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Sample records for catalyzed reporter deposition

  1. Improved catalyzed reporter deposition, iCARD.

    Science.gov (United States)

    Lohse, Jesper; Petersen, Kenneth Heesche; Woller, Nina Claire; Pedersen, Hans Christian; Skladtchikova, Galina; Jørgensen, Rikke Malene

    2014-06-18

    Novel reporters have been synthesized with extended hydrophilic linkers that in combination with polymerizing cross-linkers result in very efficient reporter deposition. By utilizing antibodies to stain HER2 proteins in a cell line model it is demonstrated that the method is highly specific and sensitive with virtually no background. The detection of HER2 proteins in tissue was used to visualize individual antigens as small dots visible in a microscope. Image analysis-assisted counting of fluorescent or colored dots allowed assessment of relative protein levels in tissue. Taken together, we have developed novel reporters that improve the CARD method allowing highly sensitive in situ detection of proteins in tissue. Our findings suggest that in situ protein quantification in biological samples can be performed by object recognition and enumeration of dots, rather than intensity-based fluorescent or colorimetric assays.

  2. Copper-vapor-catalyzed chemical vapor deposition of graphene on dielectric substrates

    Science.gov (United States)

    Yang, Chao; Wu, Tianru; Wang, Haomin; Zhang, Xuefu; Shi, Zhiyuan; Xie, Xiaoming

    2017-07-01

    Direct synthesis of high-quality graphene on dielectric substrates is important for its application in electronics. In this work, we report the process of copper-vapor-catalyzed chemical vapor deposition of high-quality and large graphene domains on various dielectric substrates. The copper vapor plays a vital role on the growth of transfer-free graphene. Both single-crystal domains that are much larger than previous reports and high-coverage graphene films can be obtained by adjusting the growth duration. The quality of the obtained graphene was verified to be comparable with that of graphene grown on Cu foil. The progress reported in this work will aid the development of the application of transfer-free graphene in the future.

  3. In situ detection of denitrifying bacteria by mRNA-targeted nucleic acid probes and catalyzed reporter deposition

    DEFF Research Database (Denmark)

    Kofoed, Michael Vedel; Stief, Peter; Poulsen, Morten

    can be designed to target a broader range of denitrifying bacteria; however, they require two-pass CARD-FISH, which may result in (too) high background fluorescence. In a first application example, habitat-specific polynucleotide probes were used to quantify bacteria expressing narG and nos...... reduction of nitrate to dinitrogen gas, is essential for the removal of fixed nitrogen from natural and engineered ecosystems. However, community structure and activity dynamics of denitrifying bacteria in most systems are poorly understood, partially due to difficulties in identifying and quantifying...... and catalyzed fluorescent reporter deposition (CARD-FISH). The general feasibility of the approach was first tested with pure cultures of Pseudomonas stutzeri and various denitrifying and nitrate-reducing isolates. Detailed studies of probe specificity and hybridization conditions using Clone-FISH of nar...

  4. Hot wire chemical vapor deposition: limits and opportunities of protecting the tungsten catalyzer from silicide with a cavity

    International Nuclear Information System (INIS)

    Frigeri, P.A.; Nos, O.; Bengoechea, S.; Frevert, C.; Asensi, J.M.; Bertomeu, J.

    2009-01-01

    Hot Wire Chemical Vapor Deposition (HW-CVD) is one of the most promising techniques for depositing the intrinsic microcrystalline silicon layer for the production of micro-morph solar cells. However, the silicide formation at the colder ends of the tungsten wire drastically reduces the lifetime of the catalyzer, thus limiting its industrial exploitation. A simple but interesting strategy to decrease the silicide formation is to hide the electrical contacts of the catalyzer in a long narrow cavity which reduces the probability of the silane molecules to reach the colder ends of the wire. In this paper, the working mechanism of the cavity is elucidated. Measurements of the thickness profile of the silicon deposited in the internal walls of the cavity have been compared with those predicted using a simple diffusion model based on the assumption of Knudsen flow. A lifetime study of the protected and unprotected wires has been carried out. The different mechanisms which determine the deterioration of the catalyzer have been identified and discussed.

  5. Catalyzed deuterium fueled tokamak reactors

    International Nuclear Information System (INIS)

    Southworth, F.H.

    1977-01-01

    Catalyzed deuterium fuel presents several advantages relative to D-T. These are, freedom from tritium breeding, high charged particle power fraction and lowered neutron energy deposition in the blanket. Higher temperature operation, lower power densities and increased confinement are simultaneously required. However, the present study has developed designs which have capitalized upon the advantages of catalyzed deuterium to overcome the difficulties associated with the fuel while obtaining high efficiency

  6. Carrier gas effects on aluminum-catalyzed nanowire growth

    International Nuclear Information System (INIS)

    Ke, Yue; Hainey, Mel Jr; Won, Dongjin; Weng, Xiaojun; Eichfeld, Sarah M; Redwing, Joan M

    2016-01-01

    Aluminum-catalyzed silicon nanowire growth under low-pressure chemical vapor deposition conditions requires higher reactor pressures than gold-catalyzed growth, but the reasons for this difference are not well understood. In this study, the effects of reactor pressure and hydrogen partial pressure on silicon nanowire growth using an aluminum catalyst were studied by growing nanowires in hydrogen and hydrogen/nitrogen carrier gas mixtures at different total reactor pressures. Nanowires grown in the nitrogen/hydrogen mixture have faceted catalyst droplet tips, minimal evidence of aluminum diffusion from the tip down the nanowire sidewalls, and significant vapor–solid deposition of silicon on the sidewalls. In comparison, wires grown in pure hydrogen show less well-defined tips, evidence of aluminum diffusion down the nanowire sidewalls at increasing reactor pressures and reduced vapor–solid deposition of silicon on the sidewalls. The results are explained in terms of a model wherein the hydrogen partial pressure plays a critical role in aluminum-catalyzed nanowire growth by controlling hydrogen termination of the silicon nanowire sidewalls. For a given reactor pressure, increased hydrogen partial pressures increase the extent of hydrogen termination of the sidewalls which suppresses SiH_4 adsorption thereby reducing vapor–solid deposition of silicon but increases the surface diffusion length of aluminum. Conversely, lower hydrogen partial pressures reduce the hydrogen termination and also increase the extent of SiH_4 gas phase decomposition, shifting the nanowire growth window to lower growth temperatures and silane partial pressures. (paper)

  7. A novel Ag catalyzation process using swelling impregnation method for electroless Ni deposition on Kevlar® fiber

    Science.gov (United States)

    Pang, Hongwei; Bai, Ruicheng; Shao, Qinsi; Gao, Yufang; Li, Aijun; Tang, Zhiyong

    2015-12-01

    A novel Ag catalyzation process using swelling impregnation pretreatment method was developed for electroless nickel (EN) deposition on Kevlar fiber. Firstly, the fiber was immersed into an aqueous dimethylsulfoxide (DMSO) solution of silver nitrate to impart silver nitrate into the inner part of the fiber near the surface. Subsequently silver nitrate was reduced to metal silver nanoparticles on the fiber surface by treatment with aqueous solution of sodium borohydride. After electroless plating, a dense and homogeneous nickel coating was obtained on the fiber surface. The silver nanoparticles formed at the fiber surface functioned as a catalyst for electroless deposition as well as an anchor for the plated layer. The study also revealed that the incorporation of surfactant sodium dodecyl sulfate (SDS) in electroless nickel plating bath can enhance the adhesion strength of EN layer with the fiber surface and minimize the surface roughness of the EN coating. The Ni plated Kevlar fiber possessed excellent corrosion resistance and high tensile strength.

  8. Synthesis and growth mechanism of Fe-catalyzed carbon nanotubes by plasma-enhanced chemical vapor deposition

    International Nuclear Information System (INIS)

    Jiang Jun; Feng Tao; Cheng Xinhong; Dai Lijuan; Cao Gongbai; Jiang Bingyao; Wang Xi; Liu Xianghuai; Zou Shichang

    2006-01-01

    Plasma-enhanced chemical vapor deposition (PECVD) was used to grow Fe-catalyzed carbon nanotubes (CNTs). The nanotubes had a uniform diameter in the range of about 10-20 nm. A base growth mode was responsible for the CNTs growth using a mixture of H 2 (60 sccm) and C 2 H 2 (15 sccm). For a mixture of H 2 (100 sccm) and C 2 H 2 (25 sccm), a complicated growth mechanism took place involving both the base growth and the tip growth. X-ray photoelectron spectroscopy measurements revealed that the grown CNTs contained C-H covalent bonds and Fe-C bonds located at the interface between them and the substrates. The factors determining the growth mechanism of CNTs are discussed and their growth mechanisms with the different gas ratios are suggested

  9. Rhodium Catalyzed Decarbonylation

    DEFF Research Database (Denmark)

    Garcia Suárez, Eduardo José; Kahr, Klara; Riisager, Anders

    2017-01-01

    Rhodium catalyzed decarbonylation has developed significantly over the last 50 years and resulted in a wide range of reported catalyst systems and reaction protocols. Besides experimental data, literature also includes mechanistic studies incorporating Hammett methods, analysis of kinetic isotope...

  10. $MNO_2$ catalyzed carbon electrodes for dioxygen reduction in concentrated alkali

    OpenAIRE

    Manoharan, R; Shulka, AK

    1984-01-01

    A process to deposit $\\gamma-MnO_2$ catalytic oxide onto coconut-shell charcoal substrate is described. Current-potential curves for electroreduction of dioxygen with electrodes fabricated from this catalyzed substrate are obtained in 6M KOH under ambient conditions. The performance of these electrodes is competitive with platinized carbon electrodes.

  11. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    KAUST Repository

    Zhao, Changgui; Guo, Donghui; Munkerup, Kristin; Huang, Kuo-Wei; Li, Fangyi; Wang, Jian

    2018-01-01

    on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a

  12. Alloying Au surface with Pd reduces the intrinsic activity in catalyzing CO oxidation

    KAUST Repository

    Qian, Kun

    2016-03-30

    © 2016. Various Au-Pd/SiO2 catalysts with a fixed Au loading but different Au:Pd molar ratios were prepared via deposition-precipitation method followed by H2 reduction. The structures were characterized and the catalytic activities in CO oxidation were evaluated. The formation of Au-Pd alloy particles was identified. The Au-Pd alloy particles exhibit enhanced dispersions on SiO2 than Au particles. Charge transfer from Pd to Au within Au-Pd alloy particles. Isolated Pd atoms dominate the surface of Au-Pd alloy particles with large Au:Pd molar ratios while contiguous Pd atoms dominate the surface of Au-Pd alloy particles with small Au:Pd molar ratios. Few synergetic effect of Au-Pd alloy occurs on catalyzing CO oxidation under employed reaction conditions. Alloying Au with Pd reduces the intrinsic activity in catalyzing CO oxidation, and contiguous Pd atoms on the Au-Pd alloy particles are capable of catalyzing CO oxidation while isolated Pd atoms are not. These results advance the fundamental understandings of Au-Pd alloy surfaces in catalyzing CO oxidation.

  13. Iron-catalyzed intermolecular cycloaddition of diazo surrogates with hexahydro-1,3,5-triazines.

    Science.gov (United States)

    Liu, Pei; Zhu, Chenghao; Xu, Guangyang; Sun, Jiangtao

    2017-09-26

    We report here an unprecedented iron-catalyzed cycloaddition reaction of diazo surrogates with hexahydro-1,3,5-triazines, providing five-membered heterocycles in moderate to high yields under mild reaction conditions. This cycloaddition features C-N and C-C bond formation using a cheap iron catalyst. Importantly, different to our former report on a gold-catalyzed system, both donor/donor and donor/acceptor diazo substrates are tolerated in this iron-catalyzed protocol.

  14. The fabrication of vertically aligned and periodically distributed carbon nanotube bundles and periodically porous carbon nanotube films through a combination of laser interference ablation and metal-catalyzed chemical vapor deposition.

    Science.gov (United States)

    Yuan, Dajun; Lin, Wei; Guo, Rui; Wong, C P; Das, Suman

    2012-06-01

    Scalable fabrication of carbon nanotube (CNT) bundles is essential to future advances in several applications. Here, we report on the development of a simple, two-step method for fabricating vertically aligned and periodically distributed CNT bundles and periodically porous CNT films at the sub-micron scale. The method involves laser interference ablation (LIA) of an iron film followed by CNT growth via iron-catalyzed chemical vapor deposition. CNT bundles with square widths ranging from 0.5 to 1.5 µm in width, and 50-200 µm in length, are grown atop the patterned catalyst over areas spanning 8 cm(2). The CNT bundles exhibit a high degree of control over square width, orientation, uniformity, and periodicity. This simple scalable method of producing well-placed and oriented CNT bundles demonstrates a high application potential for wafer-scale integration of CNT structures into various device applications, including IC interconnects, field emitters, sensors, batteries, and optoelectronics, etc.

  15. Toward Efficient Palladium-Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Jensen, Thomas; Fristrup, Peter

    2009-01-01

    Recent breakthroughs have proved that direct palladium (II)-catalyzed allylic C-H alkylation can be achieved. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalyzed allylic alkylation can be lifted. These initial reports hold great promise...... for the development of allylic C-H alkylation into a widely applicable methodology, thus providing a means to enhance synthetic efficiency in these reactions....

  16. Intracavitary deposits on Essure® hysteroscopic sterilization devices: A case report.

    Science.gov (United States)

    Maassen, L W; van Gastel, D M; Lentjes, E G W M; Bongers, M Y; Veersema, S

    2017-07-01

    To study the composition of intracavitary deposits on Essure® hysteroscopic sterilization devices. Case report. Reproductive Medicine and Gynecology department of a University Hospital. A 39 years old patient presenting with a request for surgical removal of Essure® sterilization devices. Diagnostic hysteroscopy showed a crystal like white deposit attached to one of the devices. Diagnostic hysteroscopy and surgical removal of Essure® devices was performed. The deposits were collected and infrared spectroscopy analysis was performed. Chemical composition of the deposits attached to the device. Infrared spectroscopy of the material showed patterns conclusive with calcite (calcium carbonate, CaCO 3 ). Until now, it is not clear if there is a relationship between reported complaints and formation of calcite deposits on Essure®. Infrared spectroscopy of deposits on Essure® devices showed a pattern conclusive with calcite. The relationship between reported complaints and the formation of calcite deposits on Essure® remains unclear.

  17. Kinetics of aggregation growth with competition between catalyzed birth and catalyzed death

    International Nuclear Information System (INIS)

    Wang Haifeng; Gao Yan; Lin Zhenquan

    2008-01-01

    An aggregation growth model of three species A, B and C with the competition between catalyzed birth and catalyzed death is proposed. Irreversible aggregation occurs between any two aggregates of the like species with the constant rate kernels I n (n = 1,2,3). Meanwhile, a monomer birth of an A species aggregate of size k occurs under the catalysis of a B species aggregate of size j with the catalyzed birth rate kernel K(k,j) = Kkj v and a monomer death of an A species aggregate of size k occurs under the catalysis of a C species aggregate of size j with the catalyzed death rate kernel L(k,j)=Lkj v , where v is a parameter reflecting the dependence of the catalysis reaction rates of birth and death on the size of catalyst aggregate. The kinetic evolution behaviours of the three species are investigated by the rate equation approach based on the mean-field theory. The form of the aggregate size distribution of A species a k (t) is found to be dependent crucially on the competition between the catalyzed birth and death of A species, as well as the irreversible aggregation processes of the three species: (1) In the v k (t) satisfies the conventional scaling form; (2) In the v ≥ 0 case, the competition between the catalyzed birth and death dominates the process. When the catalyzed birth controls the process, a k (t) takes the conventional or generalized scaling form. While the catalyzed death controls the process, the scaling description of the aggregate size distribution breaks down completely

  18. Rhenium and Manganese-Catalyzed Selective Alkenylation of Indoles

    KAUST Repository

    Wang, Chengming

    2018-04-06

    An efficient rhenium‐catalyzed regioselective C‐H bond alkenylation of indoles is reported. The protocol operates well for internal as well as terminal alkynes, affording products in good to excellent yields. Furthermore, a manganese catalyzed, acid free, regioselective C2‐alkenylation of indoles with internal alkynes is described. The directing groups can be easily removed after the reaction and the resulting products can be used as valuable building blocks for the synthesis of diverse heterocyclic compounds.

  19. Rhenium and Manganese-Catalyzed Selective Alkenylation of Indoles

    KAUST Repository

    Wang, Chengming; Rueping, Magnus

    2018-01-01

    An efficient rhenium‐catalyzed regioselective C‐H bond alkenylation of indoles is reported. The protocol operates well for internal as well as terminal alkynes, affording products in good to excellent yields. Furthermore, a manganese catalyzed, acid free, regioselective C2‐alkenylation of indoles with internal alkynes is described. The directing groups can be easily removed after the reaction and the resulting products can be used as valuable building blocks for the synthesis of diverse heterocyclic compounds.

  20. Enzyme-Catalyzed Transetherification of Alkoxysilanes

    Directory of Open Access Journals (Sweden)

    Peter G. Taylor

    2013-01-01

    Full Text Available We report the first evidence of an enzyme-catalyzed transetherification of model alkoxysilanes. During an extensive enzymatic screening in the search for new biocatalysts for silicon-oxygen bond formation, we found that certain enzymes promoted the transetherification of alkoxysilanes when tert-butanol or 1-octanol were used as the reaction solvents.

  1. Graphene oxide catalyzed cis-trans isomerization of azobenzene

    Directory of Open Access Journals (Sweden)

    Dongha Shin

    2014-09-01

    Full Text Available We report the fast cis-trans isomerization of an amine-substituted azobenzene catalyzed by graphene oxide (GO, where the amine functionality facilitates the charge transfer from azobenzene to graphene oxide in contrast to non-substituted azobenzene. This catalytic effect was not observed in stilbene analogues, which strongly supports the existence of different isomerization pathways between azobenzene and stilbene. The graphene oxide catalyzed isomerization is expected to be useful as a new photoisomerization based sensing platform complementary to GO-based fluorescence quenching methods.

  2. Growth of Self-Catalyzed InP Nanowires by Metalorganic Chemical Vapour Deposition

    International Nuclear Information System (INIS)

    Lv Xiao-Long; Zhang Xia; Yan Xin; Liu Xiao-Long; Cui Jian-Gong; Li Jun-Shuai; Huang Yong-Qing; Ren Xiao-Min

    2012-01-01

    The fabrication of self-catalyzed InP nanowires (NWs) is investigated under different growth conditions. Indium droplets induced by surface reconstruction act as nucleation sites for NW growth. Vertical standing NWs with uniform cross sections are obtained under optimized conditions. It is confirmed that the growth rate of NWs is strongly affected by the surface diffusion adatoms while contributions from the direct impingement of vapor species onto the In droplets can be negligible. The results indicate that the droplet acts as an adatom collector rather than a catalyst. Moreover, the diffusion flow rate of adatoms increases with time at the beginning of growth and stabilizes as the growth proceeds

  3. Caffeine-catalyzed gels.

    Science.gov (United States)

    DiCiccio, Angela M; Lee, Young-Ah Lucy; Glettig, Dean L; Walton, Elizabeth S E; de la Serna, Eva L; Montgomery, Veronica A; Grant, Tyler M; Langer, Robert; Traverso, Giovanni

    2018-07-01

    Covalently cross-linked gels are utilized in a broad range of biomedical applications though their synthesis often compromises easy implementation. Cross-linking reactions commonly utilize catalysts or conditions that can damage biologics and sensitive compounds, producing materials that require extensive post processing to achieve acceptable biocompatibility. As an alternative, we report a batch synthesis platform to produce covalently cross-linked materials appropriate for direct biomedical application enabled by green chemistry and commonly available food grade ingredients. Using caffeine, a mild base, to catalyze anhydrous carboxylate ring-opening of diglycidyl-ether functionalized monomers with citric acid as a tri-functional crosslinking agent we introduce a novel poly(ester-ether) gel synthesis platform. We demonstrate that biocompatible Caffeine Catalyzed Gels (CCGs) exhibit dynamic physical, chemical, and mechanical properties, which can be tailored in shape, surface texture, solvent response, cargo release, shear and tensile strength, among other potential attributes. The demonstrated versatility, low cost and facile synthesis of these CCGs renders them appropriate for a broad range of customized engineering applications including drug delivery constructs, tissue engineering scaffolds, and medical devices. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

  4. Acidic deposition: State of science and technology. Report 11. Historical changes in surface-water acid-base chemistry in response to acidic deposition. Final report

    International Nuclear Information System (INIS)

    Sullivan, T.J.; Small, M.J.; Kingston, J.C.; Bernert, J.A.; Thomas, D.R.

    1990-09-01

    The objectives of the analyses reported in the State of Science report are to: identify the lake and stream populations in the United States that have experienced chronic changes in biologically significant constituents of surface water chemistry (e.g. pH, Al) in response to acidic deposition; quantify biologically meaningful historical changes in chronic surface water chemistry associated with acidic deposition, with emphasis on ANC, pH, and Al; estimate the proportion of lakes nor acidic that were not acidic in pre-industrial times; estimate the proportional response of each of the major chemical constituents that have changed in response to acidic deposition using a subset of statistically selected Adirondack lakes for which paleolimnological reconstructions of pre-industrial surface water chemistry have been performed; evaluate and improve, where appropriate and feasible, empirical models of predicting changes in ANC; and evaluate the response of seepage lakes to acidic deposition

  5. The deposition of highly uniform and adhesive nanocrystalline PbS film from solution

    International Nuclear Information System (INIS)

    Yang Yujun; Hu Shengshui

    2008-01-01

    Mirror-like PbS films have been deposited by chemical deposition on glass substrates from alkaline chemical bath containing lead nitrate, sodium thiosulfate and 1-thioglycerol, which was used to catalyze the hydrolysis of thiosulfate. Nanostructure characterization was carried out by x-ray diffraction and scanning electron microscopy in order to determine the average crystallite size (61 nm) and study the surface morphologies of the as-deposited films

  6. Hydrogenation of ethene catalyzed by Ir atom deposited on γ-Al2O3(001) surface: From ab initio calculations

    International Nuclear Information System (INIS)

    Chen, Yongchang; Sun, Zhaolin; Song, Lijuan; Li, Qiang; Xu, Ming

    2012-01-01

    Ethene hydrogenation reaction, catalyzed by an iridium atom adsorbed on γ-Al 2 O 3 (001) surface, is studied via ab initio calculations based on density functional theory (DFT). The catalyzed reaction process and activation energy are compared with the counterparts of a reaction occurs in vacuum condition. It is found that the activation energy barrier is substantially lowered by the adsorbed Ir atom on the γ-Al 2 O 3 (001). The catalyzed reaction is modeled in two steps: (1) Hydrogen molecular dissolution and then bonded with C 2 H 4 molecular. (2) Desorption of the C 2 H 6 molecular from the surface. -- Highlights: ► The ethene hydrogenation reaction is simulated with nudged elastic band methods. ► The catalytic effect of the Ir atom on γ-Al 2 O 3 (001) surface is modeled. ► Details of the catalytic reaction are exhibited.

  7. Biosensor Applications of MAPLE Deposited Lipase

    Directory of Open Access Journals (Sweden)

    Valeria Califano

    2014-10-01

    Full Text Available Matrix Assisted Pulsed Laser Evaporation (MAPLE is a thin film deposition technique derived from Pulsed Laser Deposition (PLD for deposition of delicate (polymers, complex biological molecules, etc. materials in undamaged form. The main difference of MAPLE technique with respect to PLD is the target: it is a frozen solution or suspension of the (guest molecules to be deposited in a volatile substance (matrix. Since laser beam energy is mainly absorbed by the matrix, damages to the delicate guest molecules are avoided, or at least reduced. Lipase, an enzyme catalyzing reactions borne by triglycerides, has been used in biosensors for detection of β-hydroxyacid esters and triglycerides in blood serum. Enzymes immobilization on a substrate is therefore required. In this paper we show that it is possible, using MAPLE technique, to deposit lipase on a substrate, as shown by AFM observation, preserving its conformational structure, as shown by FTIR analysis.

  8. Rhodium-catalyzed chemo- and regioselective decarboxylative addition of β-ketoacids to alkynes.

    Science.gov (United States)

    Li, Changkun; Grugel, Christian P; Breit, Bernhard

    2016-04-30

    A highly efficient rhodium-catalyzed chemo- and regioselective addition of β-ketoacids to alkynes is reported. Applying a Rh(i)/(S,S)-DIOP catalyst system, γ,δ-unsaturated ketones were prepared with exclusively branched selectivity under mild conditions. This demonstrates that readily available alkynes can be an alternative entry to allyl electrophiles in transition-metal catalyzed allylic alkylation reactions.

  9. Intracavitary deposits on Essure® hysteroscopic sterilization devices: A case report

    Directory of Open Access Journals (Sweden)

    L.W. Maassen

    2017-07-01

    Capsule: Infrared spectroscopy of deposits on Essure® devices showed a pattern conclusive with calcite. The relationship between reported complaints and the formation of calcite deposits on Essure® remains unclear.

  10. Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert

    2003-01-01

    Enyne metathesis combines an alkene and an alkyne into a 1,3-diene. The first enyne metathesis reaction catalyzed by a ruthenium carbene complex was reported in 1994. This review covers the advances in this transformation during the last eight years with particular emphasis on methodology...

  11. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    KAUST Repository

    Zhao, Changgui

    2018-02-05

    Axially chiral molecules are among the most valuable substrates in organic synthesis. They are typically used as chiral ligands or catalysts in asymmetric reactions. Recent progress for the construction of these chiral molecules is mainly focused on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a catalytic C–C bond formation occurs, providing axially chiral α-pyrone−aryls in moderate to good yields and with high enantioselectivities. Control experiments indicated that alkynyl acyl azoliums, acting as active intermediates, are employed to atroposelectively assemble chiral biaryls and such a methodology may be creatively applied to other useful NHC-catalyzed asymmetric transformations.

  12. ENVIRONMENTAL TECHNOLOGY VERIFICATION, TEST REPORT OF MOBILE SOURCE EMISSIONS CONTROL DEVICES: CLEAN DIESEL TECHNOLOGIES FUEL-BORNE CATALYST WITH MITSUI/PUREARTH CATALYZED WIRE MESH FILTER

    Science.gov (United States)

    The Environmental Technology Verification report discusses the technology and performance of the Fuel-Borne Catalyst with Mitsui/PUREarth Catalyzed Wire Mesh Filter manufactured by Clean Diesel Technologies, Inc. The technology is a platinum/cerium fuel-borne catalyst in commerci...

  13. Copper-catalyzed decarboxylative trifluoromethylation of allylic bromodifluoroacetates.

    Science.gov (United States)

    Ambler, Brett R; Altman, Ryan A

    2013-11-01

    The development of new synthetic fluorination reactions has important implications in medicinal, agricultural, and materials chemistries. Given the prevalence and accessibility of alcohols, methods to convert alcohols to trifluoromethanes are desirable. However, this transformation typically requires four-step processes, specialty chemicals, and/or stoichiometric metals to access the trifluoromethyl-containing product. A two-step copper-catalyzed decarboxylative protocol for converting allylic alcohols to trifluoromethanes is reported. Preliminary mechanistic studies distinguish this reaction from previously reported Cu-mediated reactions.

  14. Primary CNS Nonamyloidogenic Light Chain Deposition Disease: Case Report and Brief Review.

    Science.gov (United States)

    Mercado, Juan Jose; Markert, James M; Meador, William; Chapman, Philip; Perry, Arie; Hackney, James R

    2017-12-01

    The true incidence of light chain deposition disease (LCDD) restricted to the central nervous system (CNS) is unknown. To our knowledge only 7 cases of LCDD restricted to the brain have been previously reported. We herein describe an unusual example. A 44-year-old man presented with a history of ischemic retinopathy in 2004 and left lower extremity hypoesthesia in 2007 that progressed gradually to left-sided weakness and numbness in the 2 years prior to his hospitalization in 2015. A stereotactic brain biopsy was performed, displaying nonspecific hyaline deposits of amorphous "amyloid-like" material involving deep brain white matter and vessels. These were Congo red negative and were accompanied by a sparse lymphoplasmacytic infiltrate. Plasma cells demonstrated kappa light chain class restriction by chromogenic in situ hybridization (CISH). There was patchy reactivity with kappa immunohistochemistry in the amorphous deposits. A diagnosis of light chain deposition disease was made. Subsequent systemic myeloma and lymphoma workups were negative. Previously reported cases have included men and women, spanning the ages of 19 and 72 years, often presenting with hemiparesis, hypoesthesia, or seizures. Deposits have been reported in the cerebrum and cerebellum. T2/FLAIR (fluid attenuation inversion recovery) changes are usual, but lesions may or may not produce contrast enhancement. The light chain deposition may be of kappa or lambda class. Most lesions have been accompanied by local lymphoid and/or plasma cell infiltrates exhibiting light chain restriction of the same class as the deposits. In summary, LCDD limited to the CNS is a rare lesion consisting of deposition of amyloid-like, but Congo red-negative monotypic light chain usually produced by local lymphoplasmacytic infiltrates.

  15. Rhodium(iii)-catalyzed ortho-olefination of aryl phosphonates.

    Science.gov (United States)

    Chary, Bathoju Chandra; Kim, Sunggak

    2013-09-25

    Rhodium(iii)-catalyzed C-H olefination of aryl phosphonic esters is reported for the first time. In this mild and efficient process, the phosphonic ester group is utilized successfully as a new directing group. In addition, mono-olefination for aryl phosphonates is observed using a phosphonic diamide directing group.

  16. Thermodynamics of Enzyme-Catalyzed Reactions Database

    Science.gov (United States)

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

  17. Catalyzed deuterium-deuterium and deuterium-tritium fusion blankets for high temperature process heat production

    International Nuclear Information System (INIS)

    Ragheb, M.M.H.; Salimi, B.

    1982-01-01

    Tritiumless blanket designs, associated with a catalyzed deuterium-deuterium (D-D) fusion cycle and using a single high temperature solid pebble or falling bed zone, for process heat production, are proposed. Neutronics and photonics calculations, using the Monte Carlo method, show that an about 90% heat deposition fraction is possible in the high temperature zone, compared to a 30 to 40% fraction if a deuterium-tritium (D-T) fusion cycle is used with separate breeding and heat deposition zones. Such a design is intended primarily for synthetic fuels manufacture through hydrogen production using high temperature water electrolysis. A system analysis involving plant energy balances and accounting for the different fusion energy partitions into neutrons and charged particles showed that plasma amplification factors in the range of 2 are needed. In terms of maximization of process heat and electricity production, and the maximization of the ratio of high temperature process heat to electricity, the catalyzed D-D system outperforms the D-T one by about 20%. The concept is thought competitive to the lithium boiler concept for such applications, with the added potential advantages of lower tritium inventories in the plasma, reduced lithium pumping (in the case of magnetic confinement) and safety problems, less radiation damage at the first wall, and minimized risks of radioactive product contamination by tritium

  18. Enzymatically-Catalyzed Polymerization (ECP)- Derived Polymer Electrolyte for Rechargeable Li-Ion Batteries

    National Research Council Canada - National Science Library

    Chua, David

    1998-01-01

    Report developed under SBIR contract covers the syntheses and electrochemical characterizations of novel polymer electrolytes derived from compounds synthesized via enzyme-catalyzed polymerization(ECP) techniques...

  19. Enhancing the muon-catalyzed fusion yield

    International Nuclear Information System (INIS)

    Jones, S.E.

    1987-01-01

    Much has been learned about muon-catalyzed fusion since the last conference on emerging nuclear energy systems. Here the authors consider what they have learned about enhancing the muon-catalyzed fusion energy yield

  20. Molecular Active Sites in Heterogeneous Ir-La/C-Catalyzed Carbonylation of Methanol to Acetates.

    Science.gov (United States)

    Kwak, Ja Hun; Dagle, Robert; Tustin, Gerald C; Zoeller, Joseph R; Allard, Lawrence F; Wang, Yong

    2014-02-06

    We report that when Ir and La halides are deposited on carbon, exposure to CO spontaneously generates a discrete molecular heterobimetallic structure, containing an Ir-La covalent bond that acts as a highly active, selective, and stable heterogeneous catalyst for the carbonylation of methanol to produce acetic acid. This catalyst exhibits a very high productivity of ∼1.5 mol acetyl/mol Ir·s with >99% selectivity to acetyl (acetic acid and methyl acetate) without detectable loss in activity or selectivity for more than 1 month of continuous operation. The enhanced activity can be mechanistically rationalized by the presence of La within the ligand sphere of the discrete molecular Ir-La heterobimetallic structure, which acts as a Lewis acid to accelerate the normally rate-limiting CO insertion in Ir-catalyzed carbonylation. Similar approaches may provide opportunities for attaining molecular (single site) behavior similar to homogeneous catalysis on heterogeneous surfaces for other industrial applications.

  1. Synthesis of a novel chemotype via sequential metal-catalyzed cycloisomerizations

    Directory of Open Access Journals (Sweden)

    Bo Leng

    2012-08-01

    Full Text Available Sequential cycloisomerizations of diynyl o-benzaldehyde substrates to access novel polycyclic cyclopropanes are reported. The reaction sequence involves initial Cu(I-mediated cycloisomerization/nucleophilic addition to an isochromene followed by diastereoselective Pt(II-catalyzed enyne cycloisomerization.

  2. Muon-catalyzed fusion experiment target and detector system. Preliminary design report

    International Nuclear Information System (INIS)

    Jones, S.E.; Watts, K.D.; Caffrey, A.J.; Walter, J.B.

    1982-03-01

    We present detailed plans for the target and particle detector systems for the muon-catalyzed fusion experiment. Requirements imposed on the target vessel by experimental conditions and safety considerations are delineated. Preliminary designs for the target vessel capsule and secondary containment vessel have been developed which meet these requirements. In addition, the particle detection system is outlined, including associated fast electronics and on-line data acquisition. Computer programs developed to study the target and detector system designs are described

  3. Uptake kinetics and biodistribution of C-14-D-luciferin-a radiolabeled substrate for the firefly luciferase catalyzed bioluminescence reaction : impact on bioluminescence based reporter gene imaging

    NARCIS (Netherlands)

    Berger, Frank; Paulmurugan, Ramasamy; Bhaumik, Srabani; Gambhir, Sanjiv Sam

    2008-01-01

    Purpose Firefly luciferase catalyzes the oxidative decarboxylation of D-luciferin to oxyluciferin in the presence of cofactors, producing bioluminescence. This reaction is used in optical bioluminescence-based molecular imaging approaches to detect the expression of the firefly luciferase reporter

  4. Atmospheric deposition, operational report for air pollution 2003. NOVA 2003; Atmosfaerisk deposition, driftsrapport for Luftforurening i 2003 NOVA 2003

    Energy Technology Data Exchange (ETDEWEB)

    Ellermann, T.; Hertel, O.; Ambelas Skjoeth, C.; Kemp, K.; Monies, C.

    2004-12-01

    This report presents measurements and calculations from the atmospheric part of NOVA 2003 and covers results for 2003. It summarises the main results concerning concentrations and depositions of nitrogen, phosphorous and sulphur compounds related to eutrofication and acidification and selected heavy metals. Depositions of atmospheric compounds to Danish marine waters as well as land surface are presented. The measurements in the monitoring programme are supplemented with model calculations of concentrations and depositions of nitrogen and sulphur compounds to Danish land surfaces as well as marine waters, fjords and bays using the ACDEP model (Atmospheric Chemistry and Deposition). The model is a so-called trajectory model and simulates the physical and chemical processes in the atmosphere using meteorological and emission data input. (BA)

  5. Rh-catalyzed linear hydroformylation of styrene

    NARCIS (Netherlands)

    Boymans, E.H.; Janssen, M.C.C.; Mueller, C.; Lutz, M.; Vogt, D.

    2012-01-01

    Usually the Rh-catalyzed hydroformylation of styrene predominantly yields the branched, chiral aldehyde. An inversion of regioselectivity can be achieved using strong p-acceptor ligands. Binaphthol-based diphosphite and bis(dipyrrolyl-phosphorodiamidite) ligands were applied in the Rh-catalyzed

  6. Intracavitary deposits on Essure® hysteroscopic sterilization devices : A case report

    OpenAIRE

    Maassen, L. W.; van Gastel, Maatje D A; Lentjes, E. G.W.M.; Bongers, M. Y.; Veersema, S.

    2017-01-01

    Objective: To study the composition of intracavitary deposits on Essure® hysteroscopic sterilization devices. Design: Case report. Setting: Reproductive Medicine and Gynecology department of a University Hospital. Patient(s): A 39 years old patient presenting with a request for surgical removal of Essure® sterilization devices. Diagnostic hysteroscopy showed a crystal like white deposit attached to one of the devices. Intervention: Diagnostic hysteroscopy and surgical removal of E...

  7. Electrophoretic Deposition of Gallium with High Deposition Rate

    Directory of Open Access Journals (Sweden)

    Hanfei Zhang

    2014-12-01

    Full Text Available In this work, electrophoretic deposition (EPD is reported to form gallium thin film with high deposition rate and low cost while avoiding the highly toxic chemicals typically used in electroplating. A maximum deposition rate of ~0.6 μm/min, almost one order of magnitude higher than the typical value reported for electroplating, is obtained when employing a set of proper deposition parameters. The thickness of the film is shown to increase with deposition time when sequential deposition is employed. The concentration of Mg(NO32, the charging salt, is also found to be a critical factor to control the deposition rate. Various gallium micropatterns are obtained by masking the substrate during the process, demonstrating process compatibility with microfabrication. The reported novel approach can potentially be employed in a broad range of applications with Ga as a raw material, including microelectronics, photovoltaic cells, and flexible liquid metal microelectrodes.

  8. Rh-Catalyzed Annulations of N-Methoxybenzamides and Ketenimines: Sterically and Electronically Controlled Synthesis of Isoquinolinones and Isoindolinones.

    Science.gov (United States)

    Zhou, Xiaorong; Zhang, Zhiyin; Zhao, Hongyang; Lu, Ping; Wang, Yanguang

    2017-04-07

    Rhodium-catalyzed C-H activation/annulation reactions of ketenimines with N-methoxybenzamides are reported. The outcome of reactions is dependent on the structure of ketenimines. The β-alkyl-substituted ketenimines furnish 3-iminoisoquinolin-1(2H)-ones in a formal [4 + 2] annulation manner, while the β-ester substituted ketenimines afford 3-aminoisoindolin-1-ones in a formal [4 + 1] annulation manner. The synthesized [4 + 2] products undergo an intramolecular Cu-catalyzed C-N coupling to be converted to benzo[4,5]imidazo[1,2-b]isoquinolin-11-ones, which can be directly prepared from ketenimines and N-methoxybenzamides by a one-pot Rh-catalyzed annulation/Cu-catalyzed C-N coupling sequence.

  9. Mechanistic studies of copper(I)-catalyzed 1,3-halogen migration.

    Science.gov (United States)

    Van Hoveln, Ryan; Hudson, Brandi M; Wedler, Henry B; Bates, Desiree M; Le Gros, Gabriel; Tantillo, Dean J; Schomaker, Jennifer M

    2015-04-29

    An ongoing challenge in modern catalysis is to identify and understand new modes of reactivity promoted by earth-abundant and inexpensive first-row transition metals. Herein, we report a mechanistic study of an unusual copper(I)-catalyzed 1,3-migration of 2-bromostyrenes that reincorporates the bromine activating group into the final product with concomitant borylation of the aryl halide bond. A combination of experimental and computational studies indicated this reaction does not involve any oxidation state changes at copper; rather, migration occurs through a series of formal sigmatropic shifts. Insight provided from these studies will be used to expand the utility of aryl copper species in synthesis and develop new ligands for enantioselective copper-catalyzed halogenation.

  10. Cytochrome c catalyzes the in vitro synthesis of arachidonoyl glycine

    International Nuclear Information System (INIS)

    McCue, Jeffrey M.; Driscoll, William J.; Mueller, Gregory P.

    2008-01-01

    Long chain fatty acyl glycines are an emerging class of biologically active molecules that occur naturally and produce a wide array of physiological effects. Their biosynthetic pathway, however, remains unknown. Here we report that cytochrome c catalyzes the synthesis of N-arachidonoyl glycine (NAGly) from arachidonoyl coenzyme A and glycine in the presence of hydrogen peroxide. The identity of the NAGly product was verified by isotope labeling and mass analysis. Other heme-containing proteins, hemoglobin and myoglobin, were considerably less effective in generating arachidonoyl glycine as compared to cytochrome c. The reaction catalyzed by cytochrome c in vitro points to its potential role in the formation of NAGly and other long chain fatty acyl glycines in vivo

  11. Muon catalyzed fusion under compressive conditions

    International Nuclear Information System (INIS)

    Cripps, G.; Goel, B.; Harms, A.A.

    1991-01-01

    The viability of a symbiotic combination of Muon Catalyzed Fusion (μCF) and high density generation processes has been investigated. The muon catalyzed fusion reaction rates are formulated in the temperature and density range found under moderate compressive conditions. Simplified energy gain and power balance calculations indicate that significant energy gain occurs only if standard type deuterium-tritium (dt) fusion is ignited. A computer simulation of the hydrodynamics and fusion kinetics of a spherical deuterium-tritium pellet implosion including muons is performed. Using the muon catalyzed fusion reaction rates formulated and under ideal conditions, the pellet ignites (and thus has a significant energy gain) only if the initial muon concentration is approximately 10 17 cm -3 . The muons need to be delivered to the pellet within a very short-time (≅ 1 ns). The muon pulse required in order to make the high density and temperature muon catalyzed fusion scheme viable is beyond the present technology for muon production. (orig.) [de

  12. Ti-Catalyzed Selective Isomerization of Terminal Mono-substituted Olefins

    International Nuclear Information System (INIS)

    Lee, Hyung Soo; Lee, Gab Yong

    2005-01-01

    The isomerization of olefins occurs either by a metal hydride addition-elimination or by a π-allyl metal hydride intermediate. HCo(CO) 4 , [(C 2 H 4 ) 2 RhCl] 2 , Ni[P(OEt) 3 ] 4 , and PtCl 2 (PPh 3 ) 2 -SnCl 2 are effective catalysts for isomerization of olefins via a metal hydride addition-elimination mechanism, 3,4 and Fe 3 (CO) 12 catalyzed isomerization of 3-ethyl-1-pentene and isomerization of 1-heptene catalyzed by (PhCN) 2 PdCl 2 occur via a π-allyl metal hydride mechanism. The cis/trans ratio of 2-butene obtained from isomerization of 1-butene by RhH(CO)(PPh 3 ) 3 has also been investigated. The skeletal isomerization of olefins catalyzed by (R 3 P) 2 NiCl 2 is developed such as conversion of cis-1,4-hexadiene to trans-2-methyl-1,3-pentadiene. Titanium complexes serve as an effective catalysts for a variety of reactions such as hydroalumination, hydroboration, and hydrogenation of unsaturated hydrocarbons. We have been interested in the selective reactions of unsaturated hydrocarbons by using titanium and zirconium compounds. The reagent system composed of LiAlH 4 /Cp 2 TiCl 2 ≤ 2 in the molar ratio promotes the isomerization of 1-octene, but the detailed reaction for isomerization of olefins has not been reported. We report here a selective isomerization of olefins with low valent titanium complex generated from Cp 2 TiCl 2 (Cp=cyclopentadienyl) and LiAlH 4

  13. Copper(I)-catalyzed olefination of N-sulfonylhydrazones with sulfones.

    Science.gov (United States)

    Xu, Shuai; Gao, Yunpeng; Chen, Ri; Wang, Kang; Zhang, Yan; Wang, Jianbo

    2016-03-25

    The Cu(I)-catalyzed olefination of N-sulfonylhydrazones with sulfones via metal carbene intermediates is reported. This reaction uses readily available starting materials and is operationally simple, thus representing a practical method for the construction of carbon-carbon double bonds. Mechanistically, Cu(I) carbene formation and subsequent carbene migratory insertion are proposed as the key steps.

