linking (especially for gallic acid), branching (for 4-hydroxybenzoic acid) and/or collapse of the polymer chains. This leads to more compact layers, which leads to increased protein adsorption. The modifications were shown to have clear potential for reduction of fouling by proteins, polysaccharides, and polyphenols, which could be related to the surface morphology.

  19. 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.

  20. Elevated Pb(II) release from the reduction of Pb(IV) corrosion product PbO2 induced by bromide-catalyzed monochloramine decomposition.

    PubMed

    Zhang, Yuanyuan; Lin, Yi-Pin

    2013-10-01

    The stability of Pb(IV) corrosion product PbO2 has been linked to lead contamination in chloraminated drinking water. Recent studies have shown that autodecomposition of monochloramine (NH2Cl) can cause lead release from PbO2 via reductive dissolution. Bromide (Br(-)) is a known catalyst for NH2Cl decomposition. In this study, we investigated whether Br(-)-catalyzed NH2Cl decomposition could further enhance lead release from PbO2. Our results showed that Br(-_)catalyzed NH2Cl decomposition did accelerate the reduction of PbO2, and the rate was enhanced by the lower pH value, higher Br(-), and NH2Cl concentrations. A single linear correlation was found between the amount of NH2Cl decomposed and the amount of total Pb(II) released either in the absence or presence of Br(-), suggesting that Br(-)-catalyzed NH2Cl decomposition and NH2Cl autodecomposition may generate the same intermediate toward PbO2 reduction. The kinetics of total Pb(II) release can be successfully modeled by considering the overall rate of NH2Cl decomposition with NOH as the reactive intermediate responsible for PbO2 reduction. Our findings suggested that special attentions on lead contamination should be paid to systems with PbO2 scales and high Br(-)-containing source waters when switching disinfectant from free chlorine to monochloramine.

  1. Biomimetic oxidation with molecular oxygen. Selective carbon-carbon bond cleavage of 1,2-diols by molecular oxygen and dihydropyridine in the presence of iron-porphyrin catalysts

    SciTech Connect

    Okamoto, T.; Sasaki, K.; Oka, S.

    1988-02-17

    The selective carbon-carbon bond cleavage of 1,2-diols in the presence of an iron-porphyrin complex, molecular oxygen, and 1-benzyl-3-carbamoyl-1,4-dihydropyridine is reported. The C-C bonds of aryl-substituted ethane-1,2-diols were cleaved exclusively to aldehydes or ketones as the oxidation products at room temperature. The reaction rates were influenced by the steric hindrance of the substituents both in the catalysts and diols, but no differences in the reactivities were observed between the two stereo isomers (meso and dl) of diols. A kinetic analysis of this bond cleavage reaction is consistent with the reaction mechanism consisting of the initial binding of diol on the active catalyst forming an intermediate complex and its subsequent breakdown in the rate-determining step of the catalytic cycle. The initial binding step is favorable for electron-deficient diols and is influenced by steric hindrance, whereas the rate-determining bond cleavage step is accelerated by electron-rich diols and unaffected by the steric effect. The mechanism of this diol cleavage reaction is discussed on the basis of these observations.

  2. 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

  3. Diastereoselective Synthesis of syn-β-Lactams Using Rh-Catalyzed Reductive Mannich-Type Reaction of α,β-Unsaturated Esters.

    PubMed

    Isoda, Motoyuki; Sato, Kazuyuki; Funakoshi, Masato; Omura, Keiko; Tarui, Atsushi; Omote, Masaaki; Ando, Akira

    2015-08-21

    The combination of Et2Zn and RhCl(PPh3)3 led to the facile generation of a rhodium-hydride complex (Rh-H) that catalyzed the 1,4-reduction of α,β-unsaturated esters. The resulting rhodium enolate performed as a Reformatsky-type reagent and reacted with various imines to give syn-β-lactams in good to excellent yields with high diastereoselectivity.

  4. Remarkable Differences in Reactivity between Benzothiazoline and Hantzsch Ester as a Hydrogen Donor in Chiral Phosphoric Acid Catalyzed Asymmetric Reductive Amination of Ketones.

    PubMed

    Kim, Kyung-Hee; Akiyama, Takahiko; Cheon, Cheol-Hong

    2016-01-01

    Described herein are differences in behavior between a Hantzsch ester and a benzothiazoline as hydrogen donors in the chiral phosphoric acid catalyzed asymmetric reductive amination of ketones with p-anisidine. The asymmetric reductive amination of ketones with a Hantzsch ester as a hydrogen donor provided the corresponding chiral amines exclusively, regardless of the structures of the ketones, whereas a similar transformation with a benzothiazoline provided chiral amines and p-methoxyphenyl-protected primary amines in variable yields, depending on the structures of both the ketones and benzothiazolines. Because a benzothiazoline has an N,S-acetal moiety that is vulnerable to p-anisidine, the primary amine can be formed through transimination of the benzothiazoline with p-anisidine followed by reduction of the resulting aldimine with remaining benzothiazoline.

  5. The Pyruvate and α-Ketoglutarate Dehydrogenase Complexes of Pseudomonas aeruginosa Catalyze Pyocyanin and Phenazine-1-carboxylic Acid Reduction via the Subunit Dihydrolipoamide Dehydrogenase.

    PubMed

    Glasser, Nathaniel R; Wang, Benjamin X; Hoy, Julie A; Newman, Dianne K

    2017-03-31

    Phenazines are a class of redox-active molecules produced by diverse bacteria and archaea. Many of the biological functions of phenazines, such as mediating signaling, iron acquisition, and redox homeostasis, derive from their redox activity. Although prior studies have focused on extracellular phenazine oxidation by oxygen and iron, here we report a search for reductants and catalysts of intracellular phenazine reduction in Pseudomonas aeruginosa Enzymatic assays in cell-free lysate, together with crude fractionation and chemical inhibition, indicate that P. aeruginosa contains multiple enzymes that catalyze the reduction of the endogenous phenazines pyocyanin and phenazine-1-carboxylic acid in both cytosolic and membrane fractions. We used chemical inhibitors to target general enzyme classes and found that an inhibitor of flavoproteins and heme-containing proteins, diphenyleneiodonium, effectively inhibited phenazine reduction in vitro, suggesting that most phenazine reduction derives from these enzymes. Using natively purified proteins, we demonstrate that the pyruvate and α-ketoglutarate dehydrogenase complexes directly catalyze phenazine reduction with pyruvate or α-ketoglutarate as electron donors. Both complexes transfer electrons to phenazines through the common subunit dihydrolipoamide dehydrogenase, a flavoprotein encoded by the gene lpdG Although we were unable to co-crystallize LpdG with an endogenous phenazine, we report its X-ray crystal structure in the apo-form (refined to 1.35 Å), bound to NAD(+) (1.45 Å), and bound to NADH (1.79 Å). In contrast to the notion that phenazines support intracellular redox homeostasis by oxidizing NADH, our work suggests that phenazines may substitute for NAD(+) in LpdG and other enzymes, achieving the same end by a different mechanism. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  6. Total Synthesis of Pumiliotoxins 209F and 251D via Late-Stage, Nickel-Catalyzed Epoxide-Alkyne Reductive Cyclization

    PubMed Central

    Woodin, Katrina S.; Jamison, Timothy F.

    2011-01-01

    Pumiliotoxins 209F and 251D were synthesized using highly selective nickel-catalyzed epoxide-alkyne reductive cyclizations as the final step. The exocyclic (Z)-alkene found in the majority of the pumiliotoxins was formed stereospecifically and regioselectively, without the use of a directing group on the alkyne, and the epoxide underwent ring opening exclusively at the less hindered carbon to provide the requisite tertiary alcohol. The epoxides were prepared using diastereoselective addition of a sulfoxonium anion to a proline-derived methyl ketone. PMID:17696401

  7. 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

    2015-06-05

    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.

  8. Manganese(I)‐Catalyzed C−H Activation: The Key Role of a 7‐Membered Manganacycle in H‐Transfer and Reductive Elimination

    PubMed Central

    Yahaya, Nasiru P.; Appleby, Kate M.; Teh, Magdalene; Wagner, Conrad; Troschke, Erik; Bray, Joshua T. W.; Duckett, Simon B.; Hammarback, L. Anders; Ward, Jonathan S.; Milani, Jessica; Pridmore, Natalie E.; Whitwood, Adrian C.

    2016-01-01

    Abstract Manganese‐catalyzed C−H bond activation chemistry is emerging as a powerful and complementary method for molecular functionalization. A highly reactive seven‐membered MnI intermediate is detected and characterized that is effective for H‐transfer or reductive elimination to deliver alkenylated or pyridinium products, respectively. The two pathways are determined at MnI by judicious choice of an electron‐deficient 2‐pyrone substrate containing a 2‐pyridyl directing group, which undergoes regioselective C−H bond activation, serving as a valuable system for probing the mechanistic features of Mn C−H bond activation chemistry. PMID:27603008

  9. Energy-Related Small Molecule Activation Reactions: Oxygen Reduction and Hydrogen and Oxygen Evolution Reactions Catalyzed by Porphyrin- and Corrole-Based Systems.

    PubMed

    Zhang, Wei; Lai, Wenzhen; Cao, Rui

    2017-02-22

    Globally increasing energy demands and environmental concerns related to the use of fossil fuels have stimulated extensive research to identify new energy systems and economies that are sustainable, clean, low cost, and environmentally benign. Hydrogen generation from solar-driven water splitting is a promising strategy to store solar energy in chemical bonds. The subsequent combustion of hydrogen in fuel cells produces electric energy, and the only exhaust is water. These two reactions compose an ideal process to provide clean and sustainable energy. In such a process, a hydrogen evolution reaction (HER), an oxygen evolution reaction (OER) during water splitting, and an oxygen reduction reaction (ORR) as a fuel cell cathodic reaction are key steps that affect the efficiency of the overall energy conversion. Catalysts play key roles in this process by improving the kinetics of these reactions. Porphyrin-based and corrole-based systems are versatile and can efficiently catalyze the ORR, OER, and HER. Because of the significance of energy-related small molecule activation, this review covers recent progress in hydrogen evolution, oxygen evolution, and oxygen reduction reactions catalyzed by porphyrins and corroles.

  10. Cobalt-Catalyzed Reductive Multicomponent Synthesis of β-Hydroxy- and β-Aminocarbonyl Compounds under Mild Conditions.

    PubMed

    Paul, Jérôme; Presset, Marc; Cantagrel, Frédéric; Le Gall, Erwan; Léonel, Eric

    2017-01-05

    The cobalt-catalyzed multicomponent reaction between sp(2) -hybridized organic halides, Michael acceptors, and unsaturated electrophiles has been developed. The reaction proceeds through a formal conjugate addition/aldol or aza-aldol (Mannich) tandem reaction initiated by the in situ metalation of the organic halide by cobalt catalysis. The essentially new reaction conditions that have been developed are very mild and atom-economic. Under these conditions, a broad range of β-hydroxy- and β-aminocarbonyl compounds are obtained in good to high yields.

  11. Reduction of Flavodoxin by Electron Bifurcation and Sodium Ion-dependent Reoxidation by NAD+ Catalyzed by Ferredoxin-NAD+ Reductase (Rnf).

    PubMed

    Chowdhury, Nilanjan Pal; Klomann, Katharina; Seubert, Andreas; Buckel, Wolfgang

    2016-06-03

    Electron-transferring flavoprotein (Etf) and butyryl-CoA dehydrogenase (Bcd) from Acidaminococcus fermentans catalyze the endergonic reduction of ferredoxin by NADH, which is also driven by the concomitant reduction of crotonyl-CoA by NADH, a process called electron bifurcation. Here we show that recombinant flavodoxin from A. fermentans produced in Escherichia coli can replace ferredoxin with almost equal efficiency. After complete reduction of the yellow quinone to the blue semiquinone, a second 1.4 times faster electron transfer affords the colorless hydroquinone. Mediated by a hydrogenase, protons reoxidize the fully reduced flavodoxin or ferredoxin to the semi-reduced species. In this hydrogen-generating system, both electron carriers act catalytically with apparent Km = 0.26 μm ferredoxin or 0.42 μm flavodoxin. Membrane preparations of A. fermentans contain a highly active ferredoxin/flavodoxin-NAD(+) reductase (Rnf) that catalyzes the irreversible reduction of flavodoxin by NADH to the blue semiquinone. Using flavodoxin hydroquinone or reduced ferredoxin obtained by electron bifurcation, Rnf can be measured in the forward direction, whereby one NADH is recycled, resulting in the simple equation: crotonyl-CoA + NADH + H(+) = butyryl-CoA + NAD(+) with Km = 1.4 μm ferredoxin or 2.0 μm flavodoxin. This reaction requires Na(+) (Km = 0.12 mm) or Li(+) (Km = 0.25 mm) for activity, indicating that Rnf acts as a Na(+) pump. The redox potential of the quinone/semiquinone couple of flavodoxin (Fld) is much higher than that of the semiquinone/hydroquinone couple. With free riboflavin, the opposite is the case. Based on this behavior, we refine our previous mechanism of electron bifurcation.

  12. Carbonyl reductase 1 catalyzes 20β-reduction of glucocorticoids, modulating receptor activation and metabolic complications of obesity.

    PubMed

    Morgan, Ruth A; Beck, Katharina R; Nixon, Mark; Homer, Natalie Z M; Crawford, Andrew A; Melchers, Diana; Houtman, René; Meijer, Onno C; Stomby, Andreas; Anderson, Anna J; Upreti, Rita; Stimson, Roland H; Olsson, Tommy; Michoel, Tom; Cohain, Ariella; Ruusalepp, Arno; Schadt, Eric E; Björkegren, Johan L M; Andrew, Ruth; Kenyon, Christopher J; Hadoke, Patrick W F; Odermatt, Alex; Keen, John A; Walker, Brian R

    2017-09-06

    Carbonyl Reductase 1 (CBR1) is a ubiquitously expressed cytosolic enzyme important in exogenous drug metabolism but the physiological function of which is unknown. Here, we describe a role for CBR1 in metabolism of glucocorticoids. CBR1 catalyzes the NADPH- dependent production of 20β-dihydrocortisol (20β-DHF) from cortisol. CBR1 provides the major route of cortisol metabolism in horses and is up-regulated in adipose tissue in obesity in horses, humans and mice. We demonstrate that 20β-DHF is a weak endogenous agonist of the human glucocorticoid receptor (GR). Pharmacological inhibition of CBR1 in diet-induced obesity in mice results in more marked glucose intolerance with evidence for enhanced hepatic GR signaling. These findings suggest that CBR1 generating 20β-dihydrocortisol is a novel pathway modulating GR activation and providing enzymatic protection against excessive GR activation in obesity.

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

    SciTech Connect

    Brown, K. A.; Harris, D. F.; Wilker, M. B.; Rasmussen, A.; Khadka, N.; Hamby, H.; Keable, S.; Dukovic, G.; Peters, J. W.; Seefeldt, L. C.; King, P. W.

    2016-04-21

    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.

  14. Oxygen reduction reaction catalyzed by cobalt(III) complexes of macrocyclic ligands supported on multiwalled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Nasini, Udaya B.; Gartia, Yashraj; Ramidi, Punnamchandar; Kazi, Abul; Shaikh, Ali U.; Ghosh, Anindya

    2013-04-01

    A class of amido-macrocyclic cobalt(III) complexes along with multiwalled carbon nanotubes have been studied for electro-catalytic activity to reduce oxygen. These complexes are efficient for oxygen reduction reaction (ORR) in wide range of pH conditions by following ideal fuel cell reduction mechanism. Depending on the stability of complexes in different pH, electrochemical studies were performed to predict the reduction mechanism. Rotating disk electrode and rotating ring-disk electrode studies show that these complexes reduce oxygen via four electron reduction process in mild acidic pH and two step two electron reduction processes in basic conditions, with negligible amount of hydrogen peroxide generation.

  15. Phosphine-catalyzed reductions of alkyl silyl peroxides by titanium hydride reducing agents: development of the method and mechanistic investigations.

    PubMed

    Harris, Jason R; Haynes, M Taylor; Thomas, Andrew M; Woerpel, K A

    2010-08-06

    A method that allows for the reduction of protected hydroperoxides by employing catalytic amounts of phosphine is presented. The combination of a titanium(IV) alkoxide and a siloxane allowed for the chemoselective reduction of phosphine oxides in the presence of alkyl silyl peroxides. Subsequent reduction of the peroxide moiety by phosphine provided the corresponding silylated alcohols in useful yields. Mechanistic experiments, including crossover experiments, support a mechanism in which the peroxide group was reduced and the silyl group was transferred in a concerted step. Labeling studies with (17)O-labeled peroxides demonstrate that the oxygen atom adjacent to the silicon atom is removed from the silyl peroxide.

  16. Iron-catalyzed, hydrogen-mediated reductive cyclization of 1,6-enynes and diynes: evidence for bis(imino)pyridine ligand participation.

    PubMed

    Sylvester, Kevin T; Chirik, Paul J

    2009-07-01

    The bis(imino)pyridine iron dinitrogen complex (((i)Pr)PDI)Fe(N(2))(2) catalyzes the hydrogen-mediated reductive cyclization of enynes and diynes with turnover frequencies comparable to those of established precious metal catalysts. Amino, oxygenated, and carbon-based substrates are readily cyclized to the corresponding hetero- and carbocycles with 5 mol % iron and 4 atm H(2) at 23 degrees C. Stoichiometric reactions between selected substrates and the iron compound under a N(2) atmosphere established transfer dehydrogenation from an isopropyl aryl substituent to either the enyne or diyne substrate. In situ monitoring of the catalytic reaction by (1)H NMR spectroscopy coupled with deuterium labeling experiments established rapid cyclization followed by turnover-limiting hydrogenation.

  17. 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. Copyright © 2016, American Association for the Advancement of Science.

  18. 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.

  19. 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.

  20. 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.

  1. 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Self-encapsulation of homogeneous catalyst species into polymer gel leading to a facile and efficient separation system of amine products in the Ru-catalyzed reduction of carboxamides with polymethylhydrosiloxane (PMHS).

    PubMed

    Motoyama, Yukihiro; Mitsui, Kaoru; Ishida, Toshiki; Nagashima, Hideo

    2005-09-28

    A practical procedure for production of amines is offered by the ruthenium-catalyzed reduction of carboxamides with polymethylhydrosiloxane, in which encapsulation of the catalyst species into the formed insoluble siloxane resins contributes to the separation of both metallic and siloxane residues from the product.

  3. Aniline-catalyzed reductive amination as a powerful method for the preparation of reducing end-"clickable" chitooligosaccharides.

    PubMed

    Guerry, Alexandre; Bernard, Julien; Samain, Eric; Fleury, Etienne; Cottaz, Sylvain; Halila, Sami

    2013-04-17

    Functionalized oligosaccharides are useful intermediates to prepare products for biological research or for the development of advanced functional materials. Here, we report the unprecedented use of aniline as an efficient organocatalyst reaction with "clickable" (azide or alkyne) amine for the transimination-mediated reductive amination of a chitooligosaccharide. Moreover, we demonstrate that alkyne-bearing aniline constitutes an excellent tool for the easy derivatization of chitosan oligosaccharides. Evidence for such improvement has been illustrated by the straightforward design of a FRET substrate to probe chitinase activity and of amphiphilic polycaprolactone-grafted-chitosan. This efficient methodology paves the way to the preparation of novel chitosan oligosaccharide-based advanced materials.

  4. 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

  5. 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.

  6. 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 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

  7. Two-electron carbon dioxide reduction catalyzed by rhenium(I) bis(imino)acenaphthene carbonyl complexes.

    PubMed

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

    2014-05-01

    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. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  8. 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

  9. One-step fabrication of carbon fiber derived from waste paper and its application for catalyzing tri-iodide reduction

    NASA Astrophysics Data System (ADS)

    Xu, Shunjian

    2017-01-01

    Two carbon fibers were first fabricated by one-step pyrolysis of papers (filter paper and facial tissue), and then employed as catalytic materials for counter electrodes in dye-sensitized solar cells (DSCs) to investigate their potential application. The results show that the microstructure transformation and main weight loss of both the papers are mainly happened in the temperature range of 300–400 °C. After pyrolysis at 800°C, the weight remaining of the filter paper and facial tissue is 1.92% and 4.95%, respectively. The obtained carbon fibers belong to an amorphous carbon consisting of the randomly oriented stacks of graphene sheets. The diameters of both the carbon fibers are about 10 μm, on which there are a certain amount of fine carbon nanofibers. The amorphous microstructure and unique fine nanofibers of the carbon fibers induce more excellent catalytic activity for triiodide ion reduction compared with the biochar (derived from poplar leaf) and the graphite. As a result, the carbon fiber based DSCs display obviously higher efficiency than the biochar or graphite based ones. The conversion efficiency of the DSCs employing the filter paper derived carbon fiber, facial tissue derived carbon fiber, biochar and graphite is 4.72%, 4.70%, 1.33% and 0.77%, respectively.

  10. Density functional theory studies on the mechanism of the reduction of CO2 to CO catalyzed by copper(I) boryl complexes.

    PubMed

    Zhao, Haitao; Lin, Zhenyang; Marder, Todd B

    2006-12-13

    The detailed reaction mechanism for the reduction of CO2 to CO catalyzed by (NHC)Cu(boryl) complexes (NHC = N-heterocyclic carbene) was studied with the aid of DFT by calculating the relevant intermediates and transition state structures. Our DFT calculations show that the reaction occurs through CO2 insertion into the Cu-B bond to give a Cu-OC(=O)-boryl species (i.e., containing Cu-O and C-B bonds), and subsequent boryl migration from C to O, followed by alpha-bond metathesis between pinB-Bpin (B2pin2, pin = pinacolate = OCMe2CMe2O) and (NHC)Cu(OBpin). The overall reaction is exergonic by 38.0 kcal/mol. It is the nucleophilicity of the Cu-B bond, a function of the very strong alpha-donor properties of the boryl ligand, rather than the oxophilicity of boron, which determines the direction of the CO2 insertion process. The boryl migration from C to O, which releases the product CO, is the rate-determining step and involves the "vacant" orbital orbital on boron. The (NHC)Cu(boryl) complexes show unique activity in the catalytic process. For the analogous (NHC)Cu(alkyl) complexes, the CO2 insertion into the Cu-C bond giving a copper acetate intermediate occurs with a readily achievable barrier. However, the elimination of CO from the acetate intermediate through a methyl migration from C to O is energetically inaccessible.

  11. Removal of dinitrotoluenes from water via reduction with iron and peroxidase-catalyzed oxidative polymerization: a comparison between Arthromyces ramosus peroxidase and soybean peroxidase.

    PubMed

    Patapas, Joey; Al-Ansari, Mohammad Mousa; Taylor, K E; Bewtra, J K; Biswas, N

    2007-04-01

    A two-step process for the removal of dinitrotoluene from water is presented: zero-valent iron reduction is coupled with peroxidase-catalyzed polymerization of the resulting diaminotoluenes (DAT). The effect of pH was examined in the reduction step: at pH 6 the reaction occurred much more rapidly than at pH 8. In the second step, optimal pH and substrate ratio, minimal enzyme concentration and effect of polyethylene glycol (PEG) as an additive for greater than 95% conversion of DAT, over a 3h reaction period were determined using high performance liquid chromatography. Two enzymes were investigated and compared: Arthromyces ramosus peroxidase (ARP) and soybean peroxidase (SBP). The optimal pH values were 5.4 and 5.2 for ARP and SBP, respectively, but SBP was more resistant to mild acid whereas ARP was more stable in neutral solutions. SBP was found to have a greater hydrogen peroxide demand (optimal peroxide/DAT molar ratio for SBP: 2.0 and 3.0 for 2,4-diaminotoluene (2,4-DAT) and 2,6-diaminotoluene (2,6-DAT), respectively; for ARP: 1.5 and 2.75 for 2,4-DAT and 2,6-DAT, respectively) but required significantly less enzyme (0.01 and 0.1 U ml(-1) for 2,4-DAT and 2,6-DAT, respectively) to convert the DAT than ARP (0.4 and 1.5 U ml(-1) for 2,4-DAT and 2,6-DAT, respectively). PEG was shown to have no effect upon the degree of substrate conversion for either enzyme.

  12. 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.

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

    DOE PAGES

    So Jeong Lee; Fowler, Joanna S.; Alexoff, David; ...

    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

  14. 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

  15. Online capillary solid-phase microextraction coupled liquid chromatography-mass spectrometry for analysis of chiral secondary alcohol products in yeast catalyzed stereoselective reduction cell culture.

    PubMed

    Cheng, Cheanyeh; Nian, Yu-Chuan

    2015-02-06

    An online solid-phase microextraction coupled liquid chromatography-electrospray ionization-ion trap mass spectrometry was developed for the analysis of trace R- and S-4-phenyl-2-butanol (R- and S-pbol) in salt rich cell culture of Saccharomyces cerevisiae catalyzed stereoselective reduction of 4-pheny-2-butanone (pbone). A Supel-Q PLOT capillary column was used for the extraction and deionized distilled water was used as the extraction mobile phase. The extraction flow rate and extraction time were at 0.1 mL min(-1) and 0.95 min, respectively. The three target analytes, pbone, R-pbol, and S-4-pbol, were desorbed and eluted by the mobile phase of water/methanol/isopropanol (55/25/20, v/v/v) with a flow rate of 0.5 mL min(-1) and analyzed by a chiral column. The mass spectrometric detection of the three target analytes was in positive ion mode with the signal [M+Na](+). The matrix-matched external standard calibration curves with linear concentration range between 0 and 50 μg mL(-1) were used for quantitative analysis. The linear regression correlation coefficients (r(2)) of the standard calibration curves were between 0.9950 and 0.9961. The yeast mediated reduction was performed with a recation culture of yeast incubation culture/glycerol (70/30, v/v) for 4 days. This biotransformation possessed 82.3% yield and 92.9% S-enantomeric excess. The limit of detection (LOD)/limit of quantification (LOQ) for pbone, R-pbol, and S-pbol was 0.02/0.067, 0.01/0.033, and 0.01/0.033 μg mL(-1), respectively. The intra-day and inter-day precisions from repeated measurements were 10.8-21.1% and 11.6-18.7%, respectively. The analysis accuracy from spike recovery was 84-91%.

  16. 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

    2011-12-06

    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.

  17. A general approach to chiral building blocks via direct amino acid-catalyzed cascade three-component reductive alkylations: formal total synthesis of HIV-1 protease inhibitors, antibiotic agglomerins, brefeldin A, and (R)-gamma-hexanolide.

    PubMed

    Ramachary, Dhevalapally B; Vijayendar Reddy, Y

    2010-01-01

    Multicatalysis cascade (MCC) process for the synthesis of highly substituted chiral building blocks (2-alkyl-CH-acids, 2-alkylcyclohexane-1,3-diones, 2-alkylcyclopentane-1,3-diones, and H-P ketone analogues) is presented based on the cascade three-component reductive alkylation's (TCRA) platform. Herein, we developed the high-yielding alkylation of a variety of CH-acids with (R)-glyceraldehyde acetonide/(S)-Garner aldehyde and Hantzsch ester through amino acid-catalyzed TCRA reaction without racemization at the alpha-position to carbonyl. Direct sequential combination of the L-proline-catalyzed TCRA reaction with other reactions like cascade alkylation/ketenization/esterification (A/K/E), alkylation/ketenization/esterification/alkylation (A/K/E/A), Brønsted acid-catalyzed cascade hydrolysis/lactonization/esterification (H/L/E), hydrolysis/esterification (H/E), hydrolysis/oxy-Michael/dehydration (H/OM/DH), and Robinson annulation (RA) of CH-acids, chiral aldehydes, Hantzsch ester, diazomethane, methyl vinyl ketone, various active olefins, and acetylenes furnished the highly functionalized chiral building blocks in good to high yields with excellent diastereoselectivities. In this context, many of the pharmaceutically applicable chiral building blocks were prepared via MCC reactions.

  18. Enantioselective synthesis of beta-aryl-gamma-amino acid derivatives via Cu-catalyzed asymmetric 1,4-reductions of gamma-phthalimido-substituted alpha,beta-unsaturated carboxylic acid esters.

    PubMed

    Deng, Jun; Hu, Xiang-Ping; Huang, Jia-Di; Yu, Sai-Bo; Wang, Dao-Yong; Duan, Zheng-Chao; Zheng, Zhuo

    2008-08-01

    A series of chiral beta-aryl-substituted gamma-amino butyric acid derivatives were synthesized in good enantioselectivities via the Cu-catalyzed asymmetric conjugate reduction of gamma-phthalimido-alpha,beta-unsaturated carboxylic acid esters using Cu(OAc)2 x H2O as a catalyst precursor, (S)-BINAP as a ligand, PMHS as a hydride source, and t-BuOH as an additive. The methodology has been applied successfully to the enantioselective synthesis of a chiral pharmaceutical, (R)-baclofen.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Role of a distal pocket in the catalytic O2 reduction by cytochrome c oxidase models immobilized on interdigitated array electrodes.

    PubMed

    Collman, James P; Decréau, Richard A; Lin, Hengwei; Hosseini, Ali; Yang, Ying; Dey, Abhishek; Eberspacher, Todd A

    2009-05-05

    Five iron porphyrins with different superstructures were immobilized on self-assembled-monolayer (SAM)-coated interdigitated-array (IDAs) gold-platinum electrodes. The selectivity of the catalysts i.e., limited formation of partially reduced oxygen species (PROS) in the electrocatalytic reduction of dioxygen, is a function of 2 rates: (i) the rate of electron transfer from the electrode to the catalyst, which is controlled by the length, and conjugation of the linker from the catalyst to the electrode and (ii) the rate of bound oxygen (superoxide) hydrolysis, which correlates with the presence of a water cluster in the gas-binding pocket influencing the rate of oxygen binding; these factors are controlled by the nature of the porphyrin superstructure. The structurally biomimetic Tris-imidazole model is the most selective.

  4. Asymmetric Synthesis of Nonracemic Primary Amines via Spiroborate Catalyzed Reduction of pure (E)- and (Z)-O-Benzyloximes: Applications toward the Synthesis of Calcimimetic Agents

    PubMed Central

    Ou, Wenhua; Espinosa, Sandraliz; Meléndez, Héctor J.; Farré, Silvia M.; Alvarez, Jaime L.; Torres, Valerie; Martínez, Ileanne; Santiago, Kiara M.; Ortiz-Marciales, Margarita

    2013-01-01

    Highly enantiopure (1-aryl)- and (1-naphthyl)-1-ethylamines were synthesized by the borane-mediated reduction of single-isomeric (E)- and (Z)-O-benzyloxime ethers using the stable spiroborate ester derived from (S)-diphenyl valinol and ethylene glycol as the chiral catalyst. Primary (R)-arylethylamines were prepared by the reduction of pure (Z)-ethanone oxime ethers in up to 99% ee using 15% of catalyst. Two convenient and facile approaches to the synthesis of new and known calcimimetic analogs employing enantiopure (1-naphthalen-1-yl)ethylamine as chiral precursor are described. PMID:23638707

  5. NHC-Ag/Pd-Catalyzed Reductive Carboxylation of Terminal Alkynes with CO2 and H2 : A Combined Experimental and Computational Study for Fine-Tuned Selectivity.

    PubMed

    Yu, Dingyi; Zhou, Feng; Lim, Diane S W; Su, Haibin; Zhang, Yugen

    2017-03-09

    Reductive carboxylation of terminal alkynes utilizing CO2 and H2 as reactants is an interesting and challenging transformation. Theoretical calculations indicated it would be kinetically possible to obtain cinnamic acid, the reductive carboxylation product, from phenylacetylene in a CO2 /H2 system with an N-heterocyclic carbene (NHC)-supported Ag/Pd bimetallic catalysts through competitive carboxylation/hydrogenation cascade reactions in one step. These calculations were verified experimentally with a poly-NHC-supported Ag/Pd catalyst. By tuning the catalyst composition and reaction temperature, phenylacetylene was selectively converted to cinnamic acid, hydrocinnamic acid, or phenylpropiolic acid in excellent yields.

  6. Oxygen reduction reaction catalyzed by nickel complexes based on thiophosphorylated calix[4]resorcinols and immobilized in the membrane electrode assembly of fuel cells.

    PubMed

    Kadirov, M K; Knyazeva, I R; Nizameev, I R; Safiullin, R A; Matveeva, V I; Kholin, K V; Khrizanforova, V V; Ismaev, T I; Burilov, A R; Budnikova, Yu H; Sinyashin, O G

    2016-10-18

    The catalytic activity of the nickel complexes of thiophosphorylated calix[4]resorcinols for oxygen reduction in a polymer electrolyte membrane fuel cell (PEMFC) has been studied. The conformation of the macrocyclic ligand determines the morphology and catalytic properties of the resulting organometallic species.

  7. Highly enantioselective reductive amination of simple aryl ketones catalyzed by Ir-f-Binaphane in the presence of titanium(IV) isopropoxide and iodine.

    PubMed

    Chi, Yongxiang; Zhou, Yong-Gui; Zhang, Xumu

    2003-05-16

    Using an Ir-f-Binaphane complex as the catalyst, complete conversions and high enantioselectivies (up to 96% ee) were achieved in the asymmetric reductive amination of aryl ketones in the presence of Ti(O(i)()Pr)(4) and I(2). A simple and efficient method of synthesizing chiral primary amines has been realized.

  8. 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.

  9. Reductive Alkylation of α-Keto Imines Catalyzed by PTSA/FeCl3: Synthesis of Indoles and 2,3'-Biindoles.

    PubMed

    Naidu, P Seetham; Kolita, Sinki; Sharma, Meenakshi; Bhuyan, Pulak J

    2015-06-19

    A simple and efficient method for the synthesis of highly functionalized indoles and biindoles was developed. In the reaction protocol, three components were used in one pot and products were obtained in high yield in an easy workup procedure. The reaction occurred via initial reductive alkylation of α-keto imines, followed by a cyclization process in the presence of PTSA/FeCl3 as catalyst.

  10. Effects of a proximal base on water oxidation and proton reduction catalyzed by geometric isomers of [Ru(tpy)(pynap)(OH2)]2+.

    PubMed

    Boyer, Julie L; Polyansky, Dmitry E; Szalda, David J; Zong, Ruifa; Thummel, Randolph P; Fujita, Etsuko

    2011-12-23

    Basic difference: The importance of a pendent base in promoting proton-coupled electron-transfer reactions with low activation barriers has been discussed for H(+) reduction or H(2) oxidation in acetonitrile. Investigation of the interaction between a base positioned in the second coordination sphere of a complex and a water ligand in water oxidation reactions using geometric isomers of [Ru(tpy)(pynap)(OH(2))](2+) (see picture) gave intriguing results.