  14. Assessment Of Surface-Catalyzed Reaction Products From High Temperature Materials In Plasmas

    Science.gov (United States)

    Allen, Luke Daniel

    Current simulations of atmospheric entry into both Mars and Earth atmospheres for the design of thermal protections systems (TPS) typically invoke conservative assumptions regarding surface-catalyzed recombination and the amount of energy deposited on the surface. The need to invoke such assumptions derives in part from lack of adequate experimental data on gas-surface interactions at trajectory relevant conditions. Addressing this issue, the University of Vermont's Plasma Test and Diagnostics Laboratory has done extensive work to measure atomic specie consumption by measuring the concentration gradient over various material surfaces. This thesis extends this work by attempting to directly diagnose molecular species production in air plasmas. A series of spectral models for the A-X and B-X systems of nitric oxide (NO), and the B-X system of boron monoxide (BO) have been developed. These models aim to predict line positions and strengths for the respective molecules in a way that is best suited for the diagnostic needs of the UVM facility. From the NO models, laser induced fluorescence strategies have been adapted with the intent of characterizing the relative quantity and thermodynamic state of NO produced bysurface-catalyzed recombination, while the BO model adds a diagnostic tool for the testing of diboride-based TPS materials. Boundary layer surveys of atomic nitrogen and NO have been carried out over water-cooled copper and nickel surfaces in air/argon plasmas. Translation temperatures and relative number densities throughout the boundary layer are reported. Additional tests were also conducted over a water-cooled copper surface to detect evidence of highly non-equilibrium effects in the form of excess population in elevated vibrational levels of the A-X system of NO. The tests showed that near the sample surface there is a much greater population in the upsilon'' = 1ground state than is predicted by a Boltzmann distribution.

  15. Rhodium(II)-catalyzed enantioselective synthesis of troponoids.

    Science.gov (United States)

    Murarka, Sandip; Jia, Zhi-Jun; Merten, Christian; Daniliuc, Constantin-G; Antonchick, Andrey P; Waldmann, Herbert

    2015-06-22

    We report a rhodium(II)-catalyzed highly enantioselective 1,3-dipolar cycloaddition reaction between the carbonyl moiety of tropone and carbonyl ylides to afford troponoids in good to high yields with excellent enantioselectivity. We demonstrate that α-diazoketone-derived carbonyl ylides, in contrast to carbonyl ylides derived from diazodiketoesters, undergo [6+3] cycloaddition reactions with tropone to yield the corresponding bridged heterocycles with excellent stereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Synthesis of heterocycles via transition-metal-catalyzed hydroarylation of alkynes.

    Science.gov (United States)

    Yamamoto, Yoshihiko

    2014-03-07

    Transition-metal (TM)-catalyzed hydroarylation reactions of alkynes have received much attention, because they enable the net insertion of alkyne C-C triple bonds into C-H bonds of aromatic precursors, resulting in regio- and stereo-selective formation of synthetically useful arylalkenes. Taking advantage of this feature, TM-catalyzed alkyne hydroarylations have been successfully used for the synthesis of heterocycles. TM-catalyzed alkyne hydroarylations can be classified into three major categories depending on the type of reaction and precursors involved: (1) palladium-catalyzed reductive Heck reactions of alkynes with aryl halides, (2) TM-catalyzed conjugate arylation reactions of activated alkynes with arylboronic acids, and (3) TM-catalyzed aromatic C-H alkenylations with alkynes. This review surveys heterocycle synthesis via TM-catalyzed hydroarylation of alkynes according to the above classification, with an emphasis on the scope and limitations, as well as the underlying mechanisms.

  17. Chalcogen-containing oxazolines in the palladium-catalyzed asymmetric allylic alkylation

    Directory of Open Access Journals (Sweden)

    Braga Antonio L.

    2006-01-01

    Full Text Available A comparative study about the ability of chiral chalcogen-containing oxazolines to act as chiral ligands in the palladium-catalyzed allylic alkylation of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate is reported. Differences in the catalytic performance are observed with sulfur, selenium and tellurium analogues.

  18. Cu-catalyzed aerobic oxidative esterification of acetophenones with alcohols to α-ketoesters.

    Science.gov (United States)

    Xu, Xuezhao; Ding, Wen; Lin, Yuanguang; Song, Qiuling

    2015-02-06

    Copper-catalyzed aerobic oxidative esterification of acetophenones with alcohols using molecular oxygen has been developed to form a broad range of α-ketoesters in good yields. In addition to reporting scope and limitations of our new method, mechanism studies are reported that reveal that the carbonyl oxygen in the ester mainly originated from dioxygen.

  19. Can laccases catalyze bond cleavage in lignin?

    DEFF Research Database (Denmark)

    Munk, Line; Sitarz, Anna Katarzyna; Kalyani, Dayanand

    2015-01-01

    illustrations of the putative laccase catalyzed reactions, including the possible reactions of the reactive radical intermediates taking place after the initial oxidation of the phenol-hydroxyl groups, we show that i) Laccase activity is able to catalyze bond cleavage in low molecular weight phenolic lignin......-substituted phenols, benzenethiols, polyphenols, and polyamines, which may be oxidized. In addition, the currently available analytical methods that can be used to detect enzyme catalyzed changes in lignin are summarized, and an improved nomenclature for unequivocal interpretation of the action of laccases on lignin...

  20. Asymmetric Stetter reactions catalyzed by thiamine diphosphate-dependent enzymes.

    Science.gov (United States)

    Kasparyan, Elena; Richter, Michael; Dresen, Carola; Walter, Lydia S; Fuchs, Georg; Leeper, Finian J; Wacker, Tobias; Andrade, Susana L A; Kolter, Geraldine; Pohl, Martina; Müller, Michael

    2014-12-01

    The intermolecular asymmetric Stetter reaction is an almost unexplored transformation for biocatalysts. Previously reported thiamine diphosphate (ThDP)-dependent PigD from Serratia marcescens is the first enzyme identified to catalyze the Stetter reaction of α,β-unsaturated ketones (Michael acceptor substrates) and α-keto acids. PigD is involved in the biosynthesis of the potent cytotoxic agent prodigiosin. Here, we describe the investigation of two new ThDP-dependent enzymes, SeAAS from Saccharopolyspora erythraea and HapD from Hahella chejuensis. Both show a high degree of homology to the amino acid sequence of PigD (39 and 51 %, respectively). The new enzymes were heterologously overproduced in Escherichia coli, and the yield of soluble protein was enhanced by co-expression of the chaperone genes groEL/ES. SeAAS and HapD catalyze intermolecular Stetter reactions in vitro with high enantioselectivity. The enzymes possess a characteristic substrate range with respect to Michael acceptor substrates. This provides support for a new type of ThDP-dependent enzymatic activity, which is abundant in various species and not restricted to prodigiosin biosynthesis in different strains. Moreover, PigD, SeAAS, and HapD are also able to catalyze asymmetric carbon-carbon bond formation reactions of aldehydes and α-keto acids, resulting in 2-hydroxy ketones.

  1. Chloride-catalyzed corrosion of plutonium in glovebox atmospheres

    International Nuclear Information System (INIS)

    Burgess, M.; Haschke, J.M.; Allen, T.H.; Morales, L.A.; Jarboe, D.M.; Puglisi, C.V.

    1998-04-01

    Characterization of glovebox atmospheres and the black reaction product formed on plutonium surfaces shows that the abnormally rapid corrosion of components in the fabrication line is consistent with a complex salt-catalyzed reaction involving gaseous hydrogen chloride (HCl) and water. Analytical data verify that chlorocarbon and HCl vapors are presented in stagnant glovebox atmospheres. Hydrogen chloride concentrations approach 7 ppm at some locations in the glovebox line. The black corrosion product is identified as plutonium monoxide monohydride (PuOH), a product formed by hydrolysis of plutonium in liquid water and salt solutions at room temperature. Plutonium trichloride (PuCl 3 ) produced by reaction of HCl at the metal surface is deliquescent and apparently forms a highly concentrated salt solution by absorbing moisture from the glovebox atmosphere. Rapid corrosion is attributed to the ensuing salt-catalyzed reaction between plutonium and water. Experimental results are discussed, possible involvement of hydrogen fluoride (HF) is examined, and methods of corrective action are presented in this report

  2. Bismuth-catalyzed and doped silicon nanowires for one-pump-down fabrication of radial junction solar cells.

    Science.gov (United States)

    Yu, Linwei; Fortuna, Franck; O'Donnell, Benedict; Jeon, Taewoo; Foldyna, Martin; Picardi, Gennaro; Roca i Cabarrocas, Pere

    2012-08-08

    Silicon nanowires (SiNWs) are becoming a popular choice to develop a new generation of radial junction solar cells. We here explore a bismuth- (Bi-) catalyzed growth and doping of SiNWs, via vapor-liquid-solid (VLS) mode, to fabricate amorphous Si radial n-i-p junction solar cells in a one-pump-down and low-temperature process in a single chamber plasma deposition system. We provide the first evidence that catalyst doping in the SiNW cores, caused by incorporating Bi catalyst atoms as n-type dopant, can be utilized to fabricate radial junction solar cells, with a record open circuit voltage of V(oc) = 0.76 V and an enhanced light trapping effect that boosts the short circuit current to J(sc) = 11.23 mA/cm(2). More importantly, this bi-catalyzed SiNW growth and doping strategy exempts the use of extremely toxic phosphine gas, leading to significant procedure simplification and cost reduction for building radial junction thin film solar cells.

  3. Palladium-Catalyzed Synthesis of Natural and Unnatural 2-, 5-, and 7-Oxygenated Carbazole Alkaloids from N-Arylcyclohexane Enaminones

    Directory of Open Access Journals (Sweden)

    Joaquín Tamariz

    2013-08-01

    Full Text Available A palladium-catalyzed synthesis of the carbazole framework is described, including the preparation of 2-, 5-, and 7-oxygenated natural and unnatural carbazole alkaloids. A series of N-arylcyclohexane enaminones, generated by condensation of cyclohexane-1,3-dione with diverse anilines, were aromatized by a Pd(0-catalyzed thermal treatment to afford the corresponding diarylamines. The latter were submitted to a Pd(II-catalyzed cyclization and methylation processes to provide the desired carbazoles, including clausine V. Following an inverse strategy, a new and short total synthesis of glycoborine is also reported.

  4. Metal-ion catalyzed polymerization in the eutectic phase in water-ice

    DEFF Research Database (Denmark)

    Monnard, Pierre-Alain; Szostak, Jack W.

    2008-01-01

    The emergence of an RNA world requires among other processes the non-enzymatic, template-directed replication of genetic polymers such as RNA or related nucleic acids, possibly catalyzed by metal ions. The absence of uridilate derivative polymerization on adenine containing templates has been...... the main issue preventing an efficient template-directed RNA polymerization. We report here the investigation of template-directed RNA polymerization in the eutectic phase in water-ice. In particular, it was found that activated Uridilate monomers in the presence of metal-ion catalysts could efficiently......-pairing opportunities. These results suggest that a template-directed RNA polymerization catalyzed by metal-ions could be carried out under eutectic phase in water-ice conditions....

  5. Biodiesel production by enzyme-catalyzed transesterification

    Directory of Open Access Journals (Sweden)

    Stamenković Olivera S.

    2005-01-01

    Full Text Available The principles and kinetics of biodiesel production from vegetable oils using lipase-catalyzed transesterification are reviewed. The most important operating factors affecting the reaction and the yield of alkyl esters, such as: the type and form of lipase, the type of alcohol, the presence of organic solvents, the content of water in the oil, temperature and the presence of glycerol are discussed. In order to estimate the prospects of lipase-catalyzed transesterification for industrial application, the factors which influence the kinetics of chemically-catalysed transesterification are also considered. The advantages of lipase-catalyzed transesterification compared to the chemically-catalysed reaction, are pointed out. The cost of down-processing and ecological problems are significantly reduced by applying lipases. It was also emphasized that lipase-catalysed transesterification should be greatly improved in order to make it commercially applicable. The further optimization of lipase-catalyzed transesterification should include studies on the development of new reactor systems with immobilized biocatalysts and the addition of alcohol in several portions, and the use of extra cellular lipases tolerant to organic solvents, intracellular lipases (i.e. whole microbial cells and genetically-modified microorganisms ("intelligent" yeasts.

  6. Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes.

    Science.gov (United States)

    Deb, Arghya; Bag, Sukdev; Kancherla, Rajesh; Maiti, Debabrata

    2014-10-01

    Palladium-catalyzed coupling between aryl halides and alkenes (Mizoroki-Heck reaction) is one of the most popular reactions for synthesizing complex organic molecules. The limited availability, problematic synthesis, and higher cost of aryl halide precursors (or their equivalents) have encouraged exploration of direct olefination of aryl carbon-hydrogen (C-H) bonds (Fujiwara-Moritani reaction). Despite significant progress, the restricted substrate scope, in particular noncompliance of unactivated aliphatic olefins, has discouraged the use of this greener alternative. Overcoming this serious limitation, we report here a palladium-catalyzed chelation-assisted ortho C-H bond olefination of phenylacetic acid derivatives with unactivated, aliphatic alkenes in good to excellent yields with high regio- and stereoselectivities. The versatility of this operationally simple method has been demonstrated through drug diversification and sequential C-H olefination for synthesizing divinylbenzene derivatives.

  7. Rhodium(III)- and iridium(III)-catalyzed C7 alkylation of indolines with diazo compounds.

    Science.gov (United States)

    Ai, Wen; Yang, Xueyan; Wu, Yunxiang; Wang, Xuan; Li, Yuanchao; Yang, Yaxi; Zhou, Bing

    2014-12-22

    A Rh(III)-catalyzed procedure for the C7-selective C-H alkylation of various indolines with α-diazo compounds at room temperature is reported. The advantages of this process are: 1) simple, mild, and pH-neutral reaction conditions, 2) broad substrate scope, 3) complete regioselectivity, 4) no need for an external oxidant, and 5) N2 as the sole byproduct. Furthermore, alkylation and bis-alkylation of carbazoles at the C1 and C8 positions have also been developed. More significantly, for the first time, a successful Ir(III)-catalyzed intermolecular insertion of arene C-H bonds into α-diazo compounds is reported. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Influence of the catalyst type on the growth of carbon nanotubes via methane chemical vapor deposition

    NARCIS (Netherlands)

    Jodin, Lucie; Dupuis, Anne-Claire; Rouvière, Emmanuelle; Reiss, Peter

    2006-01-01

    The preparation of the catalyst is one of the key parameters which governs the quality of carbon nanotubes (CNTs) grown by catalyzed chemical vapor deposition (CVD). We investigated the influence of three different procedures of catalyst preparation on the type and diameter of CNTs formed under

  9. Practical and General Palladium-Catalyzed Synthesis of Ketones from Internal Olefins

    KAUST Repository

    Morandi, Bill

    2013-01-16

    Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features.

  10. Practical and General Palladium-Catalyzed Synthesis of Ketones from Internal Olefins

    KAUST Repository

    Morandi, Bill; Wickens, Zachary K.; Grubbs, Robert H.

    2013-01-01

    Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features.

  11. Iodine-catalyzed diazo activation to access radical reactivity.

    Science.gov (United States)

    Li, Pan; Zhao, Jingjing; Shi, Lijun; Wang, Jin; Shi, Xiaodong; Li, Fuwei

    2018-05-17

    Transition-metal-catalyzed diazo activation is a classical way to generate metal carbene, which are valuable intermediates in synthetic organic chemistry. An alternative iodine-catalyzed diazo activation is disclosed herein under either photo-initiated or thermal-initiated conditions, which represents an approach to enable carbene radical reactivity. This metal-free diazo activation strategy were successfully applied into olefin cyclopropanation and epoxidation, and applying this method to pyrrole synthesis under thermal-initiated conditions further demonstrates the unique reactivity using this method over typical metal-catalyzed conditions.

  12. Linking deposit morphology and clogging in subsurface remediation: Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Mays, David C. [University of Colorado Denver

    2013-12-11

    Groundwater is a crucial resource for water supply, especially in arid and semiarid areas of the United States west of the 100th meridian. Accordingly, remediation of contaminated groundwater is an important application of science and technology, particularly for the U.S. Department of Energy (DOE), which oversees a number of groundwater remediation sites from Cold War era mining. Groundwater remediation is complex, because it depends on identifying, locating, and treating contaminants in the subsurface, where remediation reactions depend on interacting geological, hydrological, geochemical, and microbiological factors. Within this context, permeability is a fundamental concept, because it controls the rates and pathways of groundwater flow. Colloid science is intimately related to permeability, because when colloids are present (particles with equivalent diameters between 1 nanometer and 10 micrometers), changes in hydrological or geochemical conditions can trigger a detrimental reduction in permeability called clogging. Accordingly, clogging is a major concern in groundwater remediation. Several lines of evidence suggest that clogging by colloids depends on (1) colloid deposition, and (2) deposit morphology, that is, the structure of colloid deposits, which can be quantified as a fractal dimension. This report describes research, performed under a 2-year, exploratory grant from the DOE’s Subsurface Biogeochemical Research (SBR) program. This research employed a novel laboratory technique to simultaneously measure flow, colloid deposition, deposit morphology, and permeability in a flow cell, and also collected field samples from wells at the DOE’s Old Rifle remediation site. Field results indicate that suspended solids at the Old Rifle site have fractal structures. Laboratory results indicate that clogging is associated with colloid deposits with smaller fractal dimensions, in accordance with previous studies on initially clean granular media. Preliminary

  13. International Standard Problem 40 - Aerosol Deposition and Resuspension. Final Comparison Report

    International Nuclear Information System (INIS)

    De Los Reyes, Alfredo Castelo; Areia Capitao, Joaquim; De Santi, Giovanni

    1999-02-01

    -October 1997 and the deadline for submission of the results of this second phase was the end of January 1998. A first draft of this comparison report was produced in March 1998, followed by a workshop in Ispra in mid-March. Two errors in the supplied data had been detected and were communicated to the participants in this workshop, one concerning the steam flow rate in the deposition phase of the exercise and the other the size distribution of the resuspended aerosols in the resuspension phase. The decision whether or not to re-do their calculations was left to the each ISP participant and the deadline for the submission of new results, with these or other modifications relative to the previous ones, was the end of May 1998. These new calculations, having been performed in open conditions, are presented separately in this report. The final draft of the comparison report was distribute in June 1998, followed by a final workshop in Ispra the same month. This report is divided into six main sections, one concerning the experimental set-up and results, two each for the deposition and resuspension phases of the International Standard Problem (blind and open calculations), and one on general conclusions and recommendations. According to the opinion of the ISP participants, the results in the two sections on the deposition and resuspension exercises are listed by computer code and, for each code, by organisation. The calculations submitted by the Joint Research Centre are included together with the others. Although the JRC staff who performed the calculations did not have access to the experimental results before submitting their results, their knowledge of the facility puts their calculations in a separate class

  14. Enantioselective Copper-Catalyzed Carboetherification of Unactivated Alkenes**

    Science.gov (United States)

    Bovino, Michael T.; Liwosz, Timothy W.; Kendel, Nicole E.; Miller, Yan; Tyminska, Nina

    2014-01-01

    Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein is reported a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols that terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition state calculations support a cis-oxycupration stereochemistry-determining step. PMID:24798697

  15. Palladium-Catalyzed Enantioselective C-H Olefination of Diaryl Sulfoxides through Parallel Kinetic Resolution and Desymmetrization.

    Science.gov (United States)

    Zhu, Yu-Chao; Li, Yan; Zhang, Bo-Chao; Zhang, Feng-Xu; Yang, Yi-Nuo; Wang, Xi-Sheng

    2018-03-07

    The first example of Pd II -catalyzed enantioselective C-H olefination with non-chiral or racemic sulfoxides as directing groups was developed. A variety of chiral diaryl sulfoxides were synthesized with high enantioselectivity (up to 99 %) through both desymmetrization and parallel kinetic resolution (PKR). This is the first report of Pd II -catalyzed enantioselective C(sp 2 )-H functionalization through PKR, and it represents a novel strategy to construct sulfur chiral centers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Cu-Catalyzed Asymmetric Allylic Alkylation of Phosphonates and Phosphine Oxides with Grignard Reagents

    NARCIS (Netherlands)

    Hornillos, Valentin; Perez, Manuel; Fananas-Mastral, Martin; Feringa, Ben L.

    An efficient and highly enantioselective copper-catalyzed allylic alkylation of phosphonates and phosphine oxides with Grignard reagents and Taniaphos or phosphoramidites as chiral ligands is reported. Transformation of these products leads to a variety of new phosphorus-containing chiral

  17. Intracavitary deposits on Essure® hysteroscopic sterilization devices : A case report

    NARCIS (Netherlands)

    Maassen, L. W.; van Gastel, Maatje D A; Lentjes, E. G.W.M.; Bongers, M. Y.; Veersema, S.

    2017-01-01

    Objective To study the composition of intracavitary deposits on Essure® hysteroscopic sterilization devices. Design Case report. Setting Reproductive Medicine and Gynecology department of a University Hospital. Patient(s) A 39 years old patient presenting with a request for surgical removal of

  18. Representing Rate Equations for Enzyme-Catalyzed Reactions

    Science.gov (United States)

    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…

  19. Catalyzing RE Project Development

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Qinhua [Iowa State Univ., Ames, IA (United States)

    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

  1. Copper-Catalyzed Synthesis of Trifluoroethylarenes from Benzylic Bromodifluoroacetates.

    Science.gov (United States)

    Ambler, Brett R; Zhu, Lingui; Altman, Ryan A

    2015-08-21

    Trifluoroethylarenes are found in a variety of biologically active molecules, and strategies for accessing this substructure are important for developing therapeutic candidates and biological probes. Trifluoroethylarenes can be directly accessed via nucleophilic trifluoromethylation of benzylic electrophiles; however, current catalytic methods do not effectively transform electron-deficient substrates and heterocycles. To address this gap, we report a Cu-catalyzed decarboxylative trifluoromethylation of benzylic bromodifluoroacetates. To account for the tolerance of sensitive functional groups, we propose an inner-sphere mechanism of decarboxylation.

  2. High-pressure catalytic chemical vapor deposition of ferromagnetic ruthenium-containing carbon nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Khavrus, Vyacheslav O., E-mail: V.Khavrus@ifw-dresden.de; Ibrahim, E. M. M.; Bachmatiuk, Alicja; Ruemmeli, Mark H.; Wolter, A. U. B.; Hampel, Silke; Leonhardt, Albrecht [IFW Dresden (Germany)

    2012-06-15

    We report on the high-pressure catalytic chemical vapor deposition (CCVD) of ruthenium nanoparticles (NPs) and single-walled carbon nanotubes (SWCNTs) by means of gas-phase decomposition of acetonitrile and ruthenocene in a tubular quartz flow reactor at 950 Degree-Sign C and at elevated pressures (between 2 and 8 bar). The deposited material consists of Ru metal cores with sizes ranging between 1 and 3 nm surrounded by a carbon matrix. The high-pressure CCVD seems to be an effective route to obtain composite materials containing metallic NPs, Ru in this work, inside a nanostructured carbon matrix protecting them from oxidation in ambient air. We find that in contradiction to the weak paramagnetic properties characterizing bulk ruthenium, the synthesized samples are ferromagnetic as predicted for nanosized particles of nonmagnetic materials. At low pressure, the very small ruthenium catalyst particles are able to catalyze growth of SWCNTs. Their yield decreases with increasing reaction pressure. Transmission electron microscopy, selected area energy-dispersive X-ray analysis, Raman spectroscopy, and magnetic measurements were used to analyze and confirm properties of the synthesized NPs and nanotubes. A discussion on the growth mechanism of the Ru-containing nanostructures is presented.

  3. Sputter deposition on gas diffusion electrodes of Pt-Au nanoclusters for methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Giorgi, L.; Giorgi, R.; Gagliardi, S.; Serra, E. [ENEA Casaccia Research Center, Rome (Italy). Physics Technologies and New Materials; Alvisi, M.; Signore, M.A. [ENEA Brindisi Research Center, Brindisi (Italy). Physics Technologies and New Materials

    2008-07-01

    Polymer electrolyte fuel cells (PEFCs) are suited for use in commercial electrical vehicle and electric power applications. The gas diffusion electrodes of PEFCs are catalyzed by the deposition of platinum (Pt) nanoparticles on carbon powder. The particles must be localized on the electrode surface in order to achieve high electrocatalyst utilization. This study discussed a method of preparing PEFC electrodes using sputter deposition of a Pt-gold (Au) alloy nanoparticles on carbon powders. The method was designed to improve electrode performance and catalyst utilization. The nano-sized alloy clusters were deposited on a gas diffusion electrode at room temperature. The deposits were then characterized using field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) in order to examine the effect of the deposition technique on the nano-morphology and electrocatalytic performance of the electrode. Results of the study showed that the technique can be used in the large-scale manufacture of fuel cell electrodes. 3 refs., 1 fig.

  4. Copper-catalyzed oxidative Heck reactions between alkyltrifluoroborates and vinyl arenes.

    Science.gov (United States)

    Liwosz, Timothy W; Chemler, Sherry R

    2013-06-21

    We report herein that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. The reaction is catalyzed by a Cu(OTf)2/1,10-phenanthroline with MnO2 as the stoichiometric oxidant. In addition to the alkyl Heck, amination, esterification, and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Evidence for an alkyl radical intermediate is presented.

  5. Synthesis of phenanthridines via palladium-catalyzed picolinamide-directed sequential C–H functionalization

    Directory of Open Access Journals (Sweden)

    Ryan Pearson

    2013-05-01

    Full Text Available We report a new synthesis of phenanthridines based on palladium-catalyzed picolinamide-directed sequential C–H functionalization reactions starting from readily available benzylamine and aryl iodide precursors. Under the catalysis of Pd(OAc2, the ortho-C–H bond of benzylpicolinamides is first arylated with an aryl iodide. The resulting biaryl compound is then subjected to palladium-catalyzed picolinamide-directed intramolecular dehydrogenative C–H amination with PhI(OAc2 oxidant to form the corresponding cyclized dihydrophenanthridines. The benzylic position of these dihydrophenanthridines could be further oxidized with Cu(OAc2, removing the picolinamide group and providing phenathridine products. The cyclization and oxidation could be carried out in a single step and afford phenathridines in moderate to good yields.

  6. The mechanism of transition-metal (Cu or Pd)-catalyzed synthesis of benzimidazoles from amidines: theoretical investigation.

    Science.gov (United States)

    Li, Juan; Gu, Honghong; Wu, Caihong; Du, Lijuan

    2014-11-28

    In this study, the Cu(OAc)2- and [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines were theoretically investigated using density functional theory calculations. For the Cu-catalyzed system, our calculations supported a four-step-pathway involving C-H activation of an arene with Cu(II) via concerted metalation-deprotonation (CMD), followed by oxidation of the Cu(II) intermediate and deprotonation of the imino group by Cu(III), and finally reductive elimination from Cu(III). In our calculations, the barriers for the CMD step and the oxidation step are the same. The results are different from the ones reported by Fu et al. in which the whole reaction mechanism includes three steps and the CMD step is rate determining. On the basis of the calculation results for the [PdCl2(PhCN)2]-catalyzed system, C-H bond breaking by CMD occurs first, followed by the rate-determining C-N bond formation and N-H deprotonation. Pd(III) species is not involved in the [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines.

  7. Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: synergetic effect of ligands and barium enolates.

    Science.gov (United States)

    Chen, Wenyong; Chen, Ming; Hartwig, John F

    2014-11-12

    We report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from (R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures.

  8. CTR plasma engineering studies. Annual progress report, 1 November 1983-30 October 1984

    International Nuclear Information System (INIS)

    Miley, G.H.

    1984-01-01

    This report covers research on the following topics: (1) transport in compact tori, (2) bremsstrahlung energy deposition in first wall materials, (3) Coulombic energy transfer collisions, (4) magnetic helicity injection study, (5) blankets for tritium catalyzed deuterium fusion reactors, (6) exploratory studies of applications of optimal control theory, (7) design of a burn dynamic experiment, (8) alpha driven low frequency fast magnetosonic wave microinstability in tandem mirror, (9) fusion product heating and confinement in a tandem mirror, and (10) velocity-space particle loss in field reversed configurations

  9. Glutathiolactaldehyde as a probe of the overall stereochemical course of glyoxalase-I catalyzed reactions

    International Nuclear Information System (INIS)

    Brush, E.J.; Kozarich, J.W.

    1986-01-01

    The overall stereochemical course of the reactions catalyzed by glyoxalase-I (GX-I) has remained elusive as the substrates are equilibrium mixtures of rapidly interconverting diastereomeric thiohemiacetals. However, with the discovery of inverse substrate processing by Kozarich and coworkers, it is possible to design GX-I substrate analogs that are intrinsically more stable than the thiohemiacetals. Hence, Chari and Kozarich reported that glutathiohydroxyacetone (GHA, GSCH 2 COCH 2 OH) undergoes GX-I catalyzed exchange of the pro-S hydroxymethyl proton with solvent deuterium. Their data suggest that GX-I processes a single diastereomeric thiohemiacetal, and are consistent with a cis-enediol intermediate. To test this hypothesis and to follow the overall stereochemistry on a single substrate, they have prepared glutathiolactaldehyde (GLA, GSCH 2 CHOHCHO) as a potential inverse substrate. Human erythrocyte GX-I catalyzes the isomerization of GLA to GHA as evidenced by UV and NMR spectra of the product. Solvent deuterium is incorporated into the hydroxymethyl position, and NMR data suggest that incorporation is stereospecific. Furthermore, 50% of the expected amount of GHA is produced indicating that only one diastereomer of GLA is processed by GX-I. Identification of the absolute stereochemistry of the substrate diastereomer will lead to a clarification of the overall stereochemical and mechanistic course of GX-I catalyzed reactions

  10. Geology and recognition criteria for veinlike uranium deposits of the lower to middle Proterozoic unconformity and strata-related types. Final report

    International Nuclear Information System (INIS)

    Dahlkamp, F.J.; Adams, S.S.

    1981-01-01

    The discovery of the Rabbit Lake deposit, Saskatchewan, in 1968 and the East Alligator Rivers district, Northern Territory, Australia, in 1970 established the Lower-Middle Proterozoic veinlike-type deposits as one of the major types of uranium deposits. The term veinlike is used in order to distinguish it from the classical magmatic-hydrothermal vein or veintype deposits. The veinlike deposits account for between a quarter and a third of the Western World's proven uranium reserves. Lower-Middle Proterozoic veinlike deposits, as discussed in this report include several subtypes of deposits, which have some significantly different geologic characteristics. These various subtypes appear to have formed from various combinations of geologic processes ranging from synsedimentary uranium precipitation through some combination of diagenesis, metamorphism, metasomatism, weathering, and deep burial diagenesis. Some of the deposit subtypes are based on only one or two incompletely described examples; hence, even the classification presented in this report may be expected to change. Geologic characteristics of the deposits differ significantly between most districts and in some cases even between deposits within districts. Emphasis in this report is placed on deposit descriptions and the interpretations of the observers

  11. Geology and recognition criteria for veinlike uranium deposits of the lower to middle Proterozoic unconformity and strata-related types. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Dahlkamp, F.J.; Adams, S.S.

    1981-01-01

    The discovery of the Rabbit Lake deposit, Saskatchewan, in 1968 and the East Alligator Rivers district, Northern Territory, Australia, in 1970 established the Lower-Middle Proterozoic veinlike-type deposits as one of the major types of uranium deposits. The term veinlike is used in order to distinguish it from the classical magmatic-hydrothermal vein or veintype deposits. The veinlike deposits account for between a quarter and a third of the Western World's proven uranium reserves. Lower-Middle Proterozoic veinlike deposits, as discussed in this report include several subtypes of deposits, which have some significantly different geologic characteristics. These various subtypes appear to have formed from various combinations of geologic processes ranging from synsedimentary uranium precipitation through some combination of diagenesis, metamorphism, metasomatism, weathering, and deep burial diagenesis. Some of the deposit subtypes are based on only one or two incompletely described examples; hence, even the classification presented in this report may be expected to change. Geologic characteristics of the deposits differ significantly between most districts and in some cases even between deposits within districts. Emphasis in this report is placed on deposit descriptions and the interpretations of the observers.

  12. Effect of PW12–GPK on the acid characteristics of Ni-, Pd- and Pt- catalysts deposited onto pillared Al montmorillonite

    Directory of Open Access Journals (Sweden)

    D. Zhumadullaev

    2012-03-01

    Full Text Available Acid characteristics of Ni-, Pd-, Pt- catalyzers , deposited to Al pillared CaH montmorillonite modified by heteropolyacid H3PW12O40·xH2O (PW12 by ammonia thermoadsorbtion method has been studied.

  13. Material and orientation dependent activity for heterogeneously catalyzed carbon-bromine bond homolysis

    Energy Technology Data Exchange (ETDEWEB)

    Walch, Hermann; Gutzler, Rico; Sirtl, Thomas; Eder, Georg; Lackinger, Markus [LMU Munich, Section Crystallography (Germany)

    2010-07-01

    Adsorption of the organic molecule 1,3,5-tris(4-bromophenyl)benzene on different metallic substrates, namely Cu(111), Ag(111) and Ag(110) has been studied by variable temperature Scanning Tunneling Microscopy (STM). Depending on substrate temperature, material and orientation, we observe a surface-catalyzed dehalogenation reaction. Deposition onto the catalytically active substrates Cu(111) and Ag(110) held at room temperature leads to cleavage of the carbon-bromine bonds and subsequent formation of protopolymers, i.e radical metal coordination complexes. However upon deposition on Ag(111) no such reaction has been observed. Instead, various self-assembled ordered structures based on intact molecules could be identified. Also sublimation onto either substrate held at 80 K did not result in any dehalogenation, thereby exemplifying that the dehalogenation reaction is thermally activated. We explain the differences in catalytic activity by charge transfer into unoccupied molecular orbitals and subsequent destabilization of the C-Br bond, whereby enhanced molecule-substrate interaction leads to an increasing magnitude of charge transfer. The interaction strength follows the general reactivity order Cu>Ag>Au for (111) faces and is generally enhanced on higher corrugated surfaces as the (110) facet in case of fcc substrates.

  14. Palladium catalyzed selective distal C-H olefination of biaryl systems.

    Science.gov (United States)

    Maity, Soham; Hoque, Ehtasimul; Dhawa, Uttam; Maiti, Debabrata

    2016-11-29

    Palladium catalyzed selective distal C-H activation with nitrile based templates has been of significant research interest in recent times. In this report, we disclose the distal C-H olefination of biphenyl systems with high regio- and stereo-selectivity and useful synthetic yields. The utility of this method has been demonstrated through its wide olefin scope, its operation at the gram scale and the easy removal/recovery of the directing group.

  15. Investigation of the growth and in situ heating transmission electron microscopy analysis of Ag2S-catalyzed ZnS nanowires

    Science.gov (United States)

    Kim, Jung Han; Kim, Jong Gu; Song, Junghyun; Bae, Tae-Sung; Kim, Kyou-Hyun; Lee, Young-Seak; Pang, Yoonsoo; Oh, Kyu Hwan; Chung, Hee-Suk

    2018-04-01

    We investigated the semiconductor-catalyzed formation of semiconductor nanowires (NWs) - silver sulfide (Ag2S)-catalyzed zinc sulfide (ZnS) NWs - based on a vapor-liquid-solid (VLS) growth mechanism through metal-organic chemical vapor deposition (MOCVD) with a Ag thin film. The Ag2S-catalyzed ZnS NWs were confirmed to have a wurtzite structure with a width and length in the range of ∼30 nm to ∼80 nm and ∼1 μm, respectively. Using extensive transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS) analyses from plane and cross-sectional viewpoints, the ZnS NWs were determined to have a c-axis, [0001] growth direction. In addition, the catalyst at the top of the ZnS NWs was determined to consist of a Ag2S phase. To support the Ag2S-catalyzed growth of the ZnS NWs by a VLS reaction, an in situ heating TEM experiment was conducted from room temperature to 840 °C. During the experiment, the melting of the Ag2S catalyst in the direction of the ZnS NWs was first observed at approximately 480 °C along with the formation of a carbon (C) shell. Subsequently, the Ag2S catalyst melted completely into the ZnS NWs at approximately 825 °C. As the temperature further increased, the Ag2S and ZnS NWs continuously melted and vaporized up to 840 °C, leaving only the C shell behind. Finally, a possible growth mechanism was proposed based on the structural and chemical investigations.

  16. Enhanced photoelectrochemical properties of copper-assisted catalyzed etching black silicon by electrodepositing cobalt

    Science.gov (United States)

    Cai, Weidong; Xiong, Haiying; Su, Xiaodong; Zhou, Hao; Shen, Mingrong; Fang, Liang

    2017-11-01

    Black silicon (Si) photoelectrodes are promising for improving the performance of photoelectrochemical (PEC) water splitting. Here, we report the fabrication of p-black Si and n+p-black Si photocathodes via a controllable copper-assisted catalyzed etching method. The etching process affects only the topmost less than 200 nm of Si and is independent of the surface doping. The synergistic effects of the excellent light harvesting of the black Si and the improved charge transfer properties of the p-n junction boost the production and utilization of photogenerated carriers. The mean reflectance of the pristine Si samples is about 10% from 400 to 950 nm, while that of the black Si samples is reduced as low as 5%. In addition, the PEC properties of the n+p-black Si photocathode can be further enhanced by depositing a cobalt (Co) layer. Compared with the p-Si sample, the onset potential of the Co/n+p-black Si photocathode is positively shifted by 560 mV to 0.33 V vs. reversible hydrogen electrode and the saturation photocurrent density is increased from 22.7 to 32.6 mA/cm2. The design of the Co/n+p-black Si photocathode offers an efficient strategy for preparing PEC solar energy conversion devices.

  17. Energy harvesting by implantable abiotically catalyzed glucose fuel cells

    Science.gov (United States)

    Kerzenmacher, S.; Ducrée, J.; Zengerle, R.; von Stetten, F.

    Implantable glucose fuel cells are a promising approach to realize an autonomous energy supply for medical implants that solely relies on the electrochemical reaction of oxygen and glucose. Key advantage over conventional batteries is the abundant availability of both reactants in body fluids, rendering the need for regular replacement or external recharging mechanisms obsolete. Implantable glucose fuel cells, based on abiotic catalysts such as noble metals and activated carbon, have already been developed as power supply for cardiac pacemakers in the late-1960s. Whereas, in vitro and preliminary in vivo studies demonstrated their long-term stability, the performance of these fuel cells is limited to the μW-range. Consequently, no further developments have been reported since high-capacity lithium iodine batteries for cardiac pacemakers became available in the mid-1970s. In recent years research has been focused on enzymatically catalyzed glucose fuel cells. They offer higher power densities than their abiotically catalyzed counterparts, but the limited enzyme stability impedes long-term application. In this context, the trend towards increasingly energy-efficient low power MEMS (micro-electro-mechanical systems) implants has revived the interest in abiotic catalysts as a long-term stable alternative. This review covers the state-of-the-art in implantable abiotically catalyzed glucose fuel cells and their development since the 1960s. Different embodiment concepts are presented and the historical achievements of academic and industrial research groups are critically reviewed. Special regard is given to the applicability of the concept as sustainable micro-power generator for implantable devices.

  18. New process of the preparation of catalyzed gas diffusion electrode for PEM fuel cells based on ultrasonic direct solution spray reaction method

    Energy Technology Data Exchange (ETDEWEB)

    Oishi, K.; Savadogo, O. [Ecole Polytechnique de Montreal, Montreal, PQ (Canada). Laboratoire de nouveaux materiaux pour l' energie et l' electrochimie

    2008-07-01

    This paper reported on a newly developed process for in-situ catalyst deposition on gas diffusion electrodes (GDE) for polymer electrolyte fuel cells. This process has the potential to reduce the number of steps for catalyzed GDE fabrication. In addition, the process offers economic advantages for the fuel cell commercialization. In this study, a home-made catalyst maker with ultrasonic spray method was used to prepare a solution of the carbon supported platinum catalyst on the GDL. The sprayed catalyst powder consisted of carbon support. The catalyst particles did not prevent gas flow channels on the GDL. The catalyst layer was shown to be located only on the top surface of the GDL and was not packed into its flow channel. Results of Cross-section SEM image, crystallization, micro structure and electro-catalytic activity for the oxygen reduction reaction were also discussed. 1 ref., 1 fig.

  19. Chemo- and Enantioselective Intramolecular Silver-Catalyzed Aziridinations.

    Science.gov (United States)

    Ju, Minsoo; Weatherly, Cale D; Guzei, Ilia A; Schomaker, Jennifer M

    2017-08-07

    Asymmetric nitrene-transfer reactions are a powerful tool for the preparation of enantioenriched amine building blocks. Reported herein are chemo- and enantioselective silver-catalyzed aminations which transform di- and trisubstituted homoallylic carbamates into [4.1.0]-carbamate-tethered aziridines in good yields and with ee values of up to 92 %. The effects of the substrate, silver counteranion, ligand, solvent, and temperature on both the chemoselectivity and ee value were explored. Stereochemical models were proposed to rationalize the observed absolute stereochemistry of the aziridines, which undergo nucleophilic ring opening to yield enantioenriched amines with no erosion in stereochemical integrity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Enantioselective copper-catalyzed carboetherification of unactivated alkenes.

    Science.gov (United States)

    Bovino, Michael T; Liwosz, Timothy W; Kendel, Nicole E; Miller, Yan; Tyminska, Nina; Zurek, Eva; Chemler, Sherry R

    2014-06-16

    Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein reported is a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, thus yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition-state calculations support a cis-oxycupration stereochemistry-determining step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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).

  2. Gold-Catalyzed Enantio- and Diastereoselective Syntheses of Left Fragments of Azadirachtin/Meliacarpin-Type Limonoids.

    Science.gov (United States)

    Shi, Hang; Tan, Ceheng; Zhang, Weibin; Zhang, Zichun; Long, Rong; Gong, Jianxian; Luo, Tuoping; Yang, Zhen

    2016-02-05

    Meliacarpin-type limonoids are an important class of organic insecticides. Their syntheses are challenging due to their chemical complexity. Here, we report the highly enantio- and diastereoselective synthesis of the left fragments of azadirachtin I and 1-cinnamoylmelianolone, being two important family members of meliacarpin-type limonoids, via pairwise palladium- and gold-catalyzed cascade reactions. Gold-catalyzed reactions of 1,7-diynes were performed as model studies, and the efficient construction of tetracyclic late-stage intermediates was achieved on the basis of this key transformation. Our unique route gave both of the left fragments in 23 steps from the commercially available chiral starting material (-)-carvone. This study significantly advances research on the synthesis of the meliacarpin-type limonoids.

  3. Myoglobin-Catalyzed Olefination of Aldehydes.

    Science.gov (United States)

    Tyagi, Vikas; Fasan, Rudi

    2016-02-12

    The olefination of aldehydes constitutes a most valuable and widely adopted strategy for constructing carbon-carbon double bonds in organic chemistry. While various synthetic methods have been made available for this purpose, no biocatalysts are known to mediate this transformation. Reported herein is that engineered myoglobin variants can catalyze the olefination of aldehydes in the presence of α-diazoesters with high catalytic efficiency (up to 4,900 turnovers) and excellent E diastereoselectivity (92-99.9 % de). This transformation could be applied to the olefination of a variety of substituted benzaldehydes and heteroaromatic aldehydes, also in combination with different alkyl α-diazoacetate reagents. This work provides a first example of biocatalytic aldehyde olefination and extends the spectrum of synthetically valuable chemical transformations accessible using metalloprotein-based catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Nafion®-catalyzed microwave-assisted Ritter reaction: An atom-economic solvent-free synthesis of amides

    Science.gov (United States)

    An atom-economic solvent-free synthesis of amides by the Ritter reaction of alcohols and nitriles under microwave irradiation is reported. This green protocol is catalyzed by solid supported Nafion®NR50 with improved efficiency and reduced waste production.

  5. Manganese-Catalyzed C−H Functionalizations: Hydroarylations and Alkenylations Involving an Unexpected Heteroaryl Shift

    KAUST Repository

    Wang, Chengming

    2017-06-24

    A manganese-catalyzed regio- and stereoselective hydroarylation of allenes is reported. The C−H functionalization method provides access to various alkenylated indoles in excellent yields. Moreover, a hydroarylation/cyclization cascade involving an unexpected C−N bond cleavage and aryl shift has been developed, which provides a new synthetic approach to substituted pyrroloindolones.

  6. Manganese-Catalyzed C−H Functionalizations: Hydroarylations and Alkenylations Involving an Unexpected Heteroaryl Shift

    KAUST Repository

    Wang, Chengming; Wang, Ai; Rueping, Magnus

    2017-01-01

    A manganese-catalyzed regio- and stereoselective hydroarylation of allenes is reported. The C−H functionalization method provides access to various alkenylated indoles in excellent yields. Moreover, a hydroarylation/cyclization cascade involving an unexpected C−N bond cleavage and aryl shift has been developed, which provides a new synthetic approach to substituted pyrroloindolones.