  11. Four distinct types of E.C. 1.2.1.30 enzymes can catalyze the reduction of carboxylic acids to aldehydes.

    PubMed

    Stolterfoht, Holly; Schwendenwein, Daniel; Sensen, Christoph W; Rudroff, Florian; Winkler, Margit

    2017-09-10

    Increasing demand for chemicals from renewable resources calls for the development of new biotechnological methods for the reduction of oxidized bio-based compounds. Enzymatic carboxylate reduction is highly selective, both in terms of chemo- and product selectivity, but not many carboxylate reductase enzymes (CARs) have been identified on the sequence level to date. Thus far, their phylogeny is unexplored and very little is known about their structure-function-relationship. CARs minimally contain an adenylation domain, a phosphopantetheinylation domain and a reductase domain. We have recently identified new enzymes of fungal origin, using similarity searches against genomic sequences from organisms in which aldehydes were detected upon incubation with carboxylic acids. Analysis of sequences with known CAR functionality and CAR enzymes recently identified in our laboratory suggests that the three-domain architecture mentioned above is modular. The construction of a distance tree with a subsequent 1000-replicate bootstrap analysis showed that the CAR sequences included in our study fall into four distinct subgroups (one of bacterial origin and three of fungal origin, respectively), each with a bootstrap value of 100%. The multiple sequence alignment of all experimentally confirmed CAR protein sequences revealed fingerprint sequences of residues which are likely to be involved in substrate and co-substrate binding and one of the three catalytic substeps, respectively. The fingerprint sequences broaden our understanding of the amino acids that might be essential for the reduction of organic acids to the corresponding aldehydes in CAR proteins. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Mechanisms of Enzyme-Catalyzed Reduction of Two Carcinogenic Nitro-Aromatics, 3-Nitrobenzanthrone and Aristolochic Acid I: Experimental and Theoretical Approaches

    PubMed Central

    Stiborová, Marie; Frei, Eva; Schmeiser, Heinz H.; Arlt, Volker M.; Martínek, Václav

    2014-01-01

    This review summarizes the results found in studies investigating the enzymatic activation of two genotoxic nitro-aromatics, an environmental pollutant and carcinogen 3-nitrobenzanthrone (3-NBA) and a natural plant nephrotoxin and carcinogen aristolochic acid I (AAI), to reactive species forming covalent DNA adducts. Experimental and theoretical approaches determined the reasons why human NAD(P)H:quinone oxidoreductase (NQO1) and cytochromes P450 (CYP) 1A1 and 1A2 have the potential to reductively activate both nitro-aromatics. The results also contributed to the elucidation of the molecular mechanisms of these reactions. The contribution of conjugation enzymes such as N,O-acetyltransferases (NATs) and sulfotransferases (SULTs) to the activation of 3-NBA and AAI was also examined. The results indicated differences in the abilities of 3-NBA and AAI metabolites to be further activated by these conjugation enzymes. The formation of DNA adducts generated by both carcinogens during their reductive activation by the NOQ1 and CYP1A1/2 enzymes was investigated with pure enzymes, enzymes present in subcellular cytosolic and microsomal fractions, selective inhibitors, and animal models (including knock-out and humanized animals). For the theoretical approaches, flexible in silico docking methods as well as ab initio calculations were employed. The results summarized in this review demonstrate that a combination of experimental and theoretical approaches is a useful tool to study the enzyme-mediated reaction mechanisms of 3-NBA and AAI reduction. PMID:24918288

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

    PubMed

    Naraginti, Saraschandra; Sivakumar, A

    2014-07-15

    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 (111), (200), (222) and (311) 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.

  14. 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

  15. 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

    2016-09-05

    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.

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

    SciTech Connect

    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 cuboctahedra 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.

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

    DOE PAGES

    Zhang, Jiawei; Winget, Sarah A.; Wu, Yiren; ...

    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

  18. 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.

  19. 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

  20. 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.

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

    DOE PAGES

    Zhang, Sen; Hao, Yizhou; Su, Dong; ...

    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

  2. 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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Methyl-coenzyme M reductase of Methanobacterium thermoautotrophicum delta H catalyzes the reductive dechlorination of 1,2-dichloroethane to ethylene and chloroethane.

    PubMed Central

    Holliger, C; Kengen, S W; Schraa, G; Stams, A J; Zehnder, A J

    1992-01-01

    Reductive dechlorination of 1,2-dichloroethane (1,2-DCA) to ethylene and chloroethane (CA) by crude cell extracts of Methanobacterium thermoautotrophicum delta H with H2 as the electron donor was stimulated by Mg-ATP. The heterodisulfide of coenzyme M (CoM) and 7-mercaptoheptanoylthreonine phosphate together with Mg-ATP partially inhibited ethylene production but stimulated CA production compared Mg-ATP alone. The pH optimum for the dechlorination was 6.8 (at 60 degrees C). Michaelis-Menten kinetics for initial product formation rates with different 1,2-DCA concentrations indicated the enzymatic character of the dechlorination. Apparent Kms for 1,2-DCA of 89 and 119 microM and Vmaxs of 34 and 20 pmol/min/mg of protein were estimated for ethylene and CA production, respectively. 3-Bromopropanesulfonate, a specific inhibitor for methyl-CoM reductase, completely inhibited dechlorination of 1,2-DCA. Purified methyl-CoM reductase, together with flavin adenine dinucleotide and a crude component A fraction which reduced the nickel of factor F430 in methyl-CoM reductase, converted 1,2-DCA to ethylene and CA with H2 as the electron donor. In this system, methyl-CoM reductase was also able to transform its own inhibitor 2-bromoethanesulfonate to ethylene. PMID:1624435

  4. Density functional theory mechanistic study of the reduction of CO2 to CH4 catalyzed by an ammonium hydridoborate ion pair: CO2 activation via formation of a formic acid entity.

    PubMed

    Wen, Mingwei; Huang, Fang; Lu, Gang; Wang, Zhi-Xiang

    2013-10-21

    Density functional theory computations have been applied to gain insight into the CO2 reduction to CH4 with Et3SiH, catalyzed by ammonium hydridoborate 1 ([TMPH](+)[HB(C6F5)3](-), where TMP = 2,2,6,6-tetramethylpiperidine) and B(C6F5)3. The study shows that CO2 is activated through the concerted transfer of H(δ+) and H(δ-) of 1 to CO2, giving a complex (IM2) with a well-formed HCOOH entity, followed by breaking of the O-H bond of the HCOOH entity to return H(δ+) to TMP, resulting in an intermediate 2 ([TMPH](+)[HC(═O)OB(C6F5)3)](-)), with CO2 being inserted into the B-H bond of 1. However, unlike CO2 insertion into transition-metal hydrides, the direct insertion of CO2 into the B-H bond of 1 is inoperative. The computed CO2 activation mechanism agrees with the experimental synthesis of 2 via reacting HCOOH with TMP/B(C6F5)3. Subsequent to the CO2 activation and B(C6F5)3-mediated hydrosilylation of 2 to regenerate the catalyst (1), giving HC(═O)OSiEt3 (5), three hydride-transfer steps take place, sequentially transferring H(δ-) of Et3SiH to 5 to (Et3SiO)2CH2 (6, the product of the first hydride-transfer step) to Et3SiOCH3 (7, the product of the second hydride-transfer step) and finally resulting in CH4. These hydride transfers are mediated by B(C6F5)3 via two SN2 processes without involving 1. B(C6F5)3 acts as a hydride carrier that, with the assistance of a nucleophilic attack of 5-7, first grabs H(δ-) from Et3SiH (the first SN2 process), giving HB(C6F5)3(-), and then leave H(δ-) of HB(C6F5)3(-) to the electrophilic C center of 5-7 (the second SN2 process). The SN2 processes utilize the electrophilic and nucleophilic characteristics possessed by the hydride acceptors (5-7). The hydride-transfer mechanism is different from that in the CO2 reduction to methanol catalyzed by N-heterocyclic carbene (NHC) and PCP-pincer nickel hydride ([Ni]H), where the characteristic of possessing a C═O double bond of the hydride acceptors is utilized for hydride transfer

  5. Catalyzing RE Project Development

    SciTech Connect

    Anderson, Kate; Elgqvist, Emma; Walker, Andy; Cutler, Dylan; Olis, Dan; DiOrio, Nick; Simpkins, Travis

    2016-09-01

    This poster details how screenings done with REopt - NREL's software modeling platform for energy systems integration and optimization - are helping to catalyze the development of hundreds of megawatts of renewable energy.

  6. 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.

  7. Homogenous electrocatalytic oxygen reduction rates correlate with reaction overpotential in acidic organic solutions

    DOE PAGES

    Pegis, Michael L.; McKeown, Bradley A.; Kumar, Neeraj; ...

    2016-10-28

    Improvement of electrocatalysts for the oxygen reduction reaction (ORR) is critical for the advancement of fuel cell technologies. Herein, we report a series of eleven soluble iron porphyrin ORR electrocatalysts that possess turnover frequencies (TOFs) from 3 s-1 to an unprecedented 2.2 x 106 s-1. These TOFs correlate with the ORR overpotential, which can be changed by modulating the ancillary ligand, by varying the reaction conditions or by changing the catalyst’s protonation state. This is the first such correlation for homogeneous ORR electrocatalysis, and it demonstrates that the remarkably fast TOFs are a consequence of the high overpotential. Computational studiesmore » indicate that the correlation is analogous to the volcano plot analysis developed for heterogeneous ORR materials. This unique parallel between homo- and heterogeneous ORR electrocatalysts allows a fundamental understanding of intrinsic barriers associated with the ORR, which can aid the design of new catalytic systems that operate at low overpotential. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. Additional data is given in the Electronic Supporting Information.« less

  8. Homogenous Electrocatalytic Oxygen Reduction Rates Correlate with Reaction Overpotential in Acidic Organic Solutions

    SciTech Connect

    Pegis, Michael L.; McKeown, Bradley A.; Kumar, Neeraj; Lang, Kai; Wasylenko, Derek J.; Zhang, X. Peter; Raugei, Simone; Mayer, James M.

    2016-10-28

    Improvement of electrocatalysts for the oxygen reduction reaction (ORR) is critical for the advancement of fuel cell technologies. Herein, we report a series of eleven soluble iron porphyrin ORR electrocatalysts that possess turnover frequencies (TOFs) from 3 s-1 to an unprecedented 2.2 x 106 s-1. These TOFs correlate with the ORR overpotential, which can be changed by modulating the ancillary ligand, by varying the reaction conditions or by changing the catalyst’s protonation state. This is the first such correlation for homogeneous ORR electrocatalysis, and it demonstrates that the remarkably fast TOFs are a consequence of the high overpotential. Computational studies indicate that the correlation is analogous to the volcano plot analysis developed for heterogeneous ORR materials. This unique parallel between homo- and heterogeneous ORR electrocatalysts allows a fundamental understanding of intrinsic barriers associated with the ORR, which can aid the design of new catalytic systems that operate at low overpotential. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. Additional data is given in the Electronic Supporting Information.

  9. Microbial reductive dehalogenation.

    PubMed Central

    Mohn, W W; Tiedje, J M

    1992-01-01

    A wide variety of compounds can be biodegraded via reductive removal of halogen substituents. This process can degrade toxic pollutants, some of which are not known to be biodegraded by any other means. Reductive dehalogenation of aromatic compounds has been found primarily in undefined, syntrophic anaerobic communities. We discuss ecological and physiological principles which appear to be important in these communities and evaluate how widely applicable these principles are. Anaerobic communities that catalyze reductive dehalogenation appear to differ in many respects. A large number of pure cultures which catalyze reductive dehalogenation of aliphatic compounds are known, in contrast to only a few organisms which catalyze reductive dehalogenation of aromatic compounds. Desulfomonile tiedjei DCB-1 is an anaerobe which dehalogenates aromatic compounds and is physiologically and morphologically unusual in a number of respects, including the ability to exploit reductive dehalogenation for energy metabolism. When possible, we use D. tiedjei as a model to understand dehalogenating organisms in the above-mentioned undefined systems. Aerobes use reductive dehalogenation for substrates which are resistant to known mechanisms of oxidative attack. Reductive dehalogenation, especially of aliphatic compounds, has recently been found in cell-free systems. These systems give us an insight into how and why microorganisms catalyze this activity. In some cases transition metal complexes serve as catalysts, whereas in other cases, particularly with aromatic substrates, the catalysts appear to be enzymes. Images PMID:1406492

  10. 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.

  11. 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

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

    PubMed

    Tylus, Urszula; Jia, Qingying; Strickland, Kara; Ramaswamy, Nagappan; Serov, Alexey; Atanassov, Plamen; Mukerjee, Sanjeev

    2014-05-01

    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-N x 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 Fe(2+)-N4 centers and the dual-site 2e(-) × 2e(-) mechanism in acid media with the significant role of the surface bound coexisting Fe/Fe x O y nanoparticles (NPs) as the secondary active sites.

  13. 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

  14. Remediation of highly contaminated soils from an industrial site by employing a combined treatment with exogeneous humic substances and oxidative biomimetic catalysis.

    PubMed

    Sannino, Filomena; Spaccini, Riccardo; Savy, Davide; Piccolo, Alessandro

    2013-10-15

    Remediation of two polluted soils from a northern Italian industrial site heavily contaminated with organic contaminants was attempted here by subjecting soils first to addition with an exogenous humic acid (HA), and, then, to an oxidation reaction catalyzed by a water-soluble iron-porphyrin (FeP). An expected decrease of detectable organic pollutants (>50%) was already observed when soils were treated only with the H2O2 oxidant. This reduction was substantially enhanced when oxidation was catalyzed by iron-porphyrin (FeP+H2O2) and the largest effect was observed for the most highly polluted soil. Even more significant was the decrease in detectable pollutants (70-90%) when soils were first amended with HA and then subjected to the FeP+H2O2 treatment. This reduction in extractable pollutants after the combined HA+FeP+H2O2 treatment was due to formation of covalent CC and COC bonds between soil contaminants and amended humic molecules. Moreover, the concomitant detection of condensation products in soil extracts following FeP addition confirmed the occurrence of free-radical coupling reactions catalyzed by FeP. These findings indicate that a combined technique based on the action of both humic matter and a metal-porhyrin catalyst, may become useful to quantitatively reduce the toxicity of heavily contaminated soils and prevent the environmental transport of pollutants. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Antiproton catalyzed fusion

    SciTech Connect

    Morgan, D.L. Jr.; Perkins, L.J.; Haney, S.W.

    1995-05-15

    Because of the potential application to power production, it is important to investigate a wide range of possible means to achieve nuclear fusion, even those that may appear initially to be infeasible. In antiproton catalyzed fusion, the negative antiproton shields the repulsion between the positively charged nuclei of hydrogen isotopes, thus allowing a much higher level of penetration through the repulsive Coulomb barrier, and thereby greatly enhancing the fusion cross section. Because of their more compact wave function, the more massive antiprotons offer considerably more shielding than do negative muons. The effects of the shielding on fusion cross sections are most predominate, at low energies. If the antiproton could exist in the ground state with a nucleus for a sufficient time without annihilating, the fusion cross sections are so enhanced that at room temperature energies, values up to about 1,000 barns (that for d+t) would be possible. Unfortunately, the cross section for antiproton annihilation with the incoming nucleus is even higher. A model that provides an upper bound for the fusion to annihilation cross section for all relevant energies indicates that each antiproton will catalyze no more than about one fusion. Because the energy required to make one antiproton greatly exceeds the fusion energy that is released, this level of catalysis is far from adequate for power production.

  16. 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

  17. Trypsin-catalyzed deltamethrin degradation.

    PubMed

    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.

  18. Copper-catalyzed cascade reactions of α,β-unsaturated esters with keto esters

    PubMed Central

    Wang, Chongnian; Li, Zengchang

    2015-01-01

    Summary A copper-catalyzed cascade reaction of α,β-unsaturated esters with keto esters is reported. It features a copper-catalyzed reductive aldolization followed by a lactonization. This method provides a facile approach to prepare γ-carboxymethyl-γ-lactones and δ-carboxymethyl-δ-lactones under mild reaction conditions. PMID:25815072

  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. Redox Couple Involving NOx in Aerobic Pd-Catalyzed Oxidation of sp(3)-C-H Bonds: Direct Evidence for Pd-NO3(-)/NO2(-) Interactions Involved in Oxidation and Reductive Elimination.

    PubMed

    Wenzel, Margot N; Owens, Philippa K; Bray, Joshua T W; Lynam, Jason M; Aguiar, Pedro M; Reed, Christopher; Lee, James D; Hamilton, Jacqueline F; Whitwood, Adrian C; Fairlamb, Ian J S

    2017-01-25

    NaNO3 is used in oxidative Pd-catalyzed processes as a complementary co-catalyst to common oxidants, e.g., Cu(II) salts, in C-H bond activation and Wacker oxidation processes. NaNO3 and NaNO2 (with air or O2) assist the sp(3)-C-H bond acetoxylation of substrates bearing an N-directing group. It has been proposed previously that a redox couple is operative. The role played by NOx anions is examined in this investigation. Evidence for an NOx anion interaction at Pd(II) is presented. Palladacyclic complexes containing NOx anions are competent catalysts for acetoxylation of 8-methylquinoline, with and without exogenous NaNO3. The oxidation of 8-methylquinoline to the corresponding carboxylic acid has also been noted at Pd(II). (18)O-Labeling studies indicate that oxygen derived from nitrate appears in the acetoxylation product, the transfer of which can only occur by interaction of (18)O at Pd with a coordinating-acetate ligand. Nitrated organic intermediates are formed under catalytic conditions, which are converted to acetoxylation products, a process that occurs with (50 °C) and without Pd (110 °C). A catalytically competent palladacyclic dimer intermediate has been identified. Head-space analysis measurements show that NO and NO2 gases are formed within minutes on heating catalytic mixtures to 110 °C from room temperature. Measurements by in situ infrared spectroscopy show that N2O is formed in sp(3)-C-H acetoxylation reactions at 80 °C. Studies confirm that cyclopalladated NO2 complexes are rapidly oxidized to the corresponding NO3 adducts on exposure to NO2(g). The investigation shows that NOx anions act as participating ligands at Pd(II) in aerobic sp(3)-C-H bond acetoxylation processes and are involved in redox processes.

  1. Mechanistic study of iron(III) [tetrakis(pentafluorophenyl)porphyrin triflate (F(20)TPP)Fe(OTf) catalyzed cyclooctene epoxidation by hydrogen peroxide.

    PubMed

    Stephenson, Ned A; Bell, Alexis T

    2007-03-19

    We have recently proposed a mechanism for the epoxidation of cyclooctene by H2O2 catalyzed by iron(III) [tetrakis(pentafluorophenyl)]porphyrin chloride, (F20TPP)FeCl, in solvent containing methanol [Stephenson, N. A.; Bell, A.T. Inorg. Chem. 2006, 45, 2758-2766]. In that study, we found that catalysis did not occur unless (F20TPP)FeCl first dissociated, a process facilitated by the solvation of the Cl- anion by methanol and the coordination of methanol to the (F20TPP)Fe+ cation. Methanol as well as other alcohols was also found to facilitate the heterolytic cleavage of the O-O bond of H2O2 coordinated to the (F20TPP)Fe+ cation via a generalized acid mechanism. In the present study, we have shown that catalytic activity of the (F20TPP)Fe+ cation can be achieved in aprotic solvent by displacing the tightly bound chloride anion with a weakly bound triflate anion. By working in an aprotic solvent, acetonitrile, it was possible to determine the rate of heterolytic O-O bond cleavage in coordinated H2O2 unaffected by the interaction of the peroxide with methanol. A mechanism is proposed for this system and is shown to be valid over a range of reaction conditions. The mechanisms for cyclooctene epoxidation and H2O2 decomposition for the aprotic and protic solvent systems are similar with the only difference being the mechanism of proton-transfer prior to heterolytic cleavage of the oxygen-oxygen bond of coordinated hydrogen peroxide. Comparison of the rate parameters indicates that the utilization of hydrogen peroxide for cyclooctene epoxidation is higher in a protic solvent than in an aprotic solvent and results in a smaller extent of porphyrin degradation due to free radical attack. It was also shown that water can coordinate to the iron porphyrin cation in aprotic systems resulting in catalyst deactivation; this effect was not observed when methanol was present, since methanol was found to displace all of the coordinated water.

  2. 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

  3. Abiotic reduction reactions of anthropogenic organic chemicals in anaerobic systems: A critical review

    NASA Astrophysics Data System (ADS)

    Macalady, Donald L.; Tratnyek, Paul G.; Grundl, Timothy J.

    1986-02-01

    This review is predicated upon the need for a detailed process-level understanding of factors influencing the reduction of anthropogenic organic chemicals in natural aquatic systems. In particular, abiotic reductions of anthropogenic organic chemicals are reviewed. The most important reductive reaction is alkyl dehalogenation (replacement of chloride with hydrogen) which occurs in organisms, sediments, sewage sludge, and reduced iron porphyrin model systems. An abiotic mechanism involving a free radical intermediate has been proposed. The abstraction of vicinal dihalides (also termed dehalogenation) is another reduction that may have an abiotic component in natural systems. Reductive dehalogenation of aryl halides has recently been reported and further study of this reaction is needed. Several other degradation reactions of organohalides that occur in anaerobic environments are mentioned, the most important of which is dehydrohalogenation. The reduction of nitro groups to amines has also been thoroughly studied. The reactions can occur abiotically, and are affected by the redox conditions of the experimental system. However, a relationship between nitro-reduction rate and measured redox potential has not been clearly established. Reductive dealkylation of the N- and O-heteroatom of hydrocarbon pollutants has been observed but not investigated in detail. Azo compounds can be reduced to their hydrazo derivatives and a thorough study of this reaction indicates that it can be caused by extracellular electron transfer agents. Quinone-hydroquinone couples are important reactive groups in humic materials and similar structures in resazurin and indigo carmine make them useful as models for environmental redox conditions. The interconversion of sulfones, sulfoxides, and sulfides is a redox process and is implicated in the degradation of several pesticides though the reactions need more study. Two reductive heterocyclic cleavage reactions are also mentioned. Finally, several

  4. 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.

  5. Homogenous Electrocatalytic Oxygen Reduction Rates Correlate with Reaction Overpotential in Acidic Organic Solutions

    PubMed Central

    2016-01-01

    Improved electrocatalysts for the oxygen reduction reaction (ORR) are critical for the advancement of fuel cell technologies. Herein, we report a series of 11 soluble iron porphyrin ORR electrocatalysts that possess turnover frequencies (TOFs) from 3 s–1 to an unprecedented value of 2.2 × 106 s–1. These TOFs correlate with the ORR overpotential, which can be modulated by changing the E1/2 of the catalyst using different ancillary ligands, by changing the solvent and solution acidity, and by changing the catalyst’s protonation state. The overpotential is well-defined for these homogeneous electrocatalysts by the E1/2 of the catalyst and the proton activity of the solution. This is the first such correlation for homogeneous ORR electrocatalysis, and it demonstrates that the remarkably fast TOFs are a consequence of high overpotential. The correlation with overpotential is surprising since the turnover limiting steps involve oxygen binding and protonation, as opposed to turnover limiting electron transfer commonly found in Tafel analysis of heterogeneous ORR materials. Computational studies show that the free energies for oxygen binding to the catalyst and for protonation of the superoxide complex are in general linearly related to the catalyst E1/2, and that this is the origin of the overpotential correlations. This analysis thus provides detailed understanding of the ORR barriers. The best catalysts involve partial decoupling of the influence of the second coordination sphere from the properties of the metal center, which is suggested as new molecular design strategy to avoid the limitations of the traditional scaling relationships for these catalysts. PMID:27924314

  6. Non-sensitized selective photochemical reduction of CO2 to CO under visible light with an iron molecular catalyst.

    PubMed

    Rao, Heng; Bonin, Julien; Robert, Marc

    2017-03-02

    A substituted tetraphenyl iron porphyrin, bearing positively charged trimethylammonio groups at the para position of each phenyl ring, demonstrates its ability as a homogeneous molecular catalyst to selectively reduce CO2 to CO under visible light irradiation in organic media without the assistance of a sensitizer and no competitive hydrogen evolution for several days.

  7. 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.

  8. DNA-Catalyzed Amide Hydrolysis

    PubMed Central

    Zhou, Cong; Avins, Joshua L.; Klauser, Paul C.; Brandsen, Benjamin M.; Lee, Yujeong; Silverman, Scott K.

    2016-01-01

    DNA catalysts (deoxyribozymes) for a variety of reactions have been identified by in vitro selection. However, for certain reactions this identification has not been achieved. One important example is DNA-catalyzed amide hydrolysis, for which a previous selection experiment instead led to DNA-catalyzed DNA phosphodiester hydrolysis. Subsequent efforts in which the selection strategy deliberately avoided phosphodiester hydrolysis led to DNA-catalyzed ester and aromatic amide hydrolysis, but aliphatic amide hydrolysis has been elusive. In the present study, we show that including modified nucleotides that bear protein-like functional groups (any one of primary amino, carboxyl, or primary hydroxyl) enables identification of amide-hydrolyzing deoxyribozymes. In one case, the same deoxyribozyme sequence without the modifications still retains substantial catalytic activity. Overall, these findings establish the utility of introducing protein-like functional groups into deoxyribozymes for identifying new catalytic function. The results also suggest the longer-term feasibility of deoxyribozymes as artificial proteases. PMID:26854515

  9. 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

  10. Palladium-Catalyzed Arylation of Fluoroalkylamines.

    PubMed

    Brusoe, Andrew T; Hartwig, John F

    2015-07-08

    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.

  11. Rhenium and manganese bipyridine tricarbonyl catalysts for the electrochemical reduction of carbon dioxide

    NASA Astrophysics Data System (ADS)

    Sampson, Matthew Dean

    molecular catalysts on a heterogeneous platform. A Mn bipyridine catalyst attached to a highly robust Zr(IV)-based MOF is used to enhance photochemical CO2 reduction. By utilizing an iron porphyrin catalyst, anchored into the linkers of a MOF thin film, we demonstrate, in a proof of principle, electrochemical CO2 reduction by this heterogenized molecular catalyst.

  12. Iodine-Catalyzed Polysaccharide Esterification

    USDA-ARS?s Scientific Manuscript database

    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...

  13. 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.

  14. Dechlorination of carbon tetrachloride by the catalyzed Fe-Cu process.

    PubMed

    Xu, Wen-Ying; Gao, Ting-Yao

    2007-01-01

    The electrochemical reduction characteristics of carbon tetrachloride (CT) were investigated using cyclic voltammetry in this study. In addition, the difference in reduction mechanisms of CT between Master Builders' iron and the catalyzed Fe-Cu process was discussed. The results showed that CT was reduced directly on the surface of copper rather than by atomic hydrogen produced at the cathode in the catalyzed Fe-Cu process. The reduction was realized largely by atomic hydrogen in Master Builders' iron. The entire CT in 350 ml aqueous solution with 320 mg/L was reduced to trichloromethane and dichloromethane in 2.25 h when 100 g of scrap iron with Fe/Cu ratio of 10:1 (w/w) were used. Moreover, the reduction rate slowed with time. CT could be reduced at acidic, neutral and alkaline pH from solution by Fe-Cu bimetallic media, but the mechanisms were different. The degradation rate was not significantly influenced by pH in the catalyzed Fe-Cu process; in Master Builders' iron it clearly increased with decreasing pH. The kinetics of the reductions followed pseudo-first order in both cases. Furthermore, the reductions under acidic conditions proceeded faster than that under the neutral and alkaline conditions. The catalyzed Fe-Cu process was superior to Master Builders' iron in treating CT-containing water and this advantage was particularly noticeable under alkaline conditions. The reduction was investigated in the cathode (Cu) and anode (Fe) compartments respectively, the results showed that the direct reduction pathway played an important role in the reduction by the catalyzed Fe-Cu process. The catalyzed Fe-Cu process is of practical value.

  15. Pd-catalyzed nucleophilic fluorination of aryl bromides.

    PubMed

    Lee, Hong Geun; Milner, Phillip J; Buchwald, Stephen L

    2014-03-12

    On the basis of mechanism-driven reaction design, a Pd-catalyzed nucleophilic fluorination of aryl bromides and iodides has been developed. The method exhibits a broad substrate scope, especially with respect to nitrogen-containing heteroaryl bromides, and proceeds with minimal formation of the corresponding reduction products. A facilitated ligand modification process was shown to be critical to the success of the reaction.

  16. Pd-Catalyzed Nucleophilic Fluorination of Aryl Bromides

    PubMed Central

    2015-01-01

    On the basis of mechanism-driven reaction design, a Pd-catalyzed nucleophilic fluorination of aryl bromides and iodides has been developed. The method exhibits a broad substrate scope, especially with respect to nitrogen-containing heteroaryl bromides, and proceeds with minimal formation of the corresponding reduction products. A facilitated ligand modification process was shown to be critical to the success of the reaction. PMID:24559304

  17. Ligand-guided pathway selection in nickel-catalyzed couplings of enals and alkynes.

    PubMed

    Li, Wei; Montgomery, John

    2012-01-28

    Nickel-catalyzed couplings of enals and alkynes utilizing triethylborane as the reducing agent illustrate a significant dependence on ligand structure. Simple variation of monodentate phosphines allows selective access to alkylative couplings or reductive cycloadditions, while further variation of reaction conditions provides clean access to reductive couplings and redox-neutral couplings.

  18. 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.

  19. Gold-catalyzed domino reactions.

    PubMed

    Michelet, Véronique

    2015-01-01

    Gold-catalyzed reactions have appeared to be highly attractive tools for chemists to promote novel transformations to prepare elaborated structures from simple starting materials. This chapter presents selected and original examples of domino processes in the presence of gold catalysts, highlighting reports implying hydration, hydroxylation, and hydroamination as key starting point for cascade transformations. Domino processes implying 1,n-enynes, asymmetric domino transformations, and applications of all the presented processes in total synthesis are presented.

  20. 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.

  1. Enzyme-catalyzed biocathode in a photoelectrochemical biofuel cell

    NASA Astrophysics Data System (ADS)

    Yang, Jing; Hu, Donghua; Zhang, Xiaohuan; Wang, Kunqi; Wang, Bin; Sun, Bo; Qiu, Zhidong

    2014-12-01

    A novel double-enzyme photoelectrochemical biofuel cell (PEBFC) has been developed by taking glucose dehydrogenase (GDH) and horseradish peroxidase (HRP) as the enzyme of the photoanode and biocathode to catalyze the oxidation of glucose and the reduction of oxygen. A H2-mesoporphyrin IX is used as a dye for a TiO2 film electrode to fabricate a photoanode. The horseradish peroxidase (HRP) is immobilized on a glassy carbon (GC) electrode to construct a biocathode which is used to catalyze the reduction of oxygen in the PEBFC for the first time. The biocathode exhibits excellent electrocatalytic activity in the presence of O2. The performances of the PEBFC are obtained by current-voltage and power-voltage curves. The short-circuit current density (Isc), the open-circuit voltage (Voc), maximum power density (Pmax), fill factor (FF) and energy conversion efficiency (η) are 439 μA cm-2, 678 mV, 79 μW cm-2, 0.39 and 0.016%, respectively, and the incident photon-to-collected electron conversion efficiency (IPCE) is 32% at 350 nm. The Isc is higher than that of the PEBFC with Pt cathode, and the Voc is higher than that of the dye-sensitized solar cell or the enzyme-catalyzed biofuel cell operating individually, which demonstrates that the HRP is an efficient catalyst for the biocathode in the PEBFC.

  2. Asymmetric oxidoreductions catalyzed by alcohol dehydrogenase in organic solvents

    SciTech Connect

    Grunwald, J.; Wirz, B.; Scollar, M.P.; Klibanov, A.M.

    1986-10-15

    A methodology is developed for the use of alcohol dehydrogenase (and other NAD/sup +//NADH-dependent enzymes) as catalysts in organic solvents. The enzyme and the cofactor are deposited onto the surface of glass beads which are then suspended in a water-immiscible organic solvent containing the substrate. Both NADH and NAD/sup +/ are efficiently regenerated in such a system with alcohol dehydrogenase-catalyzed oxidation of ethanol and reduction of isobutyraldehyde, respectively; cofactor turnover numbers of 10/sup 5/ to greater than 10/sup 6/ have been obtained. With use of asymmetric oxidoreductions catalyzed by horse liver alcohol dehydrogenase in isopropyl ether, optically active (ee of 95 to 100%) alcohols and ketones have been prepared on a 1 to 10 mmol scale.

  3. Erythrocyte enzymes catalyze 1-nitropyrene and 3-nitrofluoranthene nitroreduction.

    PubMed

    Belisario, M A; Pecce, R; Garofalo, A; Sannolo, N; Malorni, A

    1996-04-15

    Nitroarenes are environmental contaminants produced during incomplete combustion processes. Nitroreduction, the most important pathway of nitroarene toxification, occurs mainly in the liver and intestine. In the present study, we show that human red cells may also possess the metabolic competence to reduce 1-nitropyrene (NP) and 3-nitrofluoranthene (NF), the nitroarenes chosen as model compounds, to their corresponding amino derivatives, 1-aminopyrene (AP) and 3-aminofluoranthene (AF). The requirement of the cofactor couple NADH/FMN suggests that erythrocyte nitroreductase activity occurs via one electron transfer. The presence of oxygen strongly inhibited the haemolysate-catalyzed nitroarene reduction, whether measured as amine formation or nitroarene disappearance. Intermediate reactive species, that bind covalently to haemoglobin and/or other erythrocyte proteins, are formed during nitroreduction catalyzed by human haemolysate. In fact, the reduced metabolites AP and AF were released after mild acid hydrolysis of red cell proteins exposed to NP and NF, thus suggesting that sulphinamide adducts have been formed.

  4. 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

  5. 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. 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.

  7. 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.

  8. Iodide effects in transition metal catalyzed reactions.

    PubMed

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

    2004-11-07

    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.

  9. 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.

  10. 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.

  11. 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

  12. 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

  13. Nickel-catalyzed N-vinylation of heteroaromatic amines via C-H bond activation.

    PubMed

    Landge, Vinod G; Rana, Jagannath; Subaramanian, Murugan; Balaraman, Ekambaram

    2017-08-23

    Here, we report a ligand- and reductant-free nickel-catalyzed N-vinylation of heteroaromatic amines using biorenewable p-cymene as a solvent. This unprecedented cross-coupling strategy has high functional group tolerance (halides, alkoxy, cyano, chiral motif, etc.) and proceeded via C-H bond activation.

  14. Biochemistry of Catabolic Reductive Dehalogenation.

    PubMed

    Fincker, Maeva; Spormann, Alfred M

    2017-06-20

    A wide range of phylogenetically diverse microorganisms couple the reductive dehalogenation of organohalides to energy conservation. Key enzymes of such anaerobic catabolic pathways are corrinoid and Fe-S cluster-containing, membrane-associated reductive dehalogenases. These enzymes catalyze the reductive elimination of a halide and constitute the terminal reductases of a short electron transfer chain. Enzymatic and physiological studies revealed the existence of quinone-dependent and quinone-independent reductive dehalogenases that are distinguishable at the amino acid sequence level, implying different modes of energy conservation in the respective microorganisms. In this review, we summarize current knowledge about catabolic reductive dehalogenases and the electron transfer chain they are part of. We review reaction mechanisms and the role of the corrinoid and Fe-S cluster cofactors and discuss physiological implications.