  7. Surprisingly Mild Enolate-Counterion-Free Pd(0)-Catalyzed Intramolecular Allylic Alkylations

    DEFF Research Database (Denmark)

    Madec, David; Prestat, Guillaume; Martini, Elisabetta

    2005-01-01

    Palladium-catalyzed intramolecular allylic alkylations of unsaturated EWG-activated amides can take place under phase-transfer conditions or in the presence of a crown ether. These new reaction conditions are milder and higher yielding than those previously reported. A rationalization for such an...... for such an unexpected result is put forth and validated by DFT-B3LYP calculations. The results suggest cyclization via a counterion-free (E)-enolate TS....

  8. Photoredox-Catalyzed Ketyl–Olefin Coupling for the Synthesis of Substituted Chromanols

    KAUST Repository

    Fava, Eleonora

    2016-07-21

    A visible light photoredox-catalyzed aldehyde olefin cyclization is reported. The method represents a formal hydroacylation of alkenes and alkynes and provides chromanol derivatives in good yields. The protocol takes advantage of the double role played by trialkylamines (NR3) which act as (i) electron donors for reducing the catalyst and (ii) proton donors to activate the substrate via a proton-coupled electron transfer. © 2016 American Chemical Society.

  9. Photoredox-Catalyzed Ketyl–Olefin Coupling for the Synthesis of Substituted Chromanols

    KAUST Repository

    Fava, Eleonora; Nakajima, Masaki; Nguyen, Anh L. P.; Rueping, Magnus

    2016-01-01

    A visible light photoredox-catalyzed aldehyde olefin cyclization is reported. The method represents a formal hydroacylation of alkenes and alkynes and provides chromanol derivatives in good yields. The protocol takes advantage of the double role played by trialkylamines (NR3) which act as (i) electron donors for reducing the catalyst and (ii) proton donors to activate the substrate via a proton-coupled electron transfer. © 2016 American Chemical Society.

  10. Steroid hydroxylations: A paradigm for cytochrome P450 catalyzed mammalian monooxygenation reactions

    International Nuclear Information System (INIS)

    Estabrook, Ronald W.

    2005-01-01

    The present article reviews the history of research on the hydroxylation of steroid hormones as catalyzed by enzymes present in mammalian tissues. The report describes how studies of steroid hormone synthesis have played a central role in the discovery of the monooxygenase functions of the cytochrome P450s. Studies of steroid hydroxylation reactions can be credited with showing that: (a) the adrenal mitochondrial enzyme catalyzing the 11β-hydroxylation of deoxycorticosterone was the first mammalian enzyme shown by O 18 studies to be an oxygenase; (b) the adrenal microsomal enzyme catalyzing the 21-hydroxylation of steroids was the first mammalian enzyme to show experimentally the proposed 1:1:1 stoichiometry (substrate:oxygen:reduced pyridine nucleotide) of a monooxygenase reaction; (c) application of the photochemical action spectrum technique for reversal of carbon monoxide inhibition of the 21-hydroxylation of 17α-OH progesterone was the first demonstration that cytochrome P450 was an oxygenase; (d) spectrophotometric studies of the binding of 17α-OH progesterone to bovine adrenal microsomal P450 revealed the first step in the cyclic reaction scheme of P450, as it catalyzes the 'activation' of oxygen in a monooxygenase reaction; (e) purified adrenodoxin was shown to function as an electron transport component of the adrenal mitochondrial monooxygenase system required for the activity of the 11β-hydroxylase reaction. Adrenodoxin was the first iron-sulfur protein isolated and purified from mammalian tissues and the first soluble protein identified as a reductase of a P450; (f) fractionation of adrenal mitochondrial P450 and incubation with adrenodoxin and a cytosolic (flavoprotein) fraction were the first demonstration of the reconstitution of a mammalian P450 monooxygenase reaction

  11. Kinetic Behavior of Aggregation-Exchange Growth Process with Catalyzed-Birth

    International Nuclear Information System (INIS)

    Han Anjia; Chen Yu; Lin Zhenquan; Ke Jianhong

    2007-01-01

    We propose an aggregation model of a two-species system to mimic the growth of cities' population and assets, in which irreversible coagulation reactions and exchange reactions occur between any two aggregates of the same species, and the monomer-birth reactions of one species occur by the catalysis of the other species. In the case with population-catalyzed birth of assets, the rate kernel of an asset aggregate B k of size k grows to become an aggregate B k+1 through a monomer-birth catalyzed by a population aggregate A j of size j is J(k,j) = Jkj λ . And in mutually catalyzed birth model, the birth rate kernels of population and assets are H(k,j) = Hkj η and J(k,j) = Jkj λ , respectively. The kinetics of the system is investigated based on the mean-field theory. In the model of population-catalyzed birth of assets, the long-time asymptotic behavior of the assets aggregate size distribution obeys the conventional or modified scaling form. In mutually catalyzed birth system, the asymptotic behaviors of population and assets obey the conventional scaling form in the case of η = λ = 0, and they obey the modified scaling form in the case of η = 0,λ = 1. In the case of η = λ = 1, the total mass of population aggregates and that of asset aggregates both grow much faster than those in population-catalyzed birth of assets model, and they approaches to infinite values in finite time.

  12. Novel big-bang element synthesis catalyzed by supersymmetric particle stau

    International Nuclear Information System (INIS)

    Kamimura, Masayasu; Kino, Yasushi; Hiyama, Emiko

    2010-01-01

    The extremely low isotope ratio of 6 Li had remained as a drawback of the Big-Bang Nucleosynthesis (BBN) until Pospelov proposed the 6 Li synthesis reaction catalyzed by negatively charged electroweak-scale particle X - in 2006. He remarked the catalytic enhancement of 6 Li production by about 10 8 times, as well as the life and initial abundance of X - . The present authors classified BBN catalyzed reaction into six types, i.e. (1) non-resonant transfer, (2) resonant transfer, (3) non-resonant radiative capture, (4) resonant radiative capture, (5) three-body breakup and (6) charge transfer reactions to predict absolute values of cross sections which cannot be observed experimentally. Starting from the three-body treatment for those reactions, 6 Li problems, the life-time and abundance of stau are discussed. Large change of element composition at 'late-time' big bang, generation of 9 Be by stau catalyzed reaction, 7 Li problem and stau catalyzed reactions are also discussed. Finally their relations with the supersymmetry theory and dark matter are mentioned. The basic nuclear calculations are providing quantitative base for the 'effect of nuclear reactions catalyzed by the supersymmetric particle stau on big bang nucleosynthesis'. (S. Funahashi)

  13. Muon-catalyzed fusion theory - introduction and review

    International Nuclear Information System (INIS)

    Cohen, J.S.

    1990-01-01

    Muon-catalyzed fusion (μCF) has proved to be a fruitful subject for basic physics research as well as a source of cold nuclear fusion. Experiments have demonstrated that over 100 fusions per muon can be catalyzed by formation of the dtμ molecules in mixtures of deuterium and tritium. After a brief review of the subject's history, the dtμ catalysis cycle and the principle relations used in its analysis are described. Some of the important processes in the μCF cycle are then discussed. Finally, the status of current research is appraised. (author)

  14. Metal-catalyzed living radical polymerization and radical polyaddition for precision polymer synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, M; Satoh, K [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kamigaito, M, E-mail: kamigait@apchem.nagoya-u.ac.j

    2009-08-01

    The metal-catalyzed radical addition reaction can be evolved into two different polymerization mechanisms, i.e.; chain- and step-growth polymerizations, while both the polymerizations are based on the same metal-catalyzed radical formation reaction. The former is a widely employed metal-catalyzed living radical polymerization or atom transfer radical polymerization of common vinyl monomers, and the latter is a novel metal-catalyzed radical polyaddition of designed monomer with an unconjugated C=C double bond and a reactive C-Cl bond in one molecule. The simultaneous ruthenium-catalyzed living radical polymerization of methyl acrylate and radical polyaddition of 3-butenyl 2-chloropropionate was achieved with Ru(Cp*)Cl(PPh{sub 3}){sub 2} to afford the controlled polymers, in which the homopolymer segments with the controlled chain length were connected by the ester linkage.

  15. Syntheses of Calix[4]Pyrroles by Amberlyst-15 Catalyzed Cyclocondensations of Pyrrole with Selected Ketones

    Directory of Open Access Journals (Sweden)

    Tanuja Bisht

    2007-11-01

    Full Text Available A facile and efficient protocol is reported for the synthesis of calix[4]pyrrolesand N-confused calix[4]pyrroles in moderate to excellent yields by reaction of dialkyl orcycloalkyl ketones with pyrrole catalyzed by reusable AmberlystTM-15 under eco-friendlyconditions.

  16. Respiratory trace deposition models. Final report

    International Nuclear Information System (INIS)

    Yeh, H.C.

    1980-03-01

    Respiratory tract characteristics of four mammalian species (human, dog, rat and Syrian hamster) were studied, using replica lung casts. An in situ casting techniques was developed for making the casts. Based on an idealized branch model, over 38,000 records of airway segment diameters, lengths, branching angles and gravity angles were obtained from measurements of two humans, two Beagle dogs, two rats and one Syrian hamster. From examination of the trimmed casts and morphometric data, it appeared that the structure of the human airway is closer to a dichotomous structure, whereas for dog, rat and hamster, it is monopodial. Flow velocity in the trachea and major bronchi in living Beagle dogs was measured using an implanted, subminiaturized, heated film anemometer. A physical model was developed to simulate the regional deposition characteristics proposed by the Task Group on Lung Dynamics of the ICRP. Various simulation modules for the nasopharyngeal (NP), tracheobronchial (TB) and pulmonary (P) compartments were designed and tested. Three types of monodisperse aerosols were developed for animal inhalation studies. Fifty Syrian hamsters and 50 rats were exposed to five different sizes of monodisperse fused aluminosilicate particles labeled with 169 Yb. Anatomical lung models were developed for four species (human, Beagle dog, rat and Syrian hamster) that were based on detailed morphometric measurements of replica lung casts. Emphasis was placed on developing a lobar typical-path lung model and on developing a modeling technique which could be applied to various mammalian species. A set of particle deposition equations for deposition caused by inertial impaction, sedimentation, and diffusion were developed. Theoretical models of particle deposition were developed based on these equations and on the anatomical lung models

  17. Oxygen Barrier Coating Deposited by Novel Plasma-enhanced Chemical Vapor Deposition

    DEFF Research Database (Denmark)

    Jiang, Juan; Benter, M.; Taboryski, Rafael Jozef

    2010-01-01

    We report the use of a novel plasma-enhanced chemical vapor deposition chamber with coaxial electrode geometry for the SiOx deposition. This novel plasma setup exploits the diffusion of electrons through the inner most electrode to the interior samples space as the major energy source. This confi......We report the use of a novel plasma-enhanced chemical vapor deposition chamber with coaxial electrode geometry for the SiOx deposition. This novel plasma setup exploits the diffusion of electrons through the inner most electrode to the interior samples space as the major energy source...... effect of single-layer coatings deposited under different reaction conditions was studied. The coating thickness and the carbon content in the coatings were found to be the critical parameters for the barrier property. The novel barrier coating was applied on different polymeric materials...

  18. Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex.

    Science.gov (United States)

    You, Tingjie; Wang, Zhenrong; Chen, Jiajia; Xia, Yuanzhi

    2017-02-03

    A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.

  19. Manganese Catalyzed C–H Halogenation

    Energy Technology Data Exchange (ETDEWEB)

    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

  20. Potash—A vital agricultural nutrient sourced from geologic deposits

    Science.gov (United States)

    Yager, Douglas B.

    2016-11-15

    This report summarizes the primary sources of potash in the United States. Potash is an essential nutrient that, along with phosphorus and nitrogen, is used as fertilizer for growing crops. Plants require sufficient potash to activate enzymes, which in turn catalyze chemical reactions important for water uptake and photosynthesis. When potassium is available in quantities necessary for healthy plant growth, disease resistance and physical quality are improved and crop yield and shelf life are increased. Potash is a water-soluble compound of potassium formed by geologic and hydrologic processes. The principal potash sources discussed are the large, stratiform deposits that formed during retreat and evaporation of intracontinental seas. The Paradox, Delaware, Holbrook, Michigan, and Williston sedimentary basins in the United States are examples where extensive potash beds were deposited. Ancient marine-type potash deposits that are close to the surface can be mined using conventional underground mining methods. In situ solution mining can be used where beds are too deep, making underground mining cost-prohibitive, or where underground mines are converted to in situ solution mines. Quaternary brine is another source of potash that is recovered by solar evaporation in manmade ponds. Groundwater from Pleistocene Lake Bonneville (Wendover, Utah) and the present-day Great Salt Lake in Utah are sources of potashbearing brine. Brine from these sources pumped to solar ponds is evaporated and potash concentrated for harvesting, processing, and refinement. Although there is sufficient potash to meet near-term demand, the large marine-type deposits are either geographically restricted to a few areas or are too deep to easily mine. Other regions lack sources of potash brine from groundwater or surface water. Thus, some areas of the world rely heavily on potash imports. Political, economic, and global population pressures may limit the ability of some countries from securing

  1. A theoretical study of the alkylation reaction of toluene with methanol catalyzed by acidic mordenite

    NARCIS (Netherlands)

    Vos, A.M.; Rozanska, X.; Schoonheydt, R.A.; Santen, van R.A.; Hutschka, F.; Hafner, J.

    2001-01-01

    A theoretical study of the alkylation reaction of toluene with methanol catalyzed by the acidic Mordenite (Si/Al = 23) is reported. Cluster DFT as well as periodical structure DFT calculations have been performed. Full reaction energy diagrams of the elementary reaction steps that lead to the

  2. Solvable Catalyzed Birth-Death-Exchange Competition Model of Three Species

    International Nuclear Information System (INIS)

    Wang Haifeng; Gao Yan; Zhang Heng; Lin Zhenquan

    2009-01-01

    A competition model of three species in exchange-driven aggregation growth is proposed. In the model, three distinct aggregates grow by exchange of monomers and in parallel, birth of species A is catalyzed by species B and death of species A is catalyzed by species C. The rates for both catalysis processes are proportional to kj ν and kj ω respectively, where ν(Ω) is a parameter reflecting the dependence of the catalysis reaction rate of birth (death) on the catalyst aggregate's size. The kinetic evolution behaviors of the three species are investigated by the rate equation approach based on the mean-field theory. The form of the aggregate size distribution of A-species a k (t) is found to be dependent crucially on the two catalysis rate kernel parameters. The results show that (i) in case of μ ≤ 0, the form of a k (t) mainly depends on the competition between self-exchange of species A and species-C-catalyzed death of species A; (ii) in case of ν > 0, the form of a k (t) mainly depends on the competition between species-B-catalyzed birth of species A and species-C-catalyzed death of species A. (interdisciplinary physics and related areas of science and technology)

  3. 50 CFR 600.1014 - Fee collection deposits, disbursements, records, and reports.

    Science.gov (United States)

    2010-10-01

    ... a segregated account at a federally insured financial institution for the sole purpose of depositing... calendar days before the date of deposit. Neither the deposit account nor the principal amount of deposits... entitled, at any time, to withdraw deposit interest, if any, but never deposit principal, from the deposit...

  4. Development and industrial application of catalyzer for low-temperature hydrogenation hydrolysis of Claus tail gas

    Directory of Open Access Journals (Sweden)

    Honggang Chang

    2015-10-01

    Full Text Available With the implementation of more strict national environmental protection laws, energy conservation, emission reduction and clean production will present higher requirements for sulfur recovery tail gas processing techniques and catalyzers. As for Claus tail gas, conventional hydrogenation catalyzers are gradually being replaced by low-temperature hydrogenation catalyzers. This paper concentrates on the development of technologies for low-temperature hydrogenation hydrolysis catalyzers, preparation of such catalyzers and their industrial application. In view of the specific features of SO2 hydrogenation and organic sulfur hydrolysis during low-temperature hydrogenation, a new technical process involving joint application of hydrogenation catalyzers and hydrolysis catalyzers was proposed. In addition, low-temperature hydrogenation catalyzers and low-temperature hydrolysis catalyzers suitable for low-temperature conditions were developed. Joint application of these two kinds of catalyzers may reduce the inlet temperatures in the conventional hydrogenation reactors from 280 °C to 220 °C, at the same time, hydrogenation conversion rates of SO2 can be enhanced to over 99%. To further accelerate the hydrolysis rate of organic sulfur, the catalyzers for hydrolysis of low-temperature organic sulfur were developed. In lab tests, the volume ratio of the total sulfur content in tail gas can be as low as 131 × 10−6 when these two kinds of catalyzers were used in a proportion of 5:5 in volumes. Industrial application of these catalyzers was implemented in 17 sulfur recovery tail gas processing facilities of 15 companies. As a result, Sinopec Jinling Petrochemical Company had outstanding application performances with a tail gas discharging rate lower than 77.9 mg/m3 and a total sulfur recovery of 99.97%.

  5. Heterogeneous base-catalyzed methanolysis of vegetable oils: State of art

    Directory of Open Access Journals (Sweden)

    Miladinović Marija R.

    2010-01-01

    Full Text Available Today, homogeneous base-catalyzed methanolysis is most frequently used method for industrial biodiesel production. High requirements for the quality of feedstocks and the problems related to a huge amount of wastewaters have led to the development of novel biodiesel production technologies. Among them, the most important is heterogeneous base-catalyzed methanolysis, which has been intensively investigated in the last decade in order to develop new catalytic systems, to optimize the reaction conditions and to recycle catalysts. These studies are a base for developing continuous biodiesel production on industrial scale in near future. The present work summarizes up-to-date studies on biodiesel production by heterogeneous base-catalyzed methanolysis. The main goals were to point out the application of different base compounds as catalysts, the methods of catalyst preparation, impregnation on carriers and recycling as well as the possibilities to improve existing base-catalyzed biodiesel production processes and to develop novel ones.

  6. Steady-state oxidation of cholesterol catalyzed by cholesterol oxidase in lipid bilayer membranes on platinum electrodes

    International Nuclear Information System (INIS)

    Bokoch, Michael P.; Devadoss, Anando; Palencsar, Mariela S.; Burgess, James D.

    2004-01-01

    Cholesterol oxidase is immobilized in electrode-supported lipid bilayer membranes. Platinum electrodes are initially modified with a self-assembled monolayer of thiolipid. A vesicle fusion method is used to deposit an outer leaflet of phospholipids onto the thiolipid monolayer forming a thiolipid/lipid bilayer membrane on the electrode surface. Cholesterol oxidase spontaneously inserts into the electrode-supported lipid bilayer membrane from solution and is consequently immobilized to the electrode surface. Cholesterol partitions into the membrane from buffer solutions containing cyclodextrin. Cholesterol oxidase catalyzes the oxidation of cholesterol by molecular oxygen, forming hydrogen peroxide as a product. Amperometric detection of hydrogen peroxide for continuous solution flow experiments are presented, where flow was alternated between cholesterol solution and buffer containing no cholesterol. Steady-state anodic currents were observed during exposures of cholesterol solutions ranging in concentration from 10 to 1000 μM. These data are consistent with the Michaelis-Menten kinetic model for oxidation of cholesterol as catalyzed by cholesterol oxidase immobilized in the lipid bilayer membrane. The cholesterol detection limit is below 1 μM for cholesterol solution prepared in buffered cyclodextrin. The response of the electrodes to low density lipoprotein solutions is increased upon addition of cyclodextrin. Evidence for adsorption of low density lipoprotein to the electrode surface is presented

  7. Palladium-Catalyzed Cross-Coupling Reactions of Perfluoro Organic Compounds

    Directory of Open Access Journals (Sweden)

    Masato Ohashi

    2014-09-01

    Full Text Available In this review, we summarize our recent development of palladium(0-catalyzed cross-coupling reactions of perfluoro organic compounds with organometallic reagents. The oxidative addition of a C–F bond of tetrafluoroethylene (TFE to palladium(0 was promoted by the addition of lithium iodide, affording a trifluorovinyl palladium(II iodide. Based on this finding, the first palladium-catalyzed cross-coupling reaction of TFE with diarylzinc was developed in the presence of lithium iodide, affording α,β,β-trifluorostyrene derivatives in excellent yield. This coupling reaction was expanded to the novel Pd(0/PR3-catalyzed cross-coupling reaction of TFE with arylboronates. In this reaction, the trifluorovinyl palladium(II fluoride was a key reaction intermediate that required neither an extraneous base to enhance the reactivity of organoboronates nor a Lewis acid additive to promote the oxidative addition of a C–F bond. In addition, our strategy utilizing the synergetic effect of Pd(0 and lithium iodide could be applied to the C–F bond cleavage of unreactive hexafluorobenzene (C6F6, leading to the first Pd(0-catalyzed cross-coupling reaction of C6F6 with diarylzinc compounds.

  8. Burn performance of deuterium-tritium, deuterium-deuterium, and catalyzed deuterium ICF targets

    International Nuclear Information System (INIS)

    Harris, D.B.; Blue, T.E.

    1983-01-01

    The University of Illinois hydrodynamic burn code, AFBURN, has been used to model the performance of homogeneous D-T, D 2 , and catalyzed deuterium ICF targets. Yields and gains are compared for power-producing targets. AFBURN is a one-dimensional, two-temperature, single-fluid hydrodynamic code with non-local fusion product energy deposition. The initial conditions for AFBURN are uniformly compressed targets with central hot spots. AFBURN predicts that maximum D 2 target gains are obtained for target rhoR and spark rhoR about seven times larger than the target and spark rhoR for maximum D-T target gains, that the maximum D 2 target gain is approximately one third of the maximum D-T target gain, and that the corresponding yields are approximately equal. By recycling tritium and 3 He from previous targets, D 2 target performance can be improved by about 10%. (author)

  9. Palladium-catalyzed, asymmetric Baeyer–Villiger oxidation of prochiral cyclobutanones with PHOX ligands

    KAUST Repository

    Petersen, Kimberly S.

    2011-06-01

    Described in this report is a general method for the conversion of prochiral 3-substituted cyclobutanones to enantioenriched γ-lactones through a palladium-catalyzed Baeyer-Villiger oxidation using phosphinooxazoline ligands in up to 99% yield and 81% ee. Lactones of enantiopurity ≥93% could be obtained through a single recrystallization step. Importantly, 3,3-disubtituted cyclobutanones produced enantioenriched lactones containing a β-quaternary center. © 2011 Elsevier Ltd. All rights reserved.

  10. Acid-catalyzed kinetics of indium tin oxide etching

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jae-Hyeok; Kim, Seong-Oh; Hilton, Diana L. [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Centre for Biomimetic Sensor Science, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); Cho, Nam-Joon, E-mail: njcho@ntu.edu.sg [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Centre for Biomimetic Sensor Science, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, 637459 (Singapore)

    2014-08-28

    We report the kinetic characterization of indium tin oxide (ITO) film etching by chemical treatment in acidic and basic electrolytes. It was observed that film etching increased under more acidic conditions, whereas basic conditions led to minimal etching on the time scale of the experiments. Quartz crystal microbalance was employed in order to track the reaction kinetics as a function of the concentration of hydrochloric acid and accordingly solution pH. Contact angle measurements and atomic force microscopy experiments determined that acid treatment increases surface hydrophilicity and porosity. X-ray photoelectron spectroscopy experiments identified that film etching is primarily caused by dissolution of indium species. A kinetic model was developed to explain the acid-catalyzed dissolution of ITO surfaces, and showed a logarithmic relationship between the rate of dissolution and the concentration of undisassociated hydrochloric acid molecules. Taken together, the findings presented in this work verify the acid-catalyzed kinetics of ITO film dissolution by chemical treatment, and support that the corresponding chemical reactions should be accounted for in ITO film processing applications. - Highlights: • Acidic conditions promoted indium tin oxide (ITO) film etching via dissolution. • Logarithm of the dissolution rate depended linearly on the solution pH. • Acid treatment increased ITO surface hydrophilicity and porosity. • ITO film etching led to preferential dissolution of indium species over tin species.

  11. Remote C−H Activation of Quinolines through Copper-Catalyzed Radical Cross-Coupling

    KAUST Repository

    Xu, Jun

    2016-01-12

    Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a formidable challenge in organic chemistry. Herein, we report a novel approach to activating remote C-H bonds at the C5 position of 8-aminoquinoline through copper-catalyzed sulfonylation under mild conditions. Our strategy shows high conversion efficiency, a broad substrate scope, and good toleration with different functional groups. Furthermore, our mechanistic investigations suggest that a single-electron-transfer process plays a vital role in generating sulfonyl radicals and subsequently initiating C-S cross-coupling. Importantly, our copper-catalyzed remote functionalization protocol can be expanded for the construction of a variety of chemical bonds, including C-O, C-Br, C-N, C-C, and C-I. These findings provide a fundamental insight into the activation of remote C-H bonds, while offering new possibilities for rational design of drug molecules and optoelectronic materials requiring specific modification of functional groups. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Macrocyclic bis-thioureas catalyze stereospecific glycosylation reactions.

    Science.gov (United States)

    Park, Yongho; Harper, Kaid C; Kuhl, Nadine; Kwan, Eugene E; Liu, Richard Y; Jacobsen, Eric N

    2017-01-13

    Carbohydrates are involved in nearly all aspects of biochemistry, but their complex chemical structures present long-standing practical challenges to their synthesis. In particular, stereochemical outcomes in glycosylation reactions are highly dependent on the steric and electronic properties of coupling partners; thus, carbohydrate synthesis is not easily predictable. Here we report the discovery of a macrocyclic bis-thiourea derivative that catalyzes stereospecific invertive substitution pathways of glycosyl chlorides. The utility of the catalyst is demonstrated in the synthesis of trans-1,2-, cis-1,2-, and 2-deoxy-β-glycosides. Mechanistic studies are consistent with a cooperative mechanism in which an electrophile and a nucleophile are simultaneously activated to effect a stereospecific substitution reaction. Copyright © 2017, American Association for the Advancement of Science.

  13. Large acceleration of a-chymotrypsin-catalyzed dipeptide formation by 18-crown-6 in organic solvents

    NARCIS (Netherlands)

    van Unen, D.J.; Engbersen, Johannes F.J.; Reinhoudt, David

    1998-01-01

    The effects of 18-crown-6 on the synthesis of peptides catalyzed by α-chymotrypsin are reported. Lyophilization of the enzyme in the presence of 50 equivalents of 18-crown-6 results in a 425-fold enhanced activity when the reaction between the 2-chloroethylester of N-acetyl-L-phenylalanine and

  14. Asymmetric Chemoenzymatic Reductive Acylation of Ketones by a Combined Iron-Catalyzed Hydrogenation-Racemization and Enzymatic Resolution Cascade

    KAUST Repository

    El-Sepelgy, Osama

    2017-02-28

    A general and practical process for the conversion of prochiral ketones into the corresponding chiral acetates has been realized. An iron carbonyl complex is reported to catalyze the hydrogenation-dehydrogenation-hydrogenation of prochiral ketones. By merging the iron-catalyzed redox reactions with enantioselective enzymatic acylations a wide range of benzylic, aliphatic and (hetero)aromatic ketones, as well as diketones, were reductively acylated. The corresponding products were isolated with high yields and enantioselectivities. The use of an iron catalyst together with molecular hydrogen as the hydrogen donor and readily available ethyl acetate as acyl donor make this cascade process highly interesting in terms of both economic value and environmental credentials.

  15. Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-defined Manganese(II) Complex

    KAUST Repository

    Brzozowska, Aleksandra; Azofra, Luis Miguel; Zubar, Viktoriia; Atodiresei, Iuliana; Cavallo, Luigi; Rueping, Magnus; El-Sepelgy, Osama

    2018-01-01

    The first example of manganese catalyzed semihydrogenation of internal alkynes to (Z)-alkenes using ammonia borane as a hydrogen donor is reported. The reaction is catalyzed by a pincer complex of the earth abundant manganese(II) salt in the absence of any additives, base or super hydride. The ammonia borane smoothly reduces the manganese pre-catalyst [Mn(II)-PNP][Cl]2 to the catalytically active species [Mn(I)-PNP]-hydride in the triplet spin state. This manganese hydride is highly stabilized by complexation with the alkyne substrate. Computational DFT analysis studies of the reaction mechanism rationalizes the origin of stereoselectivity towards formation of (Z)-alkenes.

  16. Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-defined Manganese(II) Complex

    KAUST Repository

    Brzozowska, Aleksandra

    2018-03-30

    The first example of manganese catalyzed semihydrogenation of internal alkynes to (Z)-alkenes using ammonia borane as a hydrogen donor is reported. The reaction is catalyzed by a pincer complex of the earth abundant manganese(II) salt in the absence of any additives, base or super hydride. The ammonia borane smoothly reduces the manganese pre-catalyst [Mn(II)-PNP][Cl]2 to the catalytically active species [Mn(I)-PNP]-hydride in the triplet spin state. This manganese hydride is highly stabilized by complexation with the alkyne substrate. Computational DFT analysis studies of the reaction mechanism rationalizes the origin of stereoselectivity towards formation of (Z)-alkenes.

  17. Acidic deposition: State of science and technology. Report 14. Methods for projecting future changes in surface water acid-base chemistry. Final report

    International Nuclear Information System (INIS)

    Thornton, K.W.; Marmorek, D.; Ryan, P.F.; Heltcher, K.; Robinson, D.

    1990-09-01

    The objectives of the report are to: critically evaluate methods for projecting future effects of acidic deposition on surface water acid-base chemistry; review and evaluate techniques and procedures for analyzing projection uncertainty; review procedures for estimating regional lake and stream population attributes; review the U.S. Environmental Protection Agency (EPA) Direct/Delayed Response Project (DDRP) methodology for projecting the effects of acidic deposition on future changes in surface water acid-base chemistry; and present the models, uncertainty estimators, population estimators, and proposed approach selected to project the effects of acidic deposition on future changes in surface water acid-base chemistry in the NAPAP 1990 Integrated Assessment and discuss the selection rationale

  18. Uranium deposits in granitic rocks

    International Nuclear Information System (INIS)

    Nishimori, R.K.; Ragland, P.C.; Rogers, J.J.W.; Greenberg, J.K.

    1977-01-01

    This report is a review of published data bearing on the geology and origin of uranium deposits in granitic, pegmatitic and migmatitic rocks with the aim of assisting in the development of predictive criteria for the search for similar deposits in the U.S. Efforts were concentrated on the so-called ''porphyry'' uranium deposits. Two types of uranium deposits are primarily considered: deposits in pegmatites and alaskites in gneiss terrains, and disseminations of uranium in high-level granites. In Chapter 1 of this report, the general data on the distribution of uranium in igneous and metamorphic rocks are reviewed. Chapter 2 contains some comments on the classification of uranium deposits associated with igneous rocks and a summary of the main features of the geology of uranium deposits in granites. General concepts of the behavior of uranium in granites during crustal evolution are reviewed in Chapter 3. Also included is a discussion of the relationship of uranium mineralization in granites to the general evolution of mobile belts, plus the influence of magmatic and post-magmatic processes on the distribution of uranium in igneous rocks and related ore deposits. Chapter 4 relates the results of experimental studies on the crystallization of granites to some of the geologic features of uranium deposits in pegmatites and alaskites in high-grade metamorphic terrains. Potential or favorable areas for igneous uranium deposits in the U.S.A. are delineated in Chapter 5. Data on the geology of specific uranium deposits in granitic rocks are contained in Appendix 1. A compilation of igneous rock formations containing greater than 10 ppM uranium is included in Appendix 2. Appendix 3 is a report on the results of a visit to the Roessing area. Appendix 4 is a report on a field excursion to eastern Canada

  19. Lewis base catalyzed enantioselective allylic hydroxylation of Morita-Baylis-Hillman carbonates with water

    KAUST Repository

    Zhu, Bo

    2011-08-19

    A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using 18O-labeling experiments. © 2011 American Chemical Society.

  20. Near-equilibrium chemical vapor deposition of high-quality single-crystal graphene directly on various dielectric substrates.

    Science.gov (United States)

    Chen, Jianyi; Guo, Yunlong; Jiang, Lili; Xu, Zhiping; Huang, Liping; Xue, Yunzhou; Geng, Dechao; Wu, Bin; Hu, Wenping; Yu, Gui; Liu, Yunqi

    2014-03-05

    By using near-equilibrium chemical vapor deposition, it is demonstrated that high-quality single-crystal graphene can be grown on dielectric substrates. The maximum size is about 11 μm. The carrier mobility can reach about 5650 cm(2) V(-1) s(-1) , which is comparable to those of some metal-catalyzed graphene crystals, reflecting the good quality of the graphene lattice. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Power-balance analysis of muon-catalyzed fusion-fission hybrid reactor systems

    International Nuclear Information System (INIS)

    Miller, R.L.; Krakowski, R.A.

    1985-01-01

    A power-balance model of a muon-catalyzed fusion system in the context of a fission-fuel factory is developed and exercised to predict the required physics performance of systems competitive with either pure muon-catalyzed fusion systems or thermonuclear fusion-fission fuel factory hybrid systems

  2. Theoretical survey of muon catalyzed fusion

    International Nuclear Information System (INIS)

    Leon, M.

    1988-01-01

    The main steps in the muon-catalyzed d-t fusion cycle are given in this report. Most of the stages are very fast, and therefore do not contribute significantly to the cycling time. Thus at liquid H 2 densities (/phi/ = 1 in the standard convention) the time for stopping the negative muon, its subsequent capture and deexcitation to the ground state is estimated to be /approximately/ 10/sup/minus/11/ sec. 1 The muon spends essentially all of its time in either the (dμ) ground state, waiting for transfer to a (tμ) ground state to occur, or in the (tμ) ground state, writing for molecular formation to occur. Following the formation of this ''mesomolecule'' (actually a muonic molecular ion), deexcitation and fusion are again fast. Then the muon is (usually) liberated to go around again. We will discuss these steps in some detail. 5 refs., 3 figs

  3. Human myeloperoxidase (MPO) and horseradish peroxidase (HRP) catalyzed oxidation of phenol

    International Nuclear Information System (INIS)

    Ross, D.; Eastmond, D.A.; Ruzo, L.O.; Smith, M.T.

    1986-01-01

    MPO-catalyzed conversion of phenolic metabolites of benzene may be involved in benzene-induced myelotoxicity. The authors have studied the metabolism and protein binding of phenol - the major metabolite of benzene - during peroxidatic oxidation. The major metabolite observed during MPO- and HRP- catalyzed oxidation was characterized as 4,4 biphenol using HPLC and combined GC-MS. When glutathione (GSH) was added to the incubation mixtures, two additional compounds were observed during HPLC analysis which were characterized as GSH-conjugates of 4,4-diphenoquinone by fast atom bombardment MS and by NMR. ESR spectroscopy showed that both MPO-and HRP-catalyzed oxidation of phenol proceeded via the generation of free radical intermediates. Using 14 C-phenol, both MPO- and HRP-catalyzed oxidations resulted in the production of species which bound covalently to boiled liver microsomal protein. The increase in binding correlated well with removal of substrate. Thus, peroxidatic oxidation of phenolic metabolites of benzene in the bone marrow may be involved in benzene-induced myelotoxicity

  4. The effects of zinc on cobalt deposition in PWRs: summary report

    International Nuclear Information System (INIS)

    Bennet, Peter

    1996-01-01

    An experiment has been performed in a PWR loop of the Halden reactor to investigate the effects of the addition of 50 ppb zinc to the coolant on the incorporation of cobalt into the oxide films on primary circuit constructional materials. This report summarises the results from the three phases of the test. It was shown that zinc addition inhibits the corrosion of both new metal surfaces and surfaces with well-established oxides; this results in thinner oxide layers and reduced incorporation of cobalt into the oxide. Generally, there were no significant differences between the deposition of cobalt-60 onto pre-oxidised and new metal surfaces. In Phase 1 of the experiment, Co-60 deposition rates (normalised to the circulating Co-60 concentration) were lower than those measured in previous experiments in the loop by factors in the range from 5 to 10. In Phase 2, differences were observed in the behaviour of iron- and nickel-based alloys: larger decreases in the deposition rate compared with Phase 1 took place for stainless steel samples (i.e. factors > 20), whilst decreases on nickel-based coupons were generally less than a factor of 5. Co-60 deposition rates onto stainless steel coupons newly installed for Phase 3 of the experiment were greater by an order of magnitude than on coupons which had been exposed for all three phases; i.e. they were similar to those observed in Phase 1. The mechanisms by which zinc acts to inhibit corrosion and the incorporation of activity into oxide layers are not fully understood. More experimental data are required to resolve this issue, including information on the chemical form of the zinc within the oxide layer. (author)

  5. Co-Cu-Au deposits in metasedimentary rocks-A preliminary report

    Science.gov (United States)

    Slack, J.F.; Causey, J.D.; Eppinger, R.G.; Gray, J.E.; Johnson, C.A.; Lund, K.I.; Schulz, K.J.

    2010-01-01

    A compilation of data on global Co-Cu-Au deposits in metasedimentary rocks refines previous descriptive models for their occurrence and provides important information for mineral resource assessments and exploration programs. This compilation forms the basis for a new classification of such deposits, which is speculative at this early stage of research. As defined herein, the Co-Cu-Au deposits contain 0.1 percent or more by weight of Co in ore or mineralized rock, comprising disseminated to semi-massive Co-bearing sulfide minerals with associated Fe- and Cu-bearing sulfides, and local gold, concentrated predominantly within rift-related, siliciclastic metasedimentary rocks of Proterozoic age. Some deposits have appreciable Ag ? Bi ? W ? Ni ? Y ? rare earth elements ? U. Deposit geometry includes stratabound and stratiform layers, lenses, and veins, and (or) discordant veins and breccias. The geometry of most deposits is controlled by stratigraphic layering, folds, axial-plane cleavage, shear zones, breccias, or faults. Ore minerals are mainly cobaltite, skutterudite, glaucodot, and chalcopyrite, with minor gold, arsenopyrite, pyrite, pyrrhotite, bismuthinite, and bismuth; some deposits have appreciable tetrahedrite, uraninite, monazite, allanite, xenotime, apatite, scheelite, or molybdenite. Magnetite can be abundant in breccias, veins, or stratabound lenses within ore or surrounding country rocks. Common gangue minerals include quartz, biotite, muscovite, K-feldspar, albite, chlorite, and scapolite; many deposits contain minor to major amounts of tourmaline. Altered wall rocks generally have abundant biotite or albite. Mesoproterozoic metasedimentary successions constitute the predominant geologic setting. Felsic and (or) mafic plutons are spatially associated with many deposits and at some localities may be contemporaneous with, and involved in, ore formation. Geoenvironmental data for the Blackbird mining district in central Idaho indicate that weathering of

  6. Desaturation reactions catalyzed by soluble methane monooxygenase.

    Science.gov (United States)

    Jin, Y; Lipscomb, J D

    2001-09-01

    Soluble methane monooxygenase (MMO) is shown to be capable of catalyzing desaturation reactions in addition to the usual hydroxylation and epoxidation reactions. Dehydrogenated products are generated from MMO-catalyzed oxidation of certain substrates including ethylbenzene and cyclohexadienes. In the reaction of ethylbenzene, desaturation of ethyl C-H occurred along with the conventional hydroxvlations of ethyl and phenyl C-Hs. As a result, styrene is formed together with ethylphenols and phenylethanols. Similarly, when 1,3- and 1,4-cyclohexadienes were used as substrates, benzene was detected as a product in addition to the corresponding alcohols and epoxides. In all cases, reaction conditions were found to significantly affect the distribution among the different products. This new activity of MMO is postulated to be associated with the chemical properties of the substrates rather than fundamental changes in the nature of the oxygen and C-H activation chemistries. The formation of the desaturated products is rationalized by formation of a substrate cationic intermediate, possibly via a radical precursor. The cationic species is then proposed to partition between recombination (alcohol formation) and elimination (alkene production) pathways. This novel function of MMO indicates close mechanistic kinship between the hydroxylation and desaturation reactions catalyzed by the nonheme diiron clusters.

  7. Rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes.

    Science.gov (United States)

    Li, Changkun; Kähny, Matthias; Breit, Bernhard

    2014-12-08

    A rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes to give branched N-allyl 2-pyridones is reported. Preliminary mechanistic studies support the hypothesis that the reaction was initiated from the more acidic 2-hydroxypyridine form, and the initial kinetic O-allylation product was finally converted into the thermodynamically more stable N-allyl 2-pyridones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Silver-Catalyzed Cyclopropanation of Alkenes Using N-Nosylhydrazones as Diazo Surrogates.

    Science.gov (United States)

    Liu, Zhaohong; Zhang, Xinyu; Zanoni, Giuseppe; Bi, Xihe

    2017-12-15

    An efficient silver-catalyzed [2 + 1] cyclopropanation of sterically hindered internal alkenes with diazo compounds in which room-temperature-decomposable N-nosylhydrazones are used as diazo surrogates is reported. The unexpected unique catalytic activity of silver was ascribed to its dual role as a Lewis acid activating alkene substrates and as a transition metal forming silver carbenoids. A wide range of internal alkenes, including challenging diarylethenes, were suitable for this protocol, thereby affording a variety of cyclopropanes with high efficiency in a stereoselective manner under mild conditions.

  9. Gold-Catalyzed Formal C-C Bond Insertion Reaction of 2-Aryl-2-diazoesters with 1,3-Diketones.

    Science.gov (United States)

    Ren, Yuan-Yuan; Chen, Mo; Li, Ke; Zhu, Shou-Fei

    2018-06-29

    The transition-metal-catalyzed formal C-C bond insertion reaction of diazo compounds with monocarbonyl compounds is well established, but the related reaction of 1,3-diketones instead gives C-H bond insertion products. Herein, we report a protocol for a gold-catalyzed formal C-C bond insertion reaction of 2-aryl-2-diazoesters with 1,3-diketones, which provides efficient access to polycarbonyl compounds with an all-carbon quaternary center. The aryl ester moiety plays a crucial role in the unusual chemoselectivity, and the addition of a Brønsted acid to the reaction mixture improves the yield of the C-C bond insertion product. A reaction mechanism involving cyclopropanation of a gold carbenoid with an enolate and ring-opening of the resulting donor-acceptor-type cyclopropane intermediate is proposed. This mechanism differs from that of the traditional Lewis-acid-catalyzed C-C bond insertion reaction of diazo compounds with monocarbonyl compounds, which involves a rearrangement of a zwitterion intermediate as a key step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Catalytic Asymmetric Piancatelli Rearrangement: Brønsted Acid Catalyzed 4π Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

    KAUST Repository

    Cai, Yunfei; Tang, Yurong; Atodiresei, Iuliana; Rueping, Magnus

    2016-01-01

    The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral Brønsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields

  11. Gold-Catalyzed Cyclizations of Alkynol-Based Compounds: Synthesis of Natural Products and Derivatives

    Directory of Open Access Journals (Sweden)

    Pedro Almendros

    2011-09-01

    Full Text Available The last decade has witnessed dramatic growth in the number of reactions catalyzed by gold complexes because of their powerful soft Lewis acid nature. In particular, the gold-catalyzed activation of propargylic compounds has progressively emerged in recent years. Some of these gold-catalyzed reactions in alkynes have been optimized and show significant utility in organic synthesis. Thus, apart from significant methodology work, in the meantime gold-catalyzed cyclizations in alkynol derivatives have become an efficient tool in total synthesis. However, there is a lack of specific review articles covering the joined importance of both gold salts and alkynol-based compounds for the synthesis of natural products and derivatives. The aim of this Review is to survey the chemistry of alkynol derivatives under gold-catalyzed cyclization conditions and its utility in total synthesis, concentrating on the advances that have been made in the last decade, and in particular in the last quinquennium.

  12. Fe(II)/Fe(III)-Catalyzed Intramolecular Didehydro-Diels-Alder Reaction of Styrene-ynes.

    Science.gov (United States)

    Mun, Hyeon Jin; Seong, Eun Young; Ahn, Kwang-Hyun; Kang, Eun Joo

    2018-02-02

    The intramolecular didehydro-Diels-Alder reaction of styrene-ynes was catalyzed by Fe(II) and Fe(III) to produce various naphthalene derivatives under microwave heating conditions. Mechanistic calculations found that the Fe(II) catalyst activates the styrenyl diene in an inverse-electron-demand Diels-Alder reaction, and the consecutive dehydrogenation reaction can be promoted by either Fe(II)-catalyzed direct dehydrogenation or an Fe(III)-catalyzed rearomatization/dehydrogenation pathway.