  15. Primary-tertiary diamine-catalyzed Michael addition of ketones to isatylidenemalononitrile derivatives

    PubMed Central

    Kumar, Akshay

    2014-01-01

    Summary Simple primary-tertiary diamines easily derived from natural primary amino acids were used to catalyze the Michael addition of ketones with isatylidenemalononitrile derivatives. Diamine 1a in combination with D-CSA as an additive provided Michael adducts in high yield (up to 94%) and excellent enantioselectivity (up to 99%). The catalyst 1a was successfully used to catalyze the three-component version of the reaction by a domino Knoevenagel–Michael sequence. The Michael adduct 4a was transformed into spirooxindole 6 by a reduction with sodium borohydride in a highly enantioselective manner. PMID:24991242

  16. Cu-Catalyzed Hydrocarbonylative C-C Coupling of Terminal Alkynes with Alkyl Iodides.

    PubMed

    Cheng, Li-Jie; Mankad, Neal P

    2017-08-02

    A Cu-catalyzed hydrocarbonylative C-C coupling of terminal alkynes with unactivated alkyl iodides has been developed, enabling highly chemo- and regioselective synthesis of unsymmetrical dialkyl ketones. A variety of functional groups are tolerated, and both primary and secondary alkyl iodides react well. An autotandem sequence of two Cu-catalyzed processes is proposed: first hydrocarbonylative coupling of the alkyne and the alkyl iodide, followed by reduction of the intermediate unsaturated ketone to the saturated product. Mechanistic experiments indicate that an alkenylcopper intermediate activates the alkyl iodide by single electron transfer to enable a radical carbonylation pathway.

  17. 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.

  18. Advances in lipase-catalyzed esterification reactions.

    PubMed

    Stergiou, Panagiota-Yiolanda; Foukis, Athanasios; Filippou, Michalis; Koukouritaki, Maria; Parapouli, Maria; Theodorou, Leonidas G; Hatziloukas, Efstathios; Afendra, Amalia; Pandey, Ashok; Papamichael, Emmanuel M

    2013-12-01

    Lipase-catalyzed esterification reactions are among the most significant chemical and biochemical processes of industrial relevance. Lipases catalyze hydrolysis as well as esterification reactions. Enzyme-catalyzed esterification has acquired increasing attention in many applications, due to the significance of the derived products. More specifically, the lipase-catalyzed esterification reactions attracted research interest during the past decade, due to an increased use of organic esters in biotechnology and the chemical industry. Lipases, as hydrolyzing agents are active in environments, which contain a minimum of two distinct phases, where all reactants are partitioned between these phases, although their distribution is not fixed and changes as the reaction proceeds. The kinetics of the lipase-catalyzed reactions is governed by a number of factors. This article presents a thorough and descriptive evaluation of the applied trends and perspectives concerning the enzymatic esterification, mainly for biofuel production; an emphasis is given on essential factors, which affect the lipase-catalyzed esterification reaction. Moreover, the art of using bacterial and/or fungal strains for whole cell biocatalysis purposes, as well as carrying out catalysis by various forms of purified lipases from bacterial and fungal sources is also reviewed.

  19. 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

  20. Rhodium-catalyzed acyloxy migration of propargylic esters in cycloadditions, inspiration from the recent "gold rush".

    PubMed

    Shu, Xing-Zhong; Shu, Dongxu; Schienebeck, Casi M; Tang, Weiping

    2012-12-07

    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.

  1. A Link between Protein Structure and Enzyme Catalyzed Hydrogen Tunneling

    NASA Astrophysics Data System (ADS)

    Bahnson, Brian J.; Colby, Thomas D.; Chin, Jodie K.; Goldstein, Barry M.; Klinman, Judith P.

    1997-11-01

    We present evidence that the size of an active site side chain may modulate the degree of hydrogen tunneling in an enzyme-catalyzed reaction. Primary and secondary kH/kT and kD/kT kinetic isotope effects have been measured for the oxidation of benzyl alcohol catalyzed by horse liver alcohol dehydrogenase at 25 degrees C. As reported in earlier studies, the relationship between secondary kH/kT and kD/kT isotope effects provides a sensitive probe for deviations from classical behavior. In the present work, catalytic efficiency and the extent of hydrogen tunneling have been correlated for the alcohol dehydrogenase-catalyzed hydride transfer among a group of site-directed mutants at position 203. Val-203 interacts with the opposite face of the cofactor NAD+ from the alcohol substrate. The reduction in size of this residue is correlated with diminished tunneling and a two orders of magnitude decrease in catalytic efficiency. Comparison of the x-ray crystal structures of a ternary complex of a high-tunneling (Phe-93 --> Trp) and a low-tunneling (Val-203 --> Ala) mutant provides a structural basis for the observed effects, demonstrating an increase in the hydrogen transfer distance for the low-tunneling mutant. The Val-203 --> Ala ternary complex crystal structure also shows a hyperclosed interdomain geometry relative to the wild-type and the Phe-93 --> Trp mutant ternary complex structures. This demonstrates a flexibility in interdomain movement that could potentially narrow the distance between the donor and acceptor carbons in the native enzyme and may enhance the role of tunneling in the hydride transfer reaction.

  2. Oligonucleotide formation catalyzed by mononucleotide matrices

    NASA Technical Reports Server (NTRS)

    Lohrmann, R.

    1982-01-01

    Pb(2+)-containing precipitates of mononucleotides form matrices which catalyze the self-condensation of nucleotide 5-prime-phosphorimidazolides and their condensation with nucleosides. The reactions exhibit base-pairing specificity between matrix nucleotide and substrate, and usually follow the Watson-Crick pairing rules. Although purine polynucleotides do not facilitate the oligomerization of pyrimidine nucleotide monomers in solution, it is interesting that purine-containing matrices do catalyze such a reaction. The significance of the results in the context of the prebiotic evolution of polynucleotides is discussed.

  3. Enantioselective, iridium-catalyzed monoallylation of ammonia.

    PubMed

    Pouy, Mark J; Stanley, Levi M; Hartwig, John F

    2009-08-19

    Highly enantioselective, iridium-catalyzed monoallylations of ammonia are reported. These reactions occur with electron-neutral, -rich, and -poor cinnamyl carbonates, alkyl and trityloxy-substituted allylic carbonates, and dienyl carbonates in moderate to good yields and excellent enantioselectivities. This process is enabled by the use of an iridium catalyst that does not require a Lewis acid for activation and that is stable toward a large excess of ammonia. This selective formation of primary allylic amines allows for one-pot syntheses of heterodiallylamines and allylic amides that are not otherwise accessible via iridium-catalyzed allylic amination without the use of blocking groups and protective group manipulations.

  4. Oligonucleotide formation catalyzed by mononucleotide matrices

    NASA Technical Reports Server (NTRS)

    Lohrmann, R.

    1982-01-01

    Pb(2+)-containing precipitates of mononucleotides form matrices which catalyze the self-condensation of nucleotide 5-prime-phosphorimidazolides and their condensation with nucleosides. The reactions exhibit base-pairing specificity between matrix nucleotide and substrate, and usually follow the Watson-Crick pairing rules. Although purine polynucleotides do not facilitate the oligomerization of pyrimidine nucleotide monomers in solution, it is interesting that purine-containing matrices do catalyze such a reaction. The significance of the results in the context of the prebiotic evolution of polynucleotides is discussed.

  5. 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.

  6. 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.

  7. Enantioselective, Iridium-Catalyzed Monoallylation of Ammonia

    PubMed Central

    Pouy, Mark J.; Stanley, Levi M.; Hartwig, John F.

    2009-01-01

    Highly enantioselective, iridium-catalyzed monoallylations of ammonia are reported. These reactions occur with electron-neutral, -rich, and -poor cinnamyl carbonates, alkyl and trityloxy-substituted allylic carbonates, and dienyl carbonates in moderate to good yields and excellent enantioselectivities. This process is enabled by the use of an iridium catalyst that does not require a Lewis acid for activation and that is stable toward a large excess of ammonia. This selective formation of primary allylic amines allows for one-pot syntheses of heterodiallylamines and allylic amides that are not otherwise accessible via iridium-catalyzed allylic amination without the use of blocking groups and protective group manipulations. PMID:19722644

  8. A comparative study of ozonation, iron coated zeolite catalyzed ozonation and granular activated carbon catalyzed ozonation of humic acid.

    PubMed

    Gümüş, Dilek; Akbal, Feryal

    2017-05-01

    This study compares ozonation (O3), iron coated zeolite catalyzed ozonation (ICZ-O3) and granular activated carbon catalyzed ozonation (GAC-O3) for removal of humic acid from an aqueous solution. The results were evaluated by the removal of DOC that specifies organic matter, UV254 absorbance, SUVA (Specific Ultraviolet Absorbance at 254 nm) and absorbance at 436 nm. When ozonation was used alone, DOC removal was 21.4% at an ozone concentration of 10 mg/L, pH 6.50 and oxidation time of 60 min. The results showed that the use of ICZ or GAC as a catalyst increased the decomposition of humic acid compared to ozonation alone. DOC removal efficiencies were 62% and 48.1% at pH 6.5, at a catalyst loading of 0.75 g/L, and oxidation time of 60 min for ICZ and GAC, respectively. The oxidation experiments were also carried out using <100 kDa and <50 kDa molecular size fractions of humic acid in the presence of ICZ or GAC. Catalytic ozonation also yielded better DOC and UV254 reduction in both <50 kDa and <100 kDa fractions of HA compared to ozonation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. 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.

  10. 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.

  11. 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.

  12. Rhenium-catalyzed deoxydehydration of diols and polyols.

    PubMed

    Dethlefsen, Johannes R; Fristrup, Peter

    2015-03-01

    The substitution of platform chemicals of fossil origin by biomass-derived analogues requires the development of chemical transformations capable of reducing the very high oxygen content of biomass. One such reaction, which has received increasing attention within the past five years, is the rhenium-catalyzed deoxydehydration (DODH) of a vicinal diol into an alkene; this is a model system for abundant polyols like glycerol and sugar alcohols. The present contribution includes a review of early investigations of stoichiometric reactions involving rhenium, diols, and alkenes followed by a discussion of the various catalytic systems that have been developed with emphasis on the nature of the reductant, the substrate scope, and mechanistic investigations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. [Ru/AC catalyzed ozonation of recalcitrant organic compounds].

    PubMed

    Wang, Jian-Bing; Hou, Shao-Pei; Zhou, Yun-Rui; Zhu, Wan-Peng; He, Xu-Wen

    2009-09-15

    Ozonation and Ru/AC catalyzed ozonation of dimethyl phthalate (DMP), phenols and disinfection by-products precursors were studied. It shows that Ru/AC catalyst can obviously enhance the mineralization of organic compounds. In the degradation of DMP, TOC removal was 28.84% by ozonation alone while it was 66.13% by catalytic ozonation. In the oxidation of 23 kinds of phenols, TOC removals were 9.57%-56.08% by ozonation alone while they were 41.81%-82.32% by catalytic ozonation. Compared to ozonation alone, Ru/AC catalyzed ozonation was more effective for the reduction of disinfection by-products formation potentials in source water. The reduction of haloacetic acids formation potentials was more obvious than thichlomethane formation potentials. After the treatment by catalytic ozonation, the haloacetic acids formation potentials decreased from 144.02 microg/L to 58.50 microg/L, which was below the standard value of EPA. However ozonation alone could not make it reach the standard. The treatments of source water by BAC, O3 + BAC, O3/AC + BAC and Ru/AC + O3 + BAC were also studied. In the four processes, TOC removal was 3.80%, 20.14%, 27.45% and 48.30% respectively, COD removal was 4.37%, 27.22%, 39.91% and 50.00% respectively, UV254 removal was 8.16%, 62.24%, 67.03% and 84.95% respectively. Ru/AC + O3 + BAC process is more effective than the other processes for the removal of TOC, COD and UV254 and no ruthenium leaching observed in the solution. It is a promising process for the treatment of micro polluted source water.

  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. 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.

  16. 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…

  17. Organic acids tunably catalyze carbonic acid decomposition.

    PubMed

    Kumar, Manoj; Busch, Daryle H; Subramaniam, Bala; Thompson, Ward H

    2014-07-10

    Density functional theory calculations predict that the gas-phase decomposition of carbonic acid, a high-energy, 1,3-hydrogen atom transfer reaction, can be catalyzed by a monocarboxylic acid or a dicarboxylic acid, including carbonic acid itself. Carboxylic acids are found to be more effective catalysts than water. Among the carboxylic acids, the monocarboxylic acids outperform the dicarboxylic ones wherein the presence of an intramolecular hydrogen bond hampers the hydrogen transfer. Further, the calculations reveal a direct correlation between the catalytic activity of a monocarboxylic acid and its pKa, in contrast to prior assumptions about carboxylic-acid-catalyzed hydrogen-transfer reactions. The catalytic efficacy of a dicarboxylic acid, on the other hand, is significantly affected by the strength of an intramolecular hydrogen bond. Transition-state theory estimates indicate that effective rate constants for the acid-catalyzed decomposition are four orders-of-magnitude larger than those for the water-catalyzed reaction. These results offer new insights into the determinants of general acid catalysis with potentially broad implications.

  18. Catalyzing curriculum evolution in graduate science education.

    PubMed

    Gutlerner, Johanna L; Van Vactor, David

    2013-05-09

    Strategies in life science graduate education must evolve in order to train a modern workforce capable of integrative solutions to challenging problems. Our institution has catalyzed such evolution through building a postdoctoral Curriculum Fellows Program that provides a collaborative and scholarly education laboratory for innovation in graduate training.

  19. 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…

  20. 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.

  1. Palladium-catalyzed substitution of allylic fluorides.

    PubMed

    Hazari, Amaruka; Gouverneur, Véronique; Brown, John M

    2009-01-01

    As unusual substrates for the Tsuji-Trost allylation reaction, allylic fluorides are responsive to palladium-catalyzed substitution. Their activity towards this reaction fits in the series OCO(2)Me>OBz>F>OAc. The classic stereoretention mechanism that involves sequential inversions does not operate in this case. Several distinct cases are considered.

  2. Dual chemistry catalyzed by human acireductone dioxygenase.

    PubMed

    Deshpande, Aditi R; Pochapsky, Thomas C; Petsko, Gregory A; Ringe, Dagmar

    2017-03-01

    Acireductone dioxygenase (ARD) from the methionine salvage pathway of Klebsiella oxytoca is the only known naturally occurring metalloenzyme that catalyzes different reactions in vivo based solely on the identity of the divalent transition metal ion (Fe2+ or Ni2+) bound in the active site. The iron-containing isozyme catalyzes the cleavage of substrate 1,2-dihydroxy-3-keto-5-(thiomethyl)pent-1-ene (acireductone) by O2 to formate and the ketoacid precursor of methionine, whereas the nickel-containing isozyme uses the same substrates to catalyze an off-pathway shunt to form methylthiopropionate, carbon monoxide and formate. This dual chemistry was recently demonstrated in vitro by ARD from Mus musculus (MmARD), providing the first example of a mammalian ARD exhibiting metal-dependent catalysis. We now show that human ARD (HsARD) is also capable of metal-dependent dual chemistry. Recombinant HsARD was expressed and purified to obtain a homogeneous enzyme with a single transition metal ion bound. As with MmARD, the Fe2+-bound HsARD shows the highest activity and catalyzes on-pathway chemistry, whereas Ni2+, Co2+ or Mn2+ forms catalyze off-pathway chemistry. The thermal stability of the HsARD isozymes is a function of the metal ion identity, with Ni2+-bound HsARD being the most stable followed by Co2+ and Fe2+, and Mn2+-bound HsARD being the least stable. As with the bacterial ARD, solution NMR data suggest that HsARD isozymes can have significant structural differences depending upon the metal ion bound. © The Author 2017. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  3. Highly Selective Palladium-Catalyzed Cross-Coupling of Secondary Alkylzinc Reagents with Heteroaryl Halides

    PubMed Central

    2015-01-01

    The highly selective palladium-catalyzed Negishi coupling of secondary alkylzinc reagents with heteroaryl halides is described. The development of a series of biarylphosphine ligands has led to the identification of an improved catalyst for the coupling of electron-deficient heterocyclic substrates. Preparation and characterization of oxidative addition complex (L)(Ar)PdBr provided insight into the unique reactivity of catalysts based on CPhos-type ligands in facilitating challenging reductive elimination processes. PMID:25153332

  4. Microwave-enhanced transition metal-catalyzed decoration of 2(1H)-pyrazinone scaffolds.

    PubMed

    Kaval, Nadya; Bisztray, Katalin; Dehaen, Wim; Kappe, C Oliver; Van der Eycken, Erik

    2003-01-01

    The 2(1H)-pyrazinones have been demonstrated to be versatile building blocks for the synthesis of biologically active compounds. Here, an efficient method is described for the decoration of these interesting scaffolds. Microwave-assisted palladium catalyzed reactions allow the easy introduction of different substituents at the C3- and even at the rather unreactive C5-position of the pyrazinones. Stille, Suzuki, Heck, Sonogashira reactions, in addition to reductive dechlorinations, and cyanation reactions are investigated.

  5. Ruthenium-catalyzed meta/ortho-selective C-H alkylation of azoarenes using alkyl bromides.

    PubMed

    Li, Gang; Ma, Xingxing; Jia, Chunqi; Han, Qingqing; Wang, Ya; Wang, Junjie; Yu, Liuyang; Yang, Suling

    2017-01-19

    meta/ortho-Selective CAr-H (di)alkylation reactions of azoarenes have been achieved via [Ru(p-cymene)Cl2]2 catalyzed ortho-metalation using various types of alkyl bromides. Particularly, dual meta-alkylation of azoarene and reduction offer an attractive strategy for the synthesis of meta-alkylanilines, which are difficult to access via traditional aniline functionalization methods.

  6. C-O hydrogenolysis catalyzed by Pd-PMHS nanoparticles in the company of chloroarenes.

    PubMed

    Rahaim, Ronald J; Maleczka, Robert E

    2011-02-18

    Catalytic Pd(OAc)(2) and polymethylhydrosiloxane (PMHS), in conjunction with aqueous KF, and a catalytic amount of an aromatic chloride, effects the chemo-, regio-, and stereoselective deoxygenation of benzylic oxygenated substrates at room temperature in THF. Preliminary mechanistic experiments suggest the process to involve palladium-nanoparticle-catalyzed hydrosilylation followed by C-O reduction. The chloroarene additive appears to facilitate the hydrogenolysis process through the slow controlled release of HCl.

  7. Palladium-catalyzed cross-coupling of benzyl chlorides with cyclopropanol-derived ketone homoenolates.

    PubMed

    Nithiy, Nisha; Orellana, Arturo

    2014-11-21

    The palladium-catalyzed cross-coupling reaction of cyclopropanol-derived ketone homoenolates with benzyl chlorides is reported. This reaction proceeds in high yields with electron-neutral and electron-rich benzyl chlorides; however, yields are low with electron-poor benzyl chlorides. In addition, a range of cyclopropanols can be coupled in good yields. The reaction can be conducted with a low catalyst loading (1% Pd) and on a gram scale without reduction in yield.

  8. Diastereoselective Construction of Functionalized Homoallylic Alcohols by Ni-Catalyzed Diboron-Promoted Coupling of Dienes and Aldehydes

    PubMed Central

    Cho, Hee Yeon; Morken, James P.

    2009-01-01

    The nickel-catalyzed reaction of carbonyls and dienes was accomplished in a regio- and stereo-selective fashion employing a stoichiometric amount of bis(pinacolato)diboron. This reductive coupling furnishes an allyl boronic esters as the reaction product, a compound which was readily converted to the derived allylic alcohol by oxidative work-up. PMID:18998642

  9. Palladium(II)-catalyzed coupling reactions with a chelating vinyl ether and arylboronic acids: a new Heck/Suzuki domino diarylation reaction.

    PubMed

    Trejos, Alejandro; Fardost, Ashkan; Yahiaoui, Samir; Larhed, Mats

    2009-12-28

    A mild and novel palladium(II)-catalyzed domino Heck/Suzuki alpha,beta-diarylation-reduction of a dimethylaminoethyl substituted chelating vinyl ether was developed by using electron-rich arylboronic acids in combination with p-benzoquinone. Based on the preparative results, a catalytic cycle is proposed. Further, highly regioselective palladium(II)-catalyzed alpha- or beta-monoarylation of the chelating vinyl ether was achieved using either a bidentate ligand or by employing ligand-less conditions.

  10. Mechanism Studies of Ir-Catalyzed Asymmetric Hydrogenation of Unsaturated Carboxylic Acids.

    PubMed

    Li, Mao-Lin; Yang, Shuang; Su, Xun-Cheng; Wu, Hui-Ling; Yang, Liang-Liang; Zhu, Shou-Fei; Zhou, Qi-Lin

    2017-01-11

    The Ir-catalyzed asymmetric hydrogenation of olefins is widely used for production of value-added bulk and fine chemicals. The iridium catalysts with chiral spiro phosphine-oxazoline ligands developed in our group show high activity and high enantioselectivity in the hydrogenation of olefins bearing a coordinative carboxyl group, such as α,β-unsaturated carboxylic acids, β,γ-unsaturated carboxylic acids, and γ,δ-unsaturated carboxylic acids. Here we conducted detailed mechanistic studies on these Ir-catalyzed asymmetric hydrogenation reactions by using (E)-2-methyl-3-phenylacrylic acid as a model substrate. We isolated and characterized several key intermediates having Ir-H bonds under the real hydrogenation conditions. Particularly, an Ir(III) migratory insertion intermediate was first isolated in an asymmetric hydrogenation reaction promoted by chiral Ir catalysts. That this intermediate cannot undergo reductive elimination in the absence of hydrogen strongly supports the involvement of an Ir(III)/Ir(V) cycle in the hydrogenation. On the basis of the structure of the Ir(III) intermediate, variable-temperature NMR spectroscopy, and density functional theory calculations, we elucidated the mechanistic details of the Ir-catalyzed hydrogenation of unsaturated carboxylic acids and explained the enantioselectivity of the reactions. These findings experimentally and computationally elucidate the mechanism of Ir-catalyzed asymmetric hydrogenation of olefins with a strong coordinative carboxyl group and will likely inspire further catalyst design.

  11. Analytical rheology of metallocene-catalyzed polyethylenes

    NASA Astrophysics Data System (ADS)

    Shanbhag, Sachin; Takeh, Arsia

    2011-03-01

    A computational algorithm that seeks to invert the linear viscoelastic spectrum of single-site metallocene-catalyzed polyethylenes is presented. The algorithm uses a general linear rheological model of branched polymers as its underlying engine, and is based on a Bayesian formulation that transforms the inverse problem into a sampling problem. Given experimental rheological data on unknown single-site metallocene- catalyzed polyethylenes, it is able to quantitatively describe the range of values of weight-averaged molecular molecular weight, MW , and average branching density, bm , consistent with the data. The algorithm uses a Markov-chain Monte Carlo method to simulate the sampling problem. If, and when information about the molecular weight is available through supplementary experiments, such as chromatography or light scattering, it can easily be incorporated into the algorithm, as demonstrated. Financial support from NSF DMR 0953002.

  12. 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.

  13. Horseradish-Peroxidase-Catalyzed Tyrosine Click Reaction.

    PubMed

    Sato, Shinichi; Nakamura, Kosuke; Nakamura, Hiroyuki

    2017-03-02

    The efficiency of protein chemical modification on tyrosine residues with N-methylluminol derivatives was drastically improved by using horseradish peroxidase (HRP). In the previous method, based on the use of hemin and H2 O2 , oxidative side reactions such as cysteine oxidation were problematic for functionalization of proteins selectively on tyrosine residues. Oxidative activation of N-methylluminol derivatives with a minimum amount of H2 O2 prevented the occurrence of oxidative side reactions under HRP-catalyzed conditions. As probes for HRP-catalyzed protein modification, N-methylluminol derivatives showed much higher efficiency than tyramide without inducing oligomerization of probe molecules. Tyrosine modification also proceeded in the presence of β-nicotinamide adenine dinucleotide (NADH, H2 O2 -free conditions).

  14. Stop-catalyzed baryogenesis beyond the MSSM

    NASA Astrophysics Data System (ADS)

    Katz, Andrey; Perelstein, Maxim; Ramsey-Musolf, Michael J.; Winslow, Peter

    2015-11-01

    Nonminimal supersymmetric models that predict a tree-level Higgs mass above the minimal supersymmetric standard model (MSSM) bound are well motivated by naturalness considerations. Indirect constraints on the stop sector parameters of such models are significantly relaxed compared to the MSSM; in particular, both stops can have weak-scale masses. We revisit the stop-catalyzed electroweak baryogenesis (EWB) scenario in this context. We find that the LHC measurements of the Higgs boson production and decay rates already rule out the possibility of stop-catalyzed EWB. We also introduce a gauge-invariant analysis framework that may generalize to other scenarios in which interactions outside the gauge sector drive the electroweak phase transition.

  15. Rhodium-catalyzed restructuring of carbon frameworks.

    PubMed

    Murakami, Masahiro

    2010-10-01

    Metal-catalyzed reactions involving an elementary step which cleaves a carbon-carbon bond provide unique organic transformations. Restructuring reactions recently developed in our laboratory, through which the carbon framework of a starting substance is restructured into a totally different carbon framework, are discussed, with the possibility of applying such methods to the synthesis of natural products. © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

  16. Nickel-Catalyzed Synthesis of Quinazolinediones.

    PubMed

    Beutner, Gregory L; Hsiao, Yi; Razler, Thomas; Simmons, Eric M; Wertjes, William

    2017-03-03

    A nickel(0)-catalyzed method for the synthesis of quinazolinediones from isatoic anhydrides and isocyanates is described. High-throughput ligand screening revealed that XANTPHOS was the optimal ligand for this transformation. Subsequent optimization studies, supported by kinetic analysis, significantly expanded the reaction scope. The reaction exhibits a case of substrate inhibition kinetics with respect to the isocyanate. Preliminary results on an asymmetric synthesis of atropisomeric quinazolinediones are reported.

  17. 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.

  18. Cu2+-catalyzed oxidative degradation of thyroglobulin.

    PubMed

    Lee, H J; Sok, D E

    2000-10-01

    Thyroglobulin (Tg) was subjected to metal-catalyzed oxidation, and the oxidative degradation was analyzed by SDS-polyacrylamide gel electrophoresis under reducing conditions. In contrast to no effect of hydrogen peroxide (H2O2) alone on the Tg degradation, the inclusion of Cu2+ (30 microM), in combination with 2 mM H2O2, caused a remarkable degradation of Tg, time- and concentration-dependent. The action of Cu2+ was not mimicked by Fe2+, suggesting that Tg may interact selectively with Cu2+. A similar degradation of Tg was also observed with Cu2+/ascorbate system, and the concentration of Cu2+ (5-10 microM), in combination with ascorbate, required for the effective degradation was smaller than that of Cu2+ (10-30 microM) in combination with H2O2. In support of involvement of H2O2 in the Cu2+/ascorbate action, catalase expressed a complete protection. However, hydroxyl radical scavengers such as dimethylsulfoxide or mannitol failed to prevent the oxidation of Tg whereas phenolic compounds, which can interact with Cu2+, diminished the oxidative degradation, presumably consistent with the mechanism for Cu2+-catalyzed oxidation of protein. Moreover, the amount of carbonyl groups in Tg was increased as the concentration (3-100 microM) of Cu2+ was enhanced, while the formation of acid-soluble peptides was not remarkable in the presence of Cu2+ up to 200 microM. In further studies, Tg pretreated with heat or trichloroacetic acid seemed to be somewhat resistant to Cu2+-catalyzed oxidation, implying a possible involvement of protein conformation in the susceptibility to the oxidation. Based on these observations, it is proposed that Tg could be degraded non-enzymatically by Cu2+-catalyzed oxidation.

  19. Metal Catalyzed Oligomerization Reactions of Organosiloxanes.

    DTIC Science & Technology

    1982-10-28

    metallacycle from a mixture of stereo- isomers of the starting disiloxane is observed. The catalytic activity of these complexes for the oligomeriza... catalysts were adsorbed on oxide supports. Although the goal of synthesizing stereoregular silicones has not yet been achieved, the results warrant further...implicated as intermediates in several transi- tion metal-catalyzed reactions, e.g. olefin metathesis . 1 3 Metallacycles are also probable

  20. Iron-catalyzed trifluoromethylation of enamide.

    PubMed

    Rey-Rodriguez, Romain; Retailleau, Pascal; Bonnet, Pascal; Gillaizeau, Isabelle

    2015-02-23

    Herein the first example of the iron(II)-catalyzed trifluoromethylation of enamide using mild and simple reaction conditions is reported. The method is cost-effective and uses the easy-to-handle Togni's reagent as the electrophilic CF3 source. This transformation is totally regioselective at the C3 position of enamides and exhibits broad substrate scope, good functional group tolerance and thus demonstrates its useful application in a late-stage fluorination strategy.

  1. Palladium-Catalyzed Fluorosulfonylvinylation of Organic Iodides.

    PubMed

    Zha, Gao-Feng; Zheng, Qinheng; Leng, Jing; Wu, Peng; Qin, Hua-Li; Sharpless, K Barry

    2017-03-29

    A palladium-catalyzed fluorosulfonylvinylation reaction of organic iodides is described. Catalytic Pd(OAc)2 with a stoichiometric amount of silver(I) trifluoroacetate enables the coupling process between either an (hetero)aryl or alkenyl iodide with ethenesulfonyl fluoride (ESF). The method is demonstrated in the successful syntheses of eighty-eight otherwise difficult to access compounds, in up to 99 % yields, including the unprecedented 2-heteroarylethenesulfonyl fluorides and 1,3-dienylsulfonyl fluorides.

  2. Nickel-catalyzed enantioselective arylation of pyridine†

    PubMed Central

    Lutz, J. Patrick; Chau, Stephen T.

    2016-01-01

    We report an enantioselective Ni-catalyzed cross coupling of arylzinc reagents with pyridiniumions formed in situ from pyridine and a chloroformate. This reaction provides enantioenriched 2-aryl-1,2-dihydropyridine products that can be elaborated to numerous piperidine derivatives with little or no loss in ee. This method is notable for its use of pyridine, a feedstock chemical, to build a versatile, chiral heterocycle in a single synthetic step. PMID:28058106

  3. Transition metal catalyzed transformations of unsaturated molecules

    SciTech Connect

    Not Available

    1989-01-01

    In this proposal, research in three areas of transition metal catalyzed transformations of small molecules is proposed. The first encompasses metal catalyzed processes for the synthesis of several classes of carbon monoxide containing polymers. This section describes plans for metal catalyzed synthesis of (a) new alternating copolymers of carbon monoxide and olefins, (b) block copolymers consisting of segments of the olefin homopolymer and the olefin- carbon monoxide alternating copolymer, and (c) polycarbonates, polyesters and polyamides. The second section involves the examination of the chemistry of metal complexes incorporating oxo and hydrocarbyl ligands as a model for the heterogeneous oxidation of olefins and alkanes by meal oxides. Specific plans are to mimic in solution two proposed key steps in the heterogeneous oxidations. These are (a) the heterolytic cleavage of an alkyl (or allyl) C-H bond that is assisted by an oxo group, and (a) the transfer of an oxo group to the resultant metal bound alkyl (or allyl) ligand. The third section concerned with the development of a hybrid catalyst system involving both homogeneous and heterogeneous components for the oxidative functionalization of alkanes. The basic idea is to employ a transition metal in the elemental state to activate C-H bonds of alkanes and form surface alkyl groups. An additional transition metal species will be present in solution which will serve to oxidize these surface alkyl groups to ultimately yield oxidatively functionalized organic products. 57 refs.

  4. 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.

  5. Biocatalytic reduction of carboxylic acids.

    PubMed

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

    2014-06-01

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

  6. 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

  7. 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

  8. Ara h 2 cross-linking catalyzed by MTGase decreases its allergenicity.

    PubMed

    Wu, Zhihua; Lian, Jun; Zhao, Ruifang; Li, Kun; Li, Xin; Yang, Anshu; Tong, Ping; Chen, Hongbing

    2017-03-22

    Peanuts, whose major allergen is Ara h 2, are included among the eight major food allergens. After reduction using dithiothreitol (DTT), cross-linking of Ara h 2 could be catalyzed by microbial transglutaminase (MTGase), a widely used enzyme in the food industry. In this study, Ara h 2 cross-linking was catalyzed by MTGase after it was reduced by DTT. Using mass spectrometry and PLINK software, five cross-linkers were identified, and five linear allergen epitopes were found to be involved in the reactions. The IgE binding capacity of cross-linked Ara h 2 was found to be significantly lower compared to that of native and reduced Ara h 2. After simulated gastric fluid (SGF) digestion, the digested products of the cross-linked Ara h 2, again, had a significantly lower IgE binding capacity compared to untreated and reduced Ara h 2. Furthermore, reduced and cross-linked Ara h 2 (RC-Ara h 2) induced lower sensitization in mice, indicating its lower allergenicity. Reduction and MTGase-catalyzed cross-linking are effective methods to decrease the allergenicity of Ara h 2. The reactions involved linear allergen epitopes destroying the material basis of the allergenicity, and this might develop a new direction for protein desensitization processes.

  9. Surface catalyzed Fenton treatment of bis(2-chloroethyl) ether and bis(2-chloroethoxy) methane.

    PubMed

    Mutuc, Maria D M; Love, Nancy G; Vikesland, Peter J

    2008-02-01

    This study examined the feasibility of using surface catalyzed Fenton treatment to remediate soil and groundwater contaminated by the chlorinated ethers, bis(2-chloroethyl) ether (BCEE) and bis(2-chloroethoxy) methane (BCEM). Parameters that affect the contaminant loss rate such as porewater pH, hydrogen peroxide concentration, and solid/water ratio were systematically evaluated. Batch reactors were set-up utilizing either contaminated or uncontaminated soil, obtained from an industrial site in Moss Point, MS, that was mixed with synthetic groundwater containing the contaminants of interest. The results show an increase in contaminant reduction with a decrease in pH, an increase in hydrogen peroxide concentration, or an increase in the solid/water ratio. For a similar set of conditions, contaminant reduction was greater for systems utilizing contaminated soil as compared to the systems containing uncontaminated soil. In addition, specific oxygen uptake rates (SOURs) were measured for biomass, collected from an activated sludge plant, exposed to different dilutions of untreated and surface catalyzed Fenton treated water to evaluate whether residual BCEE, BCEM, and their co-contaminants as well as their oxidation by-products were potentially inhibitory or can potentially serve as a substrate for the biomass. The measured SOURs show that the surface catalyzed Fenton treatment enhanced the biodegradability of the contaminated groundwater and served as a substrate for the biomass.

  10. Bimetallic Reductive Elimination from Dinuclear Pd(III) Complexes

    PubMed Central

    Powers, David C.; Benitez, Diego; Tkatchouk, Ekaterina; Goddard, William A.

    2010-01-01

    In 2009, we reported C–halogen reductive elimination reactions from dinuclear Pd(III) complexes and implicated dinuclear intermediates in Pd(OAc)2-catalyzed C–H oxidation chemistry. Herein, we report results of a thorough experimental and theoretical investigation of the mechanism of reductive elimination from such dinuclear Pd(III) complexes, which establish the role of each metal during reductive elimination. Our results implicate reductive elimination from a complex in which the dinuclear core is intact and suggest that redox synergy between both metals is responsible for the facile reductive elimination reactions observed. PMID:20858006

  11. Regiospecificity of Chlorophenol Reductive Dechlorination by Vitamin B12s

    PubMed Central

    Smith, Mark H.; Woods, Sandra L.

    1994-01-01

    Vitamin B12, reduced by titanium (III) citrate to vitamin B12s, catalyzes the reductive dechlorination of chlorophenols. Reductive dechlorination of pentachlorophenol and of all tetrachlorophenol and trichlorophenol isomers was observed. Reaction of various chlorophenols with vitamin B12 favored reductive dechlorination at positions adjacent to another chlorinated carbon, but chlorines ortho to the hydroxyl group of a phenol were particularly resistant to reductive dechlorination, even if they were also ortho to a chlorine. This resulted in a reductive dechlorination pattern favoring removal of para and meta chlorines, which differs substantially from the pattern exhibited by anaerobic microbial consortia. PMID:16349438

  12. 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

  13. Resting State and Elementary Steps of the Coupling of Aryl Halides with Thiols Catalyzed by Alkylbisphosphine Complexes of Palladium

    PubMed Central

    Alvaro, Elsa

    2010-01-01

    Detailed mechanistic studies on the coupling of aryl halides with thiols catalyzed by palladium complexes of the alkylbisphosphine ligand CyPF-tBu (1-dicyclohexylphosphino-2-di-tert-butylphosphinoethylferrocene) are reported. The elementary steps that constitute the catalytic cycle, i.e. oxidative addition, transmetalation and reductive elimination, have been studied, and their relative rates are reported. Each of the steps of the catalytic process occurs at temperatures that are much lower than those required for the reactions catalyzed by a combination of palladium precursors and CyPF-tBu. To explain these differences in rates between the catalytic and stoichiometric reactions, studies were conducted to identify the resting state of the catalyst of the reactions catalyzed by a combination of Pd(OAc)2 and CyPF-tBu, a combination of Pd(dba)2 and CyPF-tBu, or the likely intermediate Pd(CyPF-tBu)(Ar)(Br). These show that the major palladium complex in each case lies off of the catalytic cycle. The resting state of the reactions catalyzed by Pd(OAc)2 and CyPF-tBu was the palladium bis-thiolate complex [Pd(CyPF-tBu)(SR)2] (R = alkyl or aryl). The resting state in reactions catalyzed by Pd2(dba)3 and CyPF-tBu was the binuclear complex [Pd(CyPF-tBu)]2(μ2, η2-dba) (9). The resting state of reactions of both aromatic and aliphatic thiols catalyzed by [Pd(CyPF-tBu)(p-tolyl)(Br)] (3a) was the hydridopalladium thiolate complex [Pd(CyPF-tBu)(H)(SR)] (R= alkyl and aryl). All these palladium species have been prepared independently, and the mechanisms by which they enter the catalytic cycle have been examined in detail. These features of the reaction catalyzed by palladium and CyPF-tBu have been compared with those of reactions catalyzed by the alkylbisphosphine DiPPF and Pd(OAc)2 or Pd(dba)2. Our data indicate that the resting states of these reactions are similar to each other and that our mechanistic conclusions about reactions catalyzed by palladium and CyPF-tBu can be

  14. Labeling live cells by copper-catalyzed alkyne--azide click chemistry.

    PubMed

    Hong, Vu; Steinmetz, Nicole F; Manchester, Marianne; Finn, M G

    2010-10-20

    The copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, optimized for biological molecules in aqueous buffers, has been shown to rapidly label mammalian cells in culture with no loss in cell viability. Metabolic uptake and display of the azide derivative of N-acetylmannosamine developed by Bertozzi, followed by CuAAC ligation using sodium ascorbate and the ligand tris(hydroxypropyltriazolyl)methylamine (THPTA), gave rise to abundant covalent attachment of dye-alkyne reactants. THPTA serves both to accelerate the CuAAC reaction and to protect the cells from damage by oxidative agents produced by the Cu-catalyzed reduction of oxygen by ascorbate, which is required to maintain the metal in the active +1 oxidation state. This procedure extends the application of this fastest of azide-based bioorthogonal reactions to the exterior of living cells.

  15. 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

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

    PubMed

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

    2014-05-30

    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.

  17. 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.

  18. Labeling Live Cells by Copper-Catalyzed Alkyne-Azide Click Chemistry

    PubMed Central

    Hong, Vu; Steinmetz, Nicole F.; Manchester, Marianne

    2010-01-01

    The copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, optimized for biological molecules in aqueous buffers, has been shown to rapidly label mammalian cells in culture with no loss in cell viability. Metabolic uptake and display of the azide derivative of N-acetylmannosamine developed by Bertozzi, followed by CuAAC ligation using sodium ascorbate and the ligand tris(hydroxypropyltriazolyl)methylamine (THPTA), gave rise to abundant covalent attachment of dye-alkyne reactants. THPTA serves both to accelerate the CuAAC reaction and to protect the cells from damage by oxidative agents produced by the Cu-catalyzed reduction of oxygen by ascorbate, which is required to maintain the metal in the active +1 oxidation state. This procedure extends the application of this fastest of azide-based bioorthogonal reactions to the exterior of living cells. PMID:20886827

  19. 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.

  20. 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.

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

    DOE PAGES

    Stavretis, Shelby E.; Atanasov, Mihail; Podlesnyak, Andrey A.; ...

    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

  2. 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.

  3. Stable and catalytically active iron porphyrin-based porous organic polymer: Activity as both a redox and Lewis acid catalyst

    PubMed Central

    Oveisi, Ali R.; Zhang, Kainan; Khorramabadi-zad, Ahmad; Farha, Omar K.; Hupp, Joseph T.

    2015-01-01

    A new porphyrin-based porous organic polymer (POP) with BET surface area ranging from 780 to 880 m2/g was synthesized in free-base form via the reaction of meso-tetrakis(pentafluorophenyl) porphyrin and a rigid trigonal building block, hexahydroxytriphenylene. The material was then metallated with Fe(III) imparting activity for Lewis acid catalysis (regioselective methanolysis ring-opening of styrene oxide), oxidative cyclization catalysis (conversion of bis(2-hydroxy-1-naphthyl)methanes to the corresponding spirodienone), and a tandem catalytic processes: an in situ oxidation-cyclic aminal formation-oxidation sequence, which selectively converts benzyl alcohol to 2-phenyl-quinazolin-4(3H)-one. Notably, the catalyst is readily recoverable and reusable, with little loss in catalytic activity. PMID:26177563

  4. DNA‐Accelerated Catalysis of Carbene‐Transfer Reactions by a DNA/Cationic Iron Porphyrin Hybrid

    PubMed Central

    Rioz‐Martínez, Ana; Oelerich, Jens; Ségaud, Nathalie

    2016-01-01

    Abstract A novel DNA‐based hybrid catalyst comprised of salmon testes DNA and an iron(III) complex of a cationic meso‐tetrakis(N‐alkylpyridyl)porphyrin was developed. When the N‐methyl substituents were placed at the ortho position with respect to the porphyrin ring, high reactivity in catalytic carbene‐transfer reactions was observed under mild conditions, as demonstrated in the catalytic enantioselective cyclopropanation of styrene derivatives with ethyl diazoacetate (EDA) as the carbene precursor. A remarkable feature of this catalytic system is the large DNA‐induced rate acceleration observed in this reaction and the related dimerization of EDA. It is proposed that high effective molarity of all components of the reaction in or near the DNA is one of the key contributors to this unique reactivity. This study demonstrates that the concept of DNA‐based asymmetric catalysis can be expanded into the realm of organometallic chemistry. PMID:27730731

  5. Electron pathways in catalase and peroxidase enzymic catalysis. Metal and macrocycle oxidations of iron porphyrins and chlorins

    SciTech Connect

    Hanson, L.K.; Chang, C.K.; Davis, M.S.; Fajer, J.

    1981-02-11

    Charge iterative extended Hueckel calculations are presented for compound II, the one-electron oxidation intermediate of horseradish peroxidase (HRP), and for compounds I, the two-electron oxidation transients of HRP and catalase (CAT) observed in the catalytic cycles of the hydroperoxidase enzymes. Compound II is described in terms of a ferryl configuration (O = Fe/sup IV/), and compounds I are described as ferrylporphyrin ..pi..-cation radicals. The validity of the iron ..pi..-cation calculations is supported by favorable comparison of parallel computations for porphyrin ..pi.. cations of diamagnetic metals with new and previously reported ESR results for radicals of zinc tetrabenz-, meso-tetramethyl, (/sup 14/N and /sup 15/N) tetraphenyl-, and magnesium (/sup 1/H and /sup 2/H) octaethylporphyrins. The calculated electronic configurations and unpaired spin density profiles for the ferryl ..pi.. cations satisfactorily account for the physical properties reported for compounds I of HRP (in the native protoporphyrin IX form or reconstituted with deuteroporphyrin), chloroperoxidase, and CAT. The ground states of the ..pi.. cations, a/sub 1u/ or a/sub 2u/, are determined by peripheral substitution and axial ligation, and the axial ligand of CAT I is predicted to differ from that of HRP I. The combination of model studies and calculations suggests that /sup 2/H, /sup 13/C, and /sup 15/N NMR studies of isotopically substituted proto and deutero HRP I would confirm the electronic profiles predicted. /sup 15/N NMR in particular would clearly discriminate between a/sub 1u/ and a/sub 2u/ configurations. As an additional test of the ferryl ..pi..-cation hypothesis, calculations are presented for a proposed ferrylchlorin ..pi.. cation of Neurospora crassa catalase, which contains an iron chlorin prosthetic group. Compound I of this unusual heme is predicted to occupy an a/sub 2/ ground state with the spin distribution and optical spectra reported here for synthetic chlorin radicals.

  6. Hydroarylation of arynes catalyzed by silver for biaryl synthesis.

    PubMed

    Lee, Nam-Kyu; Yun, Sang Young; Mamidipalli, Phani; Salzman, Ryan M; Lee, Daesung; Zhou, Tao; Xia, Yuanzhi

    2014-03-19

    A new biaryl synthesis via silver-catalyzed hydroarylation of arynes from acyclic building blocks with unactivated arenes in intra- and intermolecular manners has been developed. The previously observed Diels-Alder reactions of arynes with arene were not observed under the current silver-catalyzed conditions. Deuterium scrambling and DFT calculations suggest a stepwise electrophilic aromatic substitution mechanism through the formation of a Wheland-type intermediate followed by a water-catalyzed proton transfer in the final step of the hydroarylation.

  7. Ligand Intermediates in Metal-Catalyzed Reactions

    SciTech Connect

    Gladysz, John A.

    1999-07-31

    The longest-running goal of this project has been the synthesis, isolation, and physical chemical characterization of homogeneous transition metal complexes containing ligand types believed to be intermediates in the metal-catalyzed conversion of CO/H{sub 2}, CO{sub 2}, CH{sub 4}, and similar raw materials to organic fuels, feedstocks, etc. In the current project period, complexes that contain unusual new types of C{sub x}(carbide) and C{sub x}O{sub y} (carbon oxide) ligands have been emphasized. A new program in homogeneous fluorous phase catalysis has been launched as described in the final report.

  8. Copper-catalyzed asymmetric oxidation of sulfides.

    PubMed

    O'Mahony, Graham E; Ford, Alan; Maguire, Anita R

    2012-04-06

    Copper-catalyzed asymmetric sulfoxidation of aryl benzyl and aryl alkyl sulfides, using aqueous hydrogen peroxide as the oxidant, has been investigated. A relationship between the steric effects of the sulfide substituents and the enantioselectivity of the oxidation has been observed, with up to 93% ee for 2-naphthylmethyl phenyl sulfoxide, in modest yield in this instance (up to 30%). The influence of variation of solvent and ligand structure was examined, and the optimized conditions were then used to oxidize a number of aryl alkyl and aryl benzyl sulfides, producing sulfoxides in excellent yields in most cases (up to 92%), and good enantiopurities in certain cases (up to 84% ee).

  9. Iron-catalyzed aminohydroxylation of olefins.

    PubMed

    Williamson, Kevin S; Yoon, Tehshik P

    2010-04-07

    We have discovered that N-sulfonyl oxaziridines react with a broad range of olefins in the presence of iron salts to afford 1,3-oxazolidines. This process provides access to 1,2-aminoalcohols with the opposite sense of regioselectivity produced from the copper-catalyzed oxyamination previously reported by our laboratories. Thus, either regioisomeric form of 1,2-aminoalcohols can easily be obtained from the reaction of oxaziridines with olefins, and the sense of regioselectivity can be controlled by the appropriate choice of inexpensive, nontoxic, first-row transition-metal catalyst.

  10. Aluminum Hydride Catalyzed Hydroboration of Alkynes.

    PubMed

    Bismuto, Alessandro; Thomas, Stephen P; Cowley, Michael J

    2016-12-05

    An aluminum-catalyzed hydroboration of alkynes using either the commercially available aluminum hydride DIBAL-H or bench-stable Et3 Al⋅DABCO as the catalyst and H-Bpin as both the boron reagent and stoichiometric hydride source has been developed. Mechanistic studies revealed a unique mode of reactivity in which the reaction is proposed to proceed through hydroalumination and σ-bond metathesis between the resultant alkenyl aluminum species and HBpin, which acts to drive turnover of the catalytic cycle. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 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.

  12. [Fragment reaction catalyzed by E. coli ribosomes].

    PubMed

    Kotusov, V V; Kukhanova, M K; Sal'nikova, N E; Nikolaeva, L V; Kraevskiĭ, A A

    1977-01-01

    It has been shown that 50S subunits of E. coli MRE-600 ribosomes catalyze the reaction of N-(formyl)-methionyl ester of adenosine 5'-phosphate acting as peptide donor, with Phe-tRNA or CACCA-Phe serving as a peptide acceptor. The reaction is stimulated by cytidine 5'phosphate and inhibited by lincomycin, puromycin and chloramphenicol. The obtained results show that the structure of the donor site of peptidyltransferase is completely assembled on the 50S subunit and 30S subunit is not required for its formation.

  13. Harm reduction

    PubMed Central

    Normand, Jacques; Li, Jih-Heng; Thomson, Nicholas; Jarlais, Don Des

    2014-01-01

    The “Harm Reduction” session was chaired by Dr. Jacques Normand, Director of the AIDS Research Program of the U.S. National Institute on Drug Abuse. The three presenters (and their presentation topics) were: Dr. Don Des Jarlais (High Coverage Needle/Syringe Programs for People Who Inject Drugs in Low and Middle Income Countries: A Systematic Review), Dr. Nicholas Thomson (Harm Reduction History, Response, and Current Trends in Asia), and Dr. Jih-Heng Li (Harm Reduction Strategies in Taiwan). PMID:25278732

  14. Catalytic reduction of O2 by cytochrome C using a synthetic model of cytochrome C oxidase.

    PubMed

    Collman, James P; Ghosh, Somdatta; Dey, Abhishek; Decréau, Richard A; Yang, Ying

    2009-04-15

    Cytochrome c oxidase (CcO) catalyzes the four-electron reduction of oxygen to water, the one-electron reductant Cytochrome c (Cytc) being the source of electrons. Recently we reported a functional model of CcO that electrochemically catalyzes the four-electron reduction of O(2) to H(2)O (Collman et al. Science 2007, 315, 1565). The current paper shows that the same functional CcO model catalyzes the four-electron reduction of O(2) using the actual biological reductant Cytc in a homogeneous solution. Both single and steady-state turnover kinetics studies indicate that O(2) binding is rate-determining and that O-O bond cleavage and electron transfer from reduced Cytc to the oxidized model complex are relatively fast.

  15. Waste Reduction.

    ERIC Educational Resources Information Center

    Bray, Marilyn; And Others

    1996-01-01

    Presents activities that focus on waste reduction in the school and community. The ideas are divided into grade level categories. Sample activities include Techno-Trash, where children use tools to take apart broken appliances or car parts, then reassemble them or build new creations. Activities are suggested for areas including language arts and…

  16. Formation of C-C Bonds via Ruthenium Catalyzed Transfer Hydrogenation: Carbonyl Addition from the Alcohol or Aldehyde Oxidation Level.

    PubMed

    Shibahara, Fumitoshi; Krische, Michael J

    2008-01-01

    Under the conditions of ruthenium catalyzed transfer hydrogenation employing isopropanol as terminal reductant, π-unsaturated compounds (1,3-dienes, allenes, 1,3-enynes and alkynes) reductively couple to aldehydes to furnish products of carbonyl addition. In the absence of isopropanol, π-unsaturated compounds couple directly from the alcohol oxidation level to form identical products of carbonyl addition. Such "alcohol-unsaturate C-C couplings" enable carbonyl allylation, propargylation and vinylation from the alcohol oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. Thus, direct catalytic C-H functionalization of alcohols at the carbinol carbon is achieved.

  17. Catalyzed D-D stellarator reactor

    SciTech Connect

    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 fusion 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.

  18. Catalyzed D-D stellarator reactor

    DOE PAGES

    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

  19. Catalyzed D-D stellarator reactor

    SciTech Connect

    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 fusion 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.

  20. Antibody-catalyzed anaerobic destruction of methamphetamine

    PubMed Central

    Xu, Yang; Hixon, Mark S.; Yamamoto, Noboru; McAllister, Laura A.; Wentworth, Anita D.; Wentworth, Paul; Janda, Kim D.

    2007-01-01

    Methamphetamine [(+)-2] abuse has emerged as a fast-rising global epidemic, with immunopharmacotherapeutic approaches being sought for its treatment. Herein, we report the generation and characterization of a monoclonal antibody, YX1-40H10, that catalyzes the photooxidation of (+)-2 into the nonpsychoactive compound benzaldehyde (14) under anaerobic conditions in the presence of riboflavin (6). Studies have revealed that the antibody facilitates the conversion of (+)-2 into 14 by binding the triplet photoexcited state of 6 in proximity to (+)-2. The antibody binds riboflavin (Kd = 180 μM), although this was not programmed into hapten design, and the YX1-40H10-catalyzed reaction is inhibited by molecular oxygen via the presumed quenching of the photoexcited triplet state of 6. Given that this reaction is another highlight in the processing of reactive intermediates by antibodies, we speculate that this process may have future significance in vivo with programmed immunoglobulins that use flavins as cofactors to destroy selectable molecular targets under hypoxic or even anoxic conditions. PMID:17360412

  1. 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

  2. Manganese Catalyzed C–H Halogenation

    SciTech Connect

    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–MnV$=$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

  3. 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

  4. Reduction Corporoplasty

    PubMed Central

    Hakky, Tariq S.; Martinez, Daniel; Yang, Christopher; Carrion, Rafael E.

    2015-01-01

    Objective Here we present the first video demonstration of reduction corporoplasty in the management of phallic disfigurement in a 17 year old man with a history sickle cell disease and priapism. Introduction Surgical management of aneurysmal dilation of the corpora has yet to be defined in the literature. Materials and Methods: We preformed bilateral elliptical incisions over the lateral corpora as management of aneurysmal dilation of the corpora to correct phallic disfigurement. Results The patient tolerated the procedure well and has resolution of his corporal disfigurement. Conclusions Reduction corporoplasty using bilateral lateral elliptical incisions in the management of aneurysmal dilation of the corpora is a safe an feasible operation in the management of phallic disfigurement. PMID:26005988

  5. Nickel-Catalyzed Cycloadditions of Unsaturated Hydrocarbons, Aldehydes, and Ketones

    PubMed Central

    Tekavec, Thomas N.

    2014-01-01

    The nickel-catalyzed cycloaddition of unsaturated hydrocarbons and carbonyls is reported. Diynes and enynes were used as coupling partners. Carbonyl substrates include both aldehdyes and ketones. Reactions of diynes and aldehydes afforded the [3, 3] electrocyclic ring-opened tautomers, rather than pyrans, in high yields. The cycloaddition reaction of enynes and aldehydes afforded two distinct products. A new carbon–carbon bond is formed, prior to a competitive β-hydrogen elimination of a nickel alkoxide, between the carbonyl carbon and either one of the carbons of the olefin or the alkyne. The steric hindrance of the enyne greatly affected the chemoselectivity of the cycloaddition of enynes and aldehydes. In some cases, dihydropyran was also formed. The scope of the cycloaddition reaction was expanded to include the coupling of enynes and ketones. No β-hydrogen elimination was observed in cycloaddition reaction of enynes and ketones. Instead, C–O bond-forming reductive elimination occurred exclusively to afford dihydropyrans in excellent yields. In all cases, complete chemoselectivity was observed; only dihydropyrans where the carbonyl carbon forms a carbon–carbon bond with a carbon of the olefin, rather than of the alkyne, were observed. All cycloaddition reactions occur at room temperature and employ nickel catalysts bearing the hindered 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or its saturated analogue, 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene (SIPr). PMID:18318544

  6. Nitrate reduction

    DOEpatents

    Dziewinski, Jacek J.; Marczak, Stanislaw

    2000-01-01

    Nitrates are reduced to nitrogen gas by contacting the nitrates with a metal to reduce the nitrates to nitrites which are then contacted with an amide to produce nitrogen and carbon dioxide or acid anions which can be released to the atmosphere. Minor amounts of metal catalysts can be useful in the reduction of the nitrates to nitrites. Metal salts which are formed can be treated electrochemically to recover the metals.

  7. DFT Studies on the Mechanism of the Vanadium-Catalyzed Deoxydehydration of Diols.

    PubMed

    Galindo, Agustín

    2016-03-07

    The mechanism of the vanadium-catalyzed deoxydehydration of glycols to alkenes by phosphanes (Chapman, G.; Nicholas, K. M. Chem. Commun. 2013, 49, 8199-8201) has been investigated with density functional calculations. Two alternative pathways, A and B, have been evaluated, and the three stages generally recognized in DODH processes have been identified: (i) activation of the diol by condensation on the vanadium complex and eventual formation of vanadium-glycolate, (ii) oxygen atom transfer to phosphane with reduction to a vanadium(III) species, and, finally, (iii) alkene extrusion from the vanadium-glycolate with regeneration of the starting catalyst. Pathway B, in which the reduction by the phosphane from vanadium(V) to V(III) species occurred before the diol condensation, is energetically preferred to pathway A, in which the diol activation preceded the oxo-transfer to the phosphane reductant.

  8. Acid-Catalyzed Isomerization of Carvone to Carvacrol

    ERIC Educational Resources Information Center

    Kjonaas, Richard A.; Mattingly, Shawn P.

    2005-01-01

    The acid-catalyzed isomerization of carvone to carvacrol, first reported by Ritter and Ginsburg, is especially well suited with a permanent-magnet FT instrument. The acid-catalyzed isomerization of carvone to carvacrol produced a 61% yield after a three hour reflux with 30% aqueous sulfuric acid.

  9. ENVIRONMENTAL TECHNOLOGY VERIFICATION REPORT: ENVIROFUELS DIESEL FUEL CATALYZER FUEL ADDITIVE

    EPA Science Inventory

    EPA's Environmental Technology Verification Program has tested EnviroFuels diesel fuel additive, called the Diesel Fuel Catalyzer. EnviroFuels has stated that heavy-duty on and off road diesel engines are the intended market for the catalyzer. Preliminary tests conducted indicate...

  10. Representing Rate Equations for Enzyme-Catalyzed Reactions

    ERIC Educational Resources Information Center

    Ault, Addison

    2011-01-01

    Rate equations for enzyme-catalyzed reactions are derived and presented in a way that makes it easier for the nonspecialist to see how the rate of an enzyme-catalyzed reaction depends upon kinetic constants and concentrations. This is done with distribution equations that show how the rate of the reaction depends upon the relative quantities of…

  11. Representing Rate Equations for Enzyme-Catalyzed Reactions

    ERIC Educational Resources Information Center

    Ault, Addison

    2011-01-01

    Rate equations for enzyme-catalyzed reactions are derived and presented in a way that makes it easier for the nonspecialist to see how the rate of an enzyme-catalyzed reaction depends upon kinetic constants and concentrations. This is done with distribution equations that show how the rate of the reaction depends upon the relative quantities of…

  12. Acid-Catalyzed Isomerization of Carvone to Carvacrol

    ERIC Educational Resources Information Center

    Kjonaas, Richard A.; Mattingly, Shawn P.

    2005-01-01

    The acid-catalyzed isomerization of carvone to carvacrol, first reported by Ritter and Ginsburg, is especially well suited with a permanent-magnet FT instrument. The acid-catalyzed isomerization of carvone to carvacrol produced a 61% yield after a three hour reflux with 30% aqueous sulfuric acid.

  13. ENVIRONMENTAL TECHNOLOGY VERIFICATION REPORT: ENVIROFUELS DIESEL FUEL CATALYZER FUEL ADDITIVE

    EPA Science Inventory

    EPA's Environmental Technology Verification Program has tested EnviroFuels diesel fuel additive, called the Diesel Fuel Catalyzer. EnviroFuels has stated that heavy-duty on and off road diesel engines are the intended market for the catalyzer. Preliminary tests conducted indicate...

  14. Key geochemical factors regulating Mn(IV)-catalyzed anaerobic nitrification in coastal marine sediments

    NASA Astrophysics Data System (ADS)

    Lin, Hui; Taillefert, Martial

    2014-05-01

    The reduction of Mn(IV) oxides coupled to the anaerobic oxidation of NH4+ has been proposed for more than a decade to contribute to the fixed nitrogen pool in marine sediments, yet the existence of this process is still under debate. In this study, surface sediments from an intertidal salt marsh were incubated with MnO2 in the presence of elevated concentrations of NH4+ to test the hypothesis that the reduction of Mn(IV) oxides catalyzes anaerobic NH4+ oxidation to NO2- or NO3-. Geochemical factors such as the ratio of Mn(IV) to NH4+, the type of Mn(IV) oxides (amorphous or colloidal MnO2), and the redox potential of the sediment significantly affect the activity of anaerobic nitrification. Incubations show that the net production of NO3- is stimulated under anaerobic conditions with external addition of colloidal but not amorphous MnO2 and is facilitated by the presence of high concentrations of NH4+. Mass balance calculations demonstrate that anaerobic NH4+ oxidation contributes to the net consumption of NH4+, providing another piece of evidence for the occurrence of Mn(IV)-catalyzed anaerobic nitrification in coastal marine sediments. Finally, anaerobic nitrification is stimulated by the amendment of small concentrations of NO3- or the absence of sulfate reduction, suggesting that moderately reducing conditions favor anaerobic NH4+ oxidation. Overall, these findings suggest that Mn(IV)-catalyzed anaerobic nitrification in suboxic sediments with high N/Mn concentration ratios and highly reactive manganese oxides may be an important source of NO2- and NO3- for subsequent marine nitrogen loss via denitrification or anammox.

  15. Self-Catalyzed Carbon Dioxide Adsorption by Metal-Organic Chains on Gold Surfaces

    SciTech Connect

    Feng, Min; Sun, Hao; Zhao, Jin; Petek, Hrvoje

    2014-08-26

    Efficient capture of CO2 by chemical means requires a microscopic understanding of the interactions of the molecule-substrate bonding and adsorption-induced collective phenomena. By molecule-resolved imaging with scanning tunneling microscopy (STM), we investigate self-catalyzed CO2 adsorption on one-dimensional (1D) substrates composed of self-assembled metal-organic chains (MOCs) supported on gold surfaces. CO2 adsorption turns on attractive interchain interactions, which induce pronounced surface structural changes; the initially uniformly dispersed chains gather into close packed bundles, which are held together by highly ordered, single molecule wide CO2 ranks. CO2 molecules create more favorable adsorption sites for further CO2 adsorption by mediating the interchain attraction, thereby self-catalyzing their capture. The release of CO2 molecules by thermal desorption returns the MOCs to their original structure, indicating that the CO2 capture and release are reversible processes. The real space microscopic characterization of the self-catalyzed CO2 adsorption on 1D substrates could be exploited as platform for design of molecular materials for CO2 capture and reduction.

  16. RNA-Catalyzed RNA Ligation on an External RNA Template

    NASA Technical Reports Server (NTRS)

    McGinness, Kathleen E.; Joyce, Gerald F.

    2002-01-01

    Variants of the hc ligase ribozyme, which catalyzes ligation of the 3' end of an RNA substrate to the 5' end of the ribozyme, were utilized to evolve a ribozyme that catalyzes ligation reactions on an external RNA template. The evolved ribozyme catalyzes the joining of an oligonucleotide 3'-hydroxyl to the 5'-triphosphate of an RNA hairpin molecule. The ribozyme can also utilize various substrate sequences, demonstrating a largely sequence-independent mechanism for substrate recognition. The ribozyme also carries out the ligation of two oligonucleotides that are bound at adjacent positions on a complementary template. Finally, it catalyzes addition of mononucleoside '5-triphosphates onto the '3 end of an oligonucleotide primer in a template-dependent manner. The development of ribozymes that catalyze polymerase-type reactions contributes to the notion that an RNA world could have existed during the early history of life on Earth.

  17. First-principles calculations of Fischer-Tropsch processes catalyzed by nitrogenase enzymes

    NASA Astrophysics Data System (ADS)

    Varley, Joel; Grabow, Lars; Nørskov, Jens

    2012-02-01

    The nitrogenase enzyme system of the bacteria Azotobacter vinelandii, which is used in nature to catalyze ammonia synthesis, has been found recently to catalyze the efficient conversion of carbon monoxide (CO) into hydrocarbons under ambient temperature and pressure [1]. These findings indicate that nitrogenase enzymes could inspire more efficient catalysts for electrochemical CO and CO2 reduction to liquid fuels. The nitrogenase variants, in which vanadium substitutes the molybdenum in the active site of the enzyme, show distinct features in their reaction pathways to hydrocarbon production. To compare and contrast the catalytic properties of these nitrogenase enzymes, we perform first-principles calculations to map out the reaction pathways for both nitrogen fixation and for the reduction of CO to higher-order hydrocarbons. We discuss the trends and differences between the two enzymes and detail the relevant chemical species and rate-limiting steps involved in the reactions. By utilizing this information, we predict the electrochemical conditions necessary for the catalytic reduction of CO into fuels by the nitrogenase active sites, analogous to a Fischer-Tropsch process requiring less extreme conditions. [4pt] [1] Y. Hu, C.C. Lee, M.W. Ribbe, Science 333, 753 (2011)

  18. Polymer multilayer films obtained by electrochemically catalyzed click chemistry.

    PubMed

    Rydzek, Gaulthier; Thomann, Jean-Sébastien; Ben Ameur, Nejla; Jierry, Loïc; Mésini, Philippe; Ponche, Arnaud; Contal, Christophe; El Haitami, Alae E; Voegel, Jean-Claude; Senger, Bernard; Schaaf, Pierre; Frisch, Benoît; Boulmedais, Fouzia

    2010-02-16

    We report the covalent layer-by-layer construction of polyelectrolyte multilayer (PEM) films by using an efficient electrochemically triggered Sharpless click reaction. The click reaction is catalyzed by Cu(I) which is generated in situ from Cu(II) (originating from the dissolution of CuSO(4)) at the electrode constituting the substrate of the film. The film buildup can be controlled by the application of a mild potential inducing the reduction of Cu(II) to Cu(I) in the absence of any reducing agent or any ligand. The experiments were carried out in an electrochemical quartz crystal microbalance cell which allows both to apply a controlled potential on a gold electrode and to follow the mass deposited on the electrode through the quartz crystal microbalance. Poly(acrylic acid) (PAA) modified with either alkyne (PAA(Alk)) or azide (PAA(Az)) functions grafted onto the PAA backbone through ethylene glycol arms were used to build the PEM films. Construction takes place on gold electrodes whose potentials are more negative than a critical value, which lies between -70 and -150 mV vs Ag/AgCl (KCl sat.) reference electrode. The film thickness increment per bilayer appears independent of the applied voltage as long as it is more negative than the critical potential, but it depends upon Cu(II) and polyelectrolyte concentrations in solution and upon the reduction time of Cu(II) during each deposition step. An increase of any of these latter parameters leads to an increase of the mass deposited per layer. For given buildup conditions, the construction levels off after a given number of deposition steps which increases with the Cu(II) concentration and/or the Cu(II) reduction time. A model based on the diffusion of Cu(II) and Cu(I) ions through the film and the dynamics of the polyelectrolyte anchoring on the film, during the reduction period of Cu(II), is proposed to explain the major buildup features.

  19. Uranium isotopes fingerprint biotic reduction

    SciTech Connect

    Stylo, Malgorzata; Neubert, Nadja; Wang, Yuheng; Monga, Nikhil; Romaniello, Stephen J.; Weyer, Stefan; Bernier-Latmani, Rizlan

    2015-04-20

    Knowledge of paleo-redox conditions in the Earth’s history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U), i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth’s crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. In addition, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium.

  20. Uranium isotopes fingerprint biotic reduction

    DOE PAGES

    Stylo, Malgorzata; Neubert, Nadja; Wang, Yuheng; ...

    2015-04-20

    Knowledge of paleo-redox conditions in the Earth’s history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U),more » i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth’s crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. In addition, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium.« less

  1. Uranium isotopes fingerprint biotic reduction

    PubMed Central

    Stylo, Malgorzata; Neubert, Nadja; Wang, Yuheng; Monga, Nikhil; Romaniello, Stephen J.; Weyer, Stefan; Bernier-Latmani, Rizlan

    2015-01-01

    Knowledge of paleo-redox conditions in the Earth’s history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U), i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth’s crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. Additionally, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium. PMID:25902522

  2. Uranium isotopes fingerprint biotic reduction.

    PubMed

    Stylo, Malgorzata; Neubert, Nadja; Wang, Yuheng; Monga, Nikhil; Romaniello, Stephen J; Weyer, Stefan; Bernier-Latmani, Rizlan

    2015-05-05

    Knowledge of paleo-redox conditions in the Earth's history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U), i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth's crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. Additionally, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium.