  13. Cyclodextrin-Catalyzed Organic Synthesis: Reactions, Mechanisms, and Applications

    Directory of Open Access Journals (Sweden)

    Chang Cai Bai

    2017-09-01

    Full Text Available Cyclodextrins are well-known macrocyclic oligosaccharides that consist of α-(1,4 linked glucose units and have been widely used as artificial enzymes, chiral separators, chemical sensors, and drug excipients, owing to their hydrophobic and chiral interiors. Due to their remarkable inclusion capabilities with small organic molecules, more recent interests focus on organic reactions catalyzed by cyclodextrins. This contribution outlines the current progress in cyclodextrin-catalyzed organic reactions. Particular emphases are given to the organic reaction mechanisms and their applications. In the end, the future directions of research in this field are proposed.

  14. Bis(trialkylsilyl) peroxides as alkylating agents in the copper-catalyzed selective mono-N-alkylation of primary amides.

    Science.gov (United States)

    Sakamoto, Ryu; Sakurai, Shunya; Maruoka, Keiji

    2017-06-13

    The copper-catalyzed selective mono-N-alkylation of primary amides with bis(trialkylsilyl) peroxides as alkylating agents was reported. The results of a mechanistic study suggest that this reaction should proceed via a free radical process that includes the generation of alkyl radicals from bis(trialkylsilyl) peroxides.

  15. Outline of UNSCEAR 2013 report (1). Radionuclide releases, dispersion and deposition

    International Nuclear Information System (INIS)

    Nagai, Haruyasu; Kurihara, Osamu

    2014-01-01

    The general assembly of the United Nations Scientific Committee on the Effects of Atomic Radiation (UNSCEAR) was held in May, 2013 and the influence of the TEPCO Fukushima Daiichi nuclear power station accident on the environment and the human body, which has been analyzed and discussed by many specialists, was reported. The detailed contents of the influence were published in April, 2014 as the UNSCEAR 2013 Report (Vol. I: Report of the UNSCEAR to the General Assembly; Scientific Annex A: Levels and effects of radiation exposure due to the nuclear accident after the 2011 great east-Japan earthquake and tsunami and Vol. II: Scientific Findings on Effects of Radiation Exposure of Children; Scientific Annex B: Effects of radiation exposure of children). In the present paper, the outlines of the Scientific Annex A and the chapter III (Radionuclide releases, dispersion and deposition) in it are described. (K. Kato)

  16. Removal of emerging pollutants by Ru/TiO2-catalyzed permanganate oxidation.

    Science.gov (United States)

    Zhang, Jing; Sun, Bo; Xiong, Xinmei; Gao, Naiyun; Song, Weihua; Du, Erdeng; Guan, Xiaohong; Zhou, Gongming

    2014-10-15

    TiO2 supported ruthenium nanoparticles, Ru/TiO2 (0.94‰ as Ru), was synthesized to catalyze permanganate oxidation for degrading emerging pollutants (EPs) with diverse organic moieties. The presence of 1.0 g L(-1) Ru/TiO2 increased the second order reaction rate constants of bisphenol A, diclofenac, acetaminophen, sulfamethoxazole, benzotriazole, carbamazepine, butylparaben, diclofenac, ciprofloxacin and aniline at mg L(-1) level (5.0 μM) by permanganate oxidation at pH 7.0 by 0.3-119 times. The second order reaction rate constants of EPs with permanganate or Ru/TiO2-catalyzed permanganate oxidation obtained at EPs concentration of mg L(-1) level (5.0 μM) underestimated those obtained at EPs concentration of μg L(-1) level (0.050 μM). Ru/TiO2-catalyzed permanganate could decompose a mixture of nine EPs at μg L(-1) level efficiently and the second order rate constant for each EP was not decreased due to the competition of other EPs. The toxicity tests revealed that Ru/TiO2-catalyzed permanganate oxidation was effective not only for elimination of EPs but also for detoxification. The removal rates of sulfamethoxazole by Ru/TiO2-catalyzed permanganate oxidation in ten successive cycles remained almost constant in ultrapure water and slightly decreased in Songhua river water since the sixth run, indicating the satisfactory stability of Ru/TiO2. Ru/TiO2-catalyzed permanganate oxidation was selective and could remove selected EPs spiked in real waters more efficiently than chlorination. Therefore, Ru/TiO2-catalyzed permanganate oxidation is promising for removing EPs with electron-rich moieties. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Plasma-plasmonics synergy in the Ga-catalyzed growth of Si-nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Bianco, Giuseppe Valerio, E-mail: giuseppevalerio.bianco@cnr.it [Institute of Inorganic Methodologies and Plasmas, IMIP-CNR, Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari (Italy); Giangregorio, Maria M.; Capezzuto, Pio [Institute of Inorganic Methodologies and Plasmas, IMIP-CNR, Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari (Italy); Losurdo, Maria [Institute of Inorganic Methodologies and Plasmas, IMIP-CNR, Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari (Italy); Department of Electrical and Computer Engineering, Duke University, Durham, NC 27708 (United States); Kim, Tong-Ho; Brown, April S. [Department of Electrical and Computer Engineering, Duke University, Durham, NC 27708 (United States); Bruno, Giovanni, E-mail: giovanni.bruno@ba.imip.cnr.it [Institute of Inorganic Methodologies and Plasmas, IMIP-CNR, Department of Chemistry, University of Bari, via Orabona 4, 70126 Bari (Italy)

    2012-06-05

    This paper reports on the growth of Si nanowires (NWs) by SiH{sub 4}/H{sub 2} plasmas using the non-noble Ga-nanoparticles (NPs) catalysts. A comparative investigation of conventional Si-NWs vapour-liquid-solid (VLS) growth catalyzed by Au NPs is also reported. We investigate the use of a hydrogen plasma and of a SiH{sub 4}/H{sub 2} plasma for removing Ga oxide shell and for enhancing the Si dissolution into the catalyst, respectively. By exploiting the Ga NPs surface plasmon resonance (SPR) sensitivity to their surface chemistry, the SPR characteristic of Ga NPs has been monitored by real time spectroscopic ellipsometry in order to control the hydrogen plasma/Ga NPs interaction and the involved processes (oxide removal and NPs dissolution by volatile gallium hydride). Using in situ laser reflectance interferometry the metal catalyzed Si NWs growth process has been investigated to find the effect of the plasma activation on the growth kinetics. The role of atomic hydrogen in the NWs growth mechanism and, in particular, in the SiH{sub 4} dissolution into the catalysts, is discussed. We show that while Au catalysts because of the re-aggregation of NPs yields NWs that do not correspond to the original size of the Au NPs catalyst, the NWs grown by the Ga catalyst retains the diameter dictated by the size of the Ga NPs. Therefore, the advantage of Ga NPs as catalysts for controlling NWs diameter is demonstrated.

  18. High pressure deuterium-tritium gas target vessels for muon-catalyzed fusion experiments

    International Nuclear Information System (INIS)

    Caffrey, A.J.; Spaletta, H.W.; Ware, A.G.; Zabriskie, J.M.; Hardwick, D.A.; Maltrud, H.R.; Paciotti, M.A.

    1989-01-01

    In experimental studies of muon-catalyzed fusion, the density of the hydrogen gas mixture is an important parameter. Catalysis of up to 150 fusions per muon has been observed in deuterium-tritium gas mixtures at liquid hydrogen density; at room temperature, such densities require a target gas pressure of the order of 1000 atmospheres (100 MPa, 15,000 psi). We report here the design considerations for hydrogen gas target vessels for muon-catalyzed fusion experiments that operate at 1000 and 10,000 atmospheres. The 1000 atmosphere high pressure target vessels are fabricated of Type A-286 stainless steel and lined with oxygen-free, high-conductivity (OFHC) copper to provide a barrier to hydrogen permeation of the stainless steel. The 10,000 atmosphere ultrahigh pressure target vessels are made from 18Ni (200 grade) maraging steel and are lined with OFHC copper, again to prevent hydrogen permeation of the steel. In addition to target design features, operating requirements, fabrication procedures, and secondary containment are discussed. 13 refs., 3 figs., 1 tab

  19. Iron-catalyzed diboration and carboboration of alkynes.

    Science.gov (United States)

    Nakagawa, Naohisa; Hatakeyama, Takuji; Nakamura, Masaharu

    2015-03-09

    An iron-catalyzed diboration reaction of alkynes with bis(pinacolato)diboron (B2pin2) and external borating agents (MeOB(OR)2) affords diverse symmetrical or unsymmetrical cis-1,2-diborylalkenes. The simple protocol for the diboration reaction can be extended to the iron-catalyzed carboboration of alkynes with primary and, unprecedentedly, secondary alkyl halides, affording various tetrasubstituted monoborylalkenes in a highly stereoselective manner. DFT calculations indicate that a boryliron intermediate adds across the triple bond of an alkyne to afford an alkenyliron intermediate, which can react with the external trapping agents, borates and alkyl halides. In situ trapping experiments support the intermediacy of the alkenyl iron species using radical probe stubstrates. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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.

  1. Fusion blankets for catalyzed D--D and D--He3 reactors

    International Nuclear Information System (INIS)

    Fillo, J.A.; Powell, J.R.

    1977-01-01

    Blanket designs are presented for catalyzed D-D (Cat-D) and D-He 3 fusion reactors. Because of relatively low neutron wall loads and the flexibility due to non-tritium breeding, blankets potentially should operate for reactor life-times of approximately 30 years. Unscheduled replacement of failed blanket modules should be relatively rapid, due to very low residual activity, by operators working either through access ports in the shield (option 1) or directly in the plasma chamber (option 2). Cat-D blanket designs are presented for high (approximately 30%) and low (approximately 12%) β noncircular Tokamak reactors. The blankets are thick graphite screens, operating at high temperature to anneal radiation damage; the deposited neutron and gamma energy is thermally radiated along internal cavities and conducted to a bank of internal SiC coolant tubes (approximately 4 cm. ID) containing high pressure helium. In the D-He 3 Tokamak reactor design, the blanket consists of multiple layers (e.g., three) of thin (approximately 10 cm.) high strength aluminum (e.g., SAP), modular plates, cooled by organic terphynyl coolant

  2. Fusion blankets for catalyzed D--D and D--3He reactors

    International Nuclear Information System (INIS)

    Fillo, J.A.; Powell, J.R.

    1977-01-01

    Blanket designs are presented for catalyzed D-D (Cat-D) and D-He 3 fusion reactors. Because of relatively low neutron wall loads and the flexibility due to non-tritium breeding, blankets potentially should operate for reactor life-times of approximately 30 years. Unscheduled replacement of failed blanket modules should be relatively rapid, due to very low residual activity, by operators working either through access ports in the shield (option 1) or directly in the plasma chamber (option 2). Cat-D blanket designs are presented for high (approximately 30%) and low (approximately 12%) β non-circular Tokamak reactors. The blankets are thick graphite screens, operating at high temperature to anneal radiation damage; the deposited neutron and gamma energy is thermally radiated along internal cavities and conducted to a bank of internal SiC coolant tubes (approximately 4 cm. ID) containing high pressure helium. In the D-He 3 Tokamak reactor design, the blanket consists of multiple layers (e.g., three) of thin (approximately 10 cm.) high strength aluminum (e.g., SAP), modular plates, cooled by organic terphenyl coolant

  3. Fat deposition in the urinary bladder wall: Incidental finding on abdominal computed tomography: A case report

    Energy Technology Data Exchange (ETDEWEB)

    Park, Min Ho; Moon, Sung Kyoung; Ahn, Sung Eun; Park, Seong Jin; Lim, Joo Won; Lee, Dong Ho [Dept. of Radiology, Kyung Hee University Medical Center, Kyung Hee University School of Medicine, Seoul (Korea, Republic of)

    2015-02-15

    In a computed tomography (CT) scan, fat deposition in the urinary bladder wall is seen as a linear hypoattenuating band surrounded by soft tissue density. It is uncommon, but is often seen in normal cases. However, there is no report of fat deposition in the urinary bladder wall in Korea. The authors encountered a 62-year-old male patient who showed an incidental hypoattenuating band in the urinary bladder wall on abdominal CT. The patient showed no clinical signs related to fat deposition in the urinary bladder wall. When the patient's previous abdominal CT was retrospectively reviewed, the same CT finding was seen. This linear hypoattenuating band within the urinary bladder wall should be considered as a normal CT finding, although it is uncommon.

  4. Intramolecular Hydroamination of Unbiased and Functionalized Primary Aminoalkenes Catalyzed by a Rhodium Aminophosphine Complex

    Science.gov (United States)

    Julian, Lisa D.; Hartwig, John F.

    2010-01-01

    We report a rhodium catalyst that exhibits high reactivity for the hydroamination of primary aminoalkenes that are unbiased toward cyclization and that possess functional groups that would not be tolerated in hydroaminations catalyzed by more electrophilic systems. This catalyst contains an unusual diaminophosphine ligand that binds to rhodium in a κ3-P,O,P mode. The reactions catalyzed by this complex typically proceed at mild temperatures (room temperature to 70 °C), occur with primary aminoalkenes lacking substituents on the alkyl chain that bias the system toward cyclization, occur with primary aminoalkenes containing chloride, ester, ether, enolizable ketone, nitrile, and unprotected alcohol functionality, and occur with primary aminoalkenes containing internal olefins. Mechanistic data imply that these reactions occur with a turnover-limiting step that is different from that of reactions catalyzed by late transition metal complexes of Pd, Pt, and Ir. This change in the turnover-limiting step and resulting high activity of the catalyst stem from favorable relative rates for protonolysis of the M-C bond to release the hydroamination product vs reversion of the aminoalkyl intermediate to regenerate the acyclic precursor. Probes for the origin of the reactivity of the rhodium complex of L1 imply that the aminophosphine groups lead to these favorable rates by effects beyond steric demands and simple electron donation to the metal center. PMID:20839807

  5. Acid-Catalyzed Preparation of Biodiesel from Waste Vegetable Oil: An Experiment for the Undergraduate Organic Chemistry Laboratory

    Science.gov (United States)

    Bladt, Don; Murray, Steve; Gitch, Brittany; Trout, Haylee; Liberko, Charles

    2011-01-01

    This undergraduate organic laboratory exercise involves the sulfuric acid-catalyzed conversion of waste vegetable oil into biodiesel. The acid-catalyzed method, although inherently slower than the base-catalyzed methods, does not suffer from the loss of product or the creation of emulsion producing soap that plagues the base-catalyzed methods when…

  6. Cold, muon-catalyzed fusion - just another swarm experiment?

    International Nuclear Information System (INIS)

    Robson, R.E.

    1992-01-01

    The paper briefly reviewed the muon-catalyzed fusion cycle and indicated how it may be likened to a swarm experiment. In particular, it has been pointed out that an external electric field can influence the properties of a muon swarm (and reactive derivatives), just as it can for ion and electron swarms. Since n 0 is typically around liquid hydrogen densities, very large fields, E≥10 9 V/m, would be required to achieve the desired outcome. This is presently achievable in small regions of intense laser focus, but it remains to be seen whether muon-catalyzed fusion experiments can actually be influenced in this way. 20 refs., 4 figs

  7. Kinetic Behavior of Exchange-Driven Growth with Catalyzed-Birth Processes

    Science.gov (United States)

    Wang, Hai-Feng; Lin, Zhen-Quan; Kong, Xiang-Mu

    2006-12-01

    Two catalyzed-birth models of n-species (n>=2) aggregates with exchange-driven growth processes are proposed and compared. In the first one, the exchange reaction occurs between any two aggregates Amk and Amj of the same species with the rate kernels Km(k,j) = Kmkj (m = 1,2,...,n, n>=2), and aggregates of An species catalyze a monomer-birth of Al species (l = 1,2,...,n-1) with the catalysis rate kernel Jl(k,j) = Jlkjυ. The kinetic behaviors are investigated by means of the mean-field theory. We find that the evolution behavior of aggregate-size distribution alk(t) of Al species depends crucially on the value of the catalysis rate parameter υ: (i) alk(t) obeys the conventional scaling law in the case of υ0. In the second model, the mechanism of monomer-birth of An-species catalyzed by Al species is added on the basis of the first model, that is, the aggregates of Al and An species catalyze each other to cause monomer-birth. The kinetic behaviors of Al and An species are found to fall into two categories for the different υ: (i) growth obeying conventional scaling form with υ0.

  8. Arc-related porphyry molybdenum deposit model: Chapter D in Mineral deposit models for resource assessment

    Science.gov (United States)

    Taylor, Ryan D.; Hammarstrom, Jane M.; Piatak, Nadine M.; Seal, Robert R.

    2012-01-01

    This report provides a descriptive model for arc-related porphyry molybdenum deposits. Presented within are geological, geochemical, and mineralogical characteristics that differentiate this deposit type from porphyry copper and alkali-feldspar rhyolite-granite porphyry molybdenum deposits. The U.S. Geological Survey's effort to update existing mineral deposit models spurred this research, which is intended to supplement previously published models for this deposit type that help guide mineral-resource and mineral-environmental assessments.

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

    Science.gov (United States)

    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.

  10. Kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid

    NARCIS (Netherlands)

    Girisuta, B.; Janssen, L. P. B. M.; Heeres, H. J.

    2007-01-01

    A variety of interesting bulk chemicals is accessible by the acid-catalyzed hydrolysis of cellulose. An interesting example is levulinic acid, a versatile precursor for fuel additives, polymers, and resins. A detailed kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid is

  11. Efficient Method for the Determination of the Activation Energy of the Iodide-Catalyzed Decomposition of Hydrogen Peroxide

    Science.gov (United States)

    Sweeney, William; Lee, James; Abid, Nauman; DeMeo, Stephen

    2014-01-01

    An experiment is described that determines the activation energy (E[subscript a]) of the iodide-catalyzed decomposition reaction of hydrogen peroxide in a much more efficient manner than previously reported in the literature. Hydrogen peroxide, spontaneously or with a catalyst, decomposes to oxygen and water. Because the decomposition reaction is…

  12. Iron Catalyzed Cycloaddition of Alkynenitriles and Alkynes

    Science.gov (United States)

    D’Souza, Brendan R.; Lane, Timothy K.

    2011-01-01

    The combination of Fe(OAc)2 and an electron-donating, sterically-hindered pyridyl bisimine ligand catalyzes the cycloaddition of alkynenitriles and alkynes. A variety of substituted pyridines were obtained in good yields. PMID:21557582

  13. Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Meng [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Gutiérrez, Oliver Y. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Lercher, Johannes A. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Department of Chemistry and Catalysis Research Institute, TU München, Lichtenbergstrasse 4 85748 Garching Germany

    2018-03-06

    Pd/C catalyzes C-O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by methanol in H2. The aromatic C-O bond is cleaved by reductive methanolysis, which is initiated by Pd-catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with methanol to form a ketal, which generates methoxycyclohexene by eliminating phenol or an alkanol. Subsequent hydrogenation leads to methoxycyclohexane.

  14. Enhanced activity and interfacial durability study of ultra low Pt based electrocatalysts prepared by ion beam assisted deposition (IBAD) method

    International Nuclear Information System (INIS)

    Ramaswamy, N.; Arruda, T.M.; Wen, W.; Hakim, N.; Saha, M.; Gulla, A.; Mukerjee, S.

    2009-01-01

    Ultra low loading noble metal (0.04-0.12 mg Pt /cm 2 ) based electrodes were obtained by direct metallization of non-catalyzed gas diffusion layers via dual ion beam assisted deposition (IBAD) method. Fuel cell performance results reported earlier indicate significant improvements in terms of mass specific power density of 0.297 g Pt /kW with 250 A thick IBAD deposit (0.04 mg Pt /cm 2 for a total MEA loading of 0.08 mg Pt /cm 2 ) at 0.65 V in contrast to the state of the art power density of 1.18 g Pt /kW using 1 mg Pt(MEA) /cm 2 at 0.65 V. In this article we report the peroxide radical initiated attack of the membrane electrode assembly utilizing IBAD electrodes in comparison to commercially available E-TEK (now BASF Fuel Cell GmbH) electrodes and find the pathway of membrane degradation as well. A novel segmented fuel cell is used for this purpose to relate membrane degradation to peroxide generation at the electrode/electrolyte interface by means of systematic pre and post analyses of the membrane are presented. Also, we present the results of in situ X-ray absorption spectroscopy (XAS) experiments to elucidate the structure/property relationships of these electrodes that lead to superior performance in terms of gravimetric power density obtained during fuel cell operation.

  15. Synthesis of oxindole from acetanilide via Ir(iii)-catalyzed C-H carbenoid functionalization.

    Science.gov (United States)

    Patel, Pitambar; Borah, Gongutri

    2016-12-22

    Herein we disclose the first report on the synthesis of oxindole derivatives from acetanilide via Ir(iii)-catalyzed intermolecular C-H functionalization with diazotized Meldrum's acid. A broad range of substituted anilides were found to react smoothly under the Ir(iii)-catalytic system to afford the corresponding N-protected oxindoles. The N-protecting groups, such as Ac, Bz or Piv, can be easily removed to furnish the oxindole. Various synthetic applications of the synthesized oxindole were also demonstrated.

  16. Transesterification of oil mixtures catalyzed by microencapsulated cutinase in reversed micelles.

    Science.gov (United States)

    Badenes, Sara M; Lemos, Francisco; Cabral, Joaquim M S

    2010-03-01

    Recombinant cutinase from Fusarium solani pisi was used to catalyze the transesterification reaction between a mixture of triglycerides (oils) and methanol in reversed micelles of bis(2-ethylhexyl) sodium sulfosuccinate (AOT) in isooctane for the purposes of producing biodiesel. The use of a bi-phase lipase-catalyzed system brings advantages in terms of catalyst re-use and the control of water activity in the medium and around the enzyme micro-environment. Small-scale batch studies were performed to study the influence of the initial enzyme and alcohol concentrations, and the substrates molar ratio. Conversions in excess of 75 were obtained with reaction times under 24 h, which makes this enzymatic process highly competitive when compared to similar lipase catalyzed reactions for biodiesel production using methanol.

  17. Geology and recognition criteria for uranium deposits of the quartz-pebble conglomerate type. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Button, A.; Adams, S.S.

    1981-03-01

    This report is concerned with Precambrian uraniferous conglomerates. This class of deposit has been estimated to contain between approximately 16 and 35 percent of the global uranium reserve in two rather small areas, one in Canada, the other in South Africa. Similar conglomerates, which are often gold-bearing, are, however, rather widespread, being found in parts of most Precambrian shield areas. Data have been synthesized on the geologic habitat and character of this deposit type. The primary objective has been to provide the most relevant geologic observations in a structural fashion to allow resource studies and exploration to focus on the most prospective targets in the shortest possible time.

  18. Geology and recognition criteria for uranium deposits of the quartz-pebble conglomerate type. Final report

    International Nuclear Information System (INIS)

    Button, A.; Adams, S.S.

    1981-03-01

    This report is concerned with Precambrian uraniferous conglomerates. This class of deposit has been estimated to contain between approximately 16 and 35 percent of the global uranium reserve in two rather small areas, one in Canada, the other in South Africa. Similar conglomerates, which are often gold-bearing, are, however, rather widespread, being found in parts of most Precambrian shield areas. Data have been synthesized on the geologic habitat and character of this deposit type. The primary objective has been to provide the most relevant geologic observations in a structural fashion to allow resource studies and exploration to focus on the most prospective targets in the shortest possible time

  19. RNA-Catalyzed Polymerization and Replication of RNA

    Science.gov (United States)

    Horning, D. P.; Samantha, B.; Tjhung, K. F.; Joyce, G. F.

    2017-07-01

    In an effort to reconstruct RNA-based life, in vitro evolution was used to obtain an RNA polymerase ribozyme that can synthesize a variety of complex functional RNAs and can catalyze the exponential amplification of short RNAs.

  20. Rhodium-Catalyzed Dehydrogenative Borylation of Cyclic Alkenes

    Science.gov (United States)

    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

  1. Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement

    OpenAIRE

    Liu, Wen-Bo; Okamoto, Noriko; Alexy, Eric J.; Hong, Allen Y.; Tran, Kristy; Stoltz, Brian M.

    2016-01-01

    A catalytic, enantioselective ? -alkylation of ?,?-unsaturated malonates and ketoesters is reported. This strategy entails a highly regio- and enantioselective iridium-catalyzed ?-alkylation of an extended enolate, and a subsequent translocation of chirality to the ?-position via a Cope rearrangement.

  2. Relative Performance of Alkynes in Copper-Catalyzed Azide-Alkyne Cycloaddition

    Science.gov (United States)

    Kislukhin, Alexander A.; Hong, Vu P.; Breitenkamp, Kurt E.; Finn, M.G.

    2013-01-01

    Copper-catalyzed azide–alkyne cycloaddition (CuAAC) has found numerous applications in a variety of fields. We report here only modest differences in the reactivity of various classes of terminal alkynes under typical bioconjugative and preparative organic conditions. Propargyl compounds represent an excellent combination of azide reactivity, ease of installation, and cost. Electronically activated propiolamides are slightly more reactive, at the expense of increased propensity for Michael addition. Certain alkynes, including tertiary propargyl carbamates, are not suitable for bioconjugation due to copper-induced fragmentation. A fluorogenic probe based on such reactivity is available in one step from rhodamine 110 and can be useful for optimization of CuAAC conditions. PMID:23566039

  3. Recent Advances in Recoverable Systems for the Copper-Catalyzed Azide-Alkyne Cycloaddition Reaction (CuAAC

    Directory of Open Access Journals (Sweden)

    Alessandro Mandoli

    2016-09-01

    Full Text Available The explosively-growing applications of the Cu-catalyzed Huisgen 1,3-dipolar cycloaddition reaction between organic azides and alkynes (CuAAC have stimulated an impressive number of reports, in the last years, focusing on recoverable variants of the homogeneous or quasi-homogeneous catalysts. Recent advances in the field are reviewed, with particular emphasis on systems immobilized onto polymeric organic or inorganic supports.

  4. Ni-Catalyzed Carbon-Carbon Bond-Forming Reductive Amination.

    Science.gov (United States)

    Heinz, Christoph; Lutz, J Patrick; Simmons, Eric M; Miller, Michael M; Ewing, William R; Doyle, Abigail G

    2018-02-14

    This report describes a three-component, Ni-catalyzed reductive coupling that enables the convergent synthesis of tertiary benzhydryl amines, which are challenging to access by traditional reductive amination methodologies. The reaction makes use of iminium ions generated in situ from the condensation of secondary N-trimethylsilyl amines with benzaldehydes, and these species undergo reaction with several distinct classes of organic electrophiles. The synthetic value of this process is demonstrated by a single-step synthesis of antimigraine drug flunarizine (Sibelium) and high yielding derivatization of paroxetine (Paxil) and metoprolol (Lopressor). Mechanistic investigations support a sequential oxidative addition mechanism rather than a pathway proceeding via α-amino radical formation. Accordingly, application of catalytic conditions to an intramolecular reductive coupling is demonstrated for the synthesis of endo- and exocyclic benzhydryl amines.

  5. Reactions of ethyl diazoacetate catalyzed by methylrhenium trioxide

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Z.; Espenson, H. [Iowa State Univ., Ames, IA (United States)

    1995-11-03

    Methylrhenium trioxide (CH{sub 3}ReO{sub 3} or MTO) has found wise use in catalysis, including the epoxidation and metathesis of olefins, aldehyde olefination, and oxygen transfer. Extensive reports have now appeared in the area of MTO-catalyzed substrate oxidations with hydrogen peroxide. Certain catalytic applications of MTO for organic reactions that do not utilize peroxide have now been realized. In particular, a catalytic amount of MTO with ethyl diazoacetate (EDA) will convert aromatic imines to aziridines and convert aldehydes and ketones to epoxides. The aziridine preparation proceeds in high yields under anaerobic conditions more conveniently than with existing methods. Compounds with a three-membered heterocyclic ring can be obtained with the EDA/MTO catalytic system. Aromatic imines undergo cycloaddition reactions to give aziridines under mild conditions.

  6. Acid base catalyzed transesterification kinetics of waste cooking oil

    Energy Technology Data Exchange (ETDEWEB)

    Jain, Siddharth; Sharma, M.P.; Rajvanshi, Shalini [Alternate Hydro Energy Centre, Indian Institute of Technology, Roorkee (India)

    2011-01-15

    The present study reports the results of kinetics study of acid base catalyzed two step transesterification process of waste cooking oil, carried out at pre-determined optimum temperature of 65 C and 50 C for esterification and transesterification process respectively under the optimum condition of methanol to oil ratio of 3:7 (v/v), catalyst concentration 1%(w/w) for H{sub 2}SO{sub 4} and NaOH and 400 rpm of stirring. The optimum temperature was determined based on the yield of ME at different temperature. Simply, the optimum concentration of H{sub 2}SO{sub 4} and NaOH was determined with respect to ME Yield. The results indicated that both esterification and transesterification reaction are of first order rate reaction with reaction rate constant of 0.0031 min{sup -1} and 0.0078 min{sup -1} respectively showing that the former is a slower process than the later. The maximum yield of 21.50% of ME during esterification and 90.6% from transesterification of pretreated WCO has been obtained. This is the first study of its kind which deals with simplified kinetics of two step acid-base catalyzed transesterification process carried under the above optimum conditions and took about 6 h for complete conversion of TG to ME with least amount of activation energy. Also various parameters related to experiments are optimized with respect to ME yield. (author)

  7. Rice cytochrome P450 MAX1 homologs catalyze distinct steps in strigolactone biosynthesis

    KAUST Repository

    Zhang, Yanxia; van Dijk, Aalt D J; Scaffidi, Adrian; Flematti, Gavin R.; Hofmann, Manuel; Charnikhova, Tatsiana; Verstappen, Francel; Hepworth, Jo; van der Krol, Sander; Leyser, Ottoline; Smith, Steven M.; Zwanenburg, Binne; Al-Babili, Salim; Ruyter-Spira, Carolien; Bouwmeester, Harro J.

    2014-01-01

    Strigolactones (SLs) are a class of phytohormones and rhizosphere signaling compounds with high structural diversity. Three enzymes, carotenoid isomerase DWARF27 and carotenoid cleavage dioxygenases CCD7 and CCD8, were previously shown to convert all-trans-β-carotene to carlactone (CL), the SL precursor. However, how CL is metabolized to SLs has remained elusive. Here, by reconstituting the SL biosynthetic pathway in Nicotiana benthamiana, we show that a rice homolog of Arabidopsis More Axillary Growth 1 (MAX1), encodes a cytochrome P450 CYP711 subfamily member that acts as a CL oxidase to stereoselectively convert CL into ent-2'-epi-5-deoxystrigol (B-C lactone ring formation), the presumed precursor of rice SLs. A protein encoded by a second rice MAX1 homolog then catalyzes the conversion of ent-2'-epi-5-deoxystrigol to orobanchol. We therefore report that two members of CYP711 enzymes can catalyze two distinct steps in SL biosynthesis, identifying the first enzymes involved in B-C ring closure and a subsequent structural diversification step of SLs.

  8. Rice cytochrome P450 MAX1 homologs catalyze distinct steps in strigolactone biosynthesis

    KAUST Repository

    Zhang, Yanxia

    2014-10-26

    Strigolactones (SLs) are a class of phytohormones and rhizosphere signaling compounds with high structural diversity. Three enzymes, carotenoid isomerase DWARF27 and carotenoid cleavage dioxygenases CCD7 and CCD8, were previously shown to convert all-trans-β-carotene to carlactone (CL), the SL precursor. However, how CL is metabolized to SLs has remained elusive. Here, by reconstituting the SL biosynthetic pathway in Nicotiana benthamiana, we show that a rice homolog of Arabidopsis More Axillary Growth 1 (MAX1), encodes a cytochrome P450 CYP711 subfamily member that acts as a CL oxidase to stereoselectively convert CL into ent-2\\'-epi-5-deoxystrigol (B-C lactone ring formation), the presumed precursor of rice SLs. A protein encoded by a second rice MAX1 homolog then catalyzes the conversion of ent-2\\'-epi-5-deoxystrigol to orobanchol. We therefore report that two members of CYP711 enzymes can catalyze two distinct steps in SL biosynthesis, identifying the first enzymes involved in B-C ring closure and a subsequent structural diversification step of SLs.

  9. A metal-catalyzed enyne-cyclization step for the synthesis of bi- and tricyclic scaffolds amenable to molecular library production

    DEFF Research Database (Denmark)

    Wu, Peng; Cohrt, Anders Emil O'Hanlon; Petersen, Rico

    2016-01-01

    A facile metal-catalyzed diversification step for the synthesis of novel bi- and tricyclic scaffolds from enyne substrates is reported in this study. From a single starting material, topologically diverse scaffolds for library synthesis can be generated and decorated in a few steps. The methodology...

  10. Iron-Catalyzed Dehydration of Aldoximes to Nitriles Requiring Neither Other Reagents Nor Nitrile Media.

    Science.gov (United States)

    Hyodo, Kengo; Kitagawa, Saki; Yamazaki, Masayuki; Uchida, Kingo

    2016-05-06

    The dehydration of aldoximes is an environmentally benign reaction affording the desired nitrile and water as a by-product. However, most of the reported catalytic dehydration reactions of aldoximes require a solvent containing nitrile to synthesize the corresponding nitrile compounds. Inspired by recent reports on the enzymatic synthesis under nitrile-free conditions, we here describe that a simple iron salt catalyzes the dehydration of aldoximes requiring neither other reagents nor nitrile media. Our method can be applied to the one-pot synthesis of nitiriles from aldehydes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Cholera toxin can catalyze ADP-ribosylation of cytoskeletal proteins

    International Nuclear Information System (INIS)

    Kaslow, H.R.; Groppi, V.E.; Abood, M.E.; Bourne, H.R.

    1981-01-01

    Cholera toxin catalyzes transfer of radiolabel from [ 32 P]NAD + to several peptides in particulate preparations of human foreskin fibroblasts. Resolution of these peptides by two-dimensional gel electrophoresis allowed identification of two peptides of M/sub r/ = 42,000 and 52,000 as peptide subunits of a regulatory component of adenylate cyclase. The radiolabeling of another group of peptides (M/sub r/ = 50,000 to 65,000) suggested that cholera toxin could catalyze ADP-ribosylation of cytoskeletal proteins. This suggestion was confirmed by showing that incubation with cholera toxin and [ 32 P]NAD + caused radiolabeling of purified microtubule and intermediate filament proteins

  12. Bio-mineralization and potential biogeochemical processes in bauxite deposits: genetic and ore quality significance

    Science.gov (United States)

    Laskou, Magdalini; Economou-Eliopoulos, Maria

    2013-08-01

    The Parnassos-Ghiona bauxite deposit in Greece of karst type is the 11th largest bauxite producer in the world. The mineralogical, major and trace-element contents and δ18O, δ12C, δ34S isotopic compositions of bauxite ores from this deposit and associated limestone provide valuable evidence for their origin and biogeochemical processes resulting in the beneficiation of low grade bauxite ores. The organic matter as thin coal layers, overlying the bauxite deposits, within limestone itself (negative δ12C isotopic values) and the negative δ34S values in sulfides within bauxite ores point to the existence of the appropriate circumstances for Fe bio-leaching and bio-mineralization. Furthermore, a consortium of microorganisms of varying morphological forms (filament-like and spherical to lenticular at an average size of 2 μm), either as fossils or presently living and producing enzymes, is a powerful factor to catalyze the redox reactions, expedite the rates of metal extraction and provide alternative pathways for metal leaching processes resulting in the beneficiation of bauxite ore.

  13. Cu(I)-catalyzed efficient synthesis of 2′-Triazolo-nucleoside conjugates

    DEFF Research Database (Denmark)

    Mathur, D.; Rana, N.; Olsen, Carl Erik

    2015-01-01

    -nucleoside conjugates, which can be evaluated for different biological activity for suitable drug development, were unambiguously identified on the basis of 1H NMR, 13C NMR, IR, and HRMS data analysis. These compounds have been synthesized for the first time and have not been reported in the literature earlier.......A small library of thirty-two 2′-triazolyl uridine and 2′-triazolyl-5-methyluridine has been synthesized by Cu(I)-catalyzed condensation of 2′-azido-2′-deoxyuridine and 2′-azido-2′-deoxy-5-methyluridine with different alkynes and aryl propargyl ethers in almost quantitative yields. Triazolo...

  14. Investigation of emulsified, acid and acid-alkali catalyzed mesoporous bioactive glass microspheres for bone regeneration and drug delivery

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Guohou [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641 China (China); National Engineering Research Center for Tissue Restoration and Reconstruction, Guangzhou 510006 China (China); Guangdong Province Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006 China (China); Chen, Xiaofeng, E-mail: chenxf@scut.edu.cn [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641 China (China); National Engineering Research Center for Tissue Restoration and Reconstruction, Guangzhou 510006 China (China); Guangdong Province Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006 China (China); Dong, Hua [National Engineering Research Center for Tissue Restoration and Reconstruction, Guangzhou 510006 China (China); Guangdong Province Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006 China (China); School of Biological Science and Engineering, South China University of Technology, Guangzhou 510006 (China); Fang, Liming; Mao, Cong; Li, Yuli; Li, Zhengmao; Hu, Qing [School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641 China (China); National Engineering Research Center for Tissue Restoration and Reconstruction, Guangzhou 510006 China (China); Guangdong Province Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006 China (China)

    2013-10-15

    Acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were successfully synthesized via combination of sol-gel and water-in-oil (W/O) micro-emulsion methods. The structural, morphological and textural properties of mesoporous bioactive glass microspheres (MBGMs) were characterized by various techniques. Results show that both MBGMs-A and MBGMs-B exhibit regularly spherical shape but with different internal porous structures, i.e., a dense microstructure for MBGMs-A and internally porous structure for MBGMs-B. {sup 29}Si NMR data reveal that MGBMs have low polymerization degree of silica network. The in vitro bioactivity tests indicate that the apatite formation rate of MBGMs-B was faster than that of MBGMs-A after soaking in simulated body fluid (SBF) solution. Furthermore, the two kinds of MBGMs have similar storage capacity of alendronate (AL), and the release behaviors of AL could be controlled due to their unique porous structure. In conclusion, the microspheres are shown to be promising candidates as bone-related drug carriers and filling materials of composite scaffold for bone repair. - Graphical abstract: The morphologies and microstructures of acid-catalyzed mesoporous bioactive glass microspheres (MBGMs-A) and acid-alkali co-catalyzed mesoporous bioactive glass microspheres (MBGMs-B) were observed by scanning electron microscope and transmission electron microscope. MBGMs-A exhibits a dense structure and a porous can be observed in MBGMs-B. The microspheres have a quick inducing-apatite formation ability and show a sustained release of alendronate (AL). Highlights: • A rapid method was reported to prepare mesoporous bioactive glass microspheres. • The addition of ammonia significantly shortens the preparation time. • Acid and acid-alkali co-catalyzed microspheres were studied for the first time. • The materials exhibited excellent in vitro bioactivity and

  15. Recent developments in gold-catalyzed cycloaddition reactions

    Directory of Open Access Journals (Sweden)

    Fernando López

    2011-08-01

    Full Text Available In the last years there have been extraordinary advances in the development of gold-catalyzed cycloaddition processes. In this review we will summarize some of the most remarkable examples, and present the mechanistic rational underlying the transformations.

  16. Unexpected Reaction Pathway for butyrylcholinesterase-catalyzed inactivation of “hunger hormone” ghrelin

    Science.gov (United States)

    Yao, Jianzhuang; Yuan, Yaxia; Zheng, Fang; Zhan, Chang-Guo

    2016-02-01

    Extensive computational modeling and simulations have been carried out, in the present study, to uncover the fundamental reaction pathway for butyrylcholinesterase (BChE)-catalyzed hydrolysis of ghrelin, demonstrating that the acylation process of BChE-catalyzed hydrolysis of ghrelin follows an unprecedented single-step reaction pathway and the single-step acylation process is rate-determining. The free energy barrier (18.8 kcal/mol) calculated for the rate-determining step is reasonably close to the experimentally-derived free energy barrier (~19.4 kcal/mol), suggesting that the obtained mechanistic insights are reasonable. The single-step reaction pathway for the acylation is remarkably different from the well-known two-step acylation reaction pathway for numerous ester hydrolysis reactions catalyzed by a serine esterase. This is the first time demonstrating that a single-step reaction pathway is possible for an ester hydrolysis reaction catalyzed by a serine esterase and, therefore, one no longer can simply assume that the acylation process must follow the well-known two-step reaction pathway.

  17. CuO-Nanoparticles Catalyzed Synthesis of 1,4-Disubstituted-1,2,3 ...

    Indian Academy of Sciences (India)

    John Paul Raj

    2018-04-13

    Apr 13, 2018 ... has been developed for the synthesis of 1,2,3-triazoles. A library of 1 ... Kuang et al., described Cu-catalyzed synthesis of 1H-. 1,2,3-triazoles from 1 ..... Tornøe C W, Christensen C and Meldal M 2002 Peptido- triazoles on solid ... 2015 Copper-catalyzed [3+2] cycloaddition/oxidation reactions between ...

  18. catalyzed oxidation of formamidine derivative by hexacyanoferrate(III)

    Indian Academy of Sciences (India)

    Both uncatalyzed and catalyzed reactions showed first order kinetics with respect to [HCF], whereas ... The rate laws associated with the reaction mechanisms ... activation and thermodynamic parameters have been computed and discussed.

  19. Deposits of the Peruvian Pisco Formation compared to layered deposits on Mars

    Science.gov (United States)

    Sowe, M.; Bishop, J. L.; Gross, C.; Walter, S.

    2013-09-01

    Deposits of the Peruvian Pisco Formation are morphologically similar to the mounds of Juventae Chasma at the equatorial region on Mars (Fig. 1). By analyzing these deposits, we hope to gain information about the environmental conditions that prevailed during sediment deposition and erosion, hence conditions that might be applicable to the Martian layered and hydrated deposits. Mariner 9 data of the Martian mid-latitudes have already shown evidence of the wind-sculptured landforms that display the powerful prevailing eolian regime [1]. In addition, [2] reported on similarities between Martian erosional landforms and those of the rainless coastal desert of central Peru from the Paracas peninsula to the Rio Ica. As indicated by similar erosional patterns, hyper-arid conditions and unidirectional winds must have dominated at least after deposition of the sediments, which are intermixed volcaniclastic materials and evaporate minerals at both locations. Likewise, variations in composition are displayed by alternating layers of different competence. The Pisco formation bears yardangs on siltstones, sandstones and clays with volcaniclastic admixtures [3] whereas the presence of sulphate minerals and the omnipresent mafic mineralogy has been reported for the layered mounds of Juventae Chasma equally [4]. Likewise, a volcanic airfall deposition and lacustrine formation have been proposed for the sulphate-rich deposits of Juventae Chasma [5,6]. In order to find out about potential spectral similarities, we performed a detailed spectral analysis of the surface by using LANDSAT and Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) VNIR/ SWIR data (visible to near-infrared and shortwave infrared region).

  20. Cold fusion catalyzed by muons and electrons

    International Nuclear Information System (INIS)

    Kulsrud, R.M.

    1990-10-01

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

  1. Preparation of biodiesel from waste cooking oil via two-step catalyzed process

    International Nuclear Information System (INIS)

    Wang Yong; Liu Pengzhan; Ou Shiyi; Zhang Zhisen

    2007-01-01

    Waste cooking oils (WCO), which contain large amounts of free fatty acids produced in restaurants, are collected by the environmental protection agency in the main cities of China and should be disposed in a suitable way. In this research, a two step catalyzed process was adopted to prepare biodiesel from waste cooking oil whose acid value was 75.92 ± 0.036 mgKOH/g. The free fatty acids of WCO were esterified with methanol catalyzed by ferric sulfate in the first step, and the triglycerides (TGs) in WCO were transesterified with methanol catalyzed by potassium hydroxide in the second step. The results showed that ferric sulfate had high activity to catalyze the esterification of free fatty acids (FFA) with methanol, The conversion rate of FFA reached 97.22% when 2 wt% of ferric sulfate was added to the reaction system containing methanol to TG in10:1 (mole ratio) composition and reacted at 95 deg. C for 4 h. The methanol was vacuum evaporated, and transesterification of the remained triglycerides was performed at 65 deg. C for 1 h in a reaction system containing 1 wt% of potassium hydroxide and 6:1 mole ratio of methanol to TG. The final product with 97.02% of biodiesel, obtained after the two step catalyzed process, was analyzed by gas chromatography. This new process has many advantages compared with the old processes, such as no acidic waste water, high efficiency, low equipment cost and easy recovery of the catalyst

  2. Understanding the hydrolysis mechanism of ethyl acetate catalyzed by an aqueous molybdocene: a computational chemistry investigation.