  3. Fabrication of catalyzed ion transport membrane systems

    DOEpatents

    Carolan, Michael Francis; Kibby, Charles Leonard

    2013-06-04

    Process for fabricating a catalyzed ion transport membrane (ITM). In one embodiment, an uncatalyzed ITM is (a) contacted with a non-reducing gaseous stream while heating to a temperature and for a time period sufficient to provide an ITM possessing anion mobility; (b) contacted with a reducing gaseous stream for a time period sufficient to provide an ITM having anion mobility and essentially constant oxygen stoichiometry; (c) cooled while contacting the ITM with the reducing gaseous stream to provide an ITM having essentially constant oxygen stoichiometry and no anion mobility; and (d) treated by applying catalyst to at least one of (1) a porous mixed conducting multicomponent metallic oxide (MCMO) layer contiguous with a first side of a dense layer of MCMO and (2) a second side of the dense MCMO layer. In another embodiment, these steps are carried out in the alternative order of (a), (d), (b), and (c).

  4. Enzyme-catalyzed, gas-phase reactions.

    PubMed

    Barzana, E; Klibanov, A M; Karel, M

    1987-06-01

    Dehydrated preparations of alcohol oxidase adsorbed on DEAE-cellulose vigorously catalyze a gas-phase oxidation of ethanol vapors with molecular oxygen. The gas-phase reaction is strongly dependent on the water activity of the system. The enzymatic activity is severely inhibited by the product hydrogen peroxide. This inhibition can be alleviated, however, by an addition of catalase or peroxidase to the dry preparation. Such dehydrated, bienzymic catalysts afford a complete and selective conversion of the substrate to acetaldehyde. Dry alcohol oxidase is much more thermostable than in aqueous solution. The results of this work suggest that dehydrated enzymes have potential applications in the analysis of gaseous compounds and in the development of novel gas-solid bioreactors.

  5. Dopant-Catalyzed Singlet Exciton Fission.

    PubMed

    Snamina, Mateusz; Petelenz, Piotr

    2017-01-04

    In acene-based molecular crystals, singlet exciton fission occurs through superexchange mediated by two virtual charge-transfer states. Hence, it is sensitive to their energies, which depend on the local environment. The crucial point is the balance between the charge-quadrupole interactions within the pair of molecules directly involved in the process and those with the surrounding crystal matrix, which are governed by local symmetry and may be influenced by breaking this symmetry. This happens, for example, in the vicinity of a vacancy or an impurity and in the latter case is complemented by polarization energy and potentially by dipolar contributions. Our model calculations indicate that the superexchange coupling is sensitive enough to these factors to enable fission to be catalyzed by judiciously designed dopant molecules. In favorable cases, dipolar dopants are expected to increase the fission rate by an order of magnitude.

  6. Rhodium-Catalyzed Alkene Difunctionalization with Nitrenes.

    PubMed

    Ciesielski, Jennifer; Dequirez, Geoffroy; Retailleau, Pascal; Gandon, Vincent; Dauban, Philippe

    2016-06-27

    The Rh(II) -catalyzed oxyamination and diamination of alkenes generate 1,2-amino alcohols and 1,2-diamines, respectively, in good to excellent yields and with complete regiocontrol. In the case of diamination, the intramolecular reaction provides an efficient method for the preparation of pyrrolidines, and the intermolecular reaction produces vicinal amines with orthogonal protecting groups. These alkene difunctionalizations proceed by aziridination followed by nucleophilic ring opening induced by an Rh-bound nitrene generated in situ, details of which were uncovered by both experimental and theoretical studies. In particular, DFT calculations show that the nitrogen atom of the putative [Rh]2 =NR metallanitrene intermediate is electrophilic and support an aziridine activation pathway by N⋅⋅⋅N=[Rh]2 bond formation, in addition to the N⋅⋅⋅[Rh]2 =NR coordination mode. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Palladium-Catalyzed Aminocarbonylation of Allylic Alcohols.

    PubMed

    Li, Haoquan; Neumann, Helfried; Beller, Matthias

    2016-07-11

    A benign and efficient palladium-catalyzed aminocarbonylation reaction of allylic alcohols is presented. The generality of this novel process is demonstrated by the synthesis of β,γ-unsaturated amides including aliphatic, cinnamyl, and terpene derivatives. The choice of ligand is crucial for optimal carbonylation processes: Whereas in most cases the combination of PdCl2 with Xantphos (L6) gave best results, sterically hindered substrates performed better in the presence of simple triphenylphosphine (L10), and primary anilines gave the best results using cataCXium® PCy (L8). The reactivity of the respective catalyst system is significantly enhanced by addition of small amounts of water. Mechanistic studies and control experiments revealed a tandem allylic alcohol amination/C-N bond carbonylation reaction sequence.

  8. A serine-substituted P450 catalyzes highly efficient carbene transfer to olefins in vivo.

    PubMed

    Coelho, Pedro S; Wang, Z Jane; Ener, Maraia E; Baril, Stefanie A; Kannan, Arvind; Arnold, Frances H; Brustad, Eric M

    2013-08-01

    Whole-cell catalysts for non-natural chemical reactions will open new routes to sustainable production of chemicals. We designed a cytochrome 'P411' with unique serine-heme ligation that catalyzes efficient and selective olefin cyclopropanation in intact Escherichia coli cells. The mutation C400S in cytochrome P450(BM3) gives a signature ferrous CO Soret peak at 411 nm, abolishes monooxygenation activity, raises the resting-state Fe(III)-to-Fe(II) reduction potential and substantially improves NAD(P)H-driven activity.

  9. Utilization of the catalyzed-DD fuel cycle in reversed-field pinch reactors (RFPRs)

    SciTech Connect

    Hagenson, R.L.; Krakowski, R.A.

    1981-01-01

    The utilization of deuterium-based fuels offers the potential advantages of greater flexibility in blanket design, significantly reduced tritium inventory, potential reduction in radioactivity level, and utilization of an inexhaustible fuel supply. The extension of the conventional DT-fueled Reversed-Field Pinch Reactor (RFPR) designs to advanced-fuel (catalyzed-DD) operation has recently been reported. Attractive and economically competitive DD/RFPR systems are identified having power densities and plasma parameters comparable to the DT systems. These designs are compared to other fusion reactor designs.

  10. Palladium-catalyzed carbonylative couplings of vinylogous enolates: application to statin structures.

    PubMed

    Makarov, Ilya S; Kuwahara, Takashi; Jusseau, Xavier; Ryu, Ilhyong; Lindhardt, Anders T; Skrydstrup, Troels

    2015-11-11

    The first Pd-catalyzed carbonylative couplings of aryl and vinyl halides with vinylogous enolates are reported generating products derived from C-C bond formation exclusively at the γ-position. Good results were obtained with a dienolate derivative of acetoacetate (1,3-dioxin-4-one). These transformations occurred at room temperature and importantly with only stoichiometric carbon monoxide in a two-chamber reactor. The methodology was applied to the synthesis of two members of the statin family generating the cis-3,5-diol acid motif by a γ-selective carbonylation followed by a cis-stereoselective reduction of the 3,5-dicarbonyl acid intermediates.

  11. A new approach to ferrocene derived alkenes via copper-catalyzed olefination

    PubMed Central

    Muzalevskiy, Vasily M; Shastin, Aleksei V; Demidovich, Alexandra D; Shikhaliev, Namiq G; Magerramov, Abel M; Khrustalev, Victor N; Rakhimov, Rustem D; Vatsadze, Sergey Z

    2015-01-01

    Summary A new approach to ferrocenyl haloalkenes and bis-alkenes was elaborated. The key procedure involves copper catalyzed olefination of N-unsubstituted hydrazones, obtained from ferrocene-containing carbonyl compounds and hydrazine, with polyhaloalkanes. The procedure is simple, cheap and could be applied for the utilization of environmentally harmful polyhalocarbons. The cyclic voltammetry study of the representative examples of the synthesized ferrocenyl alkenes shows the strong dependence of the cathodic behavior on the amount of vinyl groups: while for the monoalkene containing molecules no reduction is seen, the divinyl products are reduced in several steps. PMID:26664627

  12. A Serine-Substituted P450 Catalyzes Highly Efficient Carbene Transfer to Olefins In Vivo

    PubMed Central

    Coelho, Pedro S.; Wang, Z. Jane; Ener, Maraia E.; Baril, Stefanie A.; Kannan, Arvind A.; Arnold, Frances H.; Brustad, Eric M.

    2013-01-01

    Genetically encoded catalysts for non-natural chemical reactions will open new routes to sustainable production of chemicals. We designed a unique serine-heme ligated cytochrome “P411” that catalyzes efficient and selective carbene transfers from diazoesters to olefins in intact Escherichia coli cells. The mutation C400S in cytochrome P450BM3 gives a signature ferrous-CO Soret peak at 411 nm, abolishes monooxygenation activity, raises the resting state FeIII/II reduction potential, and significantly improves NAD(P)H-driven cyclopropanation activity. PMID:23792734

  13. In-Depth Assessment of the Palladium-Catalyzed Fluorination of Five-Membered Heteroaryl Bromides

    PubMed Central

    2015-01-01

    A thorough investigation of the challenging Pd-catalyzed fluorination of five-membered heteroaryl bromides is presented. Crystallographic studies and density functional theory (DFT) calculations suggest that the challenging step of this transformation is C–F reductive elimination of five-membered heteroaryl fluorides from Pd(II) complexes. On the basis of these studies, we have found that various heteroaryl bromides bearing phenyl groups in the ortho position can be effectively fluorinated under catalytic conditions. Highly activated 2-bromoazoles, such as 8-bromocaffeine, are also viable substrates for this reaction. PMID:27056379

  14. In-Depth Assessment of the Palladium-Catalyzed Fluorination of Five-Membered Heteroaryl Bromides.

    PubMed

    Milner, Phillip J; Yang, Yang; Buchwald, Stephen L

    2015-10-12

    A thorough investigation of the challenging Pd-catalyzed fluorination of five-membered heteroaryl bromides is presented. Crystallographic studies and density functional theory (DFT) calculations suggest that the challenging step of this transformation is C-F reductive elimination of five-membered heteroaryl fluorides from Pd(II) complexes. On the basis of these studies, we have found that various heteroaryl bromides bearing phenyl groups in the ortho position can be effectively fluorinated under catalytic conditions. Highly activated 2-bromoazoles, such as 8-bromocaffeine, are also viable substrates for this reaction.

  15. Enzyme-catalyzed degradation of carbon nanomaterials

    NASA Astrophysics Data System (ADS)

    Kotchey, Gregg P.

    Carbon nanotubes and graphene, the nanoscale sp 2 allotropes of carbon, have garnered widespread attention as a result of their remarkable electrical, mechanical, and optical properties and the promise of new technologies that harness these properties. Consequently, these carbon nanomaterials (CNMs) have been employed for diverse applications such as electronics, sensors, composite materials, energy conversion devices, and nanomedicine. The manufacture and eventual disposal of these products may result in the release of CNMs into the environment and subsequent exposure to humans, animals, and vegetation. Given the possible pro-inflammatory and toxic effects of CNMs, much attention has been focused on the distribution, toxicity, and persistence of CNMs both in living systems and the environment. This dissertation will guide the reader though recent studies aimed at elucidating fundamental insight into the persistence of CNMs such as carbon nanotubes (CNTs) and graphene derivatives (i.e., graphene oxide and reduced graphene oxide). In particular, in-testtube oxidation/degradation of CNMs catalyzed by peroxidase enzymes will be examined, and the current understanding of the mechanisms underlying these processes will be discussed. Finally, an outlook of the current field including in vitro and in vivo biodegradation experiments, which have benefits in terms of human health and environmental safety, and future directions that could have implications for nanomedical applications such as imaging and drug delivery will be presented. Armed with an understanding of how and why CNMs undergo enzyme-catalyzed oxidation/biodegradation, researchers can tailor the structure of CNMs to either promote or inhibit these processes. For example, in nanomedical applications such as drug delivery, the incorporation of carboxylate functional groups could facilitate biodegradation of the nanomaterial after delivery of the cargo. Also, the incorporation of CNMs with defect sites in consumer

  16. Asparagine and Aspartate Hydroxylation of the Cytoskeletal Ankyrin Family Is Catalyzed by Factor-inhibiting Hypoxia-inducible Factor*

    PubMed Central

    Yang, Ming; Ge, Wei; Chowdhury, Rasheduzzaman; Claridge, Timothy D. W.; Kramer, Holger B.; Schmierer, Bernhard; McDonough, Michael A.; Gong, Lingzhi; Kessler, Benedikt M.; Ratcliffe, Peter J.; Coleman, Mathew L.; Schofield, Christopher J.

    2011-01-01

    Factor-inhibiting hypoxia-inducible factor (FIH) catalyzes the β-hydroxylation of an asparagine residue in the C-terminal transcriptional activation domain of the hypoxia inducible factor (HIF), a modification that negatively regulates HIF transcriptional activity. FIH also catalyzes the hydroxylation of highly conserved Asn residues within the ubiquitous ankyrin repeat domain (ARD)-containing proteins. Hydroxylation has been shown to stabilize localized regions of the ARD fold in the case of a three-repeat consensus ankyrin protein, but this phenomenon has not been demonstrated for the extensive naturally occurring ARDs. Here we report that the cytoskeletal ankyrin family are substrates for FIH-catalyzed hydroxylations. We show that the ARD of ankyrinR is multiply hydroxylated by FIH both in vitro and in endogenous proteins purified from human and mouse erythrocytes. Hydroxylation of the D34 region of ankyrinR ARD (ankyrin repeats 13–24) increases its conformational stability and leads to a reduction in its interaction with the cytoplasmic domain of band 3 (CDB3), demonstrating the potential for FIH-catalyzed hydroxylation to modulate protein-protein interactions. Unexpectedly we found that aspartate residues in ankyrinR and ankyrinB are hydroxylated and that FIH-catalyzed aspartate hydroxylation also occurs in other naturally occurring AR sequences. The crystal structure of an FIH variant in complex with an Asp-substrate peptide together with NMR analyses of the hydroxylation product identifies the 3S regio- and stereoselectivity of the FIH-catalyzed Asp hydroxylation, revealing a previously unprecedented posttranslational modification. PMID:21177872

  17. Combinatorial synthesis of RGD model cyclic peptides utilizing a palladium-catalyzed carbonylative macrolactamization on a polymer support.

    PubMed

    Kamioka, Seiji; Shimazu, Sayaka; Doi, Takayuki; Takahashi, Takashi

    2008-01-01

    A combinatorial synthesis of 24-member RGD models was accomplished on polymer-support. Ortho-, meta-, and para-iodobenzylamines loaded on an aldehyde linker by reductive amination were coupled with RGD sequences and various omega-amino acids by a split-and-pool method. Palladium-catalyzed carbonylative macrolactamization of the polymer-supported cyclization precursors, followed by acid cleavage, provided conformationally restricted RGD model cyclic peptides.

  18. Chiral Silver Complex-Catalyzed Diastereoselective and Enantioselective Michael Addition of 1-Pyrroline-5-carboxylates to α-Enones.

    PubMed

    Koizumi, Akihiro; Harada, Masato; Haraguchi, Ryosuke; Fukuzawa, Shin-Ichi

    2017-09-01

    A AgOAc/ThioClickFerrophos complex-catalyzed the highly diastereo- and enantioselective reaction between 1-pyrroline-5-carboxylates (1) and acyclic α-enones (2) in MeOH, in the presence of DBU, to give the single isomer Michael adducts (3) in high yields (up to 99%) with excellent enantioselectivies (up to 99% ee). Subsequent reduction of the Michael adducts with sodium cyanoborohydride successfully produced the fused pyrrolizidine ester as an almost pure single stereoisomer.

  19. Ligand-Assisted Gold-Catalyzed Cross-Coupling with Aryldiazonium Salts: Redox Gold Catalysis without an External Oxidant.

    PubMed

    Cai, Rong; Lu, Mei; Aguilera, Ellen Y; Xi, Yumeng; Akhmedov, Novruz G; Petersen, Jeffrey L; Chen, Hao; Shi, Xiaodong

    2015-07-20

    Gold-catalyzed C(sp)-C(sp(2)) and C(sp(2))-C(sp(2)) cross-coupling reactions are accomplished with aryldiazonium salts as the coupling partner. With the assistance of bpy ligand, gold(I) species were oxidized to gold(III) by diazonium without any external oxidants. Monitoring the reaction with NMR and ESI-MS provided strong evidence for the nitrogen extrusion followed by Au(III) reductive elimination as the key step.

  20. Metal ion-catalyzed nucleic acid alkylation and fragmentation.

    PubMed

    Browne, Kenneth A

    2002-07-10

    Nucleic acid microarrays are a growing technology in which high densities of known sequences are attached to a substrate in known locations (addressed). Hybridization of complementary sequences leads to a detectable signal such as an electrical impulse or fluorescence. This combination of sequence addressing, hybridization, and detection increases the efficiency of a variety of genomic disciplines including those that profile genetic expression, search for single nucleotide polymorphisms (SNPs), or diagnose infectious diseases by sequencing portions of microbial or viral genomes. Incorporation of reporter molecules into nucleic acids is essential for the sensitive detection of minute amounts of nucleic acids on most types of microarrays. Furthermore, polynucleic acid size reduction increases hybridization because of increased diffusion rates and decreased competing secondary structure of the target nucleic acids. Typically, these reactions would be performed as two separate processes. An improvement to past techniques, termed labeling-during-cleavage (LDC), is presented in which DNA or RNA is alkylated with fluorescent tags and fragmented in the same reaction mixture. In model studies with 26 nucleotide-long RNA and DNA oligomers using ultraviolet/visible and fluorescence spectroscopies as well as high-pressure liquid chromatography and mass spectrometry, addition of both alkylating agents (5-(bromomethyl)fluorescein, 5- or 6-iodoacetamidofluorescein) and select metal ions (of 21 tested) to nucleic acids in aqueous solutions was critical for significant increases in both labeling and fragmentation, with >or=100-fold increases in alkylation possible relative to metal ion-free reactions. Lanthanide series metal ions, Pb(2+), and Zn(2+) were the most reactive ions in terms of catalyzing alkylation and fragmentation. While oligonucleotides were particularly susceptible to fragmentation at sites containing phosphorothioate moieties, labeling and cleavage reactions

  1. Recent advances in osmium-catalyzed hydrogenation and dehydrogenation reactions.

    PubMed

    Chelucci, Giorgio; Baldino, Salvatore; Baratta, Walter

    2015-02-17

    CONSPECTUS: A current issue in metal-catalyzed reactions is the search for highly efficient transition-metal complexes affording high productivity and selectivity in a variety of processes. Moreover, there is also a great interest in multitasking catalysts that are able to efficiently promote different organic transformations by careful switching of the reaction parameters, such as temperature, solvent, and cocatalyst. In this context, osmium complexes have shown the ability to catalyze efficiently different types of reactions involving hydrogen, proving at the same time high thermal stability and simple synthesis. In the catalytic reduction of C═X (X = O, N) bonds by both hydrogenation (HY) and transfer hydrogenation (TH) reactions, the most interest has been focused on homogeneous systems based on rhodium, iridium, and in particular ruthenium catalysts, which have proved to catalyze chemo- and stereoselective hydrogenations with remarkable efficiency. By contrast, osmium catalysts have received much less attention because they are considered less active on account of their slower ligand exchange kinetics. Thus, this area remained almost neglected until recent studies refuted these prejudices. The aim of this Account is to highlight the impressive developments achieved over the past few years by our and other groups on the design of new classes of osmium complexes and their applications in homogeneous catalytic reactions involving the hydrogenation of carbon-oxygen and carbon-nitrogen bonds by both HY and TH reactions as well as in alcohol deydrogenation (DHY) reactions. The work described in this Account demonstrates that osmium complexes are emerging as powerful catalysts for asymmetric and non-asymmetric syntheses, showing a remarkably high catalytic activity in HY and TH reactions of ketones, aldehydes, imines, and esters as well in DHY reactions of alcohols. Thus, for instance, the introduction of ligands with an NH function, possibly in combination with a

  2. Organic radicals for the enhancement of oxygen reduction reaction in Li-O2 batteries.

    PubMed

    Tesio, A Y; Blasi, D; Olivares-Marín, M; Ratera, I; Tonti, D; Veciana, J

    2015-12-25

    We examine for the first time the ability of inert carbon free-radicals as soluble redox mediators to catalyze and enhance the oxygen reduction reaction in a (TEGDME)-based electrolyte. We demonstrate that the tris(2,4,6-trichlorophenyl)methyl (TTM) radical is capable of chemically favoring the oxygen reduction reaction improving significantly the Li-O2 battery performance.

  3. Tandem oxidation/rearrangement of beta-ketoesters to tartronic esters with molecular oxygen catalyzed by calcium iodide under visible light irradiation with fluorescent lamp.

    PubMed

    Kanai, Naohiko; Nakayama, Hiroki; Tada, Norihiro; Itoh, Akichika

    2010-05-07

    It was found that beta-ketoesters were directly transformed to the corresponding alpha-hydroxymalonic esters, tartronic esters, with molecular oxygen catalyzed by calcium iodide under visible light irradiation from fluorescent lamp. This reaction includes tandem oxidation/rearrangement and has received much attention from the viewpoint of reduction of energy consumption, labor, and solvents.

  4. One-shot access to α,β-difunctionalized azepenes and dehydropiperidines by reductive cross-coupling of α-selenonyl-β-selenyl enamides with organic bromides.

    PubMed

    Beng, Timothy K; Silaire, Ann Wens V; Alwali, Amir; Bassler, Daniel P

    2015-08-07

    The synthesis of α- and α,β-functionalized azepenes and dehydropiperidines from readily prepared α-selenonyl eneformamides or enecarbamates has been achieved through Fe-catalyzed α-substitutive deselenonation, β-regioselective lithiation/trapping, and Co-catalyzed reductive cross-coupling protocols.

  5. Oxygenase-catalyzed ribosome hydroxylation occurs in prokaryotes and humans.

    PubMed

    Ge, Wei; Wolf, Alexander; Feng, Tianshu; Ho, Chia-hua; Sekirnik, Rok; Zayer, Adam; Granatino, Nicolas; Cockman, Matthew E; Loenarz, Christoph; Loik, Nikita D; Hardy, Adam P; Claridge, Timothy D W; Hamed, Refaat B; Chowdhury, Rasheduzzaman; Gong, Lingzhi; Robinson, Carol V; Trudgian, David C; Jiang, Miao; Mackeen, Mukram M; McCullagh, James S; Gordiyenko, Yuliya; Thalhammer, Armin; Yamamoto, Atsushi; Yang, Ming; Liu-Yi, Phebee; Zhang, Zhihong; Schmidt-Zachmann, Marion; Kessler, Benedikt M; Ratcliffe, Peter J; Preston, Gail M; Coleman, Mathew L; Schofield, Christopher J

    2012-12-01

    The finding that oxygenase-catalyzed protein hydroxylation regulates animal transcription raises questions as to whether the translation machinery and prokaryotic proteins are analogously modified. Escherichia coli ycfD is a growth-regulating 2-oxoglutarate oxygenase catalyzing arginyl hydroxylation of the ribosomal protein Rpl16. Human ycfD homologs, Myc-induced nuclear antigen (MINA53) and NO66, are also linked to growth and catalyze histidyl hydroxylation of Rpl27a and Rpl8, respectively. This work reveals new therapeutic possibilities via oxygenase inhibition and by targeting modified over unmodified ribosomes.

  6. Application of palladium-catalyzed carboxyl anhydride-boronic acid cross coupling in the synthesis of novel bile acids analogs with modified side chains.

    PubMed

    Mayorquín-Torres, Martha C; Flores-Álamo, Marcos; Iglesias-Arteaga, Martin A

    2015-09-01

    Palladium-catalyzed cross coupling of 4-methoxycarbonyl phenyboronic acid with acetylated bile acids in which the carboxyl functions was activated by formation of a mixed anhydride with pivalic anhydride afforded the cross coupled compounds, which were converted in novel side chain modified bile acids by one pot carbonyl reduction/removal of the protecting acetyl groups by Wolff-Kishner reduction. Unambiguous assignments of the NMR signals and crystal characterization of the heretofore unknown compounds are provided.

  7. Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Socki, Richard A.; Fu, Qi; Niles, Paul B.

    2011-01-01

    We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

  8. Contribution of flavin covalent linkage with histidine 99 to the reaction catalyzed by choline oxidase.

    PubMed

    Quaye, Osbourne; Cowins, Sharonda; Gadda, Giovanni

    2009-06-19

    The FAD-dependent choline oxidase has a flavin cofactor covalently attached to the protein via histidine 99 through an 8alpha-N(3)-histidyl linkage. The enzyme catalyzes the four-electron oxidation of choline to glycine betaine, forming betaine aldehyde as an enzyme-bound intermediate. The variant form of choline oxidase in which the histidine residue has been replaced with asparagine was used to investigate the contribution of the 8alpha-N(3)-histidyl linkage of FAD to the protein toward the reaction catalyzed by the enzyme. Decreases of 10-fold and 30-fold in the k(cat)/K(m) and k(cat) values were observed as compared with wild-type choline oxidase at pH 10 and 25 degrees C, with no significant effect on k(cat)/K(O) using choline as substrate. Both the k(cat)/K(m) and k(cat) values increased with increasing pH to limiting values at high pH consistent with the participation of an unprotonated group in the reductive half-reaction and the overall turnover of the enzyme. The pH independence of both (D)(k(cat)/K(m)) and (D)k(cat), with average values of 9.2 +/- 3.3 and 7.4 +/- 0.5, respectively, is consistent with absence of external forward and reverse commitments to catalysis, and the chemical step of CH bond cleavage being rate-limiting for both the reductive half-reaction and the overall enzyme turnover. The temperature dependence of the (D)k(red) values suggests disruption of the preorganization in the asparagine variant enzyme. Altogether, the data presented in this study are consistent with the FAD-histidyl covalent linkage being important for the optimal positioning of the hydride ion donor and acceptor in the tunneling reaction catalyzed by choline oxidase.

  9. All Carbon Quaternary Centers via Ruthenium-Catalyzed Hydroxymethylation of 2-Substituted Butadienes Mediated by Formaldehyde: Beyond Hydroformylation

    PubMed Central

    Smejkal, Tomas; Han, Hoon; Breit, Bernhard; Krische, Michael J.

    2009-01-01

    Ruthenium catalyzed transfer hydrogenation of 2-substituted dienes 1a-1i in the presence of paraformaldehyde results in reductive coupling at the 2-position to furnish products of hydroxymethylation 3a-3i, which embody all carbon quaternary centers. Reductive coupling of diene 1g to paraformaldehyde under standard conditions, but employing either deuterio-paraformaldehyde or d8-isopropanol, or both deuterio-paraformaldehyde corroborate a catalytic mechanism involving rapid and reversible diene hydrometallation with incomplete regioselectivity in advance of C-C coupling. These present method provides an alternative to the hydroformylation of conjugated dienes, for which efficient, regioselective catalytic systems remain undeveloped. PMID:19594163

  10. Peptide Bond Formation Mechanism Catalyzed by Ribosome.

    PubMed

    Świderek, Katarzyna; Marti, Sergio; Tuñón, Iñaki; Moliner, Vicent; Bertran, Juan

    2015-09-23

    In this paper we present a study of the peptide bond formation reaction catalyzed by ribosome. Different mechanistic proposals have been explored by means of Free Energy Perturbation methods within hybrid QM/MM potentials, where the chemical system has been described by the M06-2X functional and the environment by means of the AMBER force field. According to our results, the most favorable mechanism in the ribosome would proceed through an eight-membered ring transition state, involving a proton shuttle mechanism through the hydroxyl group of the sugar and a water molecule. This transition state is similar to that described for the reaction in solution (J. Am. Chem. Soc. 2013, 135, 8708-8719), but the reaction mechanisms are noticeably different. Our simulations reproduce the experimentally determined catalytic effect of ribosome that can be explained by the different behavior of the two environments. While the solvent reorganizes during the chemical process involving an entropic penalty, the ribosome is preorganized in the formation of the Michaelis complex and does not suffer important changes along the reaction, dampening the charge redistribution of the chemical system.

  11. Peptide Bond Formation Mechanism Catalyzed by Ribosome

    PubMed Central

    Świderek, Katarzyna; Marti, Sergio; Tuñón, Iñaki; Moliner, Vicent; Bertran, Juan

    2015-01-01

    In this paper we present a study of the peptide bond formation reaction catalyzed by ribosome. Different mechanistic proposals have been explored by means of Free Energy Perturbation methods within hybrid QM/MM potentials, where the chemical system has been described by the M06-2X functional and the environment by means of the AMBER force field. According to our results, the most favourable mechanism in the ribosome would proceed through an eight-membered ring transition state, involving a proton shuttle mechanism through the hydroxyl group of the sugar and a water molecule. This transition state is similar to that described for the reaction in solution (J. Am. Chem. Soc. 2013, 135, 8708–8719) but the reaction mechanisms are noticeable different. Our simulations reproduce the experimentally determined catalytic effect of ribosome that can be explained by the different behaviour of the two environments. While the solvent reorganizes during the chemical process involving an entropic penalty, the ribosome is preorganized in the formation of the Michaelis complex and does not suffer important changes along the reaction, dampening the charge redistribution of the chemical system. PMID:26325003

  12. Thioglycoside hydrolysis catalyzed by {beta}-glucosidase

    SciTech Connect

    Shen Hong; Byers, Larry D.

    2007-10-26

    Sweet almond {beta}-glucosidase (EC 3.2.1.21) has been shown to have significant thioglycohydrolase activity. While the K{sub m} values for the S- and O-glycosides are similar, the k{sub cat} values are about 1000-times lower for the S-glycosides. Remarkably, the pH-profile for k{sub cat}/K{sub m} for hydrolysis of p-nitrophenyl thioglucoside (pNPSG) shows the identical dependence on a deprotonated carboxylate (pK{sub a} 4.5) and a protonated group (pK{sub a} 6.7) as does the pH-profile for hydrolysis of the corresponding O-glycoside. Not surprisingly, in spite of the requirement for the presence of this protonated group in catalytically active {beta}-glucosidase, thioglucoside hydrolysis does not involve general acid catalysis. There is no solvent kinetic isotope effect on the enzyme-catalyzed hydrolysis of pNPSG.

  13. Toluene Monooxygenase-Catalyzed Epoxidation of Alkenes

    PubMed Central

    McClay, Kevin; Fox, Brian G.; Steffan, Robert J.

    2000-01-01

    Several toluene monooxygenase-producing organisms were tested for their ability to oxidize linear alkenes and chloroalkenes three to eight carbons long. Each of the wild-type organisms degraded all of the alkenes that were tested. Epoxides were produced during the oxidation of butene, butadiene, and pentene but not hexene or octadiene. A strain of Escherichia coli expressing the cloned toluene-4-monooxygenase (T4MO) of Pseudomonas mendocina KR1 was able to oxidize butene, butadiene, pentene, and hexene but not octadiene, producing epoxides from all of the substrates that were oxidized. A T4MO-deficient variant of P. mendocina KR1 oxidized alkenes that were five to eight carbons long, but no epoxides were detected, suggesting the presence of multiple alkene-degrading enzymes in this organism. The alkene oxidation rates varied widely (ranging from 0.01 to 0.33 μmol of substrate/min/mg of cell protein) and were specific for each organism-substrate pair. The enantiomeric purity of the epoxide products also varied widely, ranging from 54 to >90% of a single epoxide enantiomer. In the absence of more preferred substrates, such as toluene or alkenes, the epoxides underwent further toluene monooxygenase-catalyzed transformations, forming products that were not identified. PMID:10788354

  14. UDP-glucuronosyltransferases 1A6 and 1A10 catalyze reduced menadione glucuronidation

    SciTech Connect

    Nishiyama, Takahito; Ohnuma, Tomokazu; Inoue, Yuu; Kishi, Takehiko; Ogura, Kenichiro; Hiratsuka, Akira

    2008-06-27

    Menadione (2-methyl-1,4-naphthoquine), also known as vitamin K3, has been widely used as a model compound in the field of oxidative stress-related research. The metabolism of menadione has been studied, and it is known that menadione undergoes a two-electron reduction by NAD(P)H:Quinone oxidoreductase 1 (NQO1) after which the reduced form of menadione (2-methyl-1,4-naphthalenediol, menadiol) is glucuronidated and excreted in urine. To investigate which human UDP-glucuronosyltransferase (UGT) isoforms participate in the glucuronidation of menadiol reduced by NQO1 from menadione, we first constructed heterologously expressed NQO1 in Sf9 cells and tested the menadiol glucuronidating activity of 16 human recombinant UGT isoforms. Of the 16 UGT isoforms, UGTs 1A6, 1A7, 1A8, 1A9, and 1A10 catalyzed menadiol glucuronidation, and, of these, UGTs 1A6 and 1A10 catalyzed menadiol glucuronidation at much higher rates than the other UGTs. Menadiol was regioselectively glucuronidated in the manner of 4-position > 1-position by UGTs 1A7, 1A8, 1A9, and 1A10. In contrast to these UGTs, only UGT1A6 exhibited 1-menadiol-preferential glucuronidating activity. The results suggest possible detoxification pathways for quinones via NQO1 reduction followed by UGT glucuronidation.

  15. In situ Regeneration of NADH via Lipoamide Dehydrogenase-catalyzed Electron Transfer Reaction Evidenced by Spectroelectrochemistry

    SciTech Connect

    Tam, Tsz Kin; Chen, Baowei; Lei, Chenghong; Liu, Jun

    2012-08-01

    NAD/NADH is a coenzyme found in all living cells, carrying electrons from one reaction to another. We report on characterizations of in situ regeneration of NADH via lipoamide dehydrogenase (LD)-catalyzed electron transfer reaction to regenerate NADH using UV-vis spectroelectrochemistry. The Michaelis-Menten constant (Km) and maximum velocity (Vmax) of NADH regeneration were measured as 0.80 {+-} 0.15 mM and 1.91 {+-} 0.09 {micro}M s-1 in a 1-mm thin-layer spectroelectrochemical cell using gold gauze as the working electrode at the applied potential -0.75 V (vs. Ag/AgCl). The electrocatalytic reduction of the NAD system was further coupled with the enzymatic conversion of pyruvate to lactate by lactate dehydrogenase to examine the coenzymatic activity of the regenerated NADH. Although the reproducible electrocatalytic reduction of NAD into NADH is known to be difficult compared to the electrocatalytic oxidation of NADH, our spectroelectrochemical results indicate that the in situ regeneration of NADH via LD-catalyzed electron transfer reaction is fast and sustainable and can be potentially applied to many NAD/NADH-dependent enzyme systems.

  16. Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration

    DOE PAGES

    Eedugurala, Naresh; Wang, Zhuoran; Chaudhary, Umesh; ...