    Science.gov (United States)

    Tílvez, Elkin; Cárdenas-Jirón, Gloria I; Menéndez, María I; López, Ramón

    2015-02-16

    A thoroughly mechanistic investigation on the [Cp2Mo(OH)(OH2)](+)-catalyzed hydrolysis of ethyl acetate has been performed using density functional theory methodology together with continuum and discrete-continuum solvation models. The use of explicit water molecules in the PCM-B3LYP/aug-cc-pVTZ (aug-cc-pVTZ-PP for Mo)//PCM-B3LYP/aug-cc-pVDZ (aug-cc-pVDZ-PP for Mo) computations is crucial to show that the intramolecular hydroxo ligand attack is the preferred mechanism in agreement with experimental suggestions. Besides, the most stable intermediate located along this mechanism is analogous to that experimentally reported for the norbornenyl acetate hydrolysis catalyzed by molybdocenes. The three most relevant steps are the formation and cleavage of the tetrahedral intermediate immediately formed after the hydroxo ligand attack and the acetic acid formation, with the second one being the rate-determining step with a Gibbs energy barrier of 36.7 kcal/mol. Among several functionals checked, B3LYP-D3 and M06 give the best agreement with experiment as the rate-determining Gibbs energy barrier obtained only differs 0.2 and 0.7 kcal/mol, respectively, from that derived from the experimental kinetic constant measured at 296.15 K. In both cases, the acetic acid elimination becomes now the rate-determining step of the overall process as it is 0.4 kcal/mol less stable than the tetrahedral intermediate cleavage. Apart from clarifying the identity of the cyclic intermediate and discarding the tetrahedral intermediate formation as the rate-determining step for the mechanism of the acetyl acetate hydrolysis catalyzed by molybdocenes, the small difference in the Gibbs energy barrier found between the acetic acid formation and the tetrahedral intermediate cleavage also uncovers that the rate-determining step could change when studying the reactivity of carboxylic esters other than ethyl acetate substrate specific toward molybdocenes or other transition metal complexes. Therefore

  3. Sandstone-type uranium deposits. Summary and conclusions

    International Nuclear Information System (INIS)

    Finch, W.I.

    1985-01-01

    The similarity of most of the deposits described in this report is striking even though they occur in sandstone host rocks ranging in age from Carboniferous to Tertiary and on every continent outside the polar regions. Geologic environments of the uranium deposits consist of distinctive sets of tectonic and sedimentary-depositional systems, all of which have some common threads of favorable geologic processes. In this summary paper it is hoped that this report has sharpened an understanding of the deposit's ''home environment'' that will aid future exploration for these resource-important sandstone-type uranium ores

  4. catalyzed oxidation of formamidine derivative by hexacyanoferrate(III

    Indian Academy of Sciences (India)

    triazol-3-yl) formamidine (ATF) by hexacyanoferrate(III) (HCF) was studied spectrophotometrically in aqueous alkalinemedium. Both uncatalyzed and catalyzed reactions showed first order kinetics with respect to [HCF],whereas the reaction ...

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

    Science.gov (United States)

    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

  6. The Effect of Deposit Temperature on the Catalytic SO2-to-SO3 Conversion in a Copper Flash Smelting Heat Recovery Boiler

    Science.gov (United States)

    Lehmusto, Juho; Vainio, Emil; Laurén, Tor; Lindgren, Mari

    2018-02-01

    The aim of the work was to study the catalytic role of copper flash smelter deposit in the SO2-to-SO3 conversion. In addition, the effect of process gas temperature at 548 K to 1173 K (275 °C to 900 °C) on the amount of SO3 formed was addressed both in the absence and presence of genuine copper flash smelter deposit. The SO3 conversion rate changed as a function of process gas temperature, peaking at 1023 K (750 °C). A dramatic increase in the SO2-to-SO3 conversion was observed when process dust was present, clearly indicating that process dust catalyzes the SO2-to-SO3 conversion. Based on these results, the catalytic ability of the deposit may lead to sulfuric acid dew point corrosion.

  7. Highly selective cobalt-catalyzed hydrovinylation of styrene

    NARCIS (Netherlands)

    Grutters, M.M.P.; Müller, C.; Vogt, D.

    2006-01-01

    The hydrovinylation reaction is a codimerization of a 1,3-diene or vinyl arene and ethene with great potential for fine chemicals and pharmaceuticals. For the first time, enantioselective cobalt-catalyzed hydrovinylations of styrene were achieved with a cobalt-based system bearing a chiral

  8. UDP-glucuronyltransferase-catalyzed deconjugation of bilirubin monoglucuronide

    NARCIS (Netherlands)

    Cuypers, H. T.; ter Haar, E. M.; Jansen, P. L.

    1984-01-01

    Bilirubin monoglucuronide is rapidly deconjugated when incubated with UDP and rat liver microsomal preparations at pH 5.1. The following evidence was found that this reaction is catalyzed by UDP-glucuronyltransferase: (i) unconjugated bilirubin and UDP-glucuronic acid were identified as the reaction

  9. Transition Metal Catalyzed Synthesis of Carboxylic Acids, Imines, and Biaryls

    DEFF Research Database (Denmark)

    Santilli, Carola; Madsen, Robert

    the carboxylate.  Manganese catalyzed radical Kumada-type reaction between aryl halidesand aryl Grignard reagents. The reaction between aryl halides and aryl Grignard reagents catalyzed by MnCl2 has been extended to several methyl-substituted aryl iodide reagents byperforming the reaction at 120 ˚C in a microwave...... oven (Scheme ii). A limitation of the heterocoupling process is the concomitant dehalogenation of the aryl halide and homocoupling of the Grignard reagent leading low to moderate yields of the desired heterocoupling product. The mechanism of the cross-coupling process was investigated by performing two...

  10. Transition-Metal-Catalyzed Decarbonylative Coupling Reactions: Concepts, Classifications, and Applications

    KAUST Repository

    Guo, Lin; Rueping, Magnus

    2018-01-01

    Transition metal‐catalyzed decarbonylative coupling reactions have emerged as a powerful alternative to conventional cross‐coupling protocols due to the advantages associated with the use of carbonyl‐containing functionalities as coupling electrophiles instead of commonly used organohalides or sulfates. A wide variety of novel transformations based on this concept have been successfully achieved, including decarbonylative carbon–carbon and carbon–heteroatom bond forming reactions. In this Review, we summarize the recent progress in this field and present a comprehensive overview of metal‐catalyzed decarbonylative coupling reactions with carbonyl derivatives.

  11. Transition-Metal-Catalyzed Decarbonylative Coupling Reactions: Concepts, Classifications, and Applications

    KAUST Repository

    Guo, Lin

    2018-05-14

    Transition metal‐catalyzed decarbonylative coupling reactions have emerged as a powerful alternative to conventional cross‐coupling protocols due to the advantages associated with the use of carbonyl‐containing functionalities as coupling electrophiles instead of commonly used organohalides or sulfates. A wide variety of novel transformations based on this concept have been successfully achieved, including decarbonylative carbon–carbon and carbon–heteroatom bond forming reactions. In this Review, we summarize the recent progress in this field and present a comprehensive overview of metal‐catalyzed decarbonylative coupling reactions with carbonyl derivatives.

  12. Seasonal atmospheric deposition variations of polychlorinated biphenyls (PCBs) and comparison of some deposition sampling techniques.

    Science.gov (United States)

    Birgül, Askın; Tasdemir, Yücel

    2011-03-01

    Ambient air and bulk deposition samples were collected between June 2008 and June 2009. Eighty-three polychlorinated biphenyl (PCB) congeners were targeted in the samples. The average gas and particle PCB concentrations were found as 393 ± 278 and 70 ± 102 pg/m(3), respectively, and 85% of the atmospheric PCBs were in the gas phase. Bulk deposition samples were collected by using a sampler made of stainless steel. The average PCB bulk deposition flux value was determined as 6,020 ± 4,350 pg/m(2) day. The seasonal bulk deposition fluxes were not statistically different from each other, but the summer flux had higher values. Flux values differed depending on the precipitation levels. The average flux value in the rainy periods was 7,480 ± 4,080 pg/m(2) day while the average flux value in dry periods was 5,550 ± 4,420 pg/m(2) day. The obtained deposition values were lower than the reported values given for the urban and industrialized areas, yet close to the ones for the rural sites. The reported deposition values were also influenced by the type of the instruments used. The average dry deposition and total deposition velocity values calculated based on deposition and concentration values were found as 0.23 ± 0.21 and 0.13 ± 0.13 cm/s, respectively.

  13. Use of bortezomib in heavy-chain deposition disease: a report of 3 cases.

    Science.gov (United States)

    Patel, Kinjal; Dillon, John J; Leung, Nelson; Bomback, Andrew S; Appel, Gerald B; D'Agati, Vivette; Canetta, Pietro A

    2014-07-01

    Heavy-chain deposition disease (HCDD) is a rare complication of plasma cell dyscrasia in which monoclonal heavy chains deposit in glomerular and tubular basement membranes of the kidney. Clinical and pathologic features of HCDD have been well described in case reports and series, but evidence supporting specific therapies is sparse. Historically, the disease has had a poor prognosis, intensifying the need to clarify optimal treatments. We describe 3 cases of HCDD with biopsy-proven glomerular involvement, severe nephrotic syndrome, and decline in kidney function that were treated successfully with bortezomib, a proteasome inhibitor. None of these patients had multiple myeloma. In all cases, bortezomib-based therapy resulted in sustained resolution of nephrotic syndrome and improvement in kidney function. All 3 patients developed peripheral neuropathy; otherwise, treatment was well tolerated. To our knowledge, this is the first description of the clinical effectiveness of bortezomib against HCDD. Copyright © 2014 National Kidney Foundation, Inc. Published by Elsevier Inc. All rights reserved.

  14. Investigation of transition metal-catalyzed nitrene transfer reactions in water.

    Science.gov (United States)

    Alderson, Juliet M; Corbin, Joshua R; Schomaker, Jennifer M

    2018-04-11

    Transition metal-catalyzed nitrene transfer is a powerful method for incorporating new CN bonds into relatively unfunctionalized scaffolds. In this communication, we report the first examples of site- and chemoselective CH bond amination reactions in aqueous media. The unexpected ability to employ water as the solvent in these reactions is advantageous in that it eliminates toxic solvent use and enables reactions to be run at increased concentrations with lower oxidant loadings. Using water as the reaction medium has potential to expand the scope of nitrene transfer to encompass a variety of biomolecules and highly polar substrates, as well as enable pH control over the site-selectivity of CH bond amination. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. Recent advances in the ruthenium(ii)-catalyzed chelation-assisted C-H olefination of substituted aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway.

    Science.gov (United States)

    Manikandan, Rajendran; Jeganmohan, Masilamani

    2017-08-08

    The transition-metal-catalyzed chelation-assisted alkenylation at the inert C-H bond of aromatics with alkenes is one of the efficient methods to synthesize substituted vinylarenes in a highly regio- and stereoselective manner. Palladium, rhodium and ruthenium complexes are frequently used as catalysts for this type of transformation. The present review describes the recent advances in the ruthenium-catalyzed chelation-assisted alkenylation at the C-H bond of aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway. Several directing groups including 2-pyridyl, carbonyl, amidine, amide, amine, imidate, sulphonic acid, triazole, cyano, oxazolidinone and hydontoin are widely used in the reaction. The scope, limitation and mechanistic investigation of the alkenylation reactions are discussed elaborately. This feature article includes all the reported ruthenium-catalyzed alkenylation reactions via the deprotonation pathway until the end of March 2017.

  16. Acidic deposition: State of science and technology. Report 9. Current status of surface-water acid-base chemistry. Final report

    International Nuclear Information System (INIS)

    Baker, L.A.; Kaufmann, P.R.; Brakke, D.F.; Herlihy, A.T.; Eilers, J.M.

    1990-09-01

    The report is based largely upon the National Surface Water Survey (NSWS), augmented by numerous smaller state and university surveys and many detailed watershed studies. In describing the current status of surface waters, the authors go far beyond the description of population statistics, although some of this is necessary, and direct their attention to the interpretation of these data. They address the question of the sources of acidity to surface waters in order to determine the relative importance of acidic deposition compared with other sources, such as naturally produced organic acids and acid mine drainage. They also examine in some detail what they call 'high interest' populations-the specific groups of lakes and streams most likely to be impacted by acidic deposition. The authors then turn to the general question of uncertainty, and finally examine low alkalinity surface waters in several other parts of the world to develop further inferences about the acid-base status of surface waters in the United States

  17. Pd-Catalyzed Acetoxylation of γ-C(sp3)-H Bonds of Amines Directed by a Removable Bts-Protecting Group.

    Science.gov (United States)

    Zheng, Yong; Song, Weibin; Zhu, Yefu; Wei, Bole; Xuan, Lijiang

    2018-02-16

    Pd-catalyzed acetoxylation of γ-C(sp 3 )-H bonds directed by Bts-protected amines using inexpensive PhI(OAc) 2 as oxidant is reported. The Bts-protecting group is easily introduced and removed under mild conditions. This protocol provides an important strategy for the construction of γ-hydroxyl amine derivatives.

  18. Gold-catalyzed intermolecular coupling of sulfonylacetylene with allyl ethers: [3,3]- and [1,3]-rearrangements

    Directory of Open Access Journals (Sweden)

    Jungho Jun

    2013-08-01

    Full Text Available Gold-catalyzed intermolecular couplings of sulfonylacetylenes with allyl ethers are reported. A cooperative polarization of alkynes both by a gold catalyst and a sulfonyl substituent resulted in an efficient intermolecular tandem carboalkoxylation. Reactions of linear allyl ethers are consistent with the [3,3]-sigmatropic rearrangement mechanism, while those of branched allyl ethers provided [3,3]- and [1,3]-rearrangement products through the formation of a tight ion–dipole pair.

  19. Phosphine-catalyzed cycloadditions of allenic ketones: new substrates for nucleophilic catalysis.

    Science.gov (United States)

    Wallace, Debra J; Sidda, Rachel L; Reamer, Robert A

    2007-02-02

    A range of phosphine-catalyzed cycloaddition reactions of allenic ketones have been studied, extending the scope of these processes from the more widely used 2,3-butadienoates to allow access to a number of synthetically useful products. Reaction of allenyl methyl ketone 4 with exo-enones afforded spirocyclic compounds in good regioselectivity and promising enantioselectivity via a [2 + 3] cycloaddtion. Aromatic allenyl ketones undergo a phosphine-promoted dimerization to afford functionalized pyrans, leading to a formal [2 + 4] Diels-Alder product, but did not react in the [2 + 3] cycloaddition. The results from other reactions that had found utility with 2,3-butadienoates are also reported.

  20. Gold-catalyzed direct alkynylation of tryptophan in peptides using TIPS-EBX

    Directory of Open Access Journals (Sweden)

    Gergely L. Tolnai

    2016-04-01

    Full Text Available The selective functionalization of peptides containing only natural amino acids is important for the modification of biomolecules. In particular, the installation of an alkyne as a useful handle for bioconjugation is highly attractive, but the use of a carbon linker is usually required. Herein, we report the gold-catalyzed direct alkynylation of tryptophan in peptides using the hypervalent iodine reagent TIPS-EBX (1-[(triisopropylsilylethynyl]-1,2-benziodoxol-3(1H-one. The reaction proceeded in 50–78% yield under mild conditions and could be applied to peptides containing other nucleophilic and aromatic amino acids, such as serine, phenylalanine or tyrosine.

  1. Criteria for the recognition of pedogenic/supergene and nonpedogenic/hypogene deposits and their relationship to the origin of calcite/opal deposits at Yucca Mountain. Special report No. 14

    International Nuclear Information System (INIS)

    Hill, C.A.; Schluter, C.M.; Monger, H.C.

    1993-10-01

    This study is part of the research program of the Yucca Mountain Project intended to provide the State of Nevada with a detailed assessment of the geology and geochemistry of Yucca Mountain and adjacent regions. The purpose of this report is to try and establish criteria for the recognition of pedogenic/supergene deposits of calcite/opal versus non-pedogenic/hypogene deposits of calcite/opal. Far from being of esoteric concern, this subject is of paramount importance to the pedogenic-hypogene debate which rages around the suitability of Yucca Mountain as a high-level radioactive waste repository site

  2. Catalyzing alignment processes

    DEFF Research Database (Denmark)

    Lauridsen, Erik Hagelskjær; Jørgensen, Ulrik

    2004-01-01

    This paper describes how environmental management systems (EMS) spur the circulation of processes that support the constitution of environmental issues as specific environ¬mental objects and objectives. EMS catalyzes alignmentprocesses that produce coherence among the different elements involved......, the networks of environmental professionals that work in the environmental organisation, in consulting and regulatory enforcement, and dominating business cultures. These have previously been identified in the literature as individually significant in relation to the evolving environmental agendas...... they are implemented in and how the changing context is reflected in the environmental objectives that are established and prioritised. Our argument is, that the ability of the standard to achieve an impact is dependant on the constitution of ’coherent’ environmental issues in the context, where the management system...

  3. High performance polymer electrolyte fuel cells with ultra-low Pt loading electrodes prepared by dual ion-beam assisted deposition

    International Nuclear Information System (INIS)

    Saha, Madhu Sudan; Gulla, Andrea F.; Allen, Robert J.; Mukerjee, Sanjeev

    2006-01-01

    Ultra-low pure Pt-based electrodes (0.04-0.12 mg Pt /cm 2 ) were prepared by dual ion-beam assisted deposition (dual IBAD) method on the surface of a non-catalyzed gas diffusion layer (GDL) substrate. Film thicknesses ranged between 250 and 750 A, these are compared with a control, a conventional Pt/C (1.0 mg Pt(MEA) /cm 2 , E-TEK). The IBAD electrode constituted a significantly different morphology, where low density Pt deposits (largely amorphous) were formed with varying depths of penetration into the gas diffusion layer, exhibiting a gradual change towards increasing crystalline character (from 250 to 750 A). Mass specific power density of 0.297 g Pt /kW is reported with 250 A IBAD deposit (0.04 mg Pt /cm 2 for a total MEA loading of 0.08 mg Pt /cm 2 ) at 0.65 V. This is contrasted with the commercial MEA with a loading of 1 mg Pt(MEA) /cm 2 where mass specific power density obtained was 1.18 g Pt /kW (at 0.65 V), a value typical of current state of the art commercial electrodes containing Pt/C. The principal shortcoming in this effort is the area specific power density which was in the range of 0.27-0.43 W/cm 2 (for 250-750 A IBAD) at 0.65 V, hence much below the automotive target value of 0.8-0.9 W/cm 2 (at 0.65 V). An attempt to mitigate these losses is reported with the use of patterning. In this context a series of patterns ranging from 45 to 80% Pt coverage were used in conjunction with a hexagonal hole geometry. Up to 30% lowering of mass transport losses were realized

  4. Kinetic Behavior of Exchange-Driven Growth with Catalyzed-Birth Processes

    International Nuclear Information System (INIS)

    Wang Haifeng; Lin Zhenquan; Kong Xiangmu

    2006-01-01

    Two catalyzed-birth models of n-species (n≥2) aggregates with exchange-driven growth processes are proposed and compared. In the first one, the exchange reaction occurs between any two aggregates A m k and A m j of the same species with the rate kernels K m (k,j) = K m kj (m = 1,2,...,n, n≥2), and aggregates of A n species catalyze a monomer-birth of A l species (l = 1,2,...,n-1) with the catalysis rate kernel J l (k,j) = J l kj υ . The kinetic behaviors are investigated by means of the mean-field theory. We find that the evolution behavior of aggregate-size distribution a l k (t) of A l species depends crucially on the value of the catalysis rate parameter υ: (i) a l k (t) obeys the conventional scaling law in the case of υ≤0, (ii) a l k (t) satisfies a modified scaling form in the case of υ>0. In the second model, the mechanism of monomer-birth of A n -species catalyzed by A l species is added on the basis of the first model, that is, the aggregates of A l and A n species catalyze each other to cause monomer-birth. The kinetic behaviors of A l and A n species are found to fall into two categories for the different υ: (i) growth obeying conventional scaling form with υ≤0, (ii) gelling at finite time with υ>0.

  5. Applications of Palladium-Catalyzed C-N Cross-Coupling Reactions.

    Science.gov (United States)

    Ruiz-Castillo, Paula; Buchwald, Stephen L

    2016-10-12

    Pd-catalyzed cross-coupling reactions that form C-N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the widespread adoption of these methods has been the continued development of reliable and versatile catalysts that function under operationally simple, user-friendly conditions. This review provides an overview of Pd-catalyzed N-arylation reactions found in both basic and applied chemical research from 2008 to the present. Selected examples of C-N cross-coupling reactions between nine classes of nitrogen-based coupling partners and (pseudo)aryl halides are described for the synthesis of heterocycles, medicinally relevant compounds, natural products, organic materials, and catalysts.

  6. Synthesis of alpha-tetrasubstituted triazoles by copper-catalyzed silyl deprotection/azide cycloaddition

    Directory of Open Access Journals (Sweden)

    Zachary L. Palchak

    2015-08-01

    Full Text Available Propargylamines are popular substrates for triazole formation, but tetrasubstituted variants have required multistep syntheses involving stoichiometric amounts of metal. A recent cyclohexanone–amine–silylacetylene coupling forms silyl-protected tetrasubstituted propargylamines in a single copper-catalyzed step. The development of the tandem silyl deprotection–triazole formation reported herein offers rapid access to alpha-tetrasubstituted triazoles. A streamlined two-step approach to this uncommon class of hindered triazoles will accelerate exploration of their therapeutic potential. The superior activity of copper(II triflate in the formation of triazoles from sensitive alkyne substrates extends to simple terminal alkynes.

  7. Redox-Neutral Rhodium-Catalyzed [4+1] Annulation through Formal Dehydrogenative Vinylidene Insertion.

    Science.gov (United States)

    Liu, Huan; Song, Shengjin; Wang, Cheng-Qiang; Feng, Chao; Loh, Teck-Peng

    2017-01-10

    A synthetic protocol for the expedient construction of 5-methylene-1H-pyrrol-2(5H)-one derivatives through rhodium-catalyzed [4+1] annulation with gem-difluoroacrylate as the C 1 component was reported. By taking advantage of the twofold C-F bond cleavage occurring during the annulation, this reaction not only allows the synthesis of these heterocyclic compounds under overall oxidant-free conditions but also renders the transformation stereospecific. The very mild reaction conditions employed ensure compatibility with a wide variety of synthetically useful functional groups. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. The conversion of dimethyl ether over Pt/H-ZSM5. A bifunctional catalyzed reaction

    NARCIS (Netherlands)

    Engelen, C.W.R.; Wolthuizen, J.P.; Hooff, van J.H.C.; Imelik, B.; Naccache, C.; Coudurier, G.

    1985-01-01

    At low temperatures dimethylether mixed with hydrogen reacts over a platinum loaded H-ZSM5 catalyst selectivity to methane. Two successive steps can be distinguished; first the acid-catalyzed formation of a trimethyloxoniumion, followed by a metal-catalyzed hydrogenation to methane. Experiments with

  9. Development of a second generation palladium-catalyzed cycloalkenylation and its application to bioactive natural product synthesis.

    Science.gov (United States)

    Toyota, Masahiro

    2013-07-01

    A novel palladium-catalyzed intramolecular oxidative alkylation of unactivated olefins is described. This protocol was devised to solve one of the drawbacks of the original palladium-catalyzed cycloalkenylation that we developed. We call this new procedure the 'second generation palladium-catalyzed cycloalkenylation'. This protocol has been applied to the total syntheses of cis-195A, trans-195A, boonein, scholareins A, C, D, and alpha-skytanthine.

  10. Iridium‐Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols with the Liberation of Syngas

    DEFF Research Database (Denmark)

    Olsen, Esben Paul Krogh; Madsen, Robert

    2012-01-01

    A new iridium‐catalyzed reaction in which molecular hydrogen and carbon monoxide are cleaved from primary alcohols in the absence of any stoichiometric additives has been developed. The dehydrogenative decarbonylation was achieved with a catalyst generated in situ from [Ir(coe)2Cl]2 (coe=cyclooct......A new iridium‐catalyzed reaction in which molecular hydrogen and carbon monoxide are cleaved from primary alcohols in the absence of any stoichiometric additives has been developed. The dehydrogenative decarbonylation was achieved with a catalyst generated in situ from [Ir(coe)2Cl]2 (coe...... to excellent yields. Ethers, esters, imides, and aryl halides are stable under the reaction conditions, whereas olefins are partially saturated. The reaction is believed to proceed by two consecutive organometallic transformations that are catalyzed by the same iridium(I)–BINAP species. First, dehydrogenation...

  11. Enantioselective Intramolecular CH-Insertions upon Cu-Catalyzed Decomposition of Phenyliodonium Ylides

    Directory of Open Access Journals (Sweden)

    Christelle Boléa

    2001-02-01

    Full Text Available The Cu-catalyzed intramolecular CH insertion of phenyliodonium ylide 5b has been investigated at 0° C in the presence of several chiral ligands. Enantioselectivities vary in the range of 38–72 %, and are higher than those resulting from reaction of the diazo compound 5c at 65° C. The results are consistent with a carbenoid mechanism for Cu-catalyzed decomposition of phenyliodonium ylides.

  12. Aluminum-catalyzed silicon nanowires: Growth methods, properties, and applications

    Energy Technology Data Exchange (ETDEWEB)

    Hainey, Mel F.; Redwing, Joan M. [Department of Materials Science and Engineering, Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States)

    2016-12-15

    Metal-mediated vapor-liquid-solid (VLS) growth is a promising approach for the fabrication of silicon nanowires, although residual metal incorporation into the nanowires during growth can adversely impact electronic properties particularly when metals such as gold and copper are utilized. Aluminum, which acts as a shallow acceptor in silicon, is therefore of significant interest for the growth of p-type silicon nanowires but has presented challenges due to its propensity for oxidation. This paper summarizes the key aspects of aluminum-catalyzed nanowire growth along with wire properties and device results. In the first section, aluminum-catalyzed nanowire growth is discussed with a specific emphasis on methods to mitigate aluminum oxide formation. Next, the influence of growth parameters such as growth temperature, precursor partial pressure, and hydrogen partial pressure on nanowire morphology is discussed, followed by a brief review of the growth of templated and patterned arrays of nanowires. Aluminum incorporation into the nanowires is then discussed in detail, including measurements of the aluminum concentration within wires using atom probe tomography and assessment of electrical properties by four point resistance measurements. Finally, the use of aluminum-catalyzed VLS growth for device fabrication is reviewed including results on single-wire radial p-n junction solar cells and planar solar cells fabricated with nanowire/nanopyramid texturing.

  13. Cost analysis of simulated base-catalyzed biodiesel production processes

    International Nuclear Information System (INIS)

    Tasić, Marija B.; Stamenković, Olivera S.; Veljković, Vlada B.

    2014-01-01

    Highlights: • Two semi-continuous biodiesel production processes from sunflower oil are simulated. • Simulations were based on the kinetics of base-catalyzed methanolysis reactions. • The total energy consumption was influenced by the kinetic model. • Heterogeneous base-catalyzed process is a preferable industrial technology. - Abstract: The simulation and economic feasibility evaluation of semi-continuous biodiesel production from sunflower oil were based on the kinetics of homogeneously (Process I) and heterogeneously (Process II) base-catalyzed methanolysis reactions. The annual plant’s capacity was determined to be 8356 tonnes of biodiesel. The total energy consumption was influenced by the unit model describing the methanolysis reaction kinetics. The energy consumption of the Process II was more than 2.5 times lower than that of the Process I. Also, the simulation showed the Process I had more and larger process equipment units, compared with the Process II. Based on lower total capital investment costs and biodiesel selling price, the Process II was economically more feasible than the Process I. Sensitivity analysis was conducted using variable sunflower oil and biodiesel prices. Using a biodiesel selling price of 0.990 $/kg, Processes I and II were shown to be economically profitable if the sunflower oil price was 0.525 $/kg and 0.696 $/kg, respectively

  14. Protection of Wood from Microorganisms by Laccase-Catalyzed Iodination

    Science.gov (United States)

    Engel, J.; Thöny-Meyer, L.; Schwarze, F. W. M. R.; Ihssen, J.

    2012-01-01

    In the present work, Norway spruce wood (Picea abies L.) was reacted with a commercial Trametes versicolor laccase in the presence of potassium iodide salt or the phenolic compounds thymol and isoeugenol to impart an antimicrobial property to the wood surface. In order to assess the efficacy of the wood treatment, a leaching of the iodinated and polymerized wood and two biotests including bacteria, a yeast, blue stain fungi, and wood decay fungi were performed. After laccase-catalyzed oxidation of the phenols, the antimicrobial effect was significantly reduced. In contrast, the enzymatic oxidation of iodide (I−) to iodine (I2) in the presence of wood led to an enhanced resistance of the wood surface against all microorganisms, even after exposure to leaching. The efficiency of the enzymatic wood iodination was comparable to that of a chemical wood preservative, VP 7/260a. The modification of the lignocellulose by the laccase-catalyzed iodination was assessed by the Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) technique. The intensities of the selected lignin-associated bands and carbohydrate reference bands were analyzed, and the results indicated a structural change in the lignin matrix. The results suggest that the laccase-catalyzed iodination of the wood surface presents an efficient and ecofriendly method for wood protection. PMID:22865075

  15. Silver-Catalyzed Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols

    DEFF Research Database (Denmark)

    Ghalehshahi, Hajar Golshadi; Madsen, Robert

    2017-01-01

    A simple silver-catalyzed protocol has been developed for the acceptorless dehydrogenation of primary alcohols into carboxylic acids and hydrogen gas. The procedure uses 2.5 % Ag2 CO3 and 2.5-3 equiv of KOH in refluxing mesitylene to afford the potassium carboxylate which is then converted...... into the acid with HCl. The reaction can be applied to a variety of benzylic and aliphatic primary alcohols with alkyl and ether substituents, and in some cases halide, olefin, and ester functionalities are also compatible with the reaction conditions. The dehydrogenation is believed to be catalyzed by silver...

  16. Nitrous oxide-forming codenitrification catalyzed by cytochrome P450nor.

    Science.gov (United States)

    Su, Fei; Takaya, Naoki; Shoun, Hirofumi

    2004-02-01

    Intact cells of the denitrifying fungus Fusarium oxysporum were previously shown to catalyze codenitrification to form a hybrid nitrous oxide (N2O) species from nitrite and other nitrogen compounds such as azide and ammonia. Here we show that cytochrome P450nor can catalyze the codenitrification reaction to form N2O from nitric oxide (NO) but not nitrite, and azide or ammonia. The results show that the direct substrate of the codenitrification by intact cells should not be nitrite but NO, which is formed from nitrite by the reaction of a dissimilatory nitrite reductase.

  17. Structural Determinants of Alkyne Reactivity in Copper-Catalyzed Azide-Alkyne Cycloadditions

    Directory of Open Access Journals (Sweden)

    Xiaoguang Zhang

    2016-12-01

    Full Text Available This work represents our initial effort in identifying azide/alkyne pairs for optimal reactivity in copper-catalyzed azide-alkyne cycloaddition (CuAAC reactions. In previous works, we have identified chelating azides, in particular 2-picolyl azide, as “privileged” azide substrates with high CuAAC reactivity. In the current work, two types of alkynes are shown to undergo rapid CuAAC reactions under both copper(II- (via an induction period and copper(I-catalyzed conditions. The first type of the alkynes bears relatively acidic ethynyl C-H bonds, while the second type contains an N-(triazolylmethylpropargylic moiety that produces a self-accelerating effect. The rankings of reactivity under both copper(II- and copper(I-catalyzed conditions are provided. The observations on how other reaction parameters such as accelerating ligand, reducing agent, or identity of azide alter the relative reactivity of alkynes are described and, to the best of our ability, explained.

  18. Radial Growth of Self-Catalyzed GaAs Nanowires and the Evolution of the Liquid Ga-Droplet Studied by Time-Resolved in Situ X-ray Diffraction.

    Science.gov (United States)

    Schroth, Philipp; Jakob, Julian; Feigl, Ludwig; Mostafavi Kashani, Seyed Mohammad; Vogel, Jonas; Strempfer, Jörg; Keller, Thomas F; Pietsch, Ullrich; Baumbach, Tilo

    2018-01-10

    We report on a growth study of self-catalyzed GaAs nanowires based on time-resolved in situ X-ray structure characterization during molecular-beam-epitaxy in combination with ex situ scanning-electron-microscopy. We reveal the evolution of nanowire radius and polytypism and distinguish radial growth processes responsible for tapering and side-wall growth. We interpret our results using a model for diameter self-stabilization processes during growth of self-catalyzed GaAs nanowires including the shape of the liquid Ga-droplet and its evolution during growth.

  19. Influence of the catalyzer in the esterification of the sugarcane bagasse fibers

    International Nuclear Information System (INIS)

    Maia, Tatiana F.; Mulinari, Daniella R.; Suzuki, Paulo A.

    2011-01-01

    In this work chemical modification of the sugarcane bagasse fibers by anhydride system using amount Abstract: In this work chemical modification of the sugarcane bagasse fibers by anhydride system using amount different of catalyze was studied. The chemical modification of the fibers was evaluated by techniques of X-Ray Diffractometry (XRD) and Infrared Spectrophotometer (FTIR). Results showed that the amount of catalyze influenced in the chemical modification of the fibers. (author)

  20. Base catalyzed decomposition of toxic and hazardous chemicals

    International Nuclear Information System (INIS)

    Rogers, C.J.; Kornel, A.; Sparks, H.L.

    1991-01-01

    There are vast amounts of toxic and hazardous chemicals, which have pervaded our environment during the past fifty years, leaving us with serious, crucial problems of remediation and disposal. The accumulation of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), ''dioxins'' and pesticides in soil sediments and living systems is a serious problem that is receiving considerable attention concerning the cancer-causing nature of these synthetic compounds.US EPA scientists developed in 1989 and 1990 two novel chemical Processes to effect the dehalogenation of chlorinated solvents, PCBs, PCDDs, PCDFs, PCP and other pollutants in soil, sludge, sediment and liquids. This improved technology employs hydrogen as a nucleophile to replace halogens on halogenated compounds. Hydrogen as nucleophile is not influenced by steric hinderance as with other nucleophile where complete dehalogenation of organohalogens can be achieved. This report discusses catalyzed decomposition of toxic and hazardous chemicals

  1. An optimized hydrogen target for muon catalyzed fusion

    Energy Technology Data Exchange (ETDEWEB)

    Gheisari, R., E-mail: gheisari@pgu.ac.i [Physics Department, Persian Gulf University, Bushehr 75169 (Iran, Islamic Republic of)

    2011-04-01

    This paper deals with the optimization of the processes involved in muon catalyzed fusion. Muon catalyzed fusion ({mu}CF) is studied in all layers of the solid hydrogen structure H/0.1%T+D{sub 2}+HD. The layer H/T acts as an emitter source of energetic t{mu} atoms, due to the so-called Ramsauer-Townsend effect. These t{mu} atoms are slowed down in the second layer (degrader) and are forced to take place nuclear fusion in HD. The degrader affects time evolution of t{mu} atomic beam. This effect has not been considered until now in {mu}CF-multilayered targets. Due to muon cycling and this effect, considerable reactions occur in the degrader. In our calculations, it is shown that the fusion yield equals 180{+-}1.5. It is possible to separate events that overlap in time.

  2. Effects of deposition time in chemically deposited ZnS films in acidic solution

    Energy Technology Data Exchange (ETDEWEB)

    Haddad, H.; Chelouche, A., E-mail: azeddinechelouche@gmail.com; Talantikite, D.; Merzouk, H.; Boudjouan, F.; Djouadi, D.

    2015-08-31

    We report an experimental study on the synthesis and characterization of zinc sulfide (ZnS) single layer thin films deposited on glass substrates by chemical bath deposition technique in acidic solution. The effect of deposition time on the microstructure, surface morphology, optical absorption, transmittance, and photoluminescence (PL) was investigated by X-ray diffraction (XRD), scanning electronic microscopy (SEM), UV-Vis–NIR spectrophotometry and photoluminescence (PL) spectroscopy. The results showed that the samples exhibit wurtzite structure and their crystal quality is improved by increasing deposition time. The latter, was found to affect the morphology of the thin films as showed by SEM micrographs. The optical measurements revealed a high transparency in the visible range and a dependence of absorption edge and band gap on deposition time. The room temperature PL spectra indicated that all ZnS grown thin films emit a UV and blue light, while the band intensities are found to be dependent on deposition times. - Highlights: • Single layer ZnS thin films were deposited by CBD in acidic solution at 95 °C. • The effect of deposition time was investigated. • Coexistence of ZnS and ZnO hexagonal structures for time deposition below 2 h • Thicker ZnS films were achieved after monolayer deposition for 5 h. • The highest UV-blue emission observed in thin film deposited at 5 h.

  3. Synthesis of ketene N,N-acetals by copper-catalyzed double-amidation of 1,1-dibromo-1-alkenes.

    Science.gov (United States)

    Coste, Alexis; Couty, François; Evano, Gwilherm

    2009-10-01

    An efficient procedure for the preparation of ketene N,N-acetals by copper-catalyzed double amidation of 1,1-dibromo-1-alkenes is reported. The reaction was found to be general, and ketene aminals could be obtained in good yields when potassium phosphate in toluene was used at 80 degrees C. The reaction was found to proceed through a regioselective monocoupling reaction followed by dehydrobromination and hydroamidation.

  4. Glycolysis of poly (3-hydroxybutyrate) catalyzed by an enzyme system

    International Nuclear Information System (INIS)

    Campos, T.F.; Mano, V.

    2010-01-01

    In this work we report the studies of PHB glycolysis catalyzed by lipase Amano PS (Pseudomonas cepacia) in the presence of 1,2-ethanediol (ethylene glycol). The reactions were performed in toluene:dichloroethane 3:1 (v/v) at 60 deg C, varying reaction time and concentration of ethylene glycol. PHB and the products of glycolysis (polyols) were characterized by FTIR, 1 H-NMR, and TG. The FTIR spectra of polyols showed no significant change compared to the spectrum of PHB. The 1 H-NMR spectra of the products of glycolysis showed signs of interest between 3 and 4.7 ppm, related to the ethylene glycol protons inserted in the polymer chain. By analyzing the thermograms we observed that the polyols are more thermally stable than PHB. (author)

  5. Oxidation and reduction of copper and iron species in steam generator deposits - Effects of hydrazine, carbohydrazide and catalyzed hydrazine

    International Nuclear Information System (INIS)

    Marks, C.R.; Varrin, R.D.; Gorman, J.A.; McIlree, A.R.; Stanley, R.

    2002-01-01

    It has long been suspected that oxidation and reduction of secondary side deposits in PWR steam generators have a significant influence on the onset of intergranular attack and stress corrosion cracking (IGA/SCC) of mill annealed Alloy 600 steam generator tubes. It is believed that these same processes could affect the possible future occurrence of IGA/SCC of thermally treated Alloy 600 and Alloy 690 tubes that are in newer steam generators. The working hypothesis for describing the influence of oxides on accelerated tube degradation is that deposits formed during normal operation are oxidized during lay-up. During subsequent operation, these oxidized species accelerate tube degradation by raising the electrochemical potential. (authors)

  6. Lipase catalyzed ester synthesis for food processing industries

    Directory of Open Access Journals (Sweden)

    Aravindan Rajendran

    2009-02-01

    Full Text Available Lipases are one of the most important industrial biocatalyst which catalyzes the hydrolysis of lipids. It can also reverse the reaction at minimum water activity. Because of this pliable nature, it is widely exploited to catalyze the diverse bioconversion reactions, such as hydrolysis, esterification, interesterification, alcoholysis, acidolysis and aminolysis. The property to synthesize the esters from the fatty acids and glycerol promotes its use in various ester synthesis. The esters synthesized by lipase finds applications in numerous fields such as biodiesel production, resolution of the recemic drugs, fat and lipid modification, flavour synthesis, synthesis of enantiopure pharmaceuticals and nutraceuticals. It plays a crucial role in the food processing industries since the process is unaffected by the unwanted side products. Lipase modifications such as the surfactant coating, molecular imprinting to suit for the non-aqueous ester synthesis have also been reported. This review deals with lipase catalyzed ester synthesis, esterification strategies, optimum conditions and their applications in food processing industries.Lipases são catalizadores industriais dos mais importantes, os quais catalizam a hidrólise de lipídeos. Também podem reverter a reação a um mínimo de atividade de água. Devido sua natureza flexível, é amplamente explorada para catalizar uma diversidade de reações de bioconversão como hidrólise, esterificação, interesterificação, alcoólise, acidólise e aminólise. A propriedade de síntese de esteres a partir de ácidos graxos e glicerol promoveu seu uso em várias sínteses de esteres. Os esteres sintetizados por lipases encontram aplicação em numerosos campos como a produção de biodiesel, resolução de drogas racêmicas, modificação de gorduras e lipídios, sintese de aromas, síntese de produtos farmacêuticos enantiopuro e nutracêuticos. As lipases possuem um papel crucial nas indústrias de

  7. Measurements of dry-deposition parameters for the California acid-deposition monitoring program. Final report

    International Nuclear Information System (INIS)

    Watson, J.G.; Chow, J.C.; Egami, R.T.; Bowen, J.L.; Frazier, C.A.

    1991-06-01

    The State of California monitors the concentrations of acidic gases and particles at 10 sites throughout the state. Seven sites represent urban areas (South Coast Air Basin - three sites, San Francisco Bay Area, Bakersfield, Santa Barbara, and Sacramento) and three represent forested areas (Sequoia National Park, Yosemite National Park, and Gasquet). Several sites are collocated with monitoring instruments for other air quality and forest response networks. Continuous monitors for the dry deposition network collect hourly average values for ozone, wind speed, wind direction, atmospheric stability, temperature, dew point, time of wetness, and solar radiation. A newly-designed gas/particle sampler collects daytime (6 a.m. to 6 p.m.) and nighttime (6 p.m. to 6 a.m.) samples every sixth day for sulfur dioxide, ammonia, nitrogen dioxide, and nitric acid. Particles are collected on the same day/night schedule in PM(10) and PM(2.5) size ranges, and are analyzed for mass, sulfate, nitrate, chloride, ammonium, sodium, magnesium, potassium, and calcium ions. The sampling schedule follows the regulatory schedule adopted by the EPA and ARB for suspended particulate matter. Wet deposition data are collected at or nearby the dry deposition stations. The first year of the monitoring program included installation of the network, training of technicians, acquisition and validation of data, and transfer of the sampling and analysis technology to Air Resources Board operating divisions. Data have been validated and stored for the period May, 1988 through September, 1989

  8. Regioselective C2 Oxidative Olefination of Indoles and Pyrroles through Cationic Rhodium(III)-Catalyzed C-H Bond Activation.

    Science.gov (United States)

    Li, Bin; Ma, Jianfeng; Xie, Weijia; Song, Haibin; Xu, Shansheng; Wang, Baiquan

    2013-09-02

    Be economic with your atoms! An efficient Rh-catalyzed oxidative olefination of indoles and pyrroles with broad substrate scope and tolerance is reported. The catalytic reaction proceeds with excellent regio- and stereoselectivity. The directing group N,N-dimethylcarbamoyl was crucial for the reaction and could be removed easily. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Iron-Catalyzed C-O Bond Activation: Opportunity for Sustainable Catalysis.

    Science.gov (United States)

    Bisz, Elwira; Szostak, Michal

    2017-10-23

    Oxygen-based electrophiles have emerged as some of the most valuable cross-coupling partners in organic synthesis due to several major strategic and environmental benefits, such as abundance and potential to avoid toxic halide waste. In this context, iron-catalyzed C-O activation/cross-coupling holds particular promise to achieve sustainable catalytic protocols due to its natural abundance, inherent low toxicity, and excellent economic and ecological profile. Recently, tremendous progress has been achieved in the development of new methods for functional-group-tolerant iron-catalyzed cross-coupling reactions by selective C-O cleavage. These methods establish highly attractive alternatives to traditional cross-coupling reactions by using halides as electrophilic partners. In particular, new easily accessible oxygen-based electrophiles have emerged as substrates in iron-catalyzed cross-coupling reactions, which significantly broaden the scope of this catalysis platform. New mechanistic manifolds involving iron catalysis have been established; thus opening up vistas for the development of a wide range of unprecedented reactions. The synthetic potential of this sustainable mode of reactivity has been highlighted by the development of new strategies in the construction of complex motifs, including in target synthesis. The most recent advances in sustainable iron-catalyzed cross-coupling of C-O-based electrophiles are reviewed, with a focus on both mechanistic aspects and synthetic utility. It should be noted that this catalytic manifold provides access to motifs that are often not easily available by other methods, such as the assembly of stereodefined dienes or C(sp 2 )-C(sp 3 ) cross-couplings, thus emphasizing the synthetic importance of this mode of reactivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Whey protein isolate with improved film properties through cross-linking catalyzed by small laccase from Streptomyces coelicolor.