    2015-11-04

    The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe2)4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe2)n@MSN. Exhaustive characterization of Zr(NMe2)n@MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡SiOZr(NMe2)3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe2)n@MSN material reacts with pinacolborane (HBpin) to provide Me2NBpin and the material ZrH/Bpin@MSN that is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡SiOBpinmore » moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1H/2H and 11B SSNMR and infrared spectroscopy and through its reactivity with D2. The zirconium hydride material or the zirconium amide precursor Zr(NMe2)n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. These supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites.« less

  17. Base-catalyzed and cholinesterase-catalyzed hydrolysis of acetylcholine and optically active analogs.

    PubMed

    Schowen, K B; Smissman, E E; Stephen, W F

    1975-03-01

    The base- and cholinestrase-catalyzed hydrolyses of the following optically active analogs of acetylcholine were studied: 3 (a)-trimethylammonium-2(a)-acetoxy-trans-decalin iodide, threo- and erythro-alpha, beta-dimethylacetylcholine iodide, alpha-methylacetylcholine, and beta-methylacetylcholine. Evidence that the optimum dihedral +N-C-C-O angle in the transition state for acetylcholinesterase hydrolysis of acetylcholine analogs is positive and anticlinal is given. The data obtained suggest that acetylcholine undergoes a geometrically flexible mode of attachment to the enzyme.

  18. ENVIRONMENTAL ASSESSMENT OF THE BASE CATALYZED DECOMPOSITION (BCD) PROCESS

    EPA Science Inventory

    This report summarizes laboratory-scale, pilot-scale, and field performance data on BCD (Base Catalyzed Decomposition) and technology, collected to date by various governmental, academic, and private organizations.

  19. Diastereoselective Pt catalyzed cycloisomerization of polyenes to polycycles.

    PubMed

    Geier, Michael J; Gagné, Michel R

    2014-02-26

    Application of a tridentate NHC containing pincer ligand to Pt catalyzed cascade cyclization reactions has allowed for the catalytic, diastereoselective cycloisomerization of biogenic alkene terminated substrates to the their polycyclic counterparts.

  20. ENVIRONMENTAL ASSESSMENT OF THE BASE CATALYZED DECOMPOSITION (BCD) PROCESS

    EPA Science Inventory

    This report summarizes laboratory-scale, pilot-scale, and field performance data on BCD (Base Catalyzed Decomposition) and technology, collected to date by various governmental, academic, and private organizations.

  1. Rhodium-Catalyzed Dehydrogenative Borylation of Cyclic Alkenes

    PubMed Central

    Kondoh, Azusa; Jamison, Timothy F.

    2010-01-01

    A rhodium-catalyzed dehydrogenative borylation of cyclic alkenes is described. This reaction provides direct access to cyclic 1-alkenylboronic acid pinacol esters, useful intermediates in organic synthesis. Suzuki-Miyaura cross-coupling applications are also presented. PMID:20107646

  2. Pd-catalyzed arylation of chlorotrifluoroethylene using arylboronic acids.

    PubMed

    Yamamoto, Tetsuya; Yamakawa, Tetsu

    2012-07-06

    The palladium-catalyzed cross-coupling of chlorotrifluoroethylene and arylboronic acids proceeds in the presence of a base and H(2)O to provide α,β,β-trifluorostyrene derivatives in satisfactory yields.

  3. Amino acid salt catalyzed intramolecular Robinson annulation†‡

    PubMed Central

    Li, Pingfan; Yamamoto, Hisashi

    2009-01-01

    The silica gel absorbed amino acid salt catalyzed asymmetric intramolecular Robinson annulation reaction has been developed; up to 97% ee was obtained with this readily recoverable organocatalyst. PMID:19724802

  4. The Iron-Catalyzed Oxidation of Hydrazine by Nitric Acid

    SciTech Connect

    Karraker, D.G.

    2001-07-17

    To assess the importance of iron to hydrazine stability, the study of hydrazine oxidation by nitric acid has been extended to investigate the iron-catalyzed oxidation. This report describes those results.

  5. Pd-Catalyzed Decarbonylative Cross-Couplings of Aroyl Chlorides.

    PubMed

    Malapit, Christian A; Ichiishi, Naoko; Sanford, Melanie S

    2017-08-04

    This report describes a method for Pd-catalyzed decarbonylative cross-coupling that enables the conversion of carboxylic acid derivatives to biaryls, aryl amines, aryl ethers, aryl sulfides, aryl boronate esters, and trifluoromethylated arenes. The success of this transformation leverages the Pd(0)/Brettphos-catalyzed decarbonylative chlorination of aroyl chlorides, which can then participate in diverse cross-coupling reactions in situ using the same Pd catalyst.

  6. Nickel-Catalyzed Coupling of Alkenes, Aldehydes, and Silyl Triflates

    PubMed Central

    Ng, Sze-sze; Ho, Chun-Yu; Jamison, Timothy F.

    2011-01-01

    A full account of two recently developed nickel-catalyzed coupling reactions of alkenes, aldehydes and silyl triflates is presented. These reactions provide either allylic alcohol or homoallylic alcohol derivatives selectively, depending on the ligand employed. These processes are believed to be mechanistically distinct from Lewis acid-catalyzed carbonyl-ene reactions, and several lines of evidence supporting this hypothesis are discussed. PMID:16939275

  7. New mechanistic studies on the proline-catalyzed aldol reaction

    PubMed Central

    List, Benjamin; Hoang, Linh; Martin, Harry J.

    2004-01-01

    The mechanism of the proline-catalyzed aldol reaction has stimulated considerable debate, and despite limited experimental data, at least five different mechanisms have been proposed. Complementary to recent theoretical studies we have initiated an experimental program with the goal of clarifying some of the basic mechanistic questions concerning the proline-catalyzed aldol reaction. Here we summarize our discoveries in this area and provide further evidence for the involvement of enamine intermediates. PMID:15073330

  8. Surface-catalyzed air oxidation of hydrazines: Environmental chamber studies

    NASA Technical Reports Server (NTRS)

    Kilduff, Jan E.; Davis, Dennis D.; Koontz, Steven L.

    1988-01-01

    The surface-catalyzed air oxidation reactions of fuel hydrazines were studied in a 6500-liter fluorocarbon-film chamber at 80 to 100 ppm concentrations. First-order rate constants for the reactions catalyzed by aluminum, water-damaged aluminum (Al/Al2O3), stainless steel 304L, galvanized steel and titanium plates with surface areas of 2 to 24 sq m were determined. With 23.8 sq m of Al/Al2O3 the surface-catalyzed air oxidation of hydrazine had a half-life of 2 hours, diimide (N2H2) was observed as an intermediate and traces of ammonia were present in the final product mixture. The Al/Al2O3 catalyzed oxidation of monomethylhydrazine yielded methyldiazine (HN = NCH3) as an intermediate and traces of methanol. Unsymmetrical dimethylhydrazine gave no detectable products. The relative reactivities of hydrazine, MMH and UDMH were 130 : 7.3 : 1.0, respectively. The rate constants for Al/Al2O3-catalyzed oxidation of hydrazine and MMH were proportional to the square of the surface area of the plates. Mechanisms for the surface-catalyzed oxidation of hydrazine and diimide and the formation of ammonia are proposed.

  9. Reduction of Cupric Ions with Elemental Sulfur by Thiobacillus ferrooxidans.

    PubMed

    Sugio, T; Tsujita, Y; Inagaki, K; Tano, T

    1990-03-01

    In anaerobic or aerobic conditions in the presence of 5 mM sodium cyanide, an inhibitor of iron oxidase, cupric ion (Cu) was reduced enzymatically with elemental sulfur (S) by washed intact cells of Thiobacillus ferrooxidans AP19-3 to give cuprous ion (Cu). The rate of Cu reduction was proportional to the concentrations of S and Cu added to the reaction mixture. The pH optimum for the cupric ion-reducing system was 5.0, and the activity was completely destroyed by 10-min incubation of cells at 70 degrees C. The activity of Cu reduction with S by this strain was strongly inhibited by inhibitors of hydrogen sulfide: ferric ion oxidoreductase (SFORase), such as alpha,alpha'-dipyridyl, 4,5-dihydroxy-m-benzene disulfonic acid disodium salts, and diazine dicarboxylic acid bis-(N, N-dimethylamide). A SFORase purified from this strain, which catalyzes oxidation of both hydrogen sulfide and S with Fe or Mo as an electron acceptor in the presence of glutathione, catalyzed a reduction of Cu by S, and the Michaelis constant of SFORase for Cu was 7.2 mM, indicating that a SFORase catalyzes the reduction of not only Fe and Mo but also Cu.

  10. Reduction of Cupric Ions with Elemental Sulfur by Thiobacillus ferrooxidans

    PubMed Central

    Sugio, Tsuyoshi; Tsujita, Yoshihiko; Inagaki, Kenji; Tano, Tatsuo

    1990-01-01

    In anaerobic or aerobic conditions in the presence of 5 mM sodium cyanide, an inhibitor of iron oxidase, cupric ion (Cu2+) was reduced enzymatically with elemental sulfur (S0) by washed intact cells of Thiobacillus ferrooxidans AP19-3 to give cuprous ion (Cu+). The rate of Cu2+ reduction was proportional to the concentrations of S0 and Cu2+ added to the reaction mixture. The pH optimum for the cupric ion-reducing system was 5.0, and the activity was completely destroyed by 10-min incubation of cells at 70°C. The activity of Cu2+ reduction with S0 by this strain was strongly inhibited by inhibitors of hydrogen sulfide: ferric ion oxidoreductase (SFORase), such as α,α′-dipyridyl, 4,5-dihydroxy-m-benzene disulfonic acid disodium salts, and diazine dicarboxylic acid bis-(N, N-dimethylamide). A SFORase purified from this strain, which catalyzes oxidation of both hydrogen sulfide and S0 with Fe3+ or Mo6+ as an electron acceptor in the presence of glutathione, catalyzed a reduction of Cu2+ by S0, and the Michaelis constant of SFORase for Cu2+ was 7.2 mM, indicating that a SFORase catalyzes the reduction of not only Fe3+ and Mo6+ but also Cu2+. PMID:16348143

  11. Conservation Kickstart- Catalyzing Conservation Initiatives Worldwide

    NASA Astrophysics Data System (ADS)

    Treinish, G.

    2014-12-01

    Adventurers and Scientists for Conservation (ASC) is a nonprofit organization that collects environmental data to catalyze conservation initiatives worldwide. Adventure athletes have the skills and motivation to reach the most remote corners of the world. ASC utilizes those skills to provide the scientific community with data while providing the outdoor community with purpose beyond the personal high of reaching a summit or rowing across an ocean. We carefully select projects, choosing partnerships that will maximize the impact of ASC volunteers. Each project must have a clear path to a tangible conservation outcome and demonstrate a clear need for our brand of volunteers. We partner with government agencies, universities, and independant reseachers to kickstart data collection efforts around the world. Last year, through a partnership with the Olympic National Forest, 20 volunteers from the Seattle area set up and monitored camera traps in an effort to survey for costal Pacific marten. Our work led to the species' listing as "critically imperiled" with NatureServe. A partnership with the inaugural Great Pacific Race, engaging trans-Pacific rowing teams, searched for microplastics in the Pacific Ocean as part of our ongoing microplastics campaign. In a multi-year partnership with the American Prairie Reserve (APR), ASC volunteer crews live and work on the Reserve collecting wildlife data year round. The data we obtain directly informs the Reserve's wildlife management decisions. On this project, our crews have safely and effectively navigated temperature extremes from -30 degrees to 100+ degrees while traveling in a remote location. We are currently scouting projects in the Okavango Delta of Botswana and the rainforest of Suriname where we will be able to cover large amounts of area in a short periord of time. ASC is at the crossroads of the adventure and coservation science communities. Our approach of answering specific questions by using highly skilled and

  12. Polymeric bionanocomposite cast thin films with in situ laccase-catalyzed polymerization of dopamine for biosensing and biofuel cell applications.

    PubMed

    Tan, Yueming; Deng, Wenfang; Li, Yunyong; Huang, Zhao; Meng, Yue; Xie, Qingji; Ma, Ming; Yao, Shouzhuo

    2010-04-22

    We report here on the facile preparation of polymer-enzyme-multiwalled carbon nanotubes (MWCNTs) cast films accompanying in situ laccase (Lac)-catalyzed polymerization for electrochemical biosensing and biofuel cell applications. Lac-catalyzed polymerization of dopamine (DA) as a new substrate was examined in detail by UV-vis spectroscopy, cyclic voltammetry, quartz crystal microbalance, and scanning electron microscopy. Casting the aqueous mixture of DA, Lac and MWCNTs on a glassy carbon electrode (GCE) yielded a robust polydopamine (PDA)-Lac-MWCNTs/GCE that can sense hydroquinone with 643 microA mM(-1) cm(-2) sensitivity and 20-nM detection limit (S/N = 3). The DA substrate yielded the best biosensing performance, as compared with aniline, o-phenylenediamine, or o-aminophenol as the substrate for similar Lac-catalyzed polymerization. Casting the aqueous mixture of DA, glucose oxidase (GOx), Lac, and MWCNTs on a Pt electrode yielded a robust PDA-GOx-Lac-MWCNTs/Pt electrode that exhibits glucose-detection sensitivity of 68.6 microA mM(-1) cm(-2). In addition, 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS) was also coimmobilized to yield a PDA-Lac-MWCNTs-ABTS/GCE that can effectively catalyze the reduction of O(2), and it was successfully used as the biocathode of a membraneless glucose/O(2) biofuel cell (BFC) in pH 5.0 Britton-Robinson buffer. The proposed biomacromolecule-immobilization platform based on enzyme-catalyzed polymerization may be useful for preparing many other multifunctional polymeric bionanocomposites for wide applications.

  13. Effect of phosphate and sulfate on Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide mineral recrystallization

    NASA Astrophysics Data System (ADS)

    Hinkle, Margaret A. G.; Catalano, Jeffrey G.

    2015-09-01

    Dissolved Fe(II) activates coupled oxidative growth and reductive dissolution of Fe(III) oxide minerals, causing recrystallization and the repartitioning of structurally-compatible trace metals. Phosphate and sulfate, two ligands common to natural aquatic systems, alter Fe(II) adsorption onto Fe(III) oxides and affect Fe(III) oxide dissolution and precipitation. However, the effect of these oxoanions on trace metal repartitioning during Fe(II)-catalyzed Fe(III) oxide recrystallization is unclear. The effects of phosphate and sulfate on Ni adsorption and Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide recrystallization were investigated as such repartitioning may be affected by both Fe(II)-oxoanion and metal-oxoanion interactions. In most systems examined, phosphate alters Ni repartitioning during Fe(II)-catalyzed recrystallization to a larger extent than sulfate. Phosphate substantially enhances Ni adsorption onto hematite but decreases (nearly inhibiting) Fe(II)-catalyzed Ni incorporation into and release from this mineral. In the goethite system, however, phosphate suppresses Ni release but enhances Ni incorporation in the presence of aqueous Fe(II). In contrast, sulfate has little effect on macroscopic Ni adsorption and release of Ni from Fe(III) oxides, but substantially enhances Ni incorporation into goethite. This demonstrates that phosphate and sulfate have unique, mineral-specific interactions with Ni during Fe(II)-catalyzed Fe(III) oxide recrystallization. This research suggests that micronutrient bioavailability at redox interfaces in hematite-dominated systems may be especially suppressed by phosphate, while both oxoanions likely have limited effects in goethite-rich soils or sediments. Phosphate may also exert a large control on contaminant fate at redox interfaces, increasing Ni retention on iron oxide surfaces. These results further indicate that trace metal retention by iron oxides during lithification and later repartitioning during

  14. Reductive deconstruction of organosolv lignin catalyzed by zeolite supported nickel nanoparticles

    SciTech Connect

    Kasakov, Stanislav; Shi, Hui; Camaioni, Donald M.; Zhao, Chen; Barath, Eszter; Jentys, Andreas; Lercher, Johannes A.

    2015-11-01

    Mechanistic aspects of deconstruction and hydrodeoxygenation of organosolv lignin using supported Ni catalysts with (Ni/HZSM-5 and Ni/HBEA) and without Brønsted acid sites (Ni/SiO2) are reported. Lignin was deconstructed and converted to saturated cyclic hydrocarbons ranging from C5 to C14. In the one-stage reaction, full conversion with total yield of 70 ± 5 wt.% saturated hydrocarbons was achieved at 593 K and 20 bar H2. The organosolv lignin used consists of seven to eight monolignol subunits and has an average molecular weight of ca. 1200 g mol-1. The monolignols were mainly guaiacyl, syringyl and phenylcoumaran, randomly interconnected through β-O-4, 4-O-5, β-1, 5-5’ and β-β ether bonds. In situ IR spectroscopy was used to follow the changes in lignin constituents during reaction. The proposed reaction pathways for the catalytic transformation of this organosolv lignin to alkanes start with the hydrogenolysis of aryl alkyl ether bonds, followed by hydrogenation of the aromatic compounds on Ni to cyclic alcohols. Oxygen is removed from the alcohols via dehydration on Brønsted acid sites to yield cyclic alkenes that are further hydrogenated to alkanes. Formation of condensation products may occur via intermolecular recombination of aromatic monomers or alkylation of aromatic compounds by alkenes. The financial support from TUM-PNNL cooperation project “Development of new methods for in situ characterization in liquid phase reactions” (CN-177939) is highly appreciated. The work by S.K., H.S., and J.A.L was partially supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.

  15. Rhodium(II)-Catalyzed Asymmetric Sulfur(VI) Reduction of Diazo Sulfonylamidines

    PubMed Central

    Selander, Nicklas; Fokin, Valery V.

    2013-01-01

    Diazo sulfonylamidines readily undergo enantioselective oxygen transfer from sulfur to carbon atom in the presence of chiral rhodium(II) carboxylates resulting in chiral sulfinylamidines. This unusual asymmetric atom transfer “reduction” occurs rapidly under mild conditions, and sulfinylamidines are obtained in excellent yield. PMID:22233190

  16. Iridium-Catalyzed Hydrosilylative Reduction of Glucose to Hexane(s)

    DTIC Science & Technology

    2013-01-11

    modern chemical processes and infrastructure.2 Despite significant effort, most systems relevant to carbohydrate defunctionalization utilize harsh...a competitive process . To overcome the technical challenges of quantifying the volatile hexane products, the yields were estimated by an in situ 13C...2009, 15, 10132−10143. (p) Ghosh, P.; Fagan, P. J.; Marshall, W. J.; Hauptman, E.; Bullock, R. M. Inorg. Chem. 2009, 48, 6490−6500. (q) Ziegler , J. E

  17. REDUCTIVE DECHLORINATION OF TETRACHLORIDE (PCE) CATALYZED BY CYANOCOBALAMIN. (R825689C060)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  18. Combined Catalyzed Soot Filter and SCR Catalyst System for Diesel Engine Emission Reduction

    SciTech Connect

    Kakwani, R.M.

    2000-08-20

    Substantially reduces particulate emission for diesel vehicles Up to 90% effective against carbonaceous particulate matter Significantly reduces CO and HC Filter regenerates at normal diesel operation temperatures Removable design for easy cleaning and maintenance.

  19. An Investigation into Palladium-Catalyzed Reduction of Perchlorate in Water

    DTIC Science & Technology

    2005-03-01

    depth beyond the plant root zone, phytoremediation would be not affect the transport of perchlorate. Also, once perchlorate is dispersed in a large...Agrawal provided essential guidance on experimental procedures and helped me to focus my research efforts. Without his assistance and expertise...which has been contaminated by discharges from manufacturing plants near Henderson, Nevada (Hogue, 2003). Lake Mead feeds into the lower Colorado

  20. Ruthenium-catalyzed hydroformylation/reduction of olefins to alcohols: extending the scope to internal alkenes.

    PubMed

    Wu, Lipeng; Fleischer, Ivana; Jackstell, Ralf; Profir, Irina; Franke, Robert; Beller, Matthias

    2013-09-25

    In the presence of 2-phosphino-substituted imidazole ligands and Ru3(CO)12 or Ru(methylallyl)2(COD) direct hydroformylation and hydrogenation of alkenes to alcohols takes place. In addition to terminal alkenes, also more challenging internal olefins are converted preferentially to industrially important linear alcohols in high yield (up to 88%) and regioselectivity (n:iso up to 99:1).

  1. Secondary tritium and solvent deuterium isotope effects as a probe of the reaction catalyzed by porcine recombinant dihydropyrimidine dehydrogenase.

    PubMed

    Rosenbaum, K; Jahnke, K; Schnackerz, K D; Cook, P F

    1998-06-23

    Dihydropyrimidine dehydrogenase catalyzes the rate-limiting step in the degradation of pyrimidines in mammals, the reduction of uracil or thymine to their 5,6-dihydro derivatives. The reduction of uracil by enzyme-bound reduced flavin involves both proton and hydride transfer. In order to determine whether hydride and proton transfer occur in a concerted or stepwise fashion, and to determine the nature of the transition state for the reduction, secondary tritium kinetic isotope effects were measured in H2O and D2O. The tritium isotope effect using 5-3H-uracil is 0.90 +/- 0.03 in H2O and becomes more inverse, 0.85 +/- 0.04, in D2O. Data are interpreted in terms of a stepwise reduction at C-6 followed by protonation at C-5. A late transition state is proposed for the proton transfer at C-5 of uracil.

  2. Synthesis of novel and diverse naphtho[1,2-b]furans by phosphine-catalyzed [3+2] annulation of activated 1,4-naphthoquinones and acetylenecarboxylates.

    PubMed

    Xia, Likai; Magar, Krishna Bahadur Somai; Lee, Yong Rok

    2015-02-01

    A new phosphine-catalyzed [3+2] annulation reaction between activated 1,4-naphthoquinones and acetylenecarboxylates is described. This reaction provides a facile and efficient route to a variety of biologically promising and novel naphtho[1,2-b]furans. This devised method provides a first example for the synthesis of diverse naphtho[1,2-b]furan derivatives from 1,4-naphthoquinones via phosphine-catalyzed [3+2] annulation. A variety of novel naphtho[1,2-b]furans were synthesized via the phosphine-catalyzed [3+2] annulation of activated 1,4-naphthoquinones and electron-deficient acetylenecarboxylates. In some reactions, both furannulation adducts and reductive/nucleophilic conjugate addition products were produced.

  3. MICROBIAL TRANSFORMATIONS OF TRU AND MIXED WASTES: ACTINIDE SPECIATION AND WASTE VOLUME REDUCTION.

    SciTech Connect

    FRANCIS, A.J.; DODGE, C.J.

    2006-11-16

    The overall goals of this research project are to determine the mechanism of microbial dissolution and stabilization of actinides in Department of Energy's (DOE) TRU wastes, contaminated sludges, soils, and sediments. This includes (1) investigations on the fundamental aspects of microbially catalyzed radionuclide and metal transformations (oxidation/reduction reactions, dissolution, precipitation, chelation); (2) understanding of the microbiological processes that control speciation and alter the chemical forms of complex inorganic/organic contaminant mixtures; and (3) development of new and improved microbially catalyzed processes resulting in immobilization of metals and radionuclides in the waste with concomitant waste volume reduction.

  4. MICROBIAL TRANSFORMATIONS OF TRU AND MIXED WASTES: ACTINIDE SPECIATION AND WASTE VOLUME REDUCTION

    SciTech Connect

    Francis, A.J.; Dodge, C.J.

    2006-06-01

    The overall goals of this research project are to determine the mechanism of microbial dissolution and stabilization of actinides in Department of Energy’s (DOE) TRU wastes, contaminated sludges, soils, and sediments. This includes (i) investigations on the fundamental aspects of microbially catalyzed radionuclide and metal transformations (oxidation/reduction reactions, dissolution, precipitation, chelation); (ii) understanding of the microbiological processes that control speciation and alter the chemical forms of complex inorganic/organic contaminant mixtures; and (iii) development of new and improved microbially catalyzed processes resulting in immobilization of metals and radionuclides in the waste with concomitant waste volume reduction.

  5. MICROBIAL TRANSFORMATIONS OF TRU AND MIXED WASTES: ACTINIDE SPECIATION AND WASTE VOLUME REDUCTION

    SciTech Connect

    Francis, A.J.; Dodge, C.J.

    2006-06-01

    The overall goals of this research project are to determine the mechanism of microbial dissolution and stabilization of actinides in Department of Energy's (DOE) TRU wastes, contaminated sludges, soils, and sediments. This includes (1) investigations on the fundamental aspects of microbially catalyzed radionuclide and metal transformations (oxidation/reduction reactions, dissolution, precipitation, chelation); (2) understanding of the microbiological processes that control speciation and alter the chemical forms of complex inorganic/organic contaminant mixtures; and (3) development of new and improved microbially catalyzed processes resulting in immobilization of metals and radionuclides in the waste with concomitant waste volume reduction.

  6. Preparative Synthesis of Highly Substituted Tetrahydropyridines via a Rh(I)-Catalyzed C–H Functionalization Sequence

    PubMed Central

    2015-01-01

    We report a Rh(I)-catalyzed C–H activation/alkenylation/electrocyclization cascade and subsequent reduction for the synthesis of highly substituted tetrahydropyridines. These products can be accessed on a gram scale with low catalyst loadings and at high reaction concentrations. Additionally, a modified Rh-catalyst, prepared from [RhCl(cod)]2 as a robust bench-stable precatalyst was developed to enable straightforward reaction set up without the use of a glovebox. To demonstrate the practicality of this reaction, a >100 mmol scale Rh-catalyzed cascade reaction sequence utilizing the air-stable precatalyst [RhCl(cod)]2 was performed on the bench to furnish the pure tetrahydropyridine product in 93% yield. PMID:25288872

  7. Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

    PubMed Central

    Saadi, Jakub; Bentz, Christoph; Redies, Kai; Lentz, Dieter; Zimmer, Reinhold

    2016-01-01

    Summary Starting from γ-ketoesters with an o-iodobenzyl group we studied a palladium-catalyzed cyclization process that stereoselectively led to bi- and tricyclic compounds in moderate to excellent yields. Four X-ray crystal structure analyses unequivocally defined the structure of crucial cyclization products. The relative configuration of the precursor compounds is essentially transferred to that of the products and the formed hydroxy group in the newly generated cyclohexane ring is consistently in trans-arrangement with respect to the methoxycarbonyl group. A transition-state model is proposed to explain the observed stereochemical outcome. This palladium-catalyzed Barbier-type reaction requires a reduction of palladium(II) back to palladium(0) which is apparently achieved by the present triethylamine. PMID:27559374

  8. Base-Catalyzed Depolymerization of Biorefinery Lignins

    DOE PAGES

    Katahira, Rui; Mittal, Ashutosh; McKinney, Kellene; ...

    2016-01-12

    Lignocellulosic biorefineries will produce a substantial pool of lignin-enriched residues, which are currently slated to be burned for heat and power. Going forward, however, valorization strategies for residual solid lignin will be essential to the economic viability of modern biorefineries. To achieve these strategies, effective lignin depolymerization processes will be required that can convert specific lignin-enriched biorefinery substrates into products of sufficient value and market size. Base-catalyzed depolymerization (BCD) of lignin using sodium hydroxide and other basic media has been shown to be an effective depolymerization approach when using technical and isolated lignins relevant to the pulp and paper industry.more » Moreover, to gain insights in the application of BCD to lignin-rich, biofuels-relevant residues, here we apply BCD with sodium hydroxide at two catalyst loadings and temperatures of 270, 300, and 330 °C for 40 min to residual biomass from typical and emerging biochemical conversion processes. We obtained mass balances for each fraction from BCD, and characterized the resulting aqueous and solid residues using gel permeation chromatography, NMR, and GC–MS. When taken together, these results indicate that a significant fraction (45–78%) of the starting lignin-rich material can be depolymerized to low molecular weight, water-soluble species. The yield of the aqueous soluble fraction depends significantly on biomass processing method used prior to BCD. Namely, dilute acid pretreatment results in lower water-soluble yields compared to biomass processing that involves no acid pretreatment. We also find that the BCD product selectivity can be tuned with temperature to give higher yields of methoxyphenols at lower temperature, and a higher relative content of benzenediols with a greater extent of alkylation on the aromatic rings at higher temperature. Our study shows that residual, lignin-rich biomass produced from conventional and

  9. Direct detection of enzyme-catalyzed products by FET sensor with ferrocene-modified electrode.

    PubMed

    Ishige, Yu; Takeda, Sizu; Kamahori, Masao

    2010-12-15

    An FET-based biosensor with a ferrocene-modified gold electrode detects the enzyme-produced electrons by using mediators that transfer the electrons from the enzyme to the sensor. Since an extended-gate FET sensor with a light-shielding mask can be operated without a light-shielding box, a small portable instrument will soon be realised. However, when the FET sensor detected enzyme-catalyzed products with the mediators under light conditions, measurements fluctuated due to photo-reduction of the mediators, resulting in decreased sensitivity. To improve sensitivity by reducing the fluctuation, we developed a procedure for directly detecting enzyme-catalyzed products without using the mediators. The key technique used in this procedure was a measurement technique using our developed potential-keeping method, in which the modified electrode of the FET sensor was oxidised by ferricyanide solution to make its surface the same high potential every time, and this high potential was kept until measurement because of the high input impedance of the FET structure. After this method was applied, the interfacial potential of the gold electrode decreased depending on the amount of enzyme-catalyzed products due to the ferrocene molecules immobilised on the gold electrode directly reacting with the products. The results obtained in light conditions indicated that model compounds of the products were detected from 10 μM to 10 mM with the Nernstian response of 59.2 mV/decade. Also, this method was applied to pesticide detection by using the enzyme inhibition by pesticide, and 5 ppb of diazinon was successfully detected by using only a sensor chip. Copyright © 2010 Elsevier B.V. All rights reserved.

  10. Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO2

    PubMed Central

    2016-01-01

    The recent years have witnessed the development of metal-catalyzed reductive carboxylation of organic (pseudo)halides with CO2 as C1 source, representing potential powerful alternatives to existing methodologies for preparing carboxylic acids, privileged motifs in a myriad of pharmaceuticals and molecules displaying significant biological properties. While originally visualized as exotic cross-coupling reactions, a close look into the literature data indicates that these processes have become a fertile ground, allowing for the utilization of a variety of coupling partners, even with particularly challenging substrate combinations. As for other related cross-electrophile scenarios, the vast majority of reductive carboxylation of organic (pseudo)halides are characterized by their simplicity, mild conditions, and a broad functional group compatibility, suggesting that these processes could be implemented in late-stage diversification. This perspective describes the evolution of metal-catalyzed reductive carboxylation of organic (pseudo)halides from its inception in the pioneering stoichiometric work of Osakada to the present. Specific emphasis is devoted to the reactivity of these coupling processes, with substrates ranging from aryl-, vinyl-, benzyl- to unactivated alkyl (pseudo)halides. Despite the impressive advances realized, a comprehensive study detailing the mechanistic intricacies of these processes is still lacking. Some recent empirical evidence reveal an intriguing dichotomy exerted by the substitution pattern on the ligands utilized; still, however, some elementary steps within the catalytic cycle of these reactions remain speculative, in many instances invoking a canonical cross-coupling process. Although tentative, we anticipate that these processes might fall into more than one distinct mechanistic category depending on the substrate utilized, suggesting that investigations aimed at unraveling the mechanistic underpinnings of these processes will likely

  11. [Fundamental studies in oxidation reduction in relation to water photolysis

    SciTech Connect

    Hurst, J.K.

    1992-01-01

    Objectives were to understand 3 elementary processes central to developing membrane-based integrated chemical systems for water photolysis: role of interfaces in charge separation/recombination reactions, pathways for transmembrane charge separation, and mechanisms of water oxidation catalyzed by transition metal coordination complexes. Research during this period is arranged under the headings transmembrane oxidation-reduction mechanisms, optically gated transmembrane redox, and mechanisms of water oxidation catalysis. Viologens are involved.

  12. Improving the stereoselectivity of bakers' yeast reductions by genetic engineering.

    PubMed

    Rodríguez, S; Kayser, M; Stewart, J D

    1999-10-21

    [formula: see text] The stereoselectivities of bakers' yeast catalyzed reductions of beta-keto esters can be manipulated by genetic design. Strains in which two major beta-keto ester reductases are either knocked out or overexpressed have been constructed. The former approach results in whole cell biocatalysts with reversed stereoselectivity from unmodified bakers' yeast while the latter shows useful improvements in stereoselectivity. These results indicate that the "designer yeast" approach can provide useful biocatalysts for these transformations.

  13. Catalytic Leuckart-Wallach-type reductive amination of ketones.

    PubMed

    Kitamura, Masato; Lee, Donghyun; Hayashi, Shinnosuke; Tanaka, Shinji; Yoshimura, Masahiro

    2002-11-29

    A CpRh(III) complex catalyzes reductive amination of ketones using HCOONH(4) at 50-70 degrees C to give the corresponding primary amines in high yields. The reaction is clean and operationally simple and proceeds at a lower temperature and with higher chemoselectivity than the original Leuckart-Wallach reaction. The new method has been applied to the synthesis of alpha-amino acids directly from alpha-keto acids.

  14. Modelling Hydrogen Reduction and Hydrodeoxygenation of Oxygenates

    SciTech Connect

    Zhao, Y.; Xu, Q.; Cheah, S.

    2013-01-01

    Based on Density Functional Theory (DFT) simulations, we have studied the reduction of nickel oxide and biomass derived oxygenates (catechol, guaiacol, etc.) in hydrogen. Both the kinetic barrier and thermodynamic favorability are calculated with respect to the modeled reaction pathways. In early-stage reduction of the NiO(100) surface by hydrogen, the pull-off of the surface oxygen atom and simultaneous activation of the nearby Ni atoms coordinately dissociate the hydrogen molecules so that a water molecule can be formed, leaving an oxygen vacancy on the surface. In hydrogen reaction with oxygenates catalyzed by transition metals, hydrogenation of the aromatic carbon ring normally dominates. However, selective deoxygenation is of particular interest for practical application such as biofuel conversion. Our modeling shows that doping of the transition metal catalysts can change the orientation of oxygenates adsorbed on metal surfaces. The correlation between the selectivity of reaction and the orientation of adsorption are discussed.

  15. Structural basis of enzymatic benzene ring reduction.

    PubMed

    Weinert, Tobias; Huwiler, Simona G; Kung, Johannes W; Weidenweber, Sina; Hellwig, Petra; Stärk, Hans-Joachim; Biskup, Till; Weber, Stefan; Cotelesage, Julien J H; George, Graham N; Ermler, Ulrich; Boll, Matthias

    2015-08-01

    In chemical synthesis, the widely used Birch reduction of aromatic compounds to cyclic dienes requires alkali metals in ammonia as extremely low-potential electron donors. An analogous reaction is catalyzed by benzoyl-coenzyme A reductases (BCRs) that have a key role in the globally important bacterial degradation of aromatic compounds at anoxic sites. Because of the lack of structural information, the catalytic mechanism of enzymatic benzene ring reduction remained obscure. Here, we present the structural characterization of a dearomatizing BCR containing an unprecedented tungsten cofactor that transfers electrons to the benzene ring in an aprotic cavity. Substrate binding induces proton transfer from the bulk solvent to the active site by expelling a Zn(2+) that is crucial for active site encapsulation. Our results shed light on the structural basis of an electron transfer process at the negative redox potential limit in biology. They open the door for biological or biomimetic alternatives to a basic chemical synthetic tool.