    Science.gov (United States)

    Quan, Wei; Zhang, Chong; Zheng, Meixia; Lu, Zhaoxin; Lu, Fengxia

    2018-08-01

    The effects of small laccase (SLAC) from Streptomyces coelicolor on the properties of whey protein isolate (WPI) films were studied. WPI was catalyze by SLAC without phenolic acid assistance. Particle size distribution results showed that some complexes with higher relative molecular weight formed in WPI samples treated with SLAC. The content of α-helixes decreased while those of β-sheets and random coils increased following SLAC treatment according to circular dichroism results. Fourier transform infrared spectral analysis suggested that some conformational changes occurred in WPI following SLAC treatment. Analysis of WPI films prepared by casting after SLAC treatment indicated that their film properties were all improved, including mechanical properties, solubility, water vapor, oxygen and carbon dioxide barrier properties, film color, light transmission, transparency and thermal properties. Compared with that of the control film, some obvious differences in the morphology of the WPI films were observed following SLAC treatment. This report demonstrates that laccase can directly catalyze protein cross-linking, which may be useful to improve the performance of protein films. In this study, SLAC was applied to WPI edible film during the film-making process. The results showed that SLAC can catalyze WPI cross-linking without phenolic acid assistance, and WPI film properties were improved after SLAC treatment. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

  11. Generating single-photon catalyzed coherent states with quantum-optical catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Xue-xiang, E-mail: xuxuexiang@jxnu.edu.cn [Center for Quantum Science and Technology, Jiangxi Normal University, Nanchang 330022 (China); Yuan, Hong-chun [College of Electrical and Optoelectronic Engineering, Changzhou Institute of Technology, Changzhou 213002 (China)

    2016-07-15

    We theoretically generate single-photon catalyzed coherent states (SPCCSs) by means of quantum-optical catalysis based on the beam splitter (BS) or the parametric amplifier (PA). These states are obtained in one of the BS (or PA) output channels if a coherent state and a single-photon Fock state are present in two input ports and a single photon is registered in the other output port. The success probabilities of the detection (also the normalization factors) are discussed, which is different for BS and PA catalysis. In addition, we prove that the generated states catalyzed by BS and PA devices are actually the same quantum states after analyzing photon number distribution of the SPCCSs. The quantum properties of the SPCCSs, such as sub-Poissonian distribution, anti-bunching effect, quadrature squeezing effect, and the negativity of the Wigner function are investigated in detail. The results show that the SPCCSs are non-Gaussian states with an abundance of nonclassicality. - Highlights: • We generate single-photon catalyzed coherent states with quantum-optical catalysis. • We prove the equivalent effects of the lossless beam splitter and the non-degenerate parametric amplifier. • Some nonclassical properties of the generated states are investigated in detail.

  12. Identification of two alpha-ketoglutarate-dependent dioxygenases in extracts of Rhodotorula glutinis catalyzing deoxyuridine hydroxylation

    International Nuclear Information System (INIS)

    Stubbe, J.

    1985-01-01

    Attempts to isolate deoxyuridine 2'-hydroxylase from Rhodotorula glutinis J. Biol. Chem. 258, 10551-10557) have led to the identification and partial purification of a newly recognized alpha-ketoglutarate-requiring oxygenase. This activity, designated deoxyuridine (uridine) 1'-hydroxylase, in the presence of iron and ascorbate, catalyzes the conversion of deoxyuridine (uridine), O 2 , and alpha-ketoglutarate to uracil, deoxyribonolactone (ribonolactone), CO 2 , and succinate. Incubation of [1'- 3 H]uridine with this activity results in time-dependent formation of uracil concomitant with production of CO 2 and 3H 2 O. Also reported in this paper is the partial purification and characterization of the alpha-ketoglutarate-requiring enzyme, deoxyuridine 2'-hydroxylase. Incubation of [2'-alpha- 3 H]deoxyuridine with this activity results in concomitant production of uridine and 3H 2 O. Incubation with [2'-beta- 3 H] deoxyuridine results in the production of uridine whose specific activity is identical to that of the starting material. This enzyme catalyzes the conversion of deoxyuridine to uridine with retention of configuration. No isotope effect is observed on this transformation

  13. Co-deposition of Pt and ceria anode catalyst in supercritical carbon dioxide for direct methanol fuel cell applications

    International Nuclear Information System (INIS)

    You, Eunyoung; Guzmán-Blas, Rolando; Nicolau, Eduardo; Aulice Scibioh, M.; Karanikas, Christos F.; Watkins, James J.; Cabrera, Carlos R.

    2012-01-01

    Pt and mixed Pt-ceria catalysts were deposited onto gas diffusion layers using supercritical fluid deposition (SFD) to fabricate thin layer electrodes for direct methanol fuel cells. Dimethyl (1,5-cyclooctadiene) platinum (II) (CODPtMe 2 ) and tetrakis (2,2,6,6-tetramethyl 3,5-heptanedionato) cerium (IV) (Ce(tmhd) 4 ) were used as precursors. Hydrogen-assisted Pt deposition was performed in compressed carbon dioxide at 60 °C and 17.2 MPa to yield high purity Pt on carbon-black based gas diffusion layers. During the preparation of the mixed Pt-ceria catalyst, hydrogen reduction of CODPtMe 2 to yield Pt catalyzed the deposition of ceria from Ce(tmhd) 4 enabling co-deposition at 150 °C. The catalyst layers were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscope-energy dispersive spectral (SEM-EDS) analyses. Their electrochemical performance toward methanol oxidation was examined in half cell mode using a three electrode assembly as well as in fuel cell mode. The thin layer electrodes formed via SFD exhibited higher performance in fuel cell operations compared to those prepared by the conventional brush-paint method. Furthermore, the Pt-ceria catalyst with an optimized composition exhibited greater methanol oxidation activity than pure platinum.

  14. Au-Cu core-shell nanocube-catalyzed click reactions for efficient synthesis of diverse triazoles.

    Science.gov (United States)

    Madasu, Mahesh; Hsia, Chi-Fu; Huang, Michael H

    2017-06-01

    Au-Cu core-shell nanocubes and octahedra synthesized in aqueous solution were employed to catalyze a 1,3-dipolar cycloaddition reaction between phenylacetylene and benzyl azide in water at 50 °C for 3 h. Interestingly, the nanocubes were far more efficient in catalyzing this reaction, giving 91% yield of a regioselective 1,4-triazole product, while octahedra only recorded 46% yield. The Au-Cu nanocubes were subsequently employed to catalyze the click reaction between benzyl azide and a broad range of aromatic and aliphatic alkynes. The product yields ranged from 78 to 99%. Clearly the Au-Cu cubes exposing {100} surfaces are an excellent and green catalyst for click reactions.

  15. Zeolite 5A Catalyzed Etherification of Diphenylmethanol

    Science.gov (United States)

    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…

  16. Palladium-Catalyzed Asymmetric Allylic Alkylation of 4-Substituted Isoxazolidin-5-ones: Straightforward Access to β2,2 -Amino Acids.

    Science.gov (United States)

    Nascimento de Oliveira, Marllon; Arseniyadis, Stellios; Cossy, Janine

    2018-04-03

    We report here an unprecedented and highly enantioselective palladium-catalyzed allylic alkylation applied to 4-substituted isoxazolidin-5-ones. Ultimately, the process provides a straightforward access to β 2,2 -amino acids bearing an all-carbon quaternary stereogenic center in great yields and a high degree of enantioselectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. AB/sub 5/-catalyzed hydrogen evolution cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Hall, D E; Sawada, T; Shepard, V R; Tsujikawa, Y

    1984-01-01

    The AB/sub 5/ metal compounds are highly efficient hydrogen evolution electrocatalysts in alkaline electrolyte. Three types of AB/sub 5/-catalyzed cathode structures were made, using the hydride-forming AB/sub 5/ compounds in particulate form. Plastic-bonded cathodes containing >90 w/o AB/sub 5/ (finished-weight basis) were the most efficient, giving hydrogen evolution overpotentials (/eta/ /SUB H2/ ) of about 0.05 V at 200 mA cm/sup -2/. However, they tended to swell and shed material during electrolysis. Pressed, sintered cathodes containing 40-70 w/o catalyst in a nickel binder gave /eta/ /SUB H2/ about0.08 V; catalyst retention was excellent. Porous, sintered cathode coatings were made with 30-70 w/o AB/sub 5/ catalyst loadings. Their overpotentials were similar to those of the pressed, sintered cathodes. However, at catalyst loadings below about 40 w/o, high overpotentials characteristic of the nickel binder were observed. The structural and electrochemical properties of the three AB/sub 5/-catalyzed cathodes are discussed.

  18. Zirconium(IV)-Catalyzed Ring Opening of on-DNA Epoxides in Water.

    Science.gov (United States)

    Fan, Lijun; Davie, Christopher P

    2017-05-04

    DNA-encoded library technology (ELT) has spurred wide interest in the pharmaceutical industry as a powerful tool for hit and lead generation. In recent years a number of "DNA-compatible" chemical modifications have been published and used to synthesize vastly diverse screening libraries. Herein we report a newly developed, zirconium tetrakis(dodecyl sulfate) [Zr(DS) 4 ] catalyzed ring-opening of on-DNA epoxides in water with amines, including anilines. Subsequent cyclization of the resulting on-DNA β-amino alcohols leads to a variety of biologically interesting, nonaromatic heterocycles. Under these conditions, a library of 137 million on-DNA β-amino alcohols and their cyclization products was assembled. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. FeBr3-catalyzed dibromination of alkenes and alkynes

    Institute of Scientific and Technical Information of China (English)

    Yun Fa Zheng; Jian Yu; Guo Bing Yan; Xu Li; Song Luo

    2011-01-01

    The dibromination of alkenes and alkynes with bromosuccinimide and sodium bromide catalyzed by FeBr3 under mild conditions has been developed. The trans-dibromo compounds were exclusively obtained with excellent yields.

  20. On the Temperature Dependence of Enzyme-Catalyzed Rates.

    Science.gov (United States)

    Arcus, Vickery L; Prentice, Erica J; Hobbs, Joanne K; Mulholland, Adrian J; Van der Kamp, Marc W; Pudney, Christopher R; Parker, Emily J; Schipper, Louis A

    2016-03-29

    One of the critical variables that determine the rate of any reaction is temperature. For biological systems, the effects of temperature are convoluted with myriad (and often opposing) contributions from enzyme catalysis, protein stability, and temperature-dependent regulation, for example. We have coined the phrase "macromolecular rate theory (MMRT)" to describe the temperature dependence of enzyme-catalyzed rates independent of stability or regulatory processes. Central to MMRT is the observation that enzyme-catalyzed reactions occur with significant values of ΔCp(‡) that are in general negative. That is, the heat capacity (Cp) for the enzyme-substrate complex is generally larger than the Cp for the enzyme-transition state complex. Consistent with a classical description of enzyme catalysis, a negative value for ΔCp(‡) is the result of the enzyme binding relatively weakly to the substrate and very tightly to the transition state. This observation of negative ΔCp(‡) has important implications for the temperature dependence of enzyme-catalyzed rates. Here, we lay out the fundamentals of MMRT. We present a number of hypotheses that arise directly from MMRT including a theoretical justification for the large size of enzymes and the basis for their optimum temperatures. We rationalize the behavior of psychrophilic enzymes and describe a "psychrophilic trap" which places limits on the evolution of enzymes in low temperature environments. One of the defining characteristics of biology is catalysis of chemical reactions by enzymes, and enzymes drive much of metabolism. Therefore, we also expect to see characteristics of MMRT at the level of cells, whole organisms, and even ecosystems.

  1. Automated Quantum Mechanical Predictions of Enantioselectivity in a Rhodium-Catalyzed Asymmetric Hydrogenation.

    Science.gov (United States)

    Guan, Yanfei; Wheeler, Steven E

    2017-07-24

    A computational toolkit (AARON: An automated reaction optimizer for new catalysts) is described that automates the density functional theory (DFT) based screening of chiral ligands for transition-metal-catalyzed reactions with well-defined reaction mechanisms but multiple stereocontrolling transition states. This is demonstrated for the Rh-catalyzed asymmetric hydrogenation of (E)-β-aryl-N-acetyl enamides, for which a new C 2 -symmetric phosphorus ligand is designed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Biodiesel production from Jatropha curcas oil catalyzed by whole ...

    African Journals Online (AJOL)

    my mord

    2013-07-03

    Jul 3, 2013 ... catalyzed by whole cells of Aureobasidium pullulans var. melanogenum ... friendly and renewable fuel that can be used directly in diesel engines ... methanol (or supercritical ethanol) transesterification is not commercially ...

  3. Noble metal catalyzed aqueous phase hydrogenation and hydrodeoxygenation of lignin-derived pyrolysis oil and related model compounds.

    Science.gov (United States)

    Mu, Wei; Ben, Haoxi; Du, Xiaotang; Zhang, Xiaodan; Hu, Fan; Liu, Wei; Ragauskas, Arthur J; Deng, Yulin

    2014-12-01

    Aqueous phase hydrodeoxygenation of lignin pyrolysis oil and related model compounds were investigated using four noble metals supported on activated carbon. The hydrodeoxygenation of guaiacol has three major reaction pathways and the demethylation reaction, mainly catalyzed by Pd, Pt and Rh, produces catechol as the products. The presence of catechol and guaiacol in the reaction is responsible for the coke formation and the catalysts deactivation. As expected, there was a significant decrease in the specific surface area of Pd, Pt and Rh catalysts during the catalytic reaction because of the coke deposition. In contrast, no catechol was produced from guaiacol when Ru was used so a completely hydrogenation was accomplished. The lignin pyrolysis oil upgrading with Pt and Ru catalysts further validated the reaction mechanism deduced from model compounds. Fully hydrogenated bio-oil was produced with Ru catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. A Complete Reporting of MCNP6 Validation Results for Electron Energy Deposition in Single-Layer Extended Media for Source Energies <= 1-MeV

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Hughes, Henry Grady [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-05-04

    In this paper, we expand on previous validation work by Dixon and Hughes. That is, we present a more complete suite of validation results with respect to to the well-known Lockwood energy deposition experiment. Lockwood et al. measured energy deposition in materials including beryllium, carbon, aluminum, iron, copper, molybdenum, tantalum, and uranium, for both single- and multi-layer 1-D geometries. Source configurations included mono-energetic, mono-directional electron beams with energies of 0.05-MeV, 0.1-MeV, 0.3- MeV, 0.5-MeV, and 1-MeV, in both normal and off-normal angles of incidence. These experiments are particularly valuable for validating electron transport codes, because they are closely represented by simulating pencil beams incident on 1-D semi-infinite slabs with and without material interfaces. Herein, we include total energy deposition and energy deposition profiles for the single-layer experiments reported by Lockwood et al. (a more complete multi-layer validation will follow in another report).

  5. Lactam hydrolysis catalyzed by mononuclear metallo-ß-bactamases

    DEFF Research Database (Denmark)

    Olsen, Lars; Antony, J; Ryde, U

    2003-01-01

    Two central steps in the hydrolysis of lactam antibiotics catalyzed by mononuclear metallo-beta-lactamases, formation of the tetrahedral intermediate and its breakdown by proton transfer, are studied for model systems using the density functional B3LYP method. Metallo-beta-lactamases have two metal...

  6. Palladium-catalyzed allylation of tautomerizable heterocycles with alkynes.

    Science.gov (United States)

    Lu, Chuan-Jun; Chen, Dong-Kai; Chen, Hong; Wang, Hong; Jin, Hongwei; Huang, Xifu; Gao, Jianrong

    2017-07-21

    A method for the allylic amidation of tautomerizable heterocycles was developed by a palladium catalyzed allylation reaction with 100% atom economy. A series of structurally diverse N-allylic substituted heterocycles can be synthesized in good yields with high chemo-, regio-, and stereoselectivities under mild conditions.

  7. CU(II): catalyzed hydrazine reduction of ferric nitrate

    International Nuclear Information System (INIS)

    Karraker, D.G.

    1981-11-01

    A method is described for producing ferrous nitrate solutions by the cupric ion-catalyzed reduction of ferric nitrate with hydrazine. The reaction is complete in about 1.5 hours at 40 0 C. Hydrazoic acid is also produced in substantial quantities as a reaction byproduct

  8. Geology and recognition criteria for roll-type uranium deposits in continental sandstones. Final report

    International Nuclear Information System (INIS)

    Harshman, E.N.; Adams, S.S.

    1981-01-01

    The study of roll-type deposits during the past 20 years, since the first description of a deposit in the United States, has developed general concepts of ore formation which are accepted widely and are compatible with available data. If this were not the case the concepts would not have endured and could not have been so successfully applied to exploration using the relations of altered-unaltered sandstone. The comparative simplicity of the model, and the ease with which it has been applied to exploration have, oddly enough, probably inhibited detailed studies of ore districts that would have provided data now needed for refinement of ore controls for exploration and resource assessment programs. The most thorough study of a roll-type district was that of the Shirley Basin which is drawn on heavily in this report. The general concept of roll-type formation provides a strong basis for the development of geological observations and guides, or recognition criteria, for resource studies and exploration. Indeed, industry has been developing and using them for 20 years. As the objective of this study was to identify the most useful recognition criteria and develop a method for their systematic use in resource studies and exploration, the study is best summarized by reference to the important geological observations about roll-type deposits

  9. Stabilization of oil-in-water emulsions by enzyme catalyzed oxidative gelation of sugar beet pectin

    DEFF Research Database (Denmark)

    Abang Zaidel, Dayang Norulfairuz; Chronakis, Ioannis S.; Meyer, Anne S.

    2013-01-01

    Enzyme catalyzed oxidative cross-linking of feruloyl groups can promote gelation of sugar beet pectin (SBP). It is uncertain how the enzyme kinetics of this cross-linking reaction are affected in emulsion systems and whether the gelation affects emulsion stability. In this study, SBP (2.5% w...... larger average particle sizes than the emulsions in which the SBP was homogenized into the emulsion system during emulsion preparation (referred as Mix B). Mix B type emulsions were stable. Enzyme catalyzed oxidative gelation of SBP helped stabilize the emulsions in Mix A. The kinetics of the enzyme...... catalyzed oxidative gelation of SBP was evaluated by small angle oscillatory measurements for horseradish peroxidase (HRP) (EC 1.11.1.7) and laccase (EC 1.10.3.2) catalysis, respectively. HRP catalyzed gelation rates, determined from the slopes of the increase of elastic modulus (G0) with time, were higher...

  10. catalyzed oxidation of some amino acids by acid bromate

    African Journals Online (AJOL)

    Preferred Customer

    ABSTRACT: Kinetic investigations on Pd(II) catalyzed oxidation of dl-serine and dl- ... A suitable mechanism in agreement with observed kinetics has been ..... In acidic solution of potassium bromate quick .... Annual Review of Biochemistry.

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

    Science.gov (United States)

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

    2012-11-16

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

  12. Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes

    KAUST Repository

    Gó mez-Herrera, Alberto; Nahra, Fady; Brill, Marcel; Nolan, Steven P.; Cazin, Catherine S. J.

    2016-01-01

    The iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.

  13. Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes

    KAUST Repository

    Gómez-Herrera, Alberto

    2016-08-22

    The iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.

  14. Deposition of Boron in Possible Evaporite Deposits in Gale Crate

    Science.gov (United States)

    Gasda, P. J.; Peets, E.; Lamm, S. N.; Rapin, W.; Lanza, N.; Frydenvang, J.; Clark, B. C.; Herkenhoff, K. E.; Bridges, J.; Schwenzer, S. P.; Haldeman, E. B.; Wiens, R. C.; Maurice, S.; Clegg, S. M.; Delapp, D.; Sanford, V.; Bodine, M. R.; McInroy, R.

    2017-12-01

    Boron has been previously detected in Gale crater using the ChemCam instrument on board the NASA Curiosity rover within calcium sulfate fracture fill hosted by lacustrine mudstone and eolian sandstone units. Recent results show that up to 300 ppm B is present in the upper sections of the lacustrine unit. Boron has been detected in both the groundwater-emplaced calcium sulfate fracture fill materials and bedding-parallel calcium sulfate layers. The widespread bedding-parallel calcium sulfate layers within the upper strata of the lacustrine bedrock that Curiosity has encountered recently could be interpreted as primary evaporite deposits. We have two hypotheses for the history of boron in Gale crater. In both hypotheses, borates were first deposited as lake water evaporated, depositing primary evaporates that were later re-dissolved by groundwater, which redistributed the boron into secondary evaporitic calcium sulfate fracture fill deposits. In the first scenario, Gale crater may have undergone a period of perennial lake formation during a drier period of martian history, depositing layers of evaporitic minerals (including borates) among lacustrine mudstone layers. In the second scenario, lake margins could have become periodically exposed during cyclic drops in lake level and subsequently desiccated. Evaporites were deposited and desiccation features were formed in lowstand deposits. Either hypothetical scenario of evaporite deposition would promote prebiotic chemical reactions via wet-dry cycles. Boron may be an important prebiotic element, and as such, its presence in ancient martian surface and groundwater provides evidence that important prebiotic chemical reactions could occur on Mars if organics were present. The presence of boron in ancient Gale crater groundwater also provides additional evidence that a habitable environment existed in the martian subsurface well after the expected disappearance of liquid water on the surface of Mars. We will report on the

  15. Catalyzing Transdisciplinarity: A Systems Ethnography of Cancer-Obesity Comorbidity and Risk Coincidence.

    Science.gov (United States)

    Graham, S Scott; Harley, Amy; Kessler, Molly M; Roberts, Laura; DeVasto, Dannielle; Card, Daniel J; Neuner, Joan M; Kim, Sang-Yeon

    2017-05-01

    Effectively addressing wicked health problems, that is, those arising from complex multifactorial biological and socio-economic causes, requires transdisciplinary action. However, a significant body of research points toward substantial difficulties in cultivating transdisciplinary collaboration. Accordingly, this article presents the results of a study that adapts Systems Ethnography and Qualitative Modeling (SEQM) in response to wicked health problems. SEQM protocols were designed to catalyze transdisciplinary responses to national defense concerns. We adapted these protocols to address cancer-obesity comorbidity and risk coincidence. In so doing, we conducted participant-observations and interviews with a diverse range of health care providers, community health educators, and health advocacy professionals who target either cancer or obesity. We then convened a transdisciplinary conference designed to catalyze a coordinated response. The findings offer productive insights into effective ways of catalyzing transdisciplinarity in addressing wicked health problems action and demonstrate the promise of SEQM for continued use in health care contexts.

  16. Large Area Deposition of MoS2 by Pulsed Laser Deposition with In-Situ Thickness Control

    KAUST Repository

    Serna, Martha I.

    2016-05-24

    A scalable and catalyst-free method to deposit stoichiometric Molybdenum Disulfide (MoS2) films over large areas is reported with the maximum area limited by the size of the substrate holder. The method allows deposition of MoS2 layers on a wide range of substrates without any additional surface preparation including single crystals (sapphire and quartz), polycrystalline (HfO2), and amorphous (SiO2). The films are deposited using carefully designed MoS2 targets fabricated with excess of sulfur (S) and variable MoS2 and S particle size. Uniform and layered MoS2 films as thin as two monolayers, with an electrical resistivity of 1.54 × 104 Ω cm-1 were achieved. The MoS2 stoichiometry was as confirmed by High Resolution Rutherford Backscattering Spectrometry (HRRBS). With the method reported here, in situ graded MoS2 films ranging from ~1 to 10 monolayers can also be deposited.

  17. Large Area Deposition of MoS2 by Pulsed Laser Deposition with In-Situ Thickness Control

    KAUST Repository

    Serna, Martha I.; Yoo, Seong H.; Moreno, Salvador; Xi, Yang; Oviedo, Juan Pablo; Choi, Hyunjoo; Alshareef, Husam N.; Kim, Moon J.; Minary-Jolandan, Majid; Quevedo-Lopez, Manuel A.

    2016-01-01

    A scalable and catalyst-free method to deposit stoichiometric Molybdenum Disulfide (MoS2) films over large areas is reported with the maximum area limited by the size of the substrate holder. The method allows deposition of MoS2 layers on a wide range of substrates without any additional surface preparation including single crystals (sapphire and quartz), polycrystalline (HfO2), and amorphous (SiO2). The films are deposited using carefully designed MoS2 targets fabricated with excess of sulfur (S) and variable MoS2 and S particle size. Uniform and layered MoS2 films as thin as two monolayers, with an electrical resistivity of 1.54 × 104 Ω cm-1 were achieved. The MoS2 stoichiometry was as confirmed by High Resolution Rutherford Backscattering Spectrometry (HRRBS). With the method reported here, in situ graded MoS2 films ranging from ~1 to 10 monolayers can also be deposited.

  18. Experimental measurements of the thermal conductivity of ash deposits: Part 2. Effects of sintering and deposit microstructure

    Energy Technology Data Exchange (ETDEWEB)

    A. L. Robinson; S. G. Buckley; N. Yang; L. L. Baxter

    2000-04-01

    The authors report results from an experimental study that examines the influence of sintering and microstructure on ash deposit thermal conductivity. The measurements are made using a technique developed to make in situ, time-resolved measurements of the effective thermal conductivity of ash deposits formed under conditions that closely replicate those found in the convective pass of a commercial boiler. The technique is designed to minimize the disturbance of the natural deposit microstructure. The initial stages of sintering and densification are accompanied by an increase in deposit thermal conductivity. Subsequent sintering continues to densify the deposit, but has little effect on deposit thermal conductivity. SEM analyses indicates that sintering creates a layered deposit structure with a relatively unsintered innermost layer. They hypothesize that this unsintered layer largely determines the overall deposit thermal conductivity. A theoretical model that treats a deposit as a two-layered material predicts the observed trends in thermal conductivity.

  19. Dioxygenases Catalyze O-Demethylation and O,O-Demethylenation with Widespread Roles in Benzylisoquinoline Alkaloid Metabolism in Opium Poppy*

    Science.gov (United States)

    Farrow, Scott C.; Facchini, Peter J.

    2013-01-01

    In opium poppy, the antepenultimate and final steps in morphine biosynthesis are catalyzed by the 2-oxoglutarate/Fe(II)-dependent dioxygenases, thebaine 6-O-demethylase (T6ODM) and codeine O-demethylase (CODM). Further investigation into the biochemical functions of CODM and T6ODM revealed extensive and unexpected roles for such enzymes in the metabolism of protopine, benzo[c]phenanthridine, and rhoeadine alkaloids. When assayed with a wide range of benzylisoquinoline alkaloids, CODM, T6ODM, and the functionally unassigned paralog DIOX2, renamed protopine O-dealkylase, showed novel and efficient dealkylation activities, including regio- and substrate-specific O-demethylation and O,O-demethylenation. Enzymes catalyzing O,O-demethylenation, which cleave a methylenedioxy bridge leaving two hydroxyl groups, have previously not been reported in plants. Similar cleavage of methylenedioxy bridges on substituted amphetamines is catalyzed by heme-dependent cytochromes P450 in mammals. Preferred substrates for O,O-demethylenation by CODM and protopine O-dealkylase were protopine alkaloids that serve as intermediates in the biosynthesis of benzo[c]phenanthridine and rhoeadine derivatives. Virus-induced gene silencing used to suppress the abundance of CODM and/or T6ODM transcripts indicated a direct physiological role for these enzymes in the metabolism of protopine alkaloids, and they revealed their indirect involvement in the formation of the antimicrobial benzo[c]phenanthridine sanguinarine and certain rhoeadine alkaloids in opium poppy. PMID:23928311

  20. Dioxygenases catalyze O-demethylation and O,O-demethylenation with widespread roles in benzylisoquinoline alkaloid metabolism in opium poppy.

    Science.gov (United States)

    Farrow, Scott C; Facchini, Peter J

    2013-10-04

    In opium poppy, the antepenultimate and final steps in morphine biosynthesis are catalyzed by the 2-oxoglutarate/Fe(II)-dependent dioxygenases, thebaine 6-O-demethylase (T6ODM) and codeine O-demethylase (CODM). Further investigation into the biochemical functions of CODM and T6ODM revealed extensive and unexpected roles for such enzymes in the metabolism of protopine, benzo[c]phenanthridine, and rhoeadine alkaloids. When assayed with a wide range of benzylisoquinoline alkaloids, CODM, T6ODM, and the functionally unassigned paralog DIOX2, renamed protopine O-dealkylase, showed novel and efficient dealkylation activities, including regio- and substrate-specific O-demethylation and O,O-demethylenation. Enzymes catalyzing O,O-demethylenation, which cleave a methylenedioxy bridge leaving two hydroxyl groups, have previously not been reported in plants. Similar cleavage of methylenedioxy bridges on substituted amphetamines is catalyzed by heme-dependent cytochromes P450 in mammals. Preferred substrates for O,O-demethylenation by CODM and protopine O-dealkylase were protopine alkaloids that serve as intermediates in the biosynthesis of benzo[c]phenanthridine and rhoeadine derivatives. Virus-induced gene silencing used to suppress the abundance of CODM and/or T6ODM transcripts indicated a direct physiological role for these enzymes in the metabolism of protopine alkaloids, and they revealed their indirect involvement in the formation of the antimicrobial benzo[c]phenanthridine sanguinarine and certain rhoeadine alkaloids in opium poppy.

  1. Differentiating leucine incorporation of Archaea and Bacteria throughout the water column of the eastern Atlantic using metabolic inhibitors

    NARCIS (Netherlands)

    Yokokawa, Taichi; Sintes, Eva; de Corte, Daniele; Olbrich, Kerstin; Herndl, Gerhard J.

    2012-01-01

    The abundance (based on catalyzed reporter deposition-fluorescence in situ hybrid ization, CARD-FISH) and leucine incorporation rates of Archaea and Bacteria were determined throughout the water column in the eastern Atlantic. Bacteria dominated throughout the water column, although their

  2. Differentiating leucine incorporation of

    NARCIS (Netherlands)

    Yokokawa, T.; Sintes, E.; de Corte, D.; Olbrich, K.; Herndl, G.J.

    2012-01-01

    The abundance (based on catalyzed reporter deposition-fluorescence in situ hybrid ization, CARD-FISH) and leucine incorporation rates of Archaea and Bacteria were determined throughout the water column in the eastern Atlantic. Bacteria dominated throughout the water column, although their

  3. Hydroformylation of methyl oleate catalyzed by rhodium complexes

    International Nuclear Information System (INIS)

    Mendes, Ana Nery Furlan; Rosa, Ricardo Gomes da; Gregorio, Jose Ribeiro

    2012-01-01

    In this work, we describe the hydroformylation of methyl oleate catalyzed by several rhodium complexes. Parameters including total pressure, phosphorous/rhodium and CO/H 2 ratio, temperature and phosphorous ligands were scanned. Total conversion of the starting double bonds was achieved while maintaining excellent selectivity in aldehydes. (author)

  4. Palladium(II)-catalyzed oxidation of L-tryptophan by ...

    Indian Academy of Sciences (India)

    dium(II)] were obtained. The reaction exhibits fractional-second order kinetics with respect to [H ... compounds. Its use- fulness may be due to its unequivocal stability, water. ∗ ... metals are known to catalyze many oxidation–reduction reactions because they ... prepared by dissolving potassium hexacyanoferrate(II). (SD Fine ...

  5. Altitude dependence of trace substance deposition from clouds to forests. Final report; Hoehenabhaengigkeit der Spurenstoffdeposition durch Wolken auf Waelder. Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Pahl, S.; Winkler, P.

    1995-12-31

    Novel forest decline is particularly pronounced in the area of the ridges of medium-range mountains. Whereas acid precipitation was viewed as its sole cause early on in the discussions, it turned out later that the impact of trace gases, too, contributes to the damaging of forests. This report wants to point out the importance of fog interception, which equally plays a part in the pollutant receipts of forests. The deposition of fog water to a forest stand depends very much on altitude, so that trace substance deposition, too, is to be expected to be dependent on altitude. By attempting to quantify this effect, the report helps to pinpoint areas of relevance of this deposition pathway (orig./KW) [Deutsch] Die neuartigen Waldschaeden sind in den Kammlagen der Mittelgebirge besonders ausgepraegt. Waehrend in der anfaenglichen Diskussion die sauren Niederschlaege als alleinige Ursache angesehen wurden, zeigte sich spaeter, dass auch Einwirkungen von Spurengasen zur Schaedigung des Waldes beitragen. Dieser Bericht soll auf die Bedeutung der Nebelinterzeption aufmerksam machen, die ebenfalls zum Schadstoffeintrag in den Wald beitraegt. Die Deposition von Wolkenwasser auf einen Waldbestand ist stark abhaengig von der Hoehenlage, in der sich der Waldbestand befindet, so dass auch eine Hoehenabhaengigkeit des Spurenstoffeintrages zu erwarten ist. Durch den Versuch der Quantifizierung traegt dieser Bericht dazu bei, Gebiete zu erkennen, in denen dieser Eintragspfad eine Rolle spielt. (orig./KW)

  6. Palladium-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to Five-, Six-, and Seven-Membered β-Substituted Cyclic Enones: Enantioselective Construction of All-Carbon Quaternary Stereocenters

    KAUST Repository

    Kikushima, Kotaro; Holder, Jeffrey C.; Gatti, Michele; Stoltz, Brian M.

    2011-01-01

    The first enantioselective Pd-catalyzed construction of all-carbon quaternary stereocenters via 1,4-addition of arylboronic acids to β-substituted cyclic enones is reported. Reaction of a wide range of arylboronic acids and cyclic enones using a

  7. Kinetics of acid base catalyzed transesterification of Jatropha curcas oil.

    Science.gov (United States)

    Jain, Siddharth; Sharma, M P

    2010-10-01

    Out of various non-edible oil resources, Jatropha curcas oil (JCO) is considered as future feedstock for biodiesel production in India. Limited work is reported on the kinetics of transesterification of high free fatty acids containing oil. The present study reports the results of kinetic study of two-step acid base catalyzed transesterification process carried out at an optimum temperature of 65 °C and 50 °C for esterification and transesterification respectively under the optimum methanol to oil ratio of 3:7 (v/v), catalyst concentration 1% (w/w) for H₂SO₄ and NaOH. The yield of methyl ester (ME) has been used to study the effect of different parameters. The results indicate that both esterification and transesterification reaction are of first order with reaction rate constant of 0.0031 min⁻¹ and 0.008 min⁻¹ respectively. The maximum yield of 21.2% of ME during esterification and 90.1% from transesterification of pretreated JCO has been obtained. Copyright © 2010 Elsevier Ltd. All rights reserved.

  8. Uniform deposition of uranium hexafluoride (UF6): Standardized mass deposits and controlled isotopic ratios using a thermal fluorination method

    Energy Technology Data Exchange (ETDEWEB)

    McNamara, Bruce K.; O’Hara, Matthew J.; Casella, Andrew M.; Carter, Jennifer C.; Addleman, R. Shane; MacFarlan, Paul J.

    2016-07-01

    Abstract: We report a convenient method for the generation of volatile uranium hexafluoride (UF6) from solid uranium oxides and other uranium compounds, followed by uniform deposition of low levels of UF6 onto sampling coupons. Under laminar flow conditions, UF6 is shown to interact with surfaces within the chamber to a highly predictable degree. We demonstrate the preparation of uranium deposits that range between ~0.01 and 470±34 ng∙cm-2. The data suggest the method can be extended to creating depositions at the sub-picogram∙cm-2 level. Additionally, the isotopic composition of the deposits can be customized by selection of the uranium source materials. We demonstrate a layering technique whereby two uranium solids, each with a different isotopic composition, are employed to form successive layers of UF6 on a surface. The result is an ultra-thin deposit of UF6 that bears an isotopic signature that is a composite of the two uranium sources. The reported deposition method has direct application to the development of unique analytical standards for nuclear safeguards and forensics.

  9. Hemoglobin-catalyzed fluorometric method for the determination of glutathione

    Science.gov (United States)

    Wang, Ruiqiang; Tang, Lin; Li, Hua; Wang, Yi; Gou, Rong; Guo, Yuanyuan; Fang, Yudong; Chen, Fengmei

    2016-01-01

    A new spectrofluorometric method for the determination of glutathione based on the reaction catalyzed by hemoglobin was reported. The reaction product gave a highly fluorescent intensity with the excitation and emission wavelengths of 320.0 nm and 413.0 nm, respectively. The optimum experimental conditions were investigated. Results showed that low concentration glutathione enhanced the fluorescence intensity significantly. The line ranges were 1.0 × 10-6-1.0 × 10-5 mol L-1 of glutathione and 6.0 × 10-10 mol L-1-1.0 × 10-8 mol L-1, respectively. The detection limit was calculated to be 1.1 × 10-11 mol L-1. The recovery test by the standard addition method gave values in the range of 90.78%-102.20%. This method was used for the determination of glutathione in synthetic and real samples with satisfactory results.

  10. Nickel/zinc-catalyzed decarbonylative addition of anhydrides to alkynes: a DFT study.

    Science.gov (United States)

    Meng, Qingxi; Li, Ming

    2013-10-01

    Density functional theory (DFT) was used to investigate the nickel- or nickel(0)/zinc- catalyzed decarbonylative addition of phthalic anhydrides to alkynes. All intermediates and transition states were optimized completely at the B3LYP/6-31+G(d,p) level. Calculated results indicated that the decarbonylative addition of phthalic anhydrides to alkynes was exergonic, and the total free energy released was -87.6 kJ mol(-1). In the five-coordinated complexes M4a and M4b, the insertion reaction of alkynes into the Ni-C bond occurred prior to that into the Ni-O bond. The nickel(0)/zinc-catalyzed decarbonylative addition was much more dominant than the nickel-catalyzed one in whole catalytic decarbonylative addition. The reaction channel CA→M1'→T1'→M2'→T2'→M3a'→M4a'→T3a1'→M5a1' →T4a1'→M6a'→P was the most favorable among all reaction pathways of the nickel- or nickel(0)/zinc- catalyzed decarbonylative addition of phthalic anhydrides to alkynes. And the alkyne insertion reaction was the rate-determining step for this channel. The additive ZnCl2 had a significant effect, and it might change greatly the electron and geometry structures of those intermediates and transition states. On the whole, the solvent effect decreased the free energy barriers.

  11. NURE uranium deposit model studies

    International Nuclear Information System (INIS)

    Crew, M.E.

    1981-01-01

    The National Uranium Resource Evaluation (NURE) Program has sponsored uranium deposit model studies by Bendix Field Engineering Corporation (Bendix), the US Geological Survey (USGS), and numerous subcontractors. This paper deals only with models from the following six reports prepared by Samuel S. Adams and Associates: GJBX-1(81) - Geology and Recognition Criteria for Roll-Type Uranium Deposits in Continental Sandstones; GJBX-2(81) - Geology and Recognition Criteria for Uraniferous Humate Deposits, Grants Uranium Region, New Mexico; GJBX-3(81) - Geology and Recognition Criteria for Uranium Deposits of the Quartz-Pebble Conglomerate Type; GJBX-4(81) - Geology and Recognition Criteria for Sandstone Uranium Deposits in Mixed Fluvial-Shallow Marine Sedimentary Sequences, South Texas; GJBX-5(81) - Geology and Recognition Criteria for Veinlike Uranium Deposits of the Lower to Middle Proterozoic Unconformity and Strata-Related Types; GJBX-6(81) - Geology and Recognition Criteria for Sandstone Uranium Deposits of the Salt Wash Type, Colorado Plateau Province. A unique feature of these models is the development of recognition criteria in a systematic fashion, with a method for quantifying the various items. The recognition-criteria networks are used in this paper to illustrate the various types of deposits

  12. A deposit model for carbonatite and peralkaline intrusion-related rare earth element deposits: Chapter J in Mineral deposit models for resource assessment

    Science.gov (United States)

    Verplanck, Philip L.; Van Gosen, Bradley S.; Seal, Robert R.; McCafferty, Anne E.

    2014-01-01

    Carbonatite and alkaline intrusive complexes, as well as their weathering products, are the primary sources of rare earth elements. A wide variety of other commodities have been exploited from carbonatites and alkaline igneous rocks including niobium, phosphate, titanium, vermiculite, barite, fluorite, copper, calcite, and zirconium. Other elements enriched in these deposits include manganese, strontium, tantalum, thorium, vanadium, and uranium. Carbonatite and peralkaline intrusion-related rare earth element deposits are presented together in this report because of the spatial, and potentially genetic, association between carbonatite and alkaline rocks. Although these rock types occur together at many locations, carbonatite and peralkaline intrusion-related rare earth element deposits are not generally found together.

  13. Iodine-Catalyzed Isomerization of Dimethyl Muconate

    Energy Technology Data Exchange (ETDEWEB)

    Settle, Amy E [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Berstis, Laura R [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Zhang, Shuting [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Rorrer, Nicholas [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Hu, Haiming [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Richards, Ryan [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Beckham, Gregg T [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Crowley, Michael F [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Vardon, Derek R [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

    2018-04-12

    cis,cis-Muconic acid is a platform biobased chemical that can be upgraded to drop-in commodity and novel monomers. Among the possible drop-in products, dimethyl terephthalate can be synthesized via esterification, isomerization, Diels-Alder cycloaddition, and dehydrogenation. The isomerization of cis,cis-dimethyl muconate (ccDMM) to the trans,trans-form (ttDMM) can be catalyzed by iodine; however, studies have yet to address (i) the mechanism and reaction barriers unique to DMM, and (ii) the influence of solvent, potential for catalyst recycle, and recovery of high-purity ttDMM. To address this gap, we apply a joint computational and experimental approach to investigate iodine-catalyzed isomerization of DMM. Density functional theory calculations identified unique regiochemical considerations due to the large number of halogen-diene coordination schemes. Both transition state theory and experiments estimate significant barrier reductions with photodissociated iodine. Solvent selection was critical for rapid kinetics, likely due to solvent complexation with iodine. Under select conditions, ttDMM yields of 95% were achieved in <1 h with methanol, followed by high purity recovery (>98%) with crystallization. Lastly, post-reaction iodine can be recovered and recycled with minimal loss of activity. Overall, these findings provide new insight into the mechanism and conditions necessary for DMM isomerization with iodine to advance the state-of-the-art for biobased chemicals.

  14. Fullerene-catalyzed reduction of azo derivatives in water under UV irradiation

    KAUST Repository

    Guo, Yong; Li, Wengang; Yan, Jingjing; Moosa, Basem; Amad, Maan H.; Werth, Charles; Khashab, Niveen M.