  16. Continuous Reductive Amination of Biomass-Derived Molecules over Carbonized Filter Paper-Supported FeNi Alloy.

    PubMed

    Chieffi, Gianpaolo; Braun, Max; Esposito, Davide

    2015-11-01

    This paper reports the continuous reductive amination of different molecules, including biomass-related compounds, over carbon-supported FeNi nanoparticles obtained on the basis of inexpensive and abundant metal precursors and cellulose. A biorefinery case study for the preparation of pyrrolidones via acid-catalyzed hydrolysis of glucose followed by reductive amination of the obtained levulinic acid is described.

  17. Cobalt-Catalyzed Alkylation of Aromatic Amines by Alcohols.

    PubMed

    Rösler, Sina; Ertl, Michael; Irrgang, Torsten; Kempe, Rhett

    2015-12-07

    The implementation of inexpensive, Earth-abundant metals in typical noble-metal-mediated chemistry is a major goal in homogeneous catalysis. A sustainable or green reaction that has received a lot of attention in recent years and is preferentially catalyzed by Ir or Ru complexes is the alkylation of amines by alcohols. It is based on the borrowing hydrogen or hydrogen autotransfer concept. Herein, we report on the Co-catalyzed alkylation of aromatic amines by alcohols. The reaction proceeds under mild conditions, and selectively generates monoalkylated amines. The observed selectivity allows the synthesis of unsymmetrically substituted diamines. A novel Co complex stabilized by a PN5 P ligand catalyzes the reactions most efficiently. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Divergent pathways lead to ESCRT-III-catalyzed membrane fission.

    PubMed

    Peel, Suman; Macheboeuf, Pauline; Martinelli, Nicolas; Weissenhorn, Winfried

    2011-04-01

    Endosomal sorting complexes required for transport (ESCRT) have been implicated in topologically similar but diverse cellular and pathological processes including multivesicular body (MVB) biogenesis, cytokinesis and enveloped virus budding. Although receptor sorting at the endosomal membrane producing MVBs employs the regulated assembly of ESCRT-0 followed by ESCRT-I, -II, -III and the vacuolar protein sorting (VPS)4 complex, other ESCRT-catalyzed processes require only a subset of complexes which commonly includes ESCRT-III and VPS4. Recent progress has shed light on the pathway of ESCRT assembly and highlights the separation of tasks of different ESCRT complexes and associated partners. The emerging picture suggests that among all ESCRT-catalyzed processes, divergent pathways lead to ESCRT-III assembly within the neck of a budding structure catalyzing membrane fission.

  19. Palladium-catalyzed modification of unprotected nucleosides, nucleotides, and oligonucleotides.

    PubMed

    Shaughnessy, Kevin H

    2015-05-22

    Synthetic modification of nucleoside structures provides access to molecules of interest as pharmaceuticals, biochemical probes, and models to study diseases. Covalent modification of the purine and pyrimidine bases is an important strategy for the synthesis of these adducts. Palladium-catalyzed cross-coupling is a powerful method to attach groups to the base heterocycles through the formation of new carbon-carbon and carbon-heteroatom bonds. In this review, approaches to palladium-catalyzed modification of unprotected nucleosides, nucleotides, and oligonucleotides are reviewed. Polar reaction media, such as water or polar aprotic solvents, allow reactions to be performed directly on the hydrophilic nucleosides and nucleotides without the need to use protecting groups. Homogeneous aqueous-phase coupling reactions catalyzed by palladium complexes of water-soluble ligands provide a general approach to the synthesis of modified nucleosides, nucleotides, and oligonucleotides.

  20. Highly efficient palladium-catalyzed hydrostannation of ethyl ethynyl ether.

    PubMed

    Andrews, Ian P; Kwon, Ohyun

    2008-12-08

    The palladium-catalyzed hydrostannation of acetylenes is widely exploited in organic synthesis as a means of forming vinyl stannanes for use in palladium-catalyzed cross-coupling reactions. Application of this methodology to ethyl ethynyl ether results in an enol ether that is challenging to isolate from the crude reaction mixture because of incompatibility with typical silica gel chromatography. Reported here is a highly efficient procedure for the palladium-catalyzed hydrostannation of ethyl ethynyl ether using 0.1% palladium(0) catalyst and 1.0 equiv of tributyltin hydride. The product obtained is a mixture of regioisomers that can be carried forward with exclusive reaction of the beta-isomer. This method is highly reproducible; relative to previously reported procedures, it is more economical and involves a more facile purification procedure.

  1. Metal-Catalyzed Asymmetric Michael Addition in Natural Product Synthesis.

    PubMed

    Hui, Chunngai; Pu, Fan; Xu, Jing

    2016-12-19

    Asymmetric catalysis for chiral compound synthesis is a rapidly growing field in modern organic chemistry. Asymmetric catalytic processes have been indispensable for the synthesis of enantioselective materials to meet demands from various fields. Michael addition has been used extensively for the construction of C-C bonds under mild conditions. With the discovery and development of organo- and metal-catalyzed asymmetric Michael additions, the synthesis of enantioselective and/or diastereoselective Michael adducts has become possible and increasingly prevalent in the literature. In particular, metal-catalyzed asymmetric Michael addition has been employed as a key reaction in natural product synthesis for the construction of contiguous quaternary stereogenic center(s), which is still a difficult task in organic synthesis. Previously reported applications of metal-catalyzed asymmetric Michael additions in natural product synthesis are presented here and discussed in depth.

  2. Stau-catalyzed big-bang nucleosynthesis reactions

    NASA Astrophysics Data System (ADS)

    Kamimura, Masayasu; Kino, Yasushi; Hiyama, Emiko

    2010-06-01

    We study the new type of big-bang nucleosynthesis (BBN) reactions that are catalyzed by a hypothetical long-lived negatively charged, massive leptonic particle (called X-) such as the supersymmetric (SUSY) particle stau, the scalar partner of the tau lepton. It is known that if the X- particle has a lifetime of τX>~103 s, it can capture a light element previously synthesized in standard BBN and form a Coulombic bound state and induces various types of reactions in which X- acts as a catalyst. Some of these X- catalyzed reactions have significantly large cross sections so that the inclusion of the reactions into the BBN network calculation can markedly change the abundances of some elements. We use a high-accuracy three-body calculation method developed by the authors and provide precise cross sections and rates of these catalyzed BBN reactions for use in the BBN network calculation.

  3. Phosphine-Catalyzed [4 + 2] Annulation: Synthesis of Cyclohexenes

    PubMed Central

    Tran, Yang S.

    2008-01-01

    Phosphine-catalyzed [4 + 2] annulations of α-alkylallenoates with activated olefins allow the efficient syntheses of cyclohexenes. Hexamethylphosphorous triamide (HMPT)-catalyzed [4 + 2] annulations of α-alkylallenoates with arylidenemalononitriles provided highly functionalized 5,5-dicyano-4,6-disubstituted cyclohex-1-enecarboxylates in excellent yields (77–98%) and moderate to high diastereoselectivities (1:2–12:1). Remarkably, the corresponding triarylphosphine-catalyzed [4 + 2] annulations of α-methylallenoate with arylidenemalononitriles manifested a polarity inversion of the 1,4-dipole synthon, providing 4,4-dicyano-5-substituted cyclohex-1-enecarboxylates in excellent yields (80–93%). The polarity inversion of α-alkylallenoates from one 1,4-dipole to another under phosphine catalysis presumably resulted from a change in the balance of the equilibrium between the phosphonium dienolate and the vinylogous phosphonium ylide intermediate. PMID:17914823

  4. Atom transfer and rearrangement reactions catalyzed by methyltrioxorhenium, MTO

    SciTech Connect

    Jacob, Josemon

    1999-05-10

    Methyltrioxorhenium (MTO) catalyzes the desulfurization of thiiranes by triphenylphosphine. Enormous enhancement in rate is observed when the catalyst is pretreated with hydrogen sulfide prior to the reaction. Using 2-mercaptomethylthiophenol as a ligand, the author synthesized several model complexes to study the mechanism of this reaction. With suitable model systems, they were able to show that the active catalyst is a Re(V) species. The reactions are highly stereospecific and very tolerant to functional groups. As part of the studies, he synthesized and crystallographically characterized the first examples of neutral terminal and bridging Re(V)sulfidocomplexes. Some of these complexes undergo fast oxygen atom transfer reactions with organic and inorganic oxidants. Studies on these model complexes led them to the discovery that MTO catalyzes the selective oxidation of thiols to disulfides. This report contains the Introduction; ``Chapter 6: Isomerization of Propargylic Alcohols to Enones and Enals Catalyzed by Methylrhenium Trioxide``; and Conclusions.

  5. Copper-catalyzed azide alkyne cycloaddition polymer networks

    NASA Astrophysics Data System (ADS)

    Alzahrani, Abeer Ahmed

    The click reaction concept, introduced in 2001, has since spurred the rapid development and reexamination of efficient, high yield reactions which proceed rapidly under mild conditions. Prior to the discovery of facile copper catalysis in 2002, the thermally activated azide-alkyne or Huisgen cycloaddition reaction was largely ignored following its discovery in large part due to its slow kinetics, requirement for elevated temperature and limited selectivity. Now, arguably, the most prolific and capable of the click reactions, the copper-catalyzed azide alkyne cycloaddition (CuAAC) reaction is extremely efficient and affords exquisite control of the reaction. The orthogonally and chemoselectivity of this reaction enable its wide utility across varied scientific fields. Despite numerous inherent advantages and widespread use for small molecule synthesis and solution-based polymer chemistry, it has only recently and rarely been utilized to form polymer networks. This work focuses on the synthesis, mechanisms, and unique attributes of the CuAAC reaction for the fabrication of functional polymer networks. The photo-reduction of a series of copper(II)/amine complexes via ligand metal charge transfer was examined to determine their relative efficiency and selectivity in catalyzing the CuAAC reaction. The aliphatic amine ligands were used as an electron transfer species to reduce Cu(II) upon irradiation with 365 nm light while also functioning as an accelerating agent and as protecting ligands for the Cu(I) that was formed. Among the aliphatic amines studied, tertiary amines such as triethylamine (TEA), tetramethyldiamine (TMDA), N,N,N',N",N"-pentamethyldiethylenetriamine (PMDTA), and hexamethylenetetramine (HMTETA) were found to be the most effective. The reaction kinetics were accelerated by increasing the PMDETA : Cu(II) ratio with a ratio of ligand to Cu(II) of 4:1 yielding the maximum conversion in the shortest time. The sequential and orthogonal nature of the photo

  6. Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures

    NASA Technical Reports Server (NTRS)

    Fu, Qi; Socki, R. A.; Niles, Paul B.

    2011-01-01

    Observation of methane in the Martian atmosphere has been reported by different detection techniques. Reduction of CO2 and/or CO during serpentization by mineral surface catalyzed Fischer-Tropsch Type (FTT) synthesis may be one possible process responsible for methane generation on Mars. With the evidence a recent study has discovered for serpentinization in deeply buried carbon rich sediments, and more showing extensive water-rock interaction in Martian history, it seems likely that abiotic methane generation via serpentinization reactions may have been common on Mars. Experiments involving mineral-catalyzed hydrothermal organic synthesis processes were conducted at 750 C and 5.5 Kbars. Alkanes, alcohols and carboxylic acids were identified as organic compounds. No "isotopic reversal" of delta C-13 values was observed for alkanes or carboxylic acids, suggesting a different reaction pathway than polymerization. Alcohols were proposed as intermediaries formed on mineral surfaces at experimental conditions. Carbon isotope data were used in this study to unravel the reaction pathways of abiotic formation of organic compounds in hydrothermal systems at high temperatures and pressures. They are instrumental in constraining the origin and evolution history of organic compounds on Mars and other planets.

  7. Effectiveness of immobilized lipase Thermomyces lanuginosa in catalyzing interesterification of palm olein in batch reaction.

    PubMed

    Saw, Mei Huey; Siew, Wai Lin

    2014-01-01

    Lipase Thermomyces lanuginosa has shown potential in modifying oils and fats through interesterification. Analyzing the physicochemical properties of the modified oils is important to determine the effectiveness of lipase in catalyzing interesterification. In this study, the effectiveness of the immobilized lipase (Lipozyme(®) TL IM) in catalyzing interesterification of palm olein in pilot-scale batch reactor was determined. The evaluation was done by analyzing the changes of triacylglycerol (TAGs) composition, sn-2 position fatty acids composition and the physical properties of the palm olein after the interesterifications. The pilot-scale batch reaction was conducted for 8 hours with 5 %w/w enzyme dosage based on the results of TAGs composition of the laboratory-scale interesterified products. The pilot-scale results showed that Lipozyme(®) TL IM act as an effective enzyme in converting TAGs, in which 4.5% of trisaturated TAGs (PPP and PPS) were produced in the batch reaction. The formation of these new TAGs had also altered the thermal and physical properties of the palm olein. These interesterified products showed a broad peak and shoulder at high temperature, ranging from 10°C to 40°C, indicating the formation of some new TAGs with high melting points. However, the enzyme did not perform perfectly as a 1,3-specific enzyme in the reaction as a significant reduction of oleic acid and an increment of palmitic acid at the sn-2 position was observed.

  8. Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene

    DOE PAGES

    Xu, Songchen; Boschen, Jeffery S.; Biswas, Abhranil; ...

    2015-08-17

    An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ³-N,Si,C-PhB(OxMe²)(OxMe²SiHPh)ImMes}Rh(H)CO][HB(C₆F₅)₃] (2, OxMe² = 4,4-dimethyl-2-oxazoline; ImMes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(OxMe²)₂ImMes}RhH(SiH2Ph)CO (1) and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(OxMe²)₂ImMes}RhH(SiHPh)CO][HB(C₆F₅)₃] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenationmore » of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C₆F₅)₃ catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH₃ as the reducing agent.« less

  9. Evidence for coupled motion and hydrogen tunneling of the reaction catalyzed by glutamate mutase.

    PubMed

    Cheng, Mou-Chi; Marsh, E Neil G

    2007-01-23

    Glutamate mutase is one of a group of adenosylcobalamin-dependent enzymes that catalyze unusual isomerizations that proceed through organic radical intermediates generated by homolytic fission of the coenzyme's unique cobalt-carbon bond. These enzymes are part of a larger family of enzymes that catalyze radical chemistry in which a key step is the abstraction of a hydrogen atom from an otherwise inert substrate. To gain insight into the mechanism of hydrogen transfer, we previously used pre-steady-state, rapid-quench techniques to measure the alpha-secondary tritium kinetic and equilibrium isotope effects associated with the formation of 5'-deoxyadenosine when glutamate mutase was reacted with [5'-(3)H]adenosylcobalamin and L-glutamate. We showed that both the kinetic and equilibrium isotope effects are large and inverse, 0.76 and 0.72, respectively. We have now repeated these measurements using glutamate deuterated in the position of hydrogen abstraction. The effect of introducing a primary deuterium kinetic isotope effect on the hydrogen transfer step is to reduce the magnitude of the secondary kinetic isotope effect to a value close to unity, 1.05 +/- 0.08, whereas the equilibrium isotope effect is unchanged. The significant reduction in the secondary kinetic isotope effect is consistent with motions of the 5'-hydrogen atoms being coupled in the transition state to the motion of the hydrogen undergoing transfer, in a reaction that involves a large degree of quantum tunneling.

  10. Evidence for Coupled Motion and Hydrogen Tunneling the Reaction Catalyzed by Glutamate Mutase:†

    PubMed Central

    Cheng, Mou-Chi; Marsh, E. Neil G.

    2008-01-01

    Glutamate mutase is one of a group of adenosylcobalamin-dependent enzymes that catalyze unusual isomerizations that proceed through organic radical intermediates generated by homolytic fission of coenzyme's unique cobalt-carbon bond. These enzymes are part of a larger family of enzymes that catalyze radical chemistry in which a key step is the abstraction of a hydrogen atom from an otherwise inert substrate. To gain insight into the mechanism of hydrogen transfer we previously used pre-steady state, rapid quench techniques to measure the α-secondary tritium kinetic and equilibrium isotope effects associated with the formation of 5’-deoxyadenosine when glutamate mutase was reacted with [5’-3H]-adenosylcobalamin and L-glutamate. We showed that both the kinetic and equilibrium isotope effects are large and inverse, 0.76 and 0.72 respectively. We have now repeated these measurements using glutamate deuterated in the position of hydrogen abstraction. The effect of introducing a primary deuterium kinetic isotope effect on the hydrogen transfer step is to reduce the magnitude of the secondary kinetic isotope effect to a value close to unity, 1.05 ± 0.08, whereas the equilibrium isotope effect is unchanged. The significant reduction in the secondary kinetic isotope effect is consistent with motions of the 5’-hydrogen atoms being coupled in the transition state to the motion of the hydrogen undergoing transfer, in a reaction that involves a large degree of quantum tunneling. PMID:17223710

  11. Access to β-lactams by enantioselective palladium(0)-catalyzed C(sp3)-H alkylation.

    PubMed

    Pedroni, Julia; Boghi, Michele; Saget, Tanguy; Cramer, Nicolai

    2014-08-18

    β-Lactams are very important structural motifs because of their broad biological activities as well as their propensity to engage in ring-opening reactions. Transition-metal-catalyzed C-H functionalizations have emerged as strategy enabling yet uncommon highly efficient disconnections. In contrast to the significant progress of Pd(0)-catalyzed C-H functionalization for aryl-aryl couplings, related reactions involving the formation of saturated C(sp(3))-C(sp(3)) bonds are elusive. Reported here is an asymmetric C-H functionalization approach to β-lactams using readily accessible chloroacetamide substrates. Important aspects of this transformation are challenging C(sp(3))-C(sp(3)) and strain-building reductive eliminations to for the four-membered ring. In general, the β-lactams are formed in excellent yields and enantioselectivities using a bulky taddol phosphoramidite ligand in combination with adamantyl carboxylic acid as cocatalyst. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Alkane biosynthesis by decarbonylation of aldehydes catalyzed by a particulate preparation from Pisum sativum

    SciTech Connect

    Cheesbourgh, T.M.; Kolattukudy, P.E.

    1984-11-01

    Mechanism of enzymatic conversion of a fatty acid to the corresponding alkane by the loss of the carboxyl carbon was investigated with particulate preparations from Pisum sativum. A heavy particulate preparation (sp. gr., 1.30 g/cm/sup 3/) isolated by two density-gradient centrifugation steps catalyzed conversion of octadecanal to heptadecane and CO. Experiments with (1-/sup 3/H, 1-/sup 14/C)octadecanal showed the stoichiometry of the reaction and retention of the aldehydic hydrogen in the alkane during this enzymatic decarbonylation. This decarbonylase showed an optimal pH of 7.0 and a K/sub m/ of 35 ..mu..M for the aldehyde. This enzyme was severly inhibited by metal ion chelators and showed no requirement for any cofactors. Microsomal preparations and the particulate fractions from the first density-gradient step catalyzed acyl-CoA reduction to the corresponding aldehyde. Electron microscopic examination showed the presence of fragments of cell wall/cuticle but no vesicles in the decarbonylase preparation. It is concluded that the aldehydes produced by the acyl-CoA reductase located in the endomembranes of the epidermal cells are converted to alkanes by the decarbonylase located in the cell wall/cuticle region. 20 references, 4 figures, 1 tables.

  13. The oxidation of chiral alcohols catalyzed by catalase in organic solvents

    SciTech Connect

    Magner, E.; Klibanov, A.M.

    1995-04-20

    The catalytic properties of bovine liver catalase have been investigated in organic solvents. In tetrahydrofuran, dioxane, and acetone (all containing 1% to 3% of water), the enzyme breaks down tert-butyl hydroperoxide several fold faster than in pure water. Furthermore, the rate of catalase-catalyzed production of tert-butanol from tert-butyl hydroperoxide increases more than 400-fold upon transition from aqueous buffer to ethanol as the reaction medium. The mechanistic rationale for this striking effect is that in aqueous buffer the rate-limiting step of the enzymatic process involves the reduction of catalase`s compound 1 by tert-butyl hydroperoxide. In ethanol, an additional step in the reaction scheme becomes available in which ethanol, greatly outcompeting the hydroperoxide, is oxidized by compound 1 regenerating the free enzyme. In solvents, such as acetonitrile or tetrahydrofuran, which themselves are not oxidizable by compound 1, catalase catalyzes the oxidation of numerous primary and secondary alcohols with tert-butyl hydroperoxide to the corresponding aldehydes or ketones. The enzymatic oxidation of some chiral alcohols (2,3-butanediol, citronellol, and menthol) under these conditions occurs enantioselectively. Examination of the enantioselectivity for the oxidation of 2,3-butanediol in a series of organic solvents reveals a considerable solvent dependence.

  14. Gold-Catalyzed Rearrangements and Beyond

    PubMed Central

    2013-01-01

    Cycloisomerizations of enynes are probably the most representative carbon–carbon bond forming reactions catalyzed by electrophilic metal complexes. These transformations are synthetically useful because chemists can use them to build complex architectures under mild conditions from readily assembled starting materials. However, these transformations can have complex mechanisms. In general, gold(I) activates alkynes in the presence of any other unsaturated functional group by forming an (η2-alkyne)–gold complex. This species reacts readily with nucleophiles, including electron-rich alkenes. In this case, the reaction forms cyclopropyl gold(I) carbene-like intermediates. These can come from different pathways depending on the substitution pattern of the alkyne and the alkene. In the absence of external nucleophiles, 1,n-enynes can form products of skeletal rearrangement in fully intramolecular reactions, which are mechanistically very different from metathesis reactions initiated by the [2 + 2] cycloaddition of a Grubbs-type carbene or other related metal carbenes. In this Account, we discuss how cycloisomerization and addition reactions of substituted enynes, as well as intermolecular reactions between alkynes and alkenes, are best interpreted as proceeding through discrete cationic intermediates in which gold(I) plays a significant role in the stabilization of the positive charge. The most important intermediates are highly delocalized cationic species that some chemists describe as cyclopropyl gold(I) carbenes or gold(I)-stabilized cyclopropylmethyl/cyclobutyl/homoallyl carbocations. However, we prefer the cyclopropyl gold(I) carbene formulation for its simplicity and mnemonic value, highlighting the tendency of these intermediates to undergo cyclopropanation reactions with alkenes. We can add a variety of hetero- and carbonucleophiles to the enynes in the presence of gold(I) in intra- or intermolecular reactions, leading to the corresponding adducts with

  15. Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration

    SciTech Connect

    Eedugurala, Naresh; Wang, Zhuoran; Chaudhary, Umesh; Nelson, Nicholas; Kandel, Kapil; Kobayashi, Takeshi; Slowing, Igor I.; Pruski, Marek; Sadow, Aaron D.

    2015-11-04

    The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe2)4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe2)n@MSN. Exhaustive characterization of Zr(NMe2)n@MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡SiOZr(NMe2)3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe2)n@MSN material reacts with pinacolborane (HBpin) to provide Me2NBpin and the material ZrH/Bpin@MSN that is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡SiOBpin moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1H/2H and 11B SSNMR and infrared spectroscopy and through its reactivity with D2. The zirconium hydride material or the zirconium amide precursor Zr(NMe2)n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. These supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites.

  16. Microbial-Catalyzed Biotransformation of Multifunctional Triterpenoids Derived from Phytonutrients

    PubMed Central

    Shah, Syed Adnan Ali; Tan, Huey Ling; Sultan, Sadia; Mohd Faridz, Muhammad Afifi Bin; Mohd Shah, Mohamad Azlan Bin; Nurfazilah, Sharifah; Hussain, Munawar

    2014-01-01

    Microbial-catalyzed biotransformations have considerable potential for the generation of an enormous variety of structurally diversified organic compounds, especially natural products with complex structures like triterpenoids. They offer efficient and economical ways to produce semi-synthetic analogues and novel lead molecules. Microorganisms such as bacteria and fungi could catalyze chemo-, regio- and stereospecific hydroxylations of diverse triterpenoid substrates that are extremely difficult to produce by chemical routes. During recent years, considerable research has been performed on the microbial transformation of bioactive triterpenoids, in order to obtain biologically active molecules with diverse structures features. This article reviews the microbial modifications of tetranortriterpenoids, tetracyclic triterpenoids and pentacyclic triterpenoids. PMID:25003642

  17. N-Heterocyclic-Carbene-Catalyzed Umpolung of Imines.

    PubMed

    Patra, Atanu; Mukherjee, Subrata; Das, Tamal Kanti; Jain, Shailja; Gonnade, Rajesh G; Biju, Akkattu T

    2017-03-01

    N-Heterocyclic carbene (NHC) catalysis has been widely used for the umpolung of aldehydes, and recently for the umpolung of Michael acceptors. Described herein is the umpolung of aldimines catalyzed by NHCs, and the reaction likely proceeds via aza-Breslow intermediates. The NHC-catalyzed intramolecular cyclization of aldimines bearing a Michael acceptor resulted in the formation of biologically important 2-(hetero)aryl indole 3-acetic-acid derivatives in moderate to good yields. The carbene generated from the bicyclic triazolium salt was found to be efficient for this transformation.

  18. Chromium(II)-catalyzed enantioselective arylation of ketones

    PubMed Central

    Wang, Gang; Sun, Shutao; Mao, Ying; Xie, Zhiyu

    2016-01-01

    The chromium-catalyzed enantioselective addition of carbo halides to carbonyl compounds is an important transformation in organic synthesis. However, the corresponding catalytic enantioselective arylation of ketones has not been reported to date. Herein, we report the first Cr-catalyzed enantioselective addition of aryl halides to both arylaliphatic and aliphatic ketones with high enantioselectivity in an intramolecular version, providing facile access to enantiopure tetrahydronaphthalen-1-ols and 2,3-dihydro-1H-inden-1-ols containing a tertiary alcohol. PMID:28144349

  19. Zirconium-Catalyzed Asymmetric Carboalumination of Unactivated Terminal Alkenes.

    PubMed

    Xu, Shiqing; Negishi, Ei-Ichi

    2016-10-18

    Carbometalation of alkenes with stereocontrol offers an important opportunity for asymmetric C-C bond formation. However, the scope of catalytic stereoselective carbometalation of alkenes had until recently been limited to electronically biased alkenes or those with the presence of directing groups or other auxiliary functionalities to overcome the challenge associated with regio- and stereoselectivity. Catalytic asymmetric carbometalation of unactivated alkenes on the other hand remained as a formidable challenge. To address this long-standing problem, we sought to develop Zr-catalyzed asymmetric carboalumination of alkenes (namely, ZACA reaction) encouraged by our discovery of Zr-catalyzed alkyne carboalumination in 1978. Zr-catalyzed methylalumination of alkynes (ZMA) shows high regioselectivity and nearly perfect stereoselectivity. Its mechanistic studies have revealed that the ZMA reaction involves acyclic carbometalation with "superacidic" bimetallic reagents generated by interaction between two Lewis acids, i.e., alkylalanes and 16-electron zirconocene derivatives through dynamic polarization and ate complexation, affectionately termed as the "two-is-better-than-one" principle. With the encouraging results of Zr-catalyzed carboalumination of alkynes in hand, we sought to develop its alkene version for discovering a catalytic asymmetric C-C bond-forming reaction by using alkylalanes and suitable chiral zirconocene derivatives, which would generate "superacidic" bimetallic species to promote the desired carbometalation of alkenes. However, this proved to be quite challenging. Three major competing side reactions occur, i.e., (i) β-H transfer hydrometalation, (ii) bimetallic cyclic carbometalation, and (iii) Ziegler-Natta polymerization. The ZACA reaction was finally discovered by employing Erker's (-)-(NMI)2ZrCl2 as the catalyst and chlorinated hydrocarbon as solvent to suppress the undesired side reactions mentioned above. The ZACA reaction has evolved as a

  20. Coalification by clay-catalyzed oligomerization of plant monomers

    SciTech Connect

    Orchin, M.; Wilson, R.M.

    1990-01-01

    The main objective of this research program is to devise laboratory methods to mimic the processes by which plants synthesize lignans, lignins and the processes by which these materials are transformed further by geochemical reactions catalyzed by certain clays to coal-like materials. We believe that the radical cation Diels-Alder reaction is one of the principal routes which transforms simple plant materials to coal-like substances and that such reactions may be catalyzed by clays that occur in the environment of the decaying plant materials. Progress is described.

  1. Molecular Mechanism by which One Enzyme Catalyzes Two Reactions

    NASA Astrophysics Data System (ADS)

    Nishimasu, Hiroshi; Fushinobu, Shinya; Wakagi, Takayoshi

    Unlike ordinary enzymes, fructose-1,6-bisphosphate (FBP) aldolase/phosphatase (FBPA/P) catalyzes two distinct reactions : (1) the aldol condensation of dihydroxyacetone phosphate (DHAP) and glyceraldehyde-3-phosphate to FBP, and (2) the dephosphorylation of FBP to fructose-6-phosphate. We solved the crystal structures of FBPA/P in complex with DHAP (its aldolase form) and FBP (its phosphatase form). The crystal structures revealed that FBPA/P exhibits the dual activities through a dramatic conformational change in the active-site architecture. Our findings expand the conventional concept that one enzyme catalyzes one reaction.

  2. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    SciTech Connect

    Huang, Qinhua

    2004-12-19

    The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I2, ICl, PhSeCl, PhSCl and p-O2NC6H4SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement

  3. Catalyzed reactions at illuminated semiconductor interfaces

    NASA Astrophysics Data System (ADS)

    Wrighton, M. S.

    1984-06-01

    It is pointed out that thermodynamically unfavorable chemical redox reactions can be effected by using optical energy as the driving force. To date, the best man-contrived systems for the direct conversion of optical energy to high energy redox products are semiconductor-based photoelectrochemical devices. The present investigation is concerned with the possibility that the minority carrier redox process at a semiconductor electrode may be too slow to compete with the recombination of photogenerated carriers. Attention is given to the photoelectrochemical generation of hydrogen, the photoelectrochemical reduction of carbon dioxide, the photo-oxidation of halides to halogens, and photo-oxidation of water. It is concluded that redox reactions of possible significance in solar fuel generation require rate acceleration to achieve high solar energy conversion efficiency.

  4. An efficient chemoselective reduction of furan series unsaturated dinitriles.

    PubMed

    Bobal, Pavel; Bobalova, Janette

    2013-02-11

    An efficient reduction of double bonds conjugated with nitrile groups and acid or base sensitive furan rings with 2-phenylbenzimidazoline generated in situ has been successfully accomplished with high yields and excellent selectivity. The employed reducing agent was prepared in one step from ordinary chemicals. The other advantages of the presented method include mild and convenient reaction conditions, a benign and cost effective reagent, simple work-up and separation of the products. As this process does neither affect cyano and nitro groups nor furan rings, it is a valuable alternative when metal-catalyzed hydrogenations or borohydride reductions have failed.

  5. Chemo- and Diastereoselectivities in the Electrochemical Reduction of Maleimides

    PubMed Central

    Rix, Kathryn; Kelsall, Geoffrey H; Hellgardt, Klaus; Hii, King Kuok (Mimi)

    2015-01-01

    The electrochemical cathodic reduction of cyclic imides (maleimides) to succinimides can be achieved chemoselectively in the presence of alkene, alkyne, and benzyl groups. The efficiency of the system was demonstrated by using a 3D electrode in a continuous flow reactor. The reduction of 3,4-dimethylmaleimides to the corresponding succinimides proceeds with a 3:2 diastereomeric ratio, which is independent of the nitrogen substituent and electrode surface area. The stereoselectivity of the process was rationalized by using DFT calculations, involving an acid-catalyzed tautomerization of a half-enol occurring through a double hydrogen-transfer mechanism. PMID:25572428

  6. Formation of C–C Bonds via Iridium-Catalyzed Hydrogenation and Transfer Hydrogenation

    PubMed Central

    Bower, John F.; Krische, Michael J.

    2011-01-01

    The formation of C–C bonds via catalytic hydrogenation and transfer hydrogenation enables carbonyl and imine addition in the absence of stoichiometric organometallic reagents. In this review, iridium-catalyzed C–C bond-forming hydrogenations and transfer hydrogenations are surveyed. These processes encompass selective, atom-economic methods for the vinylation and allylation of carbonyl compounds and imines. Notably, under transfer hydrogenation conditions, alcohol dehydrogenation drives reductive generation of organoiridium nucleophiles, enabling carbonyl addition from the aldehyde or alcohol oxidation level. In the latter case, hydrogen exchange between alcohols and π-unsaturated reactants generates electrophile–nucleophile pairs en route to products of hydro-hydroxyalkylation, representing a direct method for the functionalization of carbinol C–H bonds. PMID:21822399

  7. 34S/32S fractionation in sulfur cycles catalyzed by anaerobic bacteria

    NASA Technical Reports Server (NTRS)

    Fry, B.; Gest, H.; Hayes, J. M.

    1988-01-01

    Stable isotopic distributions in the sulfur cycle were studied with pure and mixed cultures of the anaerobic bacteria, Chlorobium vibrioforme and Desulfovibrio vulgaris. D. vulgaris and C. vibrioforme can catalyze three reactions constituting a complete anaerobic sulfur cycle: reduction of sulfate to sulfide (D. vulgaris), oxidation of sulfide to elemental sulfur (C. vibrioforme), and oxidation of sulfur to sulfate (C. vibrioforme). In all experiments, the first and last reactions favored concentration of the light 32S isotope in products (isotopic fractionation factor epsilon = -7.2 and -1.7%, respectively), whereas oxidation of sulfide favored concentration of the heavy 34S isotope in products (epsilon = +1.7%). Experimental results and model calculations suggest that elemental sulfur enriched in 34S versus sulfide may be a biogeochemical marker for the presence of sulfide-oxidizing bacteria in modern and ancient environments.

  8. SO2-catalyzed steam pretreatment enhances the strength and stability of softwood pellets.

    PubMed

    Tooyserkani, Zahra; Kumar, Linoj; Sokhansanj, Shahab; Saddler, Jack; Bi, Xiaotao T; Lim, C Jim; Lau, Anthony; Melin, Staffan

    2013-02-01

    Densification can partially resolve the logistical challenges encountered when large volumes of biomass are required for bioconversion processes to benefit from economies-of-scale. Despite the higher bulk density of pellets, their lower mechanical strength and sensitivity to moisture are still recurring issues hindering long term transportation and storage. In this study, we have evaluated the potential benefits of SO(2)-catalyzed steam treatment to achieve both the needed size reduction prior to pelletization while improving the stability of the produced pellets. This pretreatment substantially reduced the particle size of the woodchips eliminating any further grinding. The treated pellets had a higher density and exhibited a two-time higher mechanical strength compared to untreated pellets. Despite a higher moisture adsorption capacity, treated pellets remained intact even under highly humid conditions. The high heating values, low ash content and good overall carbohydrate recovery of treated pellets indicated their potential suitability for both biochemical and thermochemical applications.

  9. Cobalt-catalyzed hydroalkylation of [60]fullerene with active alkyl bromides: selective synthesis of monoalkylated fullerenes.