    2012-01-01

    Metal-free fullerene (C60) was found to be an effective catalyst for the reduction of azo groups in basic aqueous solution under UV irradiation in the presence of NaBH4. Use of NaBH4 by itself is not sufficient to reduce the azo dyes without the assistance of a metal catalyst such as Pd and Ag. Experimental and theoretical results suggest that C 60 catalyzes this reaction by using its vacant orbital to accept the electron in the bonding orbital of azo dyes, which leads to the activation of the N=N bond. UV irradiation increases the ability of C60 to interact with electron-donor moieties in azo dyes. Filling a vacancy: Experimental and theoretical methods have been combined to show that C60-catalyzed reductions of azo compounds form aromatic amines under UV irradiation (see scheme). The obtained results show that C60 acts as an electron acceptor to catalyze the reduction of azo compounds, and the role of UV irradiation is to increase the ability of C60 to interact with electron-donor moieties in azo compounds. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Fullerene-catalyzed reduction of azo derivatives in water under UV irradiation

    KAUST Repository

    Guo, Yong

    2012-09-27

    Metal-free fullerene (C60) was found to be an effective catalyst for the reduction of azo groups in basic aqueous solution under UV irradiation in the presence of NaBH4. Use of NaBH4 by itself is not sufficient to reduce the azo dyes without the assistance of a metal catalyst such as Pd and Ag. Experimental and theoretical results suggest that C 60 catalyzes this reaction by using its vacant orbital to accept the electron in the bonding orbital of azo dyes, which leads to the activation of the N=N bond. UV irradiation increases the ability of C60 to interact with electron-donor moieties in azo dyes. Filling a vacancy: Experimental and theoretical methods have been combined to show that C60-catalyzed reductions of azo compounds form aromatic amines under UV irradiation (see scheme). The obtained results show that C60 acts as an electron acceptor to catalyze the reduction of azo compounds, and the role of UV irradiation is to increase the ability of C60 to interact with electron-donor moieties in azo compounds. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Amylase catalyzed synthesis of glycosyl acrylates and their polymerization

    NARCIS (Netherlands)

    Kloosterman, Wouter M.J.; Jovanovic, Danijela; Brouwer, Sander; Loos, Katja

    2014-01-01

    The enzymatic synthesis of novel (di)saccharide acrylates from starch and 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate (2-HEA, 2-HEMA and 4-HBA) catalyzed by various commercially available amylase preparations is demonstrated. Both liquefaction and

  17. State-of-the-art for evaluating the potential effects of erosion and deposition on a radioactive waste repository. Final report

    International Nuclear Information System (INIS)

    1980-01-01

    The potential impact of future geologic processes on the integrity of a deep, high-level radioactive-waste repository is evaluated. The following study identifies the potential consequences of surface erosion and deposition on sub-surface repository containment characteristics and assesses the ability to measure and predict quantitatively the rates and corresponding extent of these processes in the long term. Numerous studies of the magnitudes and rates of surficial erosion and deposition that have been used to determine the minimum allowable depth for a geologic repository (300 m - NRC Code of Federal Regulations, Part 60.122, Draft 10) are cited in this report. Measurement and interpretation of potential rates and extent of surficial processes in these studies involved considerable uncertainty, and the implications of this uncertainty on presently proposed repository siting criteria are addressed herein. Important concepts that should be considered when developing siting criteria to protect against deleterious effects arising from future erosion or deposition are highlighted. Erosion agents that could affect deep repositories are distinguished in this report so that their individual and combined impacts may be examined. This approach is recommended when evaluating potential repository sites in diverse environments that are susceptible to different agents of erosion. In contrast, agents of sedimentation are not differentiated in this report because of their relatively minor impact on a deep repository

  18. Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

    Science.gov (United States)

    Wang, He; Tang, Guodong; Li, Xingwei

    2015-10-26

    Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

    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.

  20. Catalytic Asymmetric Piancatelli Rearrangement: Brønsted Acid Catalyzed 4π Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

    KAUST Repository

    Cai, Yunfei

    2016-10-13

    The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral Brønsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields as well as excellent enantioselectivities and diastereoselectivities. The high value of the aza-Piancatelli rearrangement was demonstrated by the synthesis of a cyclopentane-based hNK1 antagonist analogue.

  1. Manganese-Catalyzed Aerobic Heterocoupling of Aryl Grignard Reagents

    DEFF Research Database (Denmark)

    Ghaleshahi, Hajar Golshahi; Antonacci, Giuseppe; Madsen, Robert

    2017-01-01

    An improved protocol has been developed for the MnCl2-catalyzed cross-coupling reaction of two arylmagnesium bromides under dioxygen. The reaction was achieved by using the Grignard reagents in a 2:1 ratio and 20 % of MnCl2. Very good yields of the heterocoupling product were obtained when the li...

  2. Cooperative Metal–Ligand Catalyzed Intramolecular Hydroamination and Hydroalkoxylation of Allenes Using a Stable Iron Catalyst

    KAUST Repository

    El-Sepelgy, Osama

    2018-01-18

    A new iron-catalyzed chemoselective intramolecular hydroamination and hydroalkoxylation of the readily available α-allenic amines and alcohols to valuable unsaturated 5-membered heterocycles, 2,3-dihydropyrrole and 2,3-dihydrofuran, is reported. Effective selectivity control is achieved by a metal–ligand cooperative activation of the substrates. The mild reaction conditions and the use of low amounts of an air and moisture stable iron catalyst allow for the hydrofunctionalization of a wide range of allenes bearing different functional groups in good yields in the absence of base or any sensitive additives.

  3. Cooperative Metal–Ligand Catalyzed Intramolecular Hydroamination and Hydroalkoxylation of Allenes Using a Stable Iron Catalyst

    KAUST Repository

    El-Sepelgy, Osama; Brzozowska, Aleksandra; Sklyaruk, Jan; Jang, Yoon Kyung; Zubar, Viktoriia; Rueping, Magnus

    2018-01-01

    A new iron-catalyzed chemoselective intramolecular hydroamination and hydroalkoxylation of the readily available α-allenic amines and alcohols to valuable unsaturated 5-membered heterocycles, 2,3-dihydropyrrole and 2,3-dihydrofuran, is reported. Effective selectivity control is achieved by a metal–ligand cooperative activation of the substrates. The mild reaction conditions and the use of low amounts of an air and moisture stable iron catalyst allow for the hydrofunctionalization of a wide range of allenes bearing different functional groups in good yields in the absence of base or any sensitive additives.

  4. Diazo compounds and N-tosylhydrazones: novel cross-coupling partners in transition-metal-catalyzed reactions.

    Science.gov (United States)

    Xiao, Qing; Zhang, Yan; Wang, Jianbo

    2013-02-19

    Transition-metal-catalyzed carbene transformations and cross-couplings represent two major reaction types in organometallic chemistry and organic synthesis. However, for a long period of time, these two important areas have evolved separately, with essentially no overlap or integration. Thus, an intriguing question has emerged: can cross-coupling and metal carbene transformations be merged into a single reaction cycle? Such a combination could facilitate the development of novel carbon-carbon bond-forming methodologies. Although this concept was first explored about 10 years ago, rapid developments inthis area have been achieved recently. Palladium catalysts can be used to couple diazo compounds with a wide variety of organic halides. Under oxidative coupling conditions, diazo compounds can also react with arylboronic acids and terminal alkynes. Both of these coupling reactions form carbon-carbon double bonds. As the key step in these catalytic processes, Pd carbene migratory insertion plays a vital role in merging the elementary steps of Pd intermediates, leading to novel carbon-carbon bond formations. Because the diazo substrates can be generated in situ from N-tosylhydrazones in the presence of base, the N-tosylhydrazones can be used as reaction partners, making this type of cross-coupling reaction practical in organic synthesis. N-Tosylhydrazones are easily derived from the corresponding aldehydes or ketones. The Pd-catalyzed cross-coupling of N-tosylhydrazones is considered a complementary reaction to the classic Shapiro reaction for converting carbonyl functionalities into carbon-carbon double bonds. It can also serve as an alternative approach for the Pd-catalyzed cross-coupling of carbonyl compounds, which is usually achieved via triflates. The combination of carbene formation and cross-coupling in a single catalytic cycle is not limited to Pd-catalyzed reactions. Recent studies of Cu-, Rh-, Ni-, and Co-catalyzed cross-coupling reactions with diazo

  5. Nanoparticle layer deposition for highly controlled multilayer formation based on high-coverage monolayers of nanoparticles

    International Nuclear Information System (INIS)

    Liu, Yue; Williams, Mackenzie G.; Miller, Timothy J.; Teplyakov, Andrew V.

    2016-01-01

    This paper establishes a strategy for chemical deposition of functionalized nanoparticles onto solid substrates in a layer-by-layer process based on self-limiting surface chemical reactions leading to complete monolayer formation within the multilayer system without any additional intermediate layers — nanoparticle layer deposition (NPLD). This approach is fundamentally different from previously established traditional layer-by-layer deposition techniques and is conceptually more similar to well-known atomic and molecular layer deposition processes. The NPLD approach uses efficient chemical functionalization of the solid substrate material and complementary functionalization of nanoparticles to produce a nearly 100% coverage of these nanoparticles with the use of “click chemistry”. Following this initial deposition, a second complete monolayer of nanoparticles is deposited using a copper-catalyzed “click reaction” with the azide-terminated silica nanoparticles of a different size. This layer-by-layer growth is demonstrated to produce stable covalently-bound multilayers of nearly perfect structure over macroscopic solid substrates. The formation of stable covalent bonds is confirmed spectroscopically and the stability of the multilayers produced is tested by sonication in a variety of common solvents. The 1-, 2- and 3-layer structures are interrogated by electron microscopy and atomic force microscopy and the thickness of the multilayers formed is fully consistent with that expected for highly efficient monolayer formation with each cycle of growth. This approach can be extended to include a variety of materials deposited in a predesigned sequence on different substrates with a highly conformal filling. - Highlights: • We investigate the formation of high-coverage monolayers of nanoparticles. • We use “click chemistry” to form these monolayers. • We form multiple layers based on the same strategy. • We confirm the formation of covalent bonds

  6. Synthesis of benzimidazoles via iridium-catalyzed acceptorless dehydrogenative coupling.

    Science.gov (United States)

    Sun, Xiang; Lv, Xiao-Hui; Ye, Lin-Miao; Hu, Yu; Chen, Yan-Yan; Zhang, Xue-Jing; Yan, Ming

    2015-07-21

    Iridium-catalyzed acceptorless dehydrogenative coupling of tertiary amines and arylamines has been developed. A number of benzimidazoles were prepared in good yields. An iridium-mediated C-H activation mechanism is suggested. This finding represents a novel strategy for the synthesis of benzimidazoles.

  7. Follicular Adenoma with Extensive Extracellular Mucin Deposition: Report on Two Cases

    Directory of Open Access Journals (Sweden)

    Na Rae Kim

    2012-01-01

    Full Text Available We report two cases of follicular adenoma of the thyroid with extensive extracellular mucin deposition. Fine needle aspiration in Case 1 showed singly discohesive polygonal cells in a granular mucinous background. They contained abundant eosinophilic cytoplasm, nuclear irregularities, and frequent nuclear inclusions with occasional bizarre mitoses. A right lobectomy was done. In Case 2, a 47-year-old Caucasian woman with multinodular goiter had total thyroidectomy and a yellow-tan nodule was found within the right lobe. Both tumors were well-encapsulated masses with thick capsules. Each was characterized by microfollicles without papillae in a mucinous stroma. Tumor cells were positive for thyroglobulin and negative for calcitonin, CEA, galectin-3, HBME-1, and CK19. The extracellular mucin stained with Alcian-blue and colloidal iron but not with mucicarmine and D-PAS. No BRAF gene mutation was detected. Because there were neither capsular nor vascular invasions, both cases were diagnosed as follicular adenomas of the thyroid with extensive extracellular mucin deposition, which as proposed by the WHO classification can be categorized as a mucinous variant of follicular adenoma. Retrospectively, frequent nuclear inclusions and the absence of nuclear grooves in the mucin-containing background of cytologic smears and histologic sections were shared by those of mucin-producing papillary carcinoma. It is unclear whether it belongs to an existing category of thyroid neoplasm with mucin production or whether it is truly a new tumor variant. Furthermore, pathologists should pay attention to avoid misdiagnosis of this variant of follicular neoplasm that shows an overlapping cytology with that of papillary carcinoma.

  8. Development of Copper-Catalyzed Electrophilic Trifluoromethylation and Exploiting Cu/Cu2O Nanowires with Novel Catalytic Reactivity

    KAUST Repository

    Li, Huaifeng

    2014-06-01

    area of the active component, thereby enhancing the contact between reactants and catalyst dramatically. Based on the above-mentioned concepts and with the aim of achieving one “green and sustainable” approach, C-S bond formation and click reactions catalyzed by Cu/Cu2O nanowires were investigated. It was found that the recyclable core-shell structured Cu/Cu2O nanowires could be applied as a highly reactive catalysts for the cross-coupling reaction between aryl iodides and the cycloaddition of terminal alkynes and azides under ligand-free conditions. Furthermore, these results were the first report for the crosscoupling reaction and click reaction catalyzed by one-dimensional (1D) copper nanowires.

  9. Ossifying tendinitis of the rotator cuff after arthroscopic excision of calcium deposits: report of two cases and literature review.

    Science.gov (United States)

    Merolla, Giovanni; Dave, Arpit C; Paladini, Paolo; Campi, Fabrizio; Porcellini, Giuseppe

    2015-03-01

    Ossifying tendinitis (OT) is a type of heterotopic ossification, characterized by deposition of hydroxyapatite crystals in a histologic pattern of mature lamellar bone. It is usually associated with surgical intervention or trauma and is more commonly seen in Achilles or distal biceps tendons, and also in the gluteus maximus tendon. To our knowledge, there is no description of OT as a complication of calcifying tendinitis of the rotator cuff. In this report, we describe two cases in which the patients developed an OT of the supraspinatus after arthroscopic removal of calcium deposits. The related literature is reviewed.

  10. Improvement in biodiesel production from soapstock oil by one-stage lipase catalyzed methanolysis

    International Nuclear Information System (INIS)

    Su, Erzheng; Wei, Dongzhi

    2014-01-01

    Highlights: • Soapstock is a less expensive feedstock reservoir for biodiesel production. • Addition of tert-alcohol can enhance the yield of fatty acid methyl ester significantly. • One-stage lipase catalyzed methanolysis of soapstock oil was successfully developed. • FAME yield of 95.2% was obtained with low lipase loading in a shorter reaction time. - Abstract: A major obstacle in the commercialization of biodiesel is its cost of manufacturing, primarily the raw material cost. In order to decrease the cost of biodiesel, soapstock oil was investigated as the feedstock for biodiesel production. Because the soapstock oil containing large amounts of free fatty acids (FFAs) cannot be effectively converted to biodiesel, complicated two-stage process (esterification followed by transesterification) was generally adopted. In this study, simple one-stage lipase catalyzed methanolysis of soapstock oil was developed via one-pot esterification and transesterification. Water produced by lipase catalyzed esterification of FFAs affected the lipase catalyzed transesterification of glycerides in the soapstock oil severely. Addition of tert-alcohol could overcome this problem and enhance the fatty acid methyl ester (FAME) yield from 42.8% to 76.4%. The FAME yield was further elevated to 95.2% by optimizing the methanol/oil molar ratio, lipase amount, and water absorbent. The developed process enables the simple, efficient, and green production of biodiesel from soapstock oil, providing with a potential industrial application

  11. Optimization of Two-Step Acid-Catalyzed Hydrolysis of Oil Palm Empty Fruit Bunch for High Sugar Concentration in Hydrolysate

    Directory of Open Access Journals (Sweden)

    Dongxu Zhang

    2014-01-01

    Full Text Available Getting high sugar concentrations in lignocellulosic biomass hydrolysate with reasonable yields of sugars is commercially attractive but very challenging. Two-step acid-catalyzed hydrolysis of oil palm empty fruit bunch (EFB was conducted to get high sugar concentrations in the hydrolysate. The biphasic kinetic model was used to guide the optimization of the first step dilute acid-catalyzed hydrolysis of EFB. A total sugar concentration of 83.0 g/L with a xylose concentration of 69.5 g/L and a xylose yield of 84.0% was experimentally achieved, which is in well agreement with the model predictions under optimal conditions (3% H2SO4 and 1.2% H3PO4, w/v, liquid to solid ratio 3 mL/g, 130°C, and 36 min. To further increase total sugar and xylose concentrations in hydrolysate, a second step hydrolysis was performed by adding fresh EFB to the hydrolysate at 130°C for 30 min, giving a total sugar concentration of 114.4 g/L with a xylose concentration of 93.5 g/L and a xylose yield of 56.5%. To the best of our knowledge, the total sugar and xylose concentrations are the highest among those ever reported for acid-catalyzed hydrolysis of lignocellulose.

  12. Unraveling the reaction mechanism on nitrile hydration catalyzed by [Pd(OH2)4]2+: insights from theory.

    Science.gov (United States)

    Tílvez, Elkin; Menéndez, María I; López, Ramón

    2013-07-01

    Density functional theory methodologies combined with continuum and discrete-continuum descriptions of solvent effects were used to investigate the [Pd(OH2)4](2+)-catalyzed acrylonitrile hydration to yield acrylamide. According to our results, the intramolecular hydroxide attack mechanism and the external addition mechanism of a water molecule with rate-determining Gibbs energy barriers in water solution of 27.6 and 28.3 kcal/mol, respectively, are the most favored. The experimental kinetic constants of the hydration started by hydroxide, k(OH), and water, k(H2O), attacks for the cis-[Pd(en)(OH2)2](2+)-catalyzed dichloroacetonitrile hydration rendered Gibbs energy barriers whose energy difference, 0.7 kcal/mol, is the same as that obtained in the present study. Our investigation reveals the nonexistence of the internal attack of a water ligand for Pd-catalyzed nitrile hydration. At the low pHs used experimentally, the equilibrium between [Pd(OH2)3(nitrile)](2+) and [Pd(OH2)2(OH)(nitrile)](+) is completely displaced to [Pd(OH2)3(nitrile)](2+). Experimental studies in these conditions stated that water acts as a nucleophile, but they could not distinguish whether it was a water ligand, an external water molecule, or a combination of both possibilities. Our theoretical explorations clearly indicate that the external water mechanism becomes the only operative one at low pHs. On the basis of this mechanistic proposal it is also possible to ascribe an (1)H NMR signal experimentally detected to the presence of a unidentate iminol intermediate and to explain the influence of nitrile concentration reported experimentally for nitriles other than acrylonitrile in the presence of aqua-Pd(II) complexes. Therefore, our theoretical point of view on the mechanism of nitrile hydration catalyzed by aqua-Pd(II) complexes can shed light on these relevant processes at a molecular level as well as afford valuable information that can help in designing new catalysts in milder and more

  13. Vertically aligned carbon nanotube field emitter arrays with Ohmic base contact to silicon by Fe-catalyzed chemical vapor deposition

    NARCIS (Netherlands)

    Morassutto, M.; Tiggelaar, Roald M.; Smithers, M.A.; Smithers, M.A.; Gardeniers, Johannes G.E.

    2016-01-01

    Abstract In this study, dense arrays of aligned carbon nanotubes are obtained by thermal catalytic chemical vapor deposition, using Fe catalyst dispersed on a thin Ta layer. Alignment of the carbon nanotubes depends on the original Fe layer thickness from which the catalyst dispersion is obtained by

  14. Silica metal-oxide vesicles catalyze comprehensive prebiotic chemistry.

    Science.gov (United States)

    Bizzarri, Bruno Mattia; Botta, Lorenzo; Pérez-Valverde, Maritza Iveth; Saladino, Raffaele; Di Mauro, Ernesto; Garcia Ruiz, Juan Manuel

    2018-03-30

    It has recently been demonstrated that mineral self-assembled structures catalyzing prebiotic chemical reactions may form in natural waters derived from serpentinization, a geological process widespread in the early stages of Earth-like planets. We have synthesized self-assembled membranes by mixing microdrops of metal solutions with alkaline silicate solutions in the presence of formamide (NH2CHO), a single carbon molecule, at 80ºC. We found that these bilayer membranes, made of amorphous silica and metal oxide-hydroxide nanocrystals, catalyze the condensation of formamide, yielding the four nucleobases of RNA, three aminoacids and several carboxylic acids in a single pot experiment. Besides manganese, iron and magnesium, two abundant elements in the earliest Earth crust that are key in serpentinization reactions, are enough to produce all these biochemical compounds. These results suggest that the transition from inorganic geochemistry to prebiotic organic chemistry is common on a universal scale and, most probably, earlier than ever thought for our planet. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Synthesis of Fluoroalkoxy Substituted Arylboronic Esters by Iridium-Catalyzed Aromatic C–H Borylation

    KAUST Repository

    Batool, Farhat

    2015-08-17

    The preparation of fluoroalkoxy arylboronic esters by iridium-catalyzed aromatic C–H borylation is described. The fluoroalkoxy groups employed include trifluoromethoxy, difluoromethoxy, 1,1,2,2-tetrafluoroethoxy, and 2,2-difluoro-1,3-benzodioxole. The borylation reactions were carried out neat without the use of a glovebox or Schlenk line. The regioselectivities available through the iridium-catalyzed C–H borylation are complementary to those obtained by the electrophilic aromatic substitution reactions of fluoroalkoxy arenes. Fluoroalkoxy arylboronic esters can serve as versatile building blocks.

  16. Synthesis of Fluoroalkoxy Substituted Arylboronic Esters by Iridium-Catalyzed Aromatic C–H Borylation

    KAUST Repository

    Batool, Farhat; Parveen, Shehla; Emwas, Abdul-Hamid M.; Sioud, Salim; Gao, Xin; Munawar, Munawar A.; Chotana, Ghayoor A.

    2015-01-01

    The preparation of fluoroalkoxy arylboronic esters by iridium-catalyzed aromatic C–H borylation is described. The fluoroalkoxy groups employed include trifluoromethoxy, difluoromethoxy, 1,1,2,2-tetrafluoroethoxy, and 2,2-difluoro-1,3-benzodioxole. The borylation reactions were carried out neat without the use of a glovebox or Schlenk line. The regioselectivities available through the iridium-catalyzed C–H borylation are complementary to those obtained by the electrophilic aromatic substitution reactions of fluoroalkoxy arenes. Fluoroalkoxy arylboronic esters can serve as versatile building blocks.

  17. Uniform deposition of uranium hexafluoride (UF6): Standardized mass deposits and controlled isotopic ratios using a thermal fluorination method.

    Science.gov (United States)

    McNamara, Bruce K; O'Hara, Matthew J; Casella, Andrew M; Carter, Jennifer C; Addleman, R Shane; MacFarlan, Paul J

    2016-07-01

    We report a convenient method for the generation of volatile uranium hexafluoride (UF6) from solid uranium oxides and other U compounds, followed by uniform deposition of low levels of UF6 onto sampling coupons. Under laminar flow conditions, UF6 is shown to interact with surfaces within a fixed reactor geometry to a highly predictable degree. We demonstrate the preparation of U deposits that range between approximately 0.01 and 500ngcm(-2). The data suggest the method can be extended to creating depositions at the sub-picogramcm(-2) level. The isotopic composition of the deposits can be customized by selection of the U source materials and we demonstrate a layering technique whereby two U solids, each with a different isotopic composition, are employed to form successive layers of UF6 on a surface. The result is an ultra-thin deposit that bears an isotopic signature that is a composite of the two U sources. The reported deposition method has direct application to the development of unique analytical standards for nuclear safeguards and forensics. Further, the method allows access to very low atomic or molecular coverages of surfaces. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. A cell-free fluorometric high-throughput screen for inhibitors of Rtt109-catalyzed histone acetylation.

    Directory of Open Access Journals (Sweden)

    Jayme L Dahlin

    Full Text Available The lysine acetyltransferase (KAT Rtt109 forms a complex with Vps75 and catalyzes the acetylation of histone H3 lysine 56 (H3K56ac in the Asf1-H3-H4 complex. Rtt109 and H3K56ac are vital for replication-coupled nucleosome assembly and genotoxic resistance in yeast and pathogenic fungal species such as Candida albicans. Remarkably, sequence homologs of Rtt109 are absent in humans. Therefore, inhibitors of Rtt109 are hypothesized as potential and minimally toxic antifungal agents. Herein, we report the development and optimization of a cell-free fluorometric high-throughput screen (HTS for small-molecule inhibitors of Rtt109-catalyzed histone acetylation. The KAT component of the assay consists of the yeast Rtt109-Vps75 complex, while the histone substrate complex consists of full-length Drosophila histone H3-H4 bound to yeast Asf1. Duplicated assay runs of the LOPAC demonstrated day-to-day and plate-to-plate reproducibility. Approximately 225,000 compounds were assayed in a 384-well plate format with an average Z' factor of 0.71. Based on a 3σ cut-off criterion, 1,587 actives (0.7% were identified in the primary screen. The assay method is capable of identifying previously reported KAT inhibitors such as garcinol. We also observed several prominent active classes of pan-assay interference compounds such as Mannich bases, catechols and p-hydroxyarylsulfonamides. The majority of the primary active compounds showed assay signal interference, though most assay artifacts can be efficiently removed by a series of straightforward counter-screens and orthogonal assays. Post-HTS triage demonstrated a comparatively small number of confirmed actives with IC50 values in the low micromolar range. This assay, which utilizes five label-free proteins involved in H3K56 acetylation in vivo, can in principle identify compounds that inhibit Rtt109-catalyzed H3K56 acetylation via different mechanisms. Compounds discovered via this assay or adaptations thereof could

  19. Mechanistic Investigation of Palladium–Catalyzed Allylic C–H Activation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Jensen, Thomas; Rodríguez-Rodríguez, Sergio

    2013-01-01

    The mechanism for the palladium–catalyzed allylic C–H activation was investigated using a combination of experimental and theoretical methods. A Hammett study revealed a buildup of a partial negative charge in the rate-determining step, while determination of the kinetic isotope effect (KIE...

  20. Precision Synthesis of Functional Polysaccharide Materials by Phosphorylase-Catalyzed Enzymatic Reactions

    Directory of Open Access Journals (Sweden)

    Jun-ichi Kadokawa

    2016-04-01

    Full Text Available In this review article, the precise synthesis of functional polysaccharide materials using phosphorylase-catalyzed enzymatic reactions is presented. This particular enzymatic approach has been identified as a powerful tool in preparing well-defined polysaccharide materials. Phosphorylase is an enzyme that has been employed in the synthesis of pure amylose with a precisely controlled structure. Similarly, using a phosphorylase-catalyzed enzymatic polymerization, the chemoenzymatic synthesis of amylose-grafted heteropolysaccharides containing different main-chain polysaccharide structures (e.g., chitin/chitosan, cellulose, alginate, xanthan gum, and carboxymethyl cellulose was achieved. Amylose-based block, star, and branched polymeric materials have also been prepared using this enzymatic polymerization. Since phosphorylase shows a loose specificity for the recognition of substrates, different sugar residues have been introduced to the non-reducing ends of maltooligosaccharides by phosphorylase-catalyzed glycosylations using analog substrates such as α-d-glucuronic acid and α-d-glucosamine 1-phosphates. By means of such reactions, an amphoteric glycogen and its corresponding hydrogel were successfully prepared. Thermostable phosphorylase was able to tolerate a greater variance in the substrate structures with respect to recognition than potato phosphorylase, and as a result, the enzymatic polymerization of α-d-glucosamine 1-phosphate to produce a chitosan stereoisomer was carried out using this enzyme catalyst, which was then subsequently converted to the chitin stereoisomer by N-acetylation. Amylose supramolecular inclusion complexes with polymeric guests were obtained when the phosphorylase-catalyzed enzymatic polymerization was conducted in the presence of the guest polymers. Since the structure of this polymeric system is similar to the way that a plant vine twines around a rod, this polymerization system has been named

  1. Kinetics of catalyzed tritium oxidation in air at ambient temperature

    International Nuclear Information System (INIS)

    Sherwood, A.E.

    1980-01-01

    Tritium/air oxidation kinetic data are derived from measurements carried out with three catalysts. All experiments were carried out at room temperature - a regime that provides a severe test for catalyst effectiveness. Each catalyst consists of a high-surface-area substrate in pelletized form, onto which precious metal has been dispersed. The metal/substrate combinations investigated are: platinum/alumina, palladium/kaolin, and paladium/zeolite. Each of the dispersed-metal catalysts is extremely effective in promoting tritium oxidation in comparison with self-catalyzed atmospheric conversion; equivalent first-order rate constants are higher by roughly nine orders of magnitude. Electron-microprobe scans reveal that the dispersed metal is deposited near the outer surface of the catalyst, with metal concentration decreasing exponentially from the pellet surface. The platinum-based catalyst is more effective than the palladium catalysts on a surface-area basis by about a factor of three. Rate coefficients are determined from concentration decay following a spike injection of tritium into an air-filled enclosure processed by recirculation through an oxidation/adsorption system. The catalytic reaction is first-order in tritium concentration in the range 10 to 10 5 μCi/m 3 (4 ppt-40 ppB). Addition of hydrogen carrier gas is unnecessary. Catalytic activity for all three catalysts declines with time of exposure to air after activation, following a power-law decay with an exponent of -1/2. Reactivation with hot hydrogen gas effectively restores initial catalytic activity

  2. Uranium deposits of Australia to 1975

    International Nuclear Information System (INIS)

    Spannari, S.

    1979-01-01

    This bibliography provides a retrospective account of Australian uranium deposits, particularly the unpublished materials in the Australian Capital Territory. Some abstracts are included. Occurrences, mineralogy, ore genesis, structural controls and the eonomic geology of uranium deposits are covered but the mining of uranium, exploration reports, surveys, environmental aspects and controversial materials are not

  3. Mechanism of iron catalyzed oxidation of SO/sub 2/ in oxygenated solutions

    Energy Technology Data Exchange (ETDEWEB)

    Freiberg, J

    1975-01-01

    Previous experimental work concerning the iron catalyzed oxidation of SO/sub 2/ in oxygenated acid solutions failed to provide a consistent reaction mechanism and rate expression. As iron is one of the main constituents of urban atmospheric aerosols, the rate studies of heterogeneous sulphate formation in polluted city air were hampered. The present study develops a new theory for the iron catalyzed oxidation of SO/sub 2/. The resulting new rate expression is general enough to account for the results of previous experimental investigations that were performed in different ranges of SO/sub 2/ and catalyst concentrations.

  4. Kinetics of enzyme-catalyzed cross-linking of feruloylated arabinan from sugar beet

    DEFF Research Database (Denmark)

    Abang Zaidel, Dayang Norulfairuz; Arnous, Anis; Holck, Jesper

    2011-01-01

    the kinetics of HRP catalyzed cross-linking of FA esterified to α-(1,5)-linked arabinans are affected by the length of the arabinan chains carrying the feruloyl substitutions. The kinetics of the HRP-catalyzed cross-linking of four sets of arabinan samples from sugar beet pulp, having different molecular...... weights and hence different degrees of polymerization, were monitored by the disappearance of FA absorbance at 316 nm. MALDI-TOF/TOF-MS analysis confirmed that the sugar beet arabinans were feruloyl-substituted, and HPLC analysis verified that the amounts of diFAs increased when FA levels decreased...

  5. Atmospheric deposition 2000. NOVA 2003; Atmosfaerisk deposition 2000. NOVA 2003

    Energy Technology Data Exchange (ETDEWEB)

    Ellermann, T.; Hertel, O.; Hovmand, M.F.; Kemp, K.; Skjoeth, C.A.

    2001-11-01

    This report presents measurements and calculations from the atmospheric part of NOVA 2003 and covers results for 2000. It summarises the main results concerning concentrations and depositions of nitrogen, phosphorus and sulphur compounds related to eutrophication and acidification. Depositions of atmospheric compounds to Danish marine waters as well as land surface are presented. Measurements: In 2000 the monitoring program consisted of eight stations where wet deposition of ammonium, nitrate, phosphate (semi quantitatively) and sulphate were measured using bulk precipitation samplers. Six of the stations had in addition measurements of atmospheric content of A, nitrogen, phosphorus, and sulphur compounds in gas and particulate phase carried out by use of filter pack samplers. Filters were analysed at the National Environmental Research Institute. Furthermore nitrogen dioxide were measured using nitrogen dioxide filter samplers and monitors. Model calculations: The measurements in the monitoring program were supplemented with model calculations of concentrations and depositions of nitrogen and sulphur compounds to Danish land surface, marine waters, fjords and bays using the ACDEP model (Atmospheric Chemistry and Deposition). The model is a so-called trajectory model and simulates the physical and chemical processes in the atmosphere using meteorological and emission data as input. The advantage of combining measurements with model calculations is that the strengths of both methods is obtained. Conclusions concerning: 1) actual concentration levels at the monitoring stations, 2) deposition at the monitoring stations, 3) seasonal variations and 4) long term trends in concentrations and depositions are mainly based on the direct measurements. These are furthermore used to validate the results of the model calculations. Calculations and conclusions concerning: 1) depositions to land surface and to the individual marine water, 2) contributions from different emission

  6. First Novozym 435 lipase-catalyzed Morita-Baylis-Hillman reaction in the presence of amides.

    Science.gov (United States)

    Tian, Xuemei; Zhang, Suoqin; Zheng, Liangyu

    2016-03-01

    The first Novozym 435 lipase-catalyzed Morita-Baylis-Hillman (MBH) reaction with amides as co-catalyst was realized. Results showed that neither Novozym 435 nor amide can independently catalyze the reaction. This co-catalytic system that used a catalytic amount of Novozym 435 with a corresponding amount of amide was established and optimized. The MBH reaction strongly depended on the structure of aldehyde substrate, amide co-catalyst, and reaction additives. The optimized reaction yield (43.4%) was achieved in the Novozym 435-catalyzed MBH reaction of 2, 4-dinitrobenzaldehyde and cyclohexenone with isonicotinamide as co-catalyst and β-cyclodextrin as additive only in 2 days. Although enantioselectivity of Novozym 435 was not found, the results were still significant because an MBH reaction using lipase as biocatalyst was realized for the first time. Copyright © 2015 Elsevier Inc. All rights reserved.

  7. Elucidation of Mechanisms and Selectivities of Metal-Catalyzed Reactions using Quantum Chemical Methodology.

    Science.gov (United States)

    Santoro, Stefano; Kalek, Marcin; Huang, Genping; Himo, Fahmi

    2016-05-17

    Quantum chemical techniques today are indispensable for the detailed mechanistic understanding of catalytic reactions. The development of modern density functional theory approaches combined with the enormous growth in computer power have made it possible to treat quite large systems at a reasonable level of accuracy. Accordingly, quantum chemistry has been applied extensively to a wide variety of catalytic systems. A huge number of problems have been solved successfully, and vast amounts of chemical insights have been gained. In this Account, we summarize some of our recent work in this field. A number of examples concerned with transition metal-catalyzed reactions are selected, with emphasis on reactions with various kinds of selectivities. The discussed cases are (1) copper-catalyzed C-H bond amidation of indoles, (2) iridium-catalyzed C(sp(3))-H borylation of chlorosilanes, (3) vanadium-catalyzed Meyer-Schuster rearrangement and its combination with aldol- and Mannich-type additions, (4) palladium-catalyzed propargylic substitution with phosphorus nucleophiles, (5) rhodium-catalyzed 1:2 coupling of aldehydes and allenes, and finally (6) copper-catalyzed coupling of nitrones and alkynes to produce β-lactams (Kinugasa reaction). First, the methodology adopted in these studies is presented briefly. The electronic structure method in the great majority of these kinds of mechanistic investigations has for the last two decades been based on density functional theory. In the cases discussed here, mainly the B3LYP functional has been employed in conjunction with Grimme's empirical dispersion correction, which has been shown to improve the calculated energies significantly. The effect of the surrounding solvent is described by implicit solvation techniques, and the thermochemical corrections are included using the rigid-rotor harmonic oscillator approximation. The reviewed examples are chosen to illustrate the usefulness and versatility of the adopted methodology in

  8. Palladium-catalyzed Suzuki-Miyaura coupling of amides by carbon-nitrogen cleavage: general strategy for amide N-C bond activation.

    Science.gov (United States)

    Meng, Guangrong; Szostak, Michal

    2016-06-15

    The first palladium-catalyzed Suzuki-Miyaura cross-coupling of amides with boronic acids for the synthesis of ketones by sterically-controlled N-C bond activation is reported. The transformation is characterized by operational simplicity using bench-stable, commercial reagents and catalysts, and a broad substrate scope, including substrates with electron-donating and withdrawing groups on both coupling partners, steric-hindrance, heterocycles, halides, esters and ketones. The scope and limitations are presented in the synthesis of >60 functionalized ketones. Mechanistic studies provide insight into the catalytic cycle of the cross-coupling, including the first experimental evidence for Pd insertion into the amide N-C bond. The synthetic utility is showcased by a gram-scale cross-coupling and cross-coupling at room temperature. Most importantly, this process provides a blueprint for the development of a plethora of metal catalyzed reactions of typically inert amide bonds via acyl-metal intermediates. A unified strategy for amide bond activation to enable metal insertion into N-C amide bond is outlined ().

  9. Energy deposition in NSRR test fuels

    International Nuclear Information System (INIS)

    Ohnishi, Nobuaki; Tanzawa, Sadamitsu; Tanzawa, Tomio; Kitano, Teruaki; Okazaki, Shuji

    1978-02-01

    Interpretation of fuel performance data collected during inpile testing in the NSRR requires a knowledge of the energy deposition or enthalpy increase in each sample tested. The report describes the results of absolute measurement of fission products and contents of uranium in irradiated test fuels which were performed to determine the energy deposition. (auth.)

  10. Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations

    KAUST Repository

    Vummaleti, Sai V. C.

    2015-11-13

    Density functional theory calculations have been used to investigate the reaction mechanism for the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-bis(diphenylphosphino)propane) and [Pd]/BPh3 dual catalytic system assisted intramolecular alkoxycyanation ([Pd] = Pd-Xantphos) using acylated and cyanated 2-allylphenol derivatives as substrates, respectively. Our results substantially confirm the proposed mechanism for both [Rh]- and [Pd]/ BPh3-mediated alkoxyfunctionalizations, offering a detailed geometrical and energetical understanding of all the elementary steps. Furthermore, for the [Rh]-mediated alkoxyacylation, our observations support the hypothesis that the quinoline group of the substrate is crucial to stabilize the acyl metal complex and prevent further decarbonylation. For [Pd]/BPh3-catalyzed alkoxycyanation, our findings clarify how the Lewis acid BPh3 cocatalyst accelerates the only slow step of the reaction, corresponding to the oxidative addition of the cyanate O-CN bond to the Pd center. © 2015 American Chemical Society.

  11. Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations

    KAUST Repository

    Vummaleti, Sai V. C.; Alghamdi, Miasser; Poater, Albert; Falivene, Laura; Scaranto, Jessica; Beetstra, Dirk J.; Morton, Jason G.; Cavallo, Luigi

    2015-01-01

    Density functional theory calculations have been used to investigate the reaction mechanism for the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-bis(diphenylphosphino)propane) and [Pd]/BPh3 dual catalytic system assisted intramolecular alkoxycyanation ([Pd] = Pd-Xantphos) using acylated and cyanated 2-allylphenol derivatives as substrates, respectively. Our results substantially confirm the proposed mechanism for both [Rh]- and [Pd]/ BPh3-mediated alkoxyfunctionalizations, offering a detailed geometrical and energetical understanding of all the elementary steps. Furthermore, for the [Rh]-mediated alkoxyacylation, our observations support the hypothesis that the quinoline group of the substrate is crucial to stabilize the acyl metal complex and prevent further decarbonylation. For [Pd]/BPh3-catalyzed alkoxycyanation, our findings clarify how the Lewis acid BPh3 cocatalyst accelerates the only slow step of the reaction, corresponding to the oxidative addition of the cyanate O-CN bond to the Pd center. © 2015 American Chemical Society.

  12. Iron(II)-catalyzed intermolecular amino-oxygenation of olefins through the N-O bond cleavage of functionalized hydroxylamines.

    Science.gov (United States)

    Lu, Deng-Fu; Zhu, Cheng-Liang; Jia, Zhen-Xin; Xu, Hao

    2014-09-24

    An iron-catalyzed diastereoselective intermolecular olefin amino-oxygenation reaction is reported, which proceeds via an iron-nitrenoid generated by the N-O bond cleavage of a functionalized hydroxylamine. In this reaction, a bench-stable hydroxylamine derivative is used as the amination reagent and oxidant. This method tolerates a range of synthetically valuable substrates that have been all incompatible with existing amino-oxygenation methods. It can also provide amino alcohol derivatives with regio- and stereochemical arrays complementary to known amino-oxygenation methods.

  13. Electrochemical Cobalt-Catalyzed C-H Activation.

    Science.gov (United States)

    Sauermann, Nicolas; Meyer, Tjark H; Ackermann, Lutz

    2018-06-19

    Carbon-heteroatom bonds represent omnipresent structural motifs of the vast majority of functionalized materials and bioactive compounds. C-H activation has emerged as arguably the most efficient strategy to construct C-Het bonds. Despite of major advances, these C-H transformations were largely dominated by precious transition metal catalysts, in combination with stoichiometric, toxic metal oxidants. Herein, we discuss the recent evolution of cobalt-catalyzed C-H activations that enable C-Het formations with electricity as the sole sustainable oxidant until May 2018. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Chemical bath deposited and dip coating deposited CuS thin films - Structure, Raman spectroscopy and surface study

    Science.gov (United States)

    Tailor, Jiten P.; Khimani, Ankurkumar J.; Chaki, Sunil H.

    2018-05-01

    The crystal structure, Raman spectroscopy and surface microtopography study on as-deposited CuS thin films were carried out. Thin films deposited by two techniques of solution growth were studied. The thin films used in the present study were deposited by chemical bath deposition (CBD) and dip coating deposition techniques. The X-ray diffraction (XRD) analysis of both the as-deposited thin films showed that both the films possess covellite phase of CuS and hexagonal unit cell structure. The determined lattice parameters of both the films are in agreement with the standard JCPDS as well as reported data. The crystallite size determined by Scherrer's equation and Hall-Williamsons relation using XRD data for both the as-deposited thin films showed that the respective values were in agreement with each other. The ambient Raman spectroscopy of both the as-deposited thin films showed major emission peaks at 474 cm-1 and a minor emmision peaks at 265 cm-1. The observed Raman peaks matched with the covellite phase of CuS. The atomic force microscopy of both the as-deposited thin films surfaces showed dip coating thin film to be less rough compared to CBD deposited thin film. All the obtained results are presented and deliberated in details.

  15. Manganese Catalyzed α-Olefination of Nitriles by Primary Alcohols.

    Science.gov (United States)

    Chakraborty, Subrata; Das, Uttam Kumar; Ben-David, Yehoshoa; Milstein, David

    2017-08-30

    Catalytic α-olefination of nitriles using primary alcohols, via dehydrogenative coupling of alcohols with nitriles, is presented. The reaction is catalyzed by a pincer complex of an earth-abundant metal (manganese), in the absence of any additives, base, or hydrogen acceptor, liberating dihydrogen and water as the only byproducts.

  16. High power density yeast catalyzed microbial fuel cells

    Science.gov (United States)

    Ganguli, Rahul

    increase was shown to quickly saturate with cell mass attached on the electrode. Based on recent modelling data that suggested that the electrode currents might be limited by the poor electrical conductivity of the anode, the power density versus electrical conductivity of a yeast-immobilized anode was investigated. Introduction of high aspect ratio carbon fiber filaments to the immobilization matrix increased the electrical conductivity of the anode. Although a higher electrical conductivity clearly led to an increase in power densities, it was shown that the principal limitation to power density increase was coming from proton transfer limitations in the immobilized anode. Partial overcoming of the gradients lead a power density of ca. 250 microW cm-2, which is the highest reported for yeast powered MFCs. A yeast-catalyzed microbial fuel cell was investigated as a power source for low power sensors using raw tree sap. It was shown that yeast can efficiently utilize the sucrose present in the raw tree sap to produce electricity when excess salt is added to the medium. Therefore the salinity of a potential energy source is an important consideration when MFCs are being considered for energy harvesting from natural sources.

  17. Rhodium-catalyzed C-H functionalization with N-acylsaccharins.

    Science.gov (United States)

    Wu, Hongxiang; Liu, Tingting; Cui, Ming; Li, Yue; Jian, Junsheng; Wang, Hui; Zeng, Zhuo

    2017-01-18

    A rhodium-catalyzed C-H functionalization with activated amides by decarbonylation has been developed. Notably, this is the first C-H arylation employing N-acylsaccharins as coupling partners to give biaryls in good to excellent yields. The highlight of the work is the high tolerance of functional groups such as formyl, ester, and vinyl and the use of a removable directing group.

  18. Ru(II)-Catalyzed Cross-Coupling of Cyclopropenes with Diazo Compounds: Formation of Olefins from Two Different Carbene Precursors.

    Science.gov (United States)

    Wang, Bo; Yi, Heng; Zhang, Hang; Sun, Tong; Zhang, Yan; Wang, Jianbo

    2018-01-19

    Formal carbene dimerization is a convergent method for the synthesis of alkenes. Herein, we report a Ru(II)-catalyzed carbene dimerization of cyclopropenes and diazo compounds. The yields are up to 97% and the stereoselectivity are up to >20:1. Mechanistically, it has been experimentally demonstrated that the catalyst reacts with cyclopropene first to generate a Ru(II)-carbene species, which is attacked by nucleophilic diazo substrate, followed by dinitrogen extrusion to form the double bond.