    PubMed

    Lu, Shirong; Jin, Tienan; Bao, Ming; Yamamoto, Yoshinori

    2011-08-17

    The Co-catalyzed hydroalkylation of C(60) with reactive alkyl bromides 1 (RBr) in the presence of Mn reductant and H(2)O at ambient temperature gave the monoalkylated C(60) (2) in good to high yields. The use of CoLn/Mn/H(2)O under Ar atmosphere is crucial for the success of the present transformation. The reaction most probably proceeds through the Co(0 or I) complex-promoted generation of a radical (R(•)) followed by addition to C(60). This hydroalkylation method was applied to the synthesis of zinc porphyrin attached C(60) (2l), dendrimer attached C(60) (2m), and fullerene dimer (2n), which were not easily available through the previously known methods.

  10. Menadione-catalyzed luminol chemiluminescent assay for viability of Mycobacterium bovis.

    PubMed

    Yamashoji, Shiro

    2002-01-01

    Stable luminol chemiluminescence was observed 10 min after the addition of menadione to a suspension of Mycobacterium bovis homogenized in Middlebrook 7H9 broth base including OADC enrichment. The chemiluminescence intensity was proportional to the absorbance of the bacterial suspension at 600 nm in a range of 0.005 to 0.15. Luminol chemiluminescence disappeared after 10 min incubation of M. bovis at over 60% of ethanol or 4 days of cultivation of M. bovis in the presence of 40 microg/ml of streptomycin. The bacterium showing the disappearance of chemiluminescence could not grow after being washed, suggesting that the inhibition concentration of the antimicrobials can be estimated on the basis of the disappearance of chemiluminescence. Menadione-catalyzed luminol chemiluminescent assay was rapid and sensitive in comparison to turbidimetry, tetrazolium (WST-8) reduction assay, and the assay using the Mycobacteria growth indicator tube (MGIT).

  11. Bioelectricity generation enhancement in a dual chamber microbial fuel cell under cathodic enzyme catalyzed dye decolorization.

    PubMed

    Bakhshian, Sahar; Kariminia, Hamid-Reza; Roshandel, Ramin

    2011-06-01

    Enzymatic decolorization of reactive blue 221 (RB221) using laccase was investigated in a dual-chamber microbial fuel cell (MFC). Suspended laccase was used in the cathode chamber in the absence of any mediators in order to decolorize RB221 and also improve oxygen reduction reaction in the cathode. Molasses was utilized as low cost and high strength energy source in the anode chamber. The capability of MFC for simultaneous molasses and dye removal was investigated. A decolorization efficiency of 87% was achieved in the cathode chamber and 84% COD removal for molasses was observed in the anode chamber. Laccase could catalyze the removal of RB221 and had positive effect on MFC performance as well. Maximum power density increased about 30% when enzymatic decolorization was performed in the cathode chamber. Copyright © 2011 Elsevier Ltd. All rights reserved.

  12. Lipase-Catalyzed Kinetic Resolution of Novel Antifungal N-Substituted Benzimidazole Derivatives.

    PubMed

    Łukowska-Chojnacka, Edyta; Staniszewska, Monika; Bondaryk, Małgorzata; Maurin, Jan K; Bretner, Maria

    2016-04-01

    A series of new N-substituted benzimidazole derivatives was synthesized and their antifungal activity against Candida albicans was evaluated. The chemical step included synthesis of appropriate ketones containing benzimidazole ring, reduction of ketones to the racemic alcohols, and acetylation of alcohols to the esters. All benzimidazole derivatives were obtained with satisfactory yields and in relatively short times. All synthesized compounds exhibit significant antifungal activity against Candida albicans 900028 ATCC (% cell inhibition at 0.25 μg concentration > 98%). Additionally, racemic mixtures of alcohols were separated by lipase-catalyzed kinetic resolution. In the enzymatic step a transesterification reaction was applied and the influence of a lipase type and solvent on the enantioselectivity of the reaction was studied. The most selective enzymes were Novozyme SP 435 and lipase Amano AK from Pseudomonas fluorescens (E > 100).

  13. Phosphine- and hydrogen-free: highly regioselective ruthenium-catalyzed hydroaminomethylation of olefins.

    PubMed

    Gülak, Samet; Wu, Lipeng; Liu, Qiang; Franke, Robert; Jackstell, Ralf; Beller, Matthias

    2014-07-07

    A highly regioselective ruthenium-catalyzed hydroaminomethylation of olefins is reported. Using easily available trirutheniumdodecacarbonyl an efficient sequence consisting of a water-gas shift reaction, hydroformylation of olefins, with subsequent imine or enamine formation and final reduction is realized. This novel procedure is highly practical (ligand-free, one pot) and economic (low catalyst loading and inexpensive metal). Bulk industrial as well as functionalized olefins react with various amines to give the corresponding tertiary amines generally in high yields (up to 92 %), excellent regioselectivities (n/iso>99:1), and full chemoselectivity in favor of terminal olefins. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    NASA Technical Reports Server (NTRS)

    Kilduff, Jan E.; Davis, Dennis D.; Koontz, Steven L.

    1988-01-01

    The surface-catalyzed air oxidation reactions of hydrazine, monomethylhydrazine, unsymmetrical dimethylhydrazine, symmetrical dimethylhydrazine, trimethylhydrazine and tetramethylhydrazine were investigated in a metal-powder packed turbular flow reactor at 55 plus or minus 3 C. Hydrazine was completely reacted on all surfaces studied. The major products of monomethylhydrazine (MMH) oxidation were methanol, methane and methyldiazene. The di-, tri- and tetra-methyl hydrazines were essentially unreactive under these conditions. The relative catalytic reactivities toward MMH are: Fe greater than Al2O3 greater than Ti greater than Zn greater than 316 SS greater than Cr greater than Ni greater than Al greater than 304L SS. A kinetic scheme and mechanism involving adsorption, oxidative dehydrogenation and reductive elimination reactions on a metal oxide surface are proposed.

  15. Palladium(0)-catalyzed amination, Stille coupling, and Suzuki coupling of electron-deficient aryl fluorides.

    PubMed

    Kim, Young Mi; Yu, Shu

    2003-02-19

    The amination of 2-fluoronitrobenzene was Pd(0) catalyzed at 65 degrees C in DMF, and the effectiveness of the catalysis was ligand-dependent. Among the five catalyst systems investigated, Pd(PPh3)4 was the most effective catalyst. The control experiments revealed that Pd(OAc)2 or PPh3 was not responsible for the catalysis. 4-Fluoro-3-nitro-benzonitrile and 4-fluoro-3-nitro-benzaldehyde also underwent Stille coupling and Suzuki coupling in the presence of Pd(PPh3)4, and the reactions afforded the coupling products in 28-86% yields. The control experiments showed no sign of reaction in the absence of palladium. These results were in agreement with the oxidative addition/reductive elimination pathway, where the oxidative addition could conceivably proceed via the SNAr mechanism.

  16. Palladium-Catalyzed Hydrolytic Cleavage of Aromatic C-O Bonds.

    PubMed

    Wang, Meng; Shi, Hui; Camaioni, Donald M; Lercher, Johannes A

    2017-02-13

    Metallic palladium surfaces are highly selective in promoting the reductive hydrolysis of aromatic ethers in aqueous phase at relatively mild temperatures and pressures of H2 . At quantitative conversions, the selectivity to hydrolysis products of PhOR ethers was observed to range from 50 % (R=Ph) to greater than 90 % (R=n-C4 H9 , cyclohexyl, and PhCH2 CH2 ). By analysis of the evolution of products with and without incorporation of H2(18) O, the pathway was concluded to be initiated by palladium metal catalyzed partial hydrogenation of the phenyl group to an enol ether. Water then rapidly adds to the enol ether to form a hemiacetal, which then undergoes elimination to cyclohexanone and phenol/alkanol products. A remarkable feature of the reaction is that the stronger Ph-O bond is cleaved rather than the weaker aliphatic O-R bond.

  17. Effects of Molecular Oxygen, Solvent, and Light on Iridium-Photoredox/Nickel Dual-Catalyzed Cross-Coupling Reactions.

    PubMed

    Oderinde, Martins S; Varela-Alvarez, Adrian; Aquila, Brian; Robbins, Daniel W; Johannes, Jeffrey W

    2015-08-07

    In order to achieve reproducibility during iridium-photoredox and nickel dual-catalyzed sp(3)-sp(2) carbon-carbon bond-forming reactions, we investigated the role that molecular oxygen (O2), solvent and light-source (CF lamp or blue LED) play in a variety of Ir-photoredox mediated transformations. The presence of O2 was discovered to be important for catalyst activation when air-stable Ni(II) precatalysts were used in DMF under CF lamp irradiation; however, O2 was not required for catalysis when conducted with Ni(COD)2 in the same reaction system. O2 is believed to promote rapid reduction of the Ni(II) precatalyst by Ir(II) to Ni(0). In addition to O2, the effects that solvent and light-source have on the dual-catalyzed decarboxylative cross-coupling reactions will be discussed. These findings have enabled us to develop a more robust dual-catalyzed decarboxylative cross-coupling protocol.

  18. Mechanistic aspects of metal valence change in SalenCo(III)OAc-catalyzed hydrolytic kinetic resolution of racemic epoxides.

    PubMed

    Ren, Wei-Min; Wang, Yi-Ming; Zhang, Rong; Jiang, Jing-Yang; Lu, Xiao-Bing

    2013-05-17

    The chiral SalenCo(III)OAc-catalyzed hydrolytic kinetic resolution (HKR) of racemic terminal epoxides to afford both enantioenriched epoxides and diols presents one of the most important achievements in asymmetric synthesis chemistry. Previous studies mainly focused on the development of highly efficient catalysts, while rare reports concerned the mechanistic understanding of metal valence change, associated with the formation of inactive Co(II)-Salen complex. Herein, we report the mechanistic aspects of catalyst deactivation regarding the transformation of Co(III) to Co(II) derivative in the HKR of racemic epoxides catalyzed by SalenCo(III)OAc complexes with an appended 1,5,7-triazabicyclo[4.4.0]dec-5-ene on the ligand framework by means of electrospray ionization mass spectrometry (ESI-MS). Continuous determination of transient cationic species in ESI-MS positive mode in conjunction with UV-vis spectroscopic studies at various time points provides evidence that a certain amount of SalenCo(III)OAc molecules were reduced to the corresponding Co(II) derivatives in the HKR of racemic propylene oxide or styrene oxide. To be accompanied by the reduction of Co(III) to Co(II), the resultant diols were oxidized to α-hydroxy ketones. These analyses along with some control experiments gave a mechanistic understanding of catalyst deactivation of SalenCo(III)OAc-catalyzed HKR of racemic epoxides regarding an unveiled redox reaction between Co(III)-Salen and diol, the hydrolyzed product.

  19. 1,4-Naphthoquinones and Others NADPH-Dependent Glutathione Reductase-Catalyzed Redox Cyclers as Antimalarial Agents

    PubMed Central

    Belorgey, Didier; Lanfranchi, Don Antoine; Davioud-Charvet, Elisabeth

    2013-01-01

    The homodimeric flavoenzyme glutathione reductase catalyzes NADPH-dependent glutathione disulfide reduction. This reaction is important for keeping the redox homeostasis in human cells and in the human pathogen Plasmodium falciparum. Different types of NADPH-dependent disulfide reductase inhibitors were designed in various chemical series to evaluate the impact of each inhibition mode on the propagation of the parasites. Against malaria parasites in cultures the most potent and specific effects were observed for redox-active agents acting as subversive substrates for both glutathione reductases of the Plasmodium-infected red blood cells. In their oxidized form, these redox-active compounds are reduced by NADPH-dependent flavoenzyme-catalyzed reactions in the cytosol of infected erythrocytes. In their reduced forms, these compounds can reduce molecular oxygen to reactive oxygen species, or reduce oxidants like methemoglobin, the major nutrient of the parasite, to indigestible hemoglobin. Furthermore, studies on a fluorinated suicide-substrate of the human glutathione reductase indicate that the glutathione reductase-catalyzed bioactivation of 3-benzylnaphthoquinones to the corresponding reduced 3-benzoyl metabolites is essential for the observed antimalarial activity. In conclusion, the antimalarial lead naphthoquinones are suggested to perturb the major redox equilibria of the targeted cells. These effects result in development arrest of the parasite and contribute to the removal of the parasitized erythrocytes by macrophages. PMID:23116403

  20. Mechanistic Insights into the Rh-Catalyzed Transannulation of Pyridotriazole with Phenylacetylene and Benzonitrile: A DFT Study.

    PubMed

    Wang, Chenli; Zhou, Yunfei; Bao, Xiaoguang

    2017-04-07

    Computational studies were carried out to explore the mechanisms of Rh2(OAc)4-catalyzed transannulation of pyridotriazole with phenylacetylene and benzonitrile, respectively. For the Rh2(OAc)4-catalyzed divergent cyclization with phenylacetylene, the major product (cyclopropene derivative) might be formed via [2 + 2] cycloaddition to yield a metallacyclobutene intermediate followed by a reductive elimination pathway, where carboxylate ligand lability is considered to release a vacant equatorial site for the formation of Rh-carbenoid. The cyclopropenation of phenylacetylene via a commonly proposed [2 + 1] cycloaddition pathway, where the tetrabridged framework of Rh2(OAc)4 is preserved, however, might not play a dominant role. This is because the competing formal [2 + 3] pathway leading to the indolizine as a minor product is more likely to occur. The main factors responsible for the chemoselectivity in cyclization with phenylacetylene are discussed. For the Rh2(OAc)4-catalyzed transannulation of pyridotriazole with benzonitrile, a stepwise formal [2 + 3] pathway via a ylide intermediate is proposed regardless of whether the tetrabridged framework of Rh2(OAc)4 is preserved or not.

  1. Breast Reduction Surgery

    MedlinePlus

    ... considering breast reduction surgery, consult a board-certified plastic surgeon. It's important to understand what breast reduction ... risk of complications from breast reduction surgery. Your plastic surgeon will likely: Evaluate your medical history and ...

  2. Green Reductive Homocoupling of Bromobenzene

    ERIC Educational Resources Information Center

    Ballard, C. Eric

    2011-01-01

    Although transition-metal-catalyzed reactions are important in contemporary organic chemistry, relatively few resources for the second-year organic chemistry curriculum discuss the subject. The inquiry-based experiment described here, an iron-catalyzed preparation of biphenyl from bromobenzene, introduces this topic. The reaction uses an…

  3. Green Reductive Homocoupling of Bromobenzene

    ERIC Educational Resources Information Center

    Ballard, C. Eric

    2011-01-01

    Although transition-metal-catalyzed reactions are important in contemporary organic chemistry, relatively few resources for the second-year organic chemistry curriculum discuss the subject. The inquiry-based experiment described here, an iron-catalyzed preparation of biphenyl from bromobenzene, introduces this topic. The reaction uses an…

  4. Copper-catalyzed direct amination of ortho-functionalized haloarenes with sodium azide as the amino source.

    PubMed

    Zhao, Haibo; Fu, Hua; Qiao, Renzhong

    2010-05-21

    A simple copper-catalyzed direct amination of ortho-functionalized haloarenes (2-halobenzoic acid, 2-halobenzamide, and N-(2-bromophenyl)acetamide derivatives) has been developed with use of NaN(3) as the amino source in ethanol, and the corresponding ortho-functionalized aromatic amines were synthesized in good to excellent yields. The protocol undergoes one-pot Ullmann-type coupling of ortho-functionalized haloarenes with NaN(3) to lead to ortho-functionalized azidoarenes, followed by reduction with ethanol.

  5. γ-Sultam-cored N,N-ligands in the ruthenium(ii)-catalyzed asymmetric transfer hydrogenation of aryl ketones.

    PubMed

    Rast, Slavko; Modec, Barbara; Stephan, Michel; Mohar, Barbara

    2016-02-14

    The synthesis of new enantiopure syn- and anti-3-(α-aminobenzyl)-benzo-γ-sultam ligands 6 and their application in the ruthenium(ii)-catalyzed asymmetric transfer hydrogenation (ATH) of ketones using formic acid/triethylamine is described. In particular, benzo-fused cyclic ketones afforded excellent enantioselectivities in reasonable time employing a low loading of the syn ligand-containing catalyst. A never-before-seen dynamic kinetic resolution (DKR) during reduction of a γ-keto carboxylic ester (S7) derivative of 1-indanone is realized leading as well to excellent induction.

  6. Evidence for in situ catalyst modification during the Pd-catalyzed conversion of aryl triflates to aryl fluorides.

    PubMed

    Maimone, Thomas J; Milner, Phillip J; Kinzel, Tom; Zhang, Yong; Takase, Michael K; Buchwald, Stephen L

    2011-11-16

    A mechanistic investigation of the Pd-catalyzed conversion of aryl triflates to fluorides is presented. Studies reveal that C-F reductive elimination from a LPd(II)(aryl)F complex (L = t-BuBrettPhos or RockPhos) does not occur when the aryl group is electron rich. Evidence is presented that a modified phosphine, generated in situ, serves as the actual supporting ligand during catalysis with such substrates. A preliminary study of the reactivity of a LPd(II)(aryl)F complex based on this modified ligand is reported.

  7. In Situ Generated Piers' Borane-Catalyzed Selective C-O Bond Cleavage of Sugars with Hydrosilanes.

    PubMed

    Chang, Sukbok; Zhang, Jianbo; Park, Sehoon

    2017-09-12

    Described herein is the Piers' borane (C6F5)2BH-catalyzed selective reduction of sugars with hydrosilanes. The hydrosilylative C-O bond cleavage of silyl-protected mono- and disaccharides in the presence of (C6F5)2BH catalyst, in situ generated from (C6F5)2BOH, takes place with excellent chemo- and regioselectivities to provide a range of polyols. Study of the substituent effects of sugars on the catalytic activity and selectivity revealed that the steric environment around the anomeric carbon (C1) is crucial. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Umpolung of Michael acceptors catalyzed by N-heterocyclic carbenes.

    PubMed

    Fischer, Christian; Smith, Sean W; Powell, David A; Fu, Gregory C

    2006-02-08

    N-Heterocyclic carbenes can catalyze beta-alkylations of a range of alpha,beta-unsaturated esters, amides, and nitriles that bear pendant leaving groups to form a variety of ring sizes. In this process, the nucleophilic catalyst transiently transforms the normally electrophilic beta carbon into a nucleophilic site through an unanticipated addition-tautomerization sequence.

  9. Rh-Catalyzed Asymmetric Hydrogenation of 1,2-Dicyanoalkenes.

    PubMed

    Li, Meina; Kong, Duanyang; Zi, Guofu; Hou, Guohua

    2017-01-06

    A highly efficient enantioselective hydrogenation of 1,2-dicyanoalkenes catalyzed by the complex of rhodium and f-spiroPhos has been developed. A series of 1,2-dicyanoalkenes were successfully hydrogenated to the corresponding chiral 1,2-dicyanoalkanes under mild conditions with excellent enantioselectivities (up to 98% ee). This methodology provides efficient access to the asymmetric synthesis of chiral diamines.

  10. Total Synthesis of Gelsenicine via a Catalyzed Cycloisomerization Strategy

    PubMed Central

    Newcomb, Eric T.; Knutson, Phil C.; Pedersen, Blaine A.; Ferreira, Eric M.

    2016-01-01

    The first total synthesis of (±)-gelsenicine is reported. The synthetic route is highly efficient (13 steps), featuring (1) a pivotal metal-catalyzed isomerization/rearrangement process that forges the central core of the molecule and (2) two facile C–N bond-forming steps that establish the flanking heterocycles. PMID:26716762

  11. Synthesis of Cyclic Guanidines via Pd-Catalyzed Alkene Carboamination

    PubMed Central

    Zavesky, Blane P.; Babij, Nicholas R.; Fritz, Jonathan A.

    2013-01-01

    A new approach to the synthesis of substituted 5-membered cyclic guanidines is described. Palladium-catalyzed alkene carboamination reactions between acyclic N-allyl guanidines and aryl or alkenyl halides provide these products in good yield. This method allows access to a number of different cyclic guanidine derivatives in only two steps from readily available allylic amines. PMID:24147839

  12. N-heterocyclic carbene catalyzed direct carbonylation of dimethylamine.

    PubMed

    Li, Xiaonian; Liu, Kun; Xu, Xiaoliang; Ma, Lei; Wang, Hong; Jiang, Dahao; Zhang, Qunfeng; Lu, Chunshan

    2011-07-21

    N-Heterocyclic carbene (NHC) catalyzed direct carbonylation of dimethylamine leading to the formation of DMF was successfully accomplished under metal-free conditions. The catalytic efficiency was investigated and the turnover numbers can reach as high as >300. The possible mechanism was also proposed.

  13. Catalyzing Graduate Teaching Assistants' Laboratory Teaching through Design Research

    ERIC Educational Resources Information Center

    Bond-Robinson, Janet; Rodriques, Romola A. Bernard

    2006-01-01

    We report on a study of a laboratory teaching apprenticeship program designed to improve graduate teaching assistant (GTA) performance. To catalyze GTAs as laboratory teachers we constructed learning goals, synthesized previous literature into a design model and a developmental path, and built two instruments to measure 12 strategic pedagogical…

  14. Nickel-catalyzed decarboxylative carboamination of alkynes with isatoic anhydrides.

    PubMed

    Yoshino, Yasufumi; Kurahashi, Takuya; Matsubara, Seijiro

    2009-06-10

    An intermolecular nickel-catalyzed addition reaction in which isatoic anhydrides react with alkynes to afford substituted quinolones has been developed. A mechanistic rationale is proposed, implying oxidative addition of Ni(0) to a carbamate, which allows intermolecular addition to alkynes via decarboxylation.

  15. Cu(I)-Catalyzed Asymmetric Diamination of Conjugated Dienes

    PubMed Central

    Du, Haifeng; Zhao, Baoguo; Yuan, Weicheng; Shi, Yian

    2009-01-01

    A Cu(I)-catalyzed asymmetric diamination for a variety of conjugated dienes and a triene with encouraging ee’s has been effectively achieved using (R)-DTBM-SEGPHOS as chiral ligand and di-tert-butyldiaziridinone as nitrogen source. PMID:18763785

  16. Development of a Lewis Base Catalyzed Selenocyclization Reaction

    ERIC Educational Resources Information Center

    Collins, William

    2009-01-01

    The concept of Lewis base activation of selenium Lewis acids has been effectively reduced to practice in the Lewis base catalyzed selenofunctionalization of unactivated olefins. In this reaction, the weakly acidic species, "N"-phenylselenyl succinimide, is cooperatively activated by the addition of a "soft" Lewis base donor (phosphine sulfides,…

  17. Palladium-Catalyzed Synthesis of 9-Fluorenylidenes through Aryne Annulation

    PubMed Central

    Worlikar, Shilpa A.; Larock, Richard C.

    2009-01-01

    The palladium-catalyzed annulation of arynes by substituted ortho-halostyrenes produces substituted 9- fluorenylidenes in good yields. This methodology provides this important carbocyclic ring system in a single step, which involves the generation of two new carbon-carbon bonds, occurs under relatively mild reaction conditions and tolerates a variety of functional groups, including cyano, ester, aldehyde and ketone groups. PMID:19413328

  18. Transition-Metal-Catalyzed Carbonylation of Methyl Acetate.

    ERIC Educational Resources Information Center

    Polichnowski, S. W.

    1986-01-01

    Presents a study of the rhodium-catalyzed, ioding-promoted carbonylation of methyl acetate. This study provides an interesting contrast between the carbonylation of methyl acetate and the carbonylation of methanol when similar rhodium/iodine catalyst systems are used. (JN)

  19. Acid-catalyzed dehydrogenation of amine-boranes

    DOEpatents

    Stephens, Frances Helen; Baker, Ralph Thomas

    2010-01-12

    A method of dehydrogenating an amine-borane using an acid-catalyzed reaction. The method generates hydrogen and produces a solid polymeric [R.sup.1R.sup.2B--NR.sup.3R.sup.4].sub.n product. The method of dehydrogenating amine-boranes may be used to generate H.sub.2 for portable power sources.

  20. Palladium-catalyzed direct arylation of indoles with cyclohexanones.

    PubMed

    Chen, Shanping; Liao, Yunfeng; Zhao, Feng; Qi, Hongrui; Liu, Saiwen; Deng, Guo-Jun

    2014-03-21

    A novel palladium catalyzed approach to 3-arylindoles was developed from indoles and cyclohexanones. Various cyclohexanones acted as aryl sources via an alkylation and dehydrogenation sequence using molecular oxygen as the hydrogen acceptor. This method showed good regioselectivity and afforded 3-arylindoles as the sole products.

  1. Palladium-catalyzed stereocontrolled vinylation of azoles and phenothiazine.

    PubMed

    Lebedev, Artyom Y; Izmer, Vyatcheslav V; Kazyul'kin, Denis N; Beletskaya, Irina P; Voskoboynikov, Alexander Z

    2002-02-21

    [reaction: see text] Vinylation of various azoles (pyrrole, indole, carbazole, and their derivatives) and phenothiazine with vinyl bromides catalyzed by palladium-phosphine complexes results in the respective N-vinylazoles in 30-99% yields. This reaction with cis- and trans-beta-bromostyrenes is stereospecific giving the respective products with full retention of configuration.

  2. Asymmetric gold-catalyzed lactonizations in water at room temperature.

    PubMed

    Handa, Sachin; Lippincott, Daniel J; Aue, Donald H; Lipshutz, Bruce H

    2014-09-26

    Asymmetric gold-catalyzed hydrocarboxylations are reported that show broad substrate scope. The hydrophobic effect associated with in situ-formed aqueous nanomicelles gives good to excellent ee's of product lactones. In-flask product isolation, along with the recycling of the catalyst and the reaction medium, are combined to arrive at an especially environmentally friendly process.

  3. Silver-catalyzed protodecarboxylation of heteroaromatic carboxylic acids.

    PubMed

    Lu, Pengfei; Sanchez, Carolina; Cornella, Josep; Larrosa, Igor

    2009-12-17

    A simple and highly efficient protodecarboxylation procedure for a variety of heteroaromatic carboxylic acids catalyzed by Ag(2)CO(3) and AcOH in DMSO is described. This methodology can also perform the selective monoprotodecarboxylation of several aromatic dicarboxylic acids.

  4. Cu-Catalyzed Fluorination of Diaryliodonium Salts with KF

    PubMed Central

    Ichiishi, Naoko; Canty, Allan J.; Yates, Brian F.

    2014-01-01

    A mild Cu-catalyzed nucleophilic fluorination of unsymmetrical diaryliodonium salts with KF is described. This protocol preferentially fluorinates less sterically hindered aromatic rings. The reaction exhibits a broad substrate scope and proceeds with high chemoselectivity and functional group tolerance. DFT calculations implicate a CuI/CuIII catalytic cycle. PMID:24063629

  5. Transition-Metal-Catalyzed Carbonylation of Methyl Acetate.

    ERIC Educational Resources Information Center

    Polichnowski, S. W.

    1986-01-01

    Presents a study of the rhodium-catalyzed, ioding-promoted carbonylation of methyl acetate. This study provides an interesting contrast between the carbonylation of methyl acetate and the carbonylation of methanol when similar rhodium/iodine catalyst systems are used. (JN)

  6. Palladium-catalyzed silylation of aryl chlorides with hexamethyldisilane.

    PubMed

    McNeill, Eric; Barder, Timothy E; Buchwald, Stephen L

    2007-09-13

    A method for the palladium-catalyzed silylation of aryl chlorides has been developed. The method affords desired product in good yield, is tolerant of a variety of functional groups, and provides access to a wide variety of aryltrimethylsilanes from commercially available aryl chlorides. Additionally, a one-pot procedure that converts aryl chlorides into aryl iodides has been developed.

  7. Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

    PubMed

    Liao, Zhixiong; Yi, Hong; Li, Zheng; Fan, Chao; Zhang, Xu; Liu, Jie; Deng, Zixin; Lei, Aiwen

    2015-01-01

    A simple copper-catalyzed direct radical carbooxygenation of styrenes is developed utilizing alkyl bromides as radical resources. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of styrenes in one pot. A broad range of styrenes and alcohols are well tolerated in this transformation. The EPR experiment shows that alkyl halides could oxidize Cu(I) to Cu(II) in this transformation.

  8. Metal-Catalyzed Cleavage of tRNA[superscript Phe

    ERIC Educational Resources Information Center

    Kirk, Sarah R.; Silverstein, Todd P.; McFarlane Holman, Karen L.

    2008-01-01

    This laboratory project is one component of a semester-long advanced biochemistry laboratory course that uses several complementary techniques to study tRNA[superscript Phe] conformational changes induced by ligand binding. In this article we describe a set of experiments in which students assay metal-catalyzed hydrolysis of tRNA[superscript Phe]…

  9. Enantioselective N-heterocyclic carbene-catalyzed synthesis of trifluoromethyldihydropyridinones.

    PubMed

    Wang, Dong-Ling; Liang, Zhi-Qin; Chen, Kun-Quan; Sun, De-Qun; Ye, Song

    2015-06-05

    The enantioselective N-heterocyclic carbene-catalyzed [4 + 2] cyclocondensation of α-chloroaldehydes and trifluoromethyl N-Boc azadienes was developed, giving the corresponding 3,4-disubstituted-6-trifluoromethyldihydropyridin-2(1H)-ones in good yields with exclusive cis-selectivities and excellent enantioselectivities.

  10. Ruthenium-catalyzed C–H activation of thioxanthones

    PubMed Central

    Wagner, Danny

    2015-01-01

    Summary Thioxanthones – being readily available in one step from thiosalicylic acid and arenes – were used in ruthenium-catalyzed C–H-activation reaction to produce 1-mono- or 1,8-disubstituted thioxanthones in good to excellent yields. Scope and limitation of this reaction are presented. PMID:25977717

  11. Palladium-catalyzed synthesis of functionalized tetraarylphosphonium salts.

    PubMed

    Marcoux, David; Charette, André B

    2008-01-18

    An efficient method to synthesize functionalized tetraarylphosphonium salts is described. This palladium-catalyzed coupling reaction between aryl iodides, bromides, or triflates and triphenylphosphine generates phosphonium salts in high yields. The coupling is compatible with a variety of functional groups such as alcohols, ketones, aldehydes, phenols, and amides.

  12. Palladium(II)-catalyzed direct alkenylation of nonaromatic enamides.

    PubMed

    Gigant, Nicolas; Gillaizeau, Isabelle

    2012-07-06

    A mild and efficient method for the direct alkenylation of nonaromatic enamides was achieved through a palladium(II)-catalyzed C-H functionalization. The reaction scope includes cyclic and acyclic enamides and a range of activated alkenes. This approach represents the first successful direct C(3)-functionalization of nonaromatic cyclic enamides.

  13. Zinc-catalyzed cyclopropenation of alkynes via 2-furylcarbenoids.

    PubMed

    González, María J; López, Luis A; Vicente, Rubén

    2014-11-07

    An unprecedented cyclopropenation reaction of alkynes catalyzed by ZnCl2 is reported. While Simmons-Smith-type carbenoids failed in the [2 + 1]-cycloaddition with alkynes, the use of enynones as the carbene source enables the preparation of substituted 2-furyl cyclopropene derivatives with remarkable scope.

  14. Metal-Catalyzed Cleavage of tRNA[superscript Phe

    ERIC Educational Resources Information Center

    Kirk, Sarah R.; Silverstein, Todd P.; McFarlane Holman, Karen L.

    2008-01-01

    This laboratory project is one component of a semester-long advanced biochemistry laboratory course that uses several complementary techniques to study tRNA[superscript Phe] conformational changes induced by ligand binding. In this article we describe a set of experiments in which students assay metal-catalyzed hydrolysis of tRNA[superscript Phe]…

  15. Iron-Catalyzed Synthesis of Sulfur-Containing Heterocycles.

    PubMed

    Bosset, Cyril; Lefebvre, Gauthier; Angibaud, Patrick; Stansfield, Ian; Meerpoel, Lieven; Berthelot, Didier; Guérinot, Amandine; Cossy, Janine

    2016-10-13

    An iron-catalyzed synthesis of sulfur- and sulfone-containing heterocycles is reported. The method is based on the cyclization of readily available substrates and proceeded with high efficiency and diastereoselectivity. A variety of sulfur-containing heterocycles bearing moieties suitable for subsequent functionalization are prepared. Illustrative examples of such postcyclization modifications are also presented.

  16. Palladium-catalyzed enantioselective 1,1-fluoroarylation of aminoalkenes.

    PubMed

    He, Ying; Yang, Zhenyu; Thornbury, Richard T; Toste, F Dean

    2015-09-30

    The development of an enantioselective palladium-catalyzed 1,1-fluoroarylation of unactivated aminoalkenes is described. The reaction uses arylboronic acids as the arene source and Selectfluor as the fluorine source to generate benzylic fluorides in good yields with excellent enantioselectivities. This transformation, likely proceeding through an oxidative Heck mechanism, affords 1,1-difunctionalized alkene products.

  17. Palladium-Catalyzed Enantioselective 1,1-Fluoroarylation of Aminoalkenes

    PubMed Central

    2016-01-01

    The development of an enantioselective palladium-catalyzed 1,1-fluoroarylation of unactivated aminoalkenes is described. The reaction uses arylboronic acids as the arene source and Selectfluor as the fluorine source to generate benzylic fluorides in good yields with excellent enantioselectivities. This transformation, likely proceeding through an oxidative Heck mechanism, affords 1,1-difunctionalized alkene products. PMID:26378886

  18. Pd-catalyzed C-H fluorination with nucleophilic fluoride.

    PubMed

    McMurtrey, Kate B; Racowski, Joy M; Sanford, Melanie S

    2012-08-17

    The palladium-catalyzed C-H fluorination of 8-methylquinoline derivatives with nucleophilic fluoride is reported. This transformation involves the use of AgF as the fluoride source in combination with a hypervalent iodine oxidant. Both the scope and mechanism of the reaction are discussed.

  19. Palladium(III)-Catalyzed Fluorination of Arylboronic Acid Derivatives

    PubMed Central

    Tang, Pingping; Murphy, Jennifer M.; Ritter, Tobias

    2013-01-01

    A practical, palladium-catalyzed synthesis of aryl fluorides from arylboronic acid derivatives is presented. The reaction is operationally simple and amenable to multi-gram-scale synthesis. Evaluation of the reaction mechanism suggests a single-electron-transfer pathway, involving a Pd(III) intermediate that has been isolated and characterized. PMID:24040932

  20. Palladium(III)-catalyzed fluorination of arylboronic acid derivatives.

    PubMed

    Mazzotti, Anthony R; Campbell, Michael G; Tang, Pingping; Murphy, Jennifer M; Ritter, Tobias

    2013-09-25

    A practical, palladium-catalyzed synthesis of aryl fluorides from arylboronic acid derivatives is presented. The reaction is operationally simple and amenable to multigram-scale synthesis. Evaluation of the reaction mechanism suggests a single-electron-transfer pathway, involving a Pd(III) intermediate that has been isolated and characterized.