  19. Visible-Light-Induced Nickel-Catalyzed Negishi Cross-Couplings by Exogenous-Photosensitizer-Free Photocatalysis.

    Science.gov (United States)

    Abdiaj, Irini; Fontana, Alberto; Gomez, M Victoria; de la Hoz, Antonio; Alcázar, Jesús

    2018-03-22

    The merging of photoredox and transition-metal catalysis has become one of the most attractive approaches for carbon-carbon bond formation. Such reactions require the use of two organo-transition-metal species, one of which acts as a photosensitizer and the other one as a cross-coupling catalyst. We report herein an exogenous-photosensitizer-free photocatalytic process for the formation of carbon-carbon bonds by direct acceleration of the well-known nickel-catalyzed Negishi cross-coupling that is based on the use of two naturally abundant metals. This finding will open new avenues in cross-coupling chemistry that involve the direct visible-light absorption of organometallic catalytic complexes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Gold-Catalyzed Formal [4+1]/[4+3] Cycloadditions of Diazo Esters with Triazines.

    Science.gov (United States)

    Zhu, Chenghao; Xu, Guangyang; Sun, Jiangtao

    2016-09-19

    Reported herein is the unprecedented gold-catalyzed formal [4+1]/[4+3] cycloadditions of diazo esters with hexahydro-1,3,4-triazines, thus providing five- and seven-membered heterocycles in moderate to high yields under mild reaction conditions. These reactions feature the use of a gold complex to accomplish the diverse annulations and the first example of the involvement of a gold metallo-enolcarbene in a cycloaddition. It is also the first utilization of stable triazines as formal dipolar adducts in the carbene-involved cycloadditions. Mechanistic investigations reveal that the triazines reacted directly, rather than as formaldimine precursors, in the reaction process. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Manganese-catalyzed Dehydrogenative Alkylation or α-Olefination of Alkyl-N-Heteroaromatics by Alcohols.

    Science.gov (United States)

    Kempe, Rhett; Zhang, Guoying; Irrgang, Torsten; Dietel, Thomas; Kallmeier, Fabian

    2018-05-02

    Catalysis involving earth-abundant transition metals is an option to help save our rare noble metal resources and is especially interesting if novel reactivity or selectivity patterns are observed. We report here on a novel reaction: the dehydrogenative alkylation or α-olefination of alkyl-N-heteroaromatics by alcohols. Manganese complexes developed in our laboratory catalyze the reaction efficiently. Fe and Co complexes stabilized by such ligands are essentially inactive. Hydrogen is liberated during the reaction and bromo or iodo functional groups and olefins can be tolerated. A variety of alkyl-N-heteroaromatics can be functionalized, and benzyl and aliphatic alcohols undergo the reaction. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Diversity of Archaea and detection of crenarchaeotal amoA genes in the rivers Rhine and Têt

    NARCIS (Netherlands)

    Herfort, L.; Kim, J.H.; Coolen, M.J.L.; Abbas, B.; Schouten, S.; Herndl, G.J.; Sinninghe Damste, J.S.

    2009-01-01

    Pelagic archaeal phylogenetic diversity and the potential for crenarchaeotal nitrification of Group 1.1a were determined in the rivers Rhine and Têt by 16S rRNA sequencing, catalyzed reported deposition-fluorescence in situ hybridization (CARD–FISH) and quantification of 16S rRNA and functional

  3. Water evaporation in silica colloidal deposits.

    Science.gov (United States)

    Peixinho, Jorge; Lefèvre, Grégory; Coudert, François-Xavier; Hurisse, Olivier

    2013-10-15

    The results of an experimental study on the evaporation and boiling of water confined in the pores of deposits made of mono-dispersed silica colloidal micro-spheres are reported. The deposits are studied using scanning electron microscopy, adsorption of nitrogen, and adsorption of water through attenuated total reflection-infrared spectroscopy. The evaporation is characterized using differential scanning calorimetry and thermal gravimetric analysis. Optical microscopy is used to observe the patterns on the deposits after evaporation. When heating at a constant rate and above boiling temperature, the release of water out of the deposits is a two step process. The first step is due to the evaporation and boiling of the surrounding and bulk water and the second is due to the desorption of water from the pores. Additional experiments on the evaporation of water from membranes having cylindrical pores and of heptane from silica deposits suggest that the second step is due to the morphology of the deposits. Copyright © 2013 Elsevier Inc. All rights reserved.

  4. Rhodium-catalyzed enantioselective intramolecular C-H silylation for the syntheses of planar-chiral metallocene siloles.

    Science.gov (United States)

    Zhang, Qing-Wei; An, Kun; Liu, Li-Chuan; Yue, Yuan; He, Wei

    2015-06-01

    Reported herein is the rhodium-catalyzed enantioselective C-H bond silylation of the cyclopentadiene rings in Fe and Ru metallocenes. Thus, in the presence of (S)-TMS-Segphos, the reactions took place under very mild conditions to afford metallocene-fused siloles in good to excellent yields and with ee values of up to 97%. During this study it was observed that the steric hindrance of chiral ligands had a profound influence on the reactivity and enantioselectivity of the reaction, and might hold the key to accomplishing conventionally challenging asymmetric C-H silylations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Emissions, transport, deposition and effects of base cations in relation to acidification. Report from the UNECE LRTAP workshop in Gothenburg November 2003

    Energy Technology Data Exchange (ETDEWEB)

    Westling, Olle; Loevblad, Gun (eds.)

    2004-06-01

    The workshop on base cation deposition took place in Gothenburg on 26-28 November 2003. It was an official workshop of the Co-operative Programme for Monitoring and Evaluation of the Long Range Transboundary Air Pollution, EMEP and Working Group on Effects under the UNECE/CLRTAP. The workshop report summarises the state-of-knowledge of emissions, dispersion and deposition of base cations over Europe. The workshop evaluated in particular the knowledge with respect to mapping the base cation deposition over Europe as a basis for the application of dynamic models in the coming air pollution abatement strategies in Europe. The knowledge reflects the present situation, historical development and prospects for the coming 10-20 years.

  6. Dependence of silicon carbide coating properties on deposition parameters: preliminary report

    International Nuclear Information System (INIS)

    Lauf, R.J.; Braski, D.N.

    1980-05-01

    Fuel particles for the High-Temperature Gas-Cooled Reactor (HTGR) contain a layer of pyrolytic silicon carbide, which acts as a pressure vessel and provides containment of metallic fission products. The silicon carbide (SiC) is deposited by the thermal decomposition of methyltrichlorosilane (CH 3 SiCl 3 or MTS) in an excess of hydrogen. The purpose of the current study is to determine how the deposition variables affect the structure and properties of the SiC layer

  7. Post-depositional fracturing and subsidence of pumice flow deposits: Lascar Volcano, Chile.

    Science.gov (United States)

    Whelley, Patrick L; Jay, J; Calder, E S; Pritchard, M E; Cassidy, N J; Alcaraz, S; Pavez, A

    Unconsolidated pyroclastic flow deposits of the 1993 eruption of Lascar Volcano, Chile, have, with time, become increasingly dissected by a network of deeply penetrating fractures. The fracture network comprises orthogonal sets of decimeter-wide linear voids that form a pseudo-polygonal grid visible on the deposit surface. In this work, we combine shallow surface geophysical imaging tools with remote sensing observations and direct field measurements of the deposit to investigate these fractures and their underlying causal mechanisms. Based on ground penetrating radar images, the fractures are observed to have propagated to depths of up to 10 m. In addition, orbiting radar interferometry shows that deposit subsidence of up to 1 cm/year -1 occurred between 1993 and 1996 with continued subsidence occurring at a slower rate thereafter. In situ measurements show that 1 m below the surface, the 1993 deposits remain 5°C to 15°C hotter, 18 years after emplacement, than adjacent deposits. Based on the observed subsidence as well as estimated cooling rates, the fractures are inferred to be the combined result of deaeration, thermal contraction, and sedimentary compaction in the months to years following deposition. Significant environmental factors, including regional earthquakes in 1995 and 2007, accelerated settling at punctuated moments in time. The spatially variable fracture pattern relates to surface slope and lithofacies variations as well as substrate lithology. Similar fractures have been reported in other ignimbrites but are generally exposed only in cross section and are often attributed to formation by external forces. Here we suggest that such interpretations should be invoked with caution, and deformation including post-emplacement subsidence and fracturing of loosely packed ash-rich deposits in the months to years post-emplacement is a process inherent in the settling of pyroclastic material.

  8. Remediation of spent block in Uvanas deposit

    International Nuclear Information System (INIS)

    Nurgaziev, M.A.; Iskakov, M.M.

    2012-01-01

    In 2007 by 'Kazatomprom' and 'Mining company' board decision, the branch of 'Mining company', 'Steppe ore management body' is reorganized in structure subdivision, the basic activity of which is organization and carrying out remediation works on spent blocks of PSV uranium deposit. In 2002 works are completed on OVOS for operating deposits Uvanas, Kanjugan, Northern Karamurun and Eastern Minkuduk. The results of present work were reported in IAEA conference. The working project 'Remediation of spent blocks of PSV uranium deposit PV-17 polygon of Steppe ore management body' approved in 2005 was developed for carrying out the remediation works. Works funding were carried out from liquidation fund of the current deposit established in accordance with the Republic of Kazakhstan law 'About interior and interior use'. Deposits remediation is the part of deposit operation life cycle which obliges to operate deposits with minimum expenditures for remediation.

  9. Vein type uranium deposits

    International Nuclear Information System (INIS)

    1986-01-01

    Veins are tabular- or sheet-like masses of minerals occupying or following a fracture or a set of fractures in the enclosing rock. They have been formed later than the country rock and fractures, either by filling of the open spaces or by partial or complete replacement of the adjoining rock or most commonly by both of these processes combined. This volume begins with the occurrences and deposits known from old shield areas and the sedimentary belts surrounding them. They are followed by papers describing the European deposits mostly of Variscan age, and by similar deposits known from China being of Jurassic age. The volume is completed by two papers which do not fit exactly in the given scheme. A separate abstract was prepared for each of the 25 papers in this report

  10. Cu and Cu(Mn) films deposited layer-by-layer via surface-limited redox replacement and underpotential deposition

    Energy Technology Data Exchange (ETDEWEB)

    Fang, J.S., E-mail: jsfang@nfu.edu.tw [Department of Materials Science and Engineering, National Formosa University, Huwei 63201, Taiwan (China); Sun, S.L. [Department of Materials Science and Engineering, National Formosa University, Huwei 63201, Taiwan (China); Cheng, Y.L. [Department of Electrical Engineering, National Chi-Nan University, Nan-Tou 54561, Taiwan (China); Chen, G.S.; Chin, T.S. [Department of Materials Science and Engineering, Feng Chia University, Taichung 40724, Taiwan (China)

    2016-02-28

    Graphical abstract: - Abstract: The present paper reports Cu and Cu(Mn) films prepared layer-by-layer using an electrochemical atomic layer deposition (ECALD) method. The structure and properties of the films were investigated to elucidate their suitability as Cu interconnects for microelectronics. Previous studies have used primarily a vacuum-based atomic layer deposition to form a Cu metallized film. Herein, an entirely wet chemical process was used to fabricate a Cu film using the ECALD process by combining underpotential deposition (UPD) and surface-limited redox replacement (SLRR). The experimental results indicated that an inadequate UPD of Pb affected the subsequent SLRR of Cu and lead to the formation of PbSO{sub 4}. A mechanism is proposed to explain the results. Layer-by-layer deposition of Cu(Mn) films was successfully performed by alternating the deposition cycle-ratios of SLRR-Cu and UPD-Mn. The proposed self-limiting growth method offers a layer-by-layer wet chemistry-based deposition capability for fabricating Cu interconnects.

  11. Hydrolyses of 2- and 4-fluoro N-heterocycles. 3. Nucleophilic catalysis by buffer bases in the general acid catalyzed hydrolysis of 4-fluoroquinaldine

    International Nuclear Information System (INIS)

    Muscio, O.J. Jr.; Theobald, P.G.; Rutherford, D.R.

    1989-01-01

    Pseudo-first-order rate constants and catalytic rate constants are reported for the buffer-catalyzed hydrolysis of 4-fluoroquinaldine (1) in carboxylic acid and phosphoric acid buffers. The buffer catalysis is consistent with specific acid, general base catalysis. Hydrolyses in 99% 18 O-labeled acetate, indicate that the predominant catalytic mode for the acetic acid/acetate buffer system is nucleophilic catalysis by the acetate anion coupled with specific acid catalysis. The other buffers presumably react in a similar manner. A Broensted-type plot of the catalytic rate constants for hydrolysis of protonated 1 has a slope of 0.57, with formate deviating positively from the line determined by acetate, chloroacetate, monohydrogen phosphate, and water. This Broensted slope is less than that found for hydrolysis of the 2-fluoro-1-methylpyridinium ion, 2, but is still within the range expected for aromatic nucleophilic substitution. Rate constants and 18 O-labeling results for hydrolysis in acetate buffer are also reported for 4-acetoxyquinaldine (3), the proposed intermediate in the acetate-catalyzed hydrolysis of 1. 15 references, 5 figures, 3 tables

  12. Straightforward uranium-catalyzed dehydration of primary amides to nitriles

    International Nuclear Information System (INIS)

    Enthaler, Stephan

    2011-01-01

    The efficient uranium-catalyzed dehydration of a variety of primary amides, using N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) as a dehydration reagent, to the corresponding nitriles has been investigated. With this catalyst system, extraordinary catalyst activities and selectivities were feasible. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Mechanism of Brønsted acid catalyzed conversion of carbohydrates

    NARCIS (Netherlands)

    Yang, G.; Pidko, E.A.; Hensen, E.J.M.

    2012-01-01

    A comprehensive DFT study of acid-catalyzed glucose and fructose reactions in water covering more than 100 potential reaction paths is performed with the aim to identify the main reaction channels for obtaining such desirable biorefinery platform products as 5-hydroxymethylfurfural (HMF) and

  14. DNA strand exchange catalyzed by molecular crowding in PEG solutions

    KAUST Repository

    Feng, Bobo; Frykholm, Karolin; Nordé n, Bengt; Westerlund, Fredrik

    2010-01-01

    DNA strand exchange is catalyzed by molecular crowding and hydrophobic interactions in concentrated aqueous solutions of polyethylene glycol, a discovery of relevance for understanding the function of recombination enzymes and with potential applications to DNA nanotechnology. © 2010 The Royal Society of Chemistry.

  15. Transglutaminase catalyzed cross-linking of sodium caseinate improves oxidative stability of flaxseed oil emulsion.

    Science.gov (United States)

    Ma, Hairan; Forssell, Pirkko; Kylli, Petri; Lampi, Anna-Maija; Buchert, Johanna; Boer, Harry; Partanen, Riitta

    2012-06-20

    Sodium caseinate was modified by transglutaminase catalyzed cross-linking reaction prior to the emulsification process in order to study the effect of cross-linking on the oxidative stability of protein stabilized emulsions. The extent of the cross-linking catalyzed by different dosages of transglutaminase was investigated by following the ammonia production during the reaction and using SDS-PAGE gel. O/W emulsions prepared with the cross-linked and non-cross-linked sodium caseinates were stored for 30 days under the same conditions. Peroxide value measurement, oxygen consumption measurement, and headspace gas chromatography analysis were used to study the oxidative stability of the emulsions. The emulsion made of the cross-linked sodium caseinate showed an improved oxidative stability with reduced formation of fatty acid hydroperoxides and volatiles and a longer period of low rate oxygen consumption. The improving effect of transglutaminase catalyzed cross-linking could be most likely attributed to the enhanced physical stability of the interfacial protein layer against competitive adsorption by oil oxidation products.

  16. Enantioconvergent synthesis by sequential asymmetric Horner-Wadsworth-Emmons and palladium-catalyzed allylic substitution reactions

    DEFF Research Database (Denmark)

    Pedersen, Torben Møller; Hansen, E. Louise; Kane, John

    2001-01-01

    A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different $alpha@-oxygen-substituted, racemic aldehydes were initially transformed by asy...... the allylic stereocenter and the alkene geometry. Thus, a single $gamma@-substituted ester was obtained as the overall product, in high isomeric purity. The method was applied to a synthesis of a subunit of the iejimalides, a group of cytotoxic macrolides.......A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different $alpha@-oxygen-substituted, racemic aldehydes were initially transformed...... by asymmetric HWE reactions into mixtures of two major $alpha@,$beta@-unsaturated esters, possessing opposite configurations at their allylic stereocenters as well as opposite alkene geometry. Subsequently, these isomeric mixtures of alkenes could be subjected to palladium-catalyzed allylic substitution...

  17. Effect of a base-catalyzed dechlorination process on the genotoxicity of PCB-contaminated soil

    Energy Technology Data Exchange (ETDEWEB)

    DeMarini, D.M.; Houk, V.S.; Kornel, A.; Rogers, C.J.

    1992-01-01

    We evaluated the genotoxicity of dichloromethane (DCM) extracts of PCB-contaminated soil before and after the soil had been treated by a base-catalyzed dechlorination process, which involved heating a mixture of the soil, polyethylene glycol, and sodium hydroxide to 250-350 C. This dechlorination process reduced by over 99% the PCB concentration in the soil, which was initially 2,200 ppm. The DCM extracts of both control and treated soils were not mutagenic in strain TA100 of Salmonella, but they were mutagenic in strain TA98. The base-catalyzed dechlorination process reduced the mutagenic potency of the soil by approximately one-half. The DCM extracts of the soils before and after treatment were equally genotoxic in a prophage-induction assay in E. coli, which detects some chlorinated organic carcinogens that were not detected by the Salmonella mutagenicity assay. These results show that treatment of PCB-contaminated soil by this base-catalyzed dechlorination process did not increase the genotoxicity of the soil.

  18. Reactor prospects of muon-catalyzed fusion of deuterium and tritium concentrated in transition metals

    International Nuclear Information System (INIS)

    Stacey, W.M. Jr.

    1989-01-01

    It is conjectured that the number of fusion events catalyzed by a single muon is orders of magnitude greater for deuterium and tritium concentrated in a transition metal than in gaseous form and that the recent observation of 2.5-MeV neutrons from a D 2 O electrolytic cell with palladium and titanium cathodes can thereby be interpreted in terms of cosmic muon-catalyzed deuterium-deuterium fusion. This suggests a new fusion reactor reactor consisting of deuterium and tritium concentrated in transition metal fuel elements in a fusion core that surrounds an accelerator-produced muon source. The feasibility of net energy production in such a reactor is established in terms of requirements on the number of fusion events catalyzed per muon. The technological implications for a power reactor based on this concept are examined. The potential of such a concept as a neutron source for materials testing and tritium and plutonium production is briefly discussed

  19. 1987 wet deposition temporal and spatial patterns in North America

    Energy Technology Data Exchange (ETDEWEB)

    Simpson, J.C.; Olsen, A.R.

    1990-03-01

    The focus of this report is on North American wet deposition temporal patterns from 1979 to 1987 and spatial patterns for 1987. The report investigates the patterns of annual precipitation-weighted average concentration and annual deposition for nine ion species: hydrogen, sulfate, nitrate, ammonium, calcium, chloride, sodium, potassium, and magnesium. Data are from the Acid Deposition System (ADS) for the statistical reporting of North American deposition data which includes the National Atmospheric Deposition Program/National Trends Network (NADP/NTN), the MAP3S precipitation chemistry network, the Utility Acid Precipitation Study Program (UAPSP), the Canadian Precipitation Monitoring Network (CAPMoN), and the daily and 4-weekly Acidic Precipitation in Ontario Study (APIOS-D and APIOS-C). Mosaic maps, based on surface estimation using kriging, display concentration and deposition spatial patterns of pH, hydrogen, sulfate, nitrate, ammonium, and calcium ion species for 1987 annual, winter, and summer periods. The temporal pattern analyses use a subset of 39 sites over a 9-year (1979--1987) period and an expanded subset of 140 sites with greater spatial coverage over a 6-year (1982--1987) period. 68 refs., 15 figs., 15 tabs.

  20. Stability of nanocrystalline electrochemically deposited layers

    DEFF Research Database (Denmark)

    Pantleon, Karen; Somers, Marcel A. J.

    2009-01-01

    have different microstructure and properties compared to bulk materials and the thermodynamic non-equilibrium state of as-deposited layers frequently results in changes of the microstructure as a function of time and/or temperature. The evolving microstructure affects the functionality and reliability......The technological demand for manufacturing components with complex geometries of micrometer or sub-micrometer dimensions and ambitions for ongoing miniaturization have attracted particular attention to electrochemical deposition methods. Thin layers of electrochemically deposited metals and alloys...... of electrodeposited components, which can be beneficial, as for the electrical conductivity of copper interconnect lines, or detrimental, as for reduced strength of nickel in MEMS applications. The present work reports on in-situ studies of the microstructure stability of as-deposited nanocrystalline Cu-, Ag- and Ni...

  1. Alkylsilyl Peroxides as Alkylating Agents in the Copper-Catalyzed Selective Mono-N-Alkylation of Primary Amides and Arylamines.

    Science.gov (United States)

    Sakamoto, Ryu; Sakurai, Shunya; Maruoka, Keiji

    2017-07-06

    The copper-catalyzed selective mono-N-alkylation of primary amides or arylamines using alkylsilyl peroxides as alkylating agents is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the alkylsilyl peroxides, as well as to the primary amides and arylamines. Mechanistic studies suggest that the present reaction should proceed through a free-radical process that includes alkyl radicals generated from the alkylsilyl peroxides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Quantitative measurement of aerosol deposition on skin, hair and clothing for dosimetric assessment. Final report

    DEFF Research Database (Denmark)

    Fogh, C.L.; Byrne, M.A.; Andersson, Kasper Grann

    1999-01-01

    the deposition and subsequent fate of contaminant aerosol on skin, hair and clothing. The main technique applied involves the release and subsequent deposition on volunteers in test rooms of particles of differentsizes labelled with neutron activatable rare earth tracers. Experiments indicate that the deposition...... of magnitudeas the gamma doses received over the first year from contamination on outdoor surfaces. According to the calculations, beta doses from skin deposition to individuals in areas of Russia, where dry deposition of Chernobyl fallout led to very high levels ofcontamination, may have amounted to several...

  3. Iridium/Bipyridine-Catalyzed ortho-Selective C-H Borylation of Phenol and Aniline Derivatives.

    Science.gov (United States)

    Li, Hong-Liang; Kanai, Motomu; Kuninobu, Yoichiro

    2017-11-03

    An iridium-catalyzed ortho-selective C-H borylation of phenol and aniline derivatives has been successfully developed. Iridium/bipyridine-catalyzed C-H borylation generally occurred at the meta- and para-positions of aromatic substrates. Introduction of an electron-withdrawing substituent on the bipyridine-type ligand and a methylthiomethyl group on the hydroxy and amino groups of the phenol and aniline substrates, however, dramatically altered the regioselectivity, affording exclusively ortho-borylated products. The reaction proceeded in good to excellent yields with good functional group tolerance. C-H borylation was applied to the synthesis of a calcium receptor modulator.

  4. Managing Distrust-Induced Risk with Deposit in Supply Chain Contract Decisions

    Science.gov (United States)

    Han, Guanghua; Dong, Ming; Sun, Qi

    2014-01-01

    This paper studies the trust issue in a two-echelon supply chain information sharing process. In a supply chain, the retailer reports the forecasted demand to the supplier. Traditionally, the supplier's trust in the retailer's reported information is based on the retailer's reputation. However, this paper considers that trust is random and is also affected by the reputation and the demand gap. The supplier and retailer have been shown to have different evaluations regarding the degree of trust. Furthermore, distrust is inherently linked to perceived risk. To mitigate perceived risk, a two-stage decision process with an unpayback deposit contract is proposed. At the first stage, the supplier and the retailer negotiate the deposit contract. At the second stage, a Stackelberg game is used to determine the retailer's reported demand and the supplier's production quantity. We show that the deposits from the retailer's and supplier's perspectives are different. When the retailer's reported demand is equal to the supplier's forecasted demand, the retailer's evaluation of the deposit is more than that of supplier's. When the retailer's reported demand is equal to the retailer's forecasted demand, the deposit from the retailer's perspective is at the lowest level. PMID:25054190

  5. Managing distrust-induced risk with deposit in supply chain contract decisions.

    Science.gov (United States)

    Han, Guanghua; Dong, Ming; Sun, Qi

    2014-01-01

    This paper studies the trust issue in a two-echelon supply chain information sharing process. In a supply chain, the retailer reports the forecasted demand to the supplier. Traditionally, the supplier's trust in the retailer's reported information is based on the retailer's reputation. However, this paper considers that trust is random and is also affected by the reputation and the demand gap. The supplier and retailer have been shown to have different evaluations regarding the degree of trust. Furthermore, distrust is inherently linked to perceived risk. To mitigate perceived risk, a two-stage decision process with an unpayback deposit contract is proposed. At the first stage, the supplier and the retailer negotiate the deposit contract. At the second stage, a Stackelberg game is used to determine the retailer's reported demand and the supplier's production quantity. We show that the deposits from the retailer's and supplier's perspectives are different. When the retailer's reported demand is equal to the supplier's forecasted demand, the retailer's evaluation of the deposit is more than that of supplier's. When the retailer's reported demand is equal to the retailer's forecasted demand, the deposit from the retailer's perspective is at the lowest level.

  6. Synthesis of pyrrolo(2,3-b)quinolines by palladium-catalyzed heteroannulation

    International Nuclear Information System (INIS)

    Gee, Moon Bae; Lee, Won Jung; Yum, Eul Kgun

    2003-01-01

    Palladium-catalyzed heteroannulation of 2-amino-3-iodoquinoline derivatives and 1-trimethylsilyl internal alkynes provided highly regioselective pyrrolo(2,3-b)quinolines with trimethylsilyl group next to the nitrogen atom in the pyrrole ring

  7. Manganese Catalyzed Regioselective C–H Alkylation: Experiment and Computation

    KAUST Repository

    Wang, Chengming

    2018-05-08

    A new efficient manganese-catalyzed selective C2-alkylation of indoles via carbenoid insertion has been achieved. The newly developed C-H functionalization protocol provides access to diverse products and shows good functional group tolerance. Mechanistic and computational studies support the formation of a Mn(CO)3 acetate complex as the catalytically active species.

  8. Manganese Catalyzed Regioselective C–H Alkylation: Experiment and Computation

    KAUST Repository

    Wang, Chengming; Maity, Bholanath; Cavallo, Luigi; Rueping, Magnus

    2018-01-01

    A new efficient manganese-catalyzed selective C2-alkylation of indoles via carbenoid insertion has been achieved. The newly developed C-H functionalization protocol provides access to diverse products and shows good functional group tolerance. Mechanistic and computational studies support the formation of a Mn(CO)3 acetate complex as the catalytically active species.

  9. Muon-catalyzed fusion: A new direction in fusion research

    International Nuclear Information System (INIS)

    Jones, S.E.

    1986-01-01

    In four years of intensive research, muon-catalyzed fusion has been raised from the level of a scientific curiosity to a potential means of achieving clean fusion energy. This novel approach to fusion is based on the fact that a sub-atomic particle known as a ''muon'' can induce numerous energy-releasing fusion reactions without the need for high temperatures or plasmas. Thus, the muon serves as a catalyst to facilitate production for fusion energy. The success of the research effort stems from the recent discovery of resonances in the reaction cycle which make the muon-induced fusion process extremely efficient. Prior estimates were pessimistic in that only one fusion per muon was expected. In that case energy balance would be impossible since energy must be invested to generate the muons. However, recent work has gone approximately half-way to energy balance and further improvements are being worked on. There has been little time to assess the full implications of these discoveries. However, various ways to use muon-catalyzed fusion for electrical power production are now being explored

  10. Muon-catalyzed fusion: a new direction in fusion research

    International Nuclear Information System (INIS)

    Jones, S.E.

    1986-01-01

    In four years of intensive research, muon-catalyzed fusion has been raised from the level of a scientific curiosity to a potential means of achieving clean fusion energy. This novel approach to fusion is based on the fact that a sub-atomic particle known as a ''muon'' can induce numerous energy-releasing fusion reactions without the need for high temperatures or plasmas. Thus, the muon serves as a catalyst to facilitate production for fusion energy. The success of the research effort stems from the recent discovery of resonances in the reaction cycle which make the muon-induced fusion process extremely efficient. Prior estimates were pessimistic in that only one fusion per muon was expected. In that case energy balance would be impossible since energy must be invested to generate the muons. However, recent work has gone approximately half-way to energy balance and further improvements are being worked on. There has been little time to assess the full implications of these discoveries. However, various ways to use muon-catalyzed fusion for electrical power production are now being explored

  11. Development of target capsules for muon catalyzed fusion experiments

    International Nuclear Information System (INIS)

    Watts, K.D.; Jones, S.E.; Caffrey, A.J.

    1983-01-01

    A series of Muon Catalyzed Fusion experiments has been conducted at the Los Alamos Meson Physics Facility to determine how many fusion reactions one muon would catalyze under various temperature, pressure, contamination, and tritium concentration conditions. Target capsules to contain deuterium and tritium at elevated temperatures and pressures were engineered for a maximum temperature of 540 K (512 0 F) and a maximum pressure of 103 MPa (15,000 psig). Experimental data collected with these capsules indicated that the number of fusion reactions per muon continued to increase with temperature up to the 540-K design limit. Theory had indicated that the reaction rate should peak at approximately 540 K, but this was not confirmed during the experiments. A second generation of capsules which have a maximum design temperature of 800 K (980 0 F) and a maximum design pressure of 103 MPa (15,000 psig) has now been engineered. These new capsules will be used to further study the muon catalysis rate versus deuterium-tritium mixture temperature

  12. Synthesis of glycoluril catalyzed by potassium hydroxide under ultrasound irradiation.

    Science.gov (United States)

    Li, Ji-Tai; Liu, Xiao-Ru; Sun, Ming-Xuan

    2010-01-01

    Synthesis of the glycolurils catalyzed by potassium hydroxide was carried out in 17-75% yield at 40 degrees C in EtOH under ultrasound irradiation. Compared to the method using stirring, the main advantage of the present procedure is milder conditions and shorter reaction time.

  13. Mechanistic investigation of the gold-catalyzed aerobic oxidation of alcohols

    DEFF Research Database (Denmark)

    Fristrup, Peter; Johansen, Louise Bahn; Christensen, Claus Hviid

    2008-01-01

    The mechanism for the gold-catalyzed aerobic oxidation of alcohols was studied using a series of para-substituted benzyl alcohols (Hammett methodology). The competition experiments clearly show that the rate-determining step of the reaction involves the generation of a partial positive charge in ...

  14. Enzyme-Catalyzed Synthesis of Saccharide Acrylate Monomers from Nonedible Biomass

    NARCIS (Netherlands)

    Kloosterman, Wouter M. J.; Brouwer, Sander; Loos, Katja

    Various cellulase preparations were found to catalyze the transglycosidation between cotton linters and 2-hydroxyethyl acrylate. The conversion and enzyme activity were found to be optimal in reaction mixtures that contained 5 vol% of the acrylate. The structures of the products were revealed by

  15. Pd(II)-Catalyzed Enantioselective C-H Olefination of Diphenylacetic Acids

    Science.gov (United States)

    Shi, Bing-Feng; Zhang, Yang-Hui; Lam, Jonathan K.; Wang, Dong-Hui; Yu, Jin-Quan

    2009-01-01

    Pd(II)-catalyzed enantioselective C-H olefination of diphenylacetic acid substrates has been achieved through the use of mono-protected chiral amino acid ligands. The absolute configuration of the resulting olefinated products is consistent with that of a proposed C-H insertion intermediate. PMID:20017549

  16. DFT Study of the Molybdenum-Catalyzed Deoxydehydration of Vicinal Diols

    DEFF Research Database (Denmark)

    Lupp, Daniel; Christensen, Niels Johan; Dethlefsen, Johannes Rytter

    2015-01-01

    , and extrusion of the alkene. We have compared the proposed pathway with several alternatives, and the results have been corroborated by comparison with the molybdenum- catalyzed sulfoxide reduction recently published by Sanz et al. and with experimental observations for the DODH itself. Improved understanding...

  17. Trace element and REE composition of five samples of the Yucca Mountain calcite-silica deposits. Special report No. 8

    International Nuclear Information System (INIS)

    Livingston, D.

    1993-07-01

    The attached materials document the results of part of a recent effort of geochemical sampling and analysis at Yucca Mountain and nearby regions. The efforts come as a result of interest in comprehensive analyses of rare earth elements (REE), lanthanum (La) through lutecium (Lu). Several additional, non-REE analyses were obtained as well. Commercially available REE analyses have proved to be insufficiently sensitive for geochemical purposes. Dr. Roman Schmitt at the Radiation Center at Oregon State University in Corvallis was sent five samples as a trial effort. The results are very encouraging. The purpose of compiling Dr. Schmitt's report and the other materials is to inform the sponsor of his independent observations of these results and other information that sent to him. To provide a more complete appreciation of the utility of REE analyses a copy of Dave Vaniman's recent article is included in which he notes that REE analyses from Yucca Mountain indicate the occurrence of two distinctly different REE patterns as do several other chemical parameters of the calcite-silica deposits. Our four samples with high equivalent CaCO 3 were collected from sites we believe to be spring deposits. One sample, 24D, is from southern Crater Flat which is acknowledged by U.S.G.S. investigators to be a spring deposit. All four of these samples have REE patterns similar to those from the saturated zone reported by Vaniman

  18. Simulation of the geochemical interactions in a natural CO2 deposit: the example of Springerville - Saint-Johns (USA). Final report

    International Nuclear Information System (INIS)

    Le Guern, C.; Gaus, I.

    2004-01-01

    The aim of the study is a better understanding of the geochemical operating of natural analogues by the simulation of scenario representative of the evolution of site since the arrival of CO 2 still today. This exercise concerns the Springerville site. Simulation tests with the PHREEQC code have been realized. This final report presents in the first part how the data are collected on a natural CO 2 , then a bibliographic synthesis on the observed impacts of the CO 2 on a deposit. The fourth part is the simulation of the geochemical interactions in the natural CO 2 deposit of Springerville. (A.L.B.)

  19. Palladium(II)-Catalyzed meta-C-H Olefination: Constructing Multisubstituted Arenes through Homo-Diolefination and Sequential Hetero-Diolefination.

    Science.gov (United States)

    Bera, Milan; Maji, Arun; Sahoo, Santosh K; Maiti, Debabrata

    2015-07-13

    Divinylbenzene derivatives represent an important class of molecular building blocks in organic chemistry and materials science. Reported herein is the palladium-catalyzed synthesis of divinylbenzenes by meta-C-H olefination of sulfone-based arenes. Successful sequential olefinations in a position-selective manner provided a novel route for the synthesis of hetero-dialkenylated products, which are difficult to access using conventional methods. Additionally, 1,3,5-trialkenylated compounds can be generated upon successful removal of the directing group. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Process and machinery description of equipment for deposition of canisters in medium-long deposition holes

    International Nuclear Information System (INIS)

    Kalbantner, P.

    2001-08-01

    In this report twelve methods are presented to deposit a canister with spent nuclear fuel in a horizontal hole, several canisters per hole (MLH). These methods are part of the KBS-3 system. They have been developed successively, after an analysis of weak points and strong points in previously described methods. In conformance with the guidelines for Project JADE, a choices of system has been considered during the development work. This is whether canister and bentonite buffer should be deposited 'in parts', i.e. at different occasions, but shortly after each other or 'in a package', i.e. together in a single package. The other choice in the guidelines for the JADE project, whether the canister should be placed in a radiation shield or not during transport in the secondary tunnels, was not relevant to MLR. The basic technical problem is depositing heavy objects, the canister and the buffer components, in an horizontal hole which is approximately 200 m deep. Two methods for depositing of the bentonite barrier and the canisters in separate processes have been studied. For depositing of the bentonite barrier and the canister 'in a package', four alternative techniques have been studied: a metallic sleeve around the package, a loading scoop that is rotated, a fork carriage and rails. The repeated transports in a hole, a consequence of depositing several canisters in the same hole, could lead to the rock being crushed. The mutual impact of machines, load and rock wall has therefore been particularly considered. In several methods, the use of a gangway has been proposed (steel plates or layer of ice). A failure mode and effect analysis has been performed for one of the twelve methods. When comparing with a method to deposit one canister per hole using the same technique, the need for equipment and resources is far larger for this MLH method if incidents should occur during depositing. The development work reported here has not yet yielded a definitive method for placing

  1. Flavin-catalyzed redox tailoring reactions in natural product biosynthesis.

    Science.gov (United States)

    Teufel, Robin

    2017-10-15

    Natural products are distinct and often highly complex organic molecules that constitute not only an important drug source, but have also pushed the field of organic chemistry by providing intricate targets for total synthesis. How the astonishing structural diversity of natural products is enzymatically generated in biosynthetic pathways remains a challenging research area, which requires detailed and sophisticated approaches to elucidate the underlying catalytic mechanisms. Commonly, the diversification of precursor molecules into distinct natural products relies on the action of pathway-specific tailoring enzymes that catalyze, e.g., acylations, glycosylations, or redox reactions. This review highlights a selection of tailoring enzymes that employ riboflavin (vitamin B2)-derived cofactors (FAD and FMN) to facilitate unusual redox catalysis and steer the formation of complex natural product pharmacophores. Remarkably, several such recently reported flavin-dependent tailoring enzymes expand the classical paradigms of flavin biochemistry leading, e.g., to the discovery of the flavin-N5-oxide - a novel flavin redox state and oxygenating species. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. Coupled ferredoxin and crotonyl coenzyme A (CoA) reduction with NADH catalyzed by the butyryl-CoA dehydrogenase/Etf complex from Clostridium kluyveri.

    Science.gov (United States)

    Li, Fuli; Hinderberger, Julia; Seedorf, Henning; Zhang, Jin; Buckel, Wolfgang; Thauer, Rudolf K

    2008-02-01

    Cell extracts of butyrate-forming clostridia have been shown to catalyze acetyl-coenzyme A (acetyl-CoA)- and ferredoxin-dependent formation of H2 from NADH. It has been proposed that these bacteria contain an NADH:ferredoxin oxidoreductase which is allosterically regulated by acetyl-CoA. We report here that ferredoxin reduction with NADH in cell extracts from Clostridium kluyveri is catalyzed by the butyryl-CoA dehydrogenase/Etf complex and that the acetyl-CoA dependence previously observed is due to the fact that the cell extracts catalyze the reduction of acetyl-CoA with NADH via crotonyl-CoA to butyryl-CoA. The cytoplasmic butyryl-CoA dehydrogenase complex was purified and is shown to couple the endergonic reduction of ferredoxin (E0' = -410 mV) with NADH (E0' = -320 mV) to the exergonic reduction of crotonyl-CoA to butyryl-CoA (E0' = -10 mV) with NADH. The stoichiometry of the fully coupled reaction is extrapolated to be as follows: 2 NADH + 1 oxidized ferredoxin + 1 crotonyl-CoA = 2 NAD+ + 1 ferredoxin reduced by two electrons + 1 butyryl-CoA. The implications of this finding for the energy metabolism of butyrate-forming anaerobes are discussed in the accompanying paper.

  3. Vanadium-Catalyzed Enantioselective Desymmetrization of meso-Secondary Allylic Alcohols and Homoallylic Alcohols

    OpenAIRE

    Li, Zhi; Zhang, Wei; Hisashi Yamamoto, H.

    2008-01-01

    Vanadium-catalyzed epoxidation has extended substrate scope. In addition to various bis-allylic alcohols, bis-homoallylic alcohols can also be desymmetrized using our Vanadium-Bis-hydroxamic acid complexes.

  4. Characterisation by optical spectroscopy of a plasma of depositions of thins layers

    International Nuclear Information System (INIS)

    Chouan, Yannick

    1984-01-01

    This research thesis reports a work which, by correlating emission and absorption spectroscopic measurements with properties of deposited thin layers, aimed at being a complement to works undertaken by a team in charge of the realisation of a flat screen. In a first part, the author reports the study of a cathodic pulverisation of a silicon target. He describes the experimental set-up, presents correlations obtained between plasma electric properties (target self-polarisation voltage), emission spectroscopic measurements (line profile and intensity) and absorption spectroscopic measurements (density of metastables), and the composition of deposited thin layers for two reactive pulverisation plasmas (Ar-H_2 and Ar-CH_4). The second part addresses the relationship between experimental conditions and spectroscopic characteristics (emission and absorption lines, excitation and rotation temperature) of a He-SiH_4 plasma. The author also determined the most adapted spectroscopic measurements to the 'control' of deposition, and which result in an optimisation of electronic properties and of the deposition rate for the hydrogenated amorphous silicon. The third part reports the characterisation of depositions. Electric and optic measurements are reported. Then, for both deposition techniques, the author relates the influence of experimental conditions to deposition properties and to spectroscopic diagnosis. The author finally presents static characteristics of a thin-layer-based transistor

  5. Pd-Catalyzed Cross-Coupling Reactions of Amides and Aryl Mesylates

    Science.gov (United States)

    Dooleweerdt, Karin; Fors, Brett P.; Buchwald, Stephen L.

    2010-01-01

    A catalyst, based on a biarylphosphine ligand, for the Pd-catalyzed cross-coupling reactions of amides and aryl mesylates is described. This system allows an array of aryl and heteroaryl mesylates to be transformed into the corresponding N-arylamides in moderate to excellent yields. PMID:20420379

  6. xanthen-11-ones by ZnO Nanoparticles Catalyzed Three Co

    African Journals Online (AJOL)

    NICO

    Highly effective zinc oxide nanoparticles catalyzed solvent-free synthesis of some tetrahydrobenzo[a]xanthen-11-one derivatives ... efficient, green and simple method for the preparation of ... Characterization of ZnO NPs structure was continued by SEM ... catalysts may be related to higher surface area available for.

  7. Dry deposition and resuspension of particulate matter in city environments

    International Nuclear Information System (INIS)

    Jensen, N.O.

    1984-06-01

    The report describes, mostly in qualitative terms, the deposition and resuspension of particles and how the mechanics depend on particle size. The effect of rough surfaces is discussed. It is concluded that knowledge on the subject, at relevant large Reynolds numbers, is indeed lacking. Various methods for measurements of deposition is mentioned and further the report gives some general ideas on how a suitable full scale experiment should be laid out in order to produce some data on the problems of dry deposition to city surfaces. (author)

  8. Manganese-Catalyzed Aminomethylation of Aromatic Compounds with Methanol as a Sustainable C1 Building Block.

    Science.gov (United States)

    Mastalir, Matthias; Pittenauer, Ernst; Allmaier, Günter; Kirchner, Karl

    2017-07-05

    This study represents the first example of a manganese-catalyzed environmentally benign, practical three-component aminomethylation of activated aromatic compounds including naphtols, phenols, pyridines, indoles, carbazoles, and thiophenes in combination with amines and MeOH as a C1 source. These reactions proceed with high atom efficiency via a sequence of dehydrogenation and condensation steps which give rise to selective C-C and C-N bond formations, thereby releasing hydrogen and water. A well-defined hydride Mn(I) PNP pincer complex, recently developed in our laboratory, catalyzes this process in a very efficient way, and a total of 28 different aminomethylated products were synthesized and isolated yields of up to 91%. In a preliminary study, a related Fe(II) PNP pincer complex was shown to catalyze the methylation of 2-naphtol rather than its aminomethylation displaying again the divergent behavior of isoelectronic Mn(I) and Fe(II) PNP pincer systems.

  9. Comparing Ru and Fe-catalyzed olefin metathesis

    KAUST Repository

    Poater, Albert; Chaitanya Vummaleti, Sai Vikrama; Pump, Eva; Cavallo, Luigi

    2014-01-01

    Density functional theory calculations have been used to explore the potential of Fe-based complexes with an N-heterocyclic carbene ligand, as olefin metathesis catalysts. Apart from a less endothermic reaction energy profile, a small reduction in the predicted upper energy barriers (≈ 2 kcal mol -1) is calculated in the Fe catalyzed profile with respect to the Ru catalysed profile. Overall, this study indicates that Fe-based catalysts have the potential to be very effective olefin metathesis catalysts. This journal is © the Partner Organisations 2014.

  10. Palladium-Catalyzed alpha-Arylation of Tetramic Acids

    DEFF Research Database (Denmark)

    Storgaard, Morten; Dorwald, F. Z.; Peschke, B.

    2009-01-01

    A mild, racemization-free, palladium-Catalyzed alpha-arylation of tetramic acids (2,4-pyrrolidinediones) has been developed. Various amino acid-derived tetramic acids were cleanly arylated by treatment with 2 mol % of Pd(OAc)(2), 4 mol % of a sterically demanding biaryl phosphine, 2.3 equiv of K2CO...... no effect on their reactivity: both electron-rich and electron-poor aryl chlorides and bromides or triflates led to good yields. Ortho-substituted aryl halides and heteroaryl halides, however, did not undergo the title reaction....

  11. Synthesis of Dihydrobenzofurans via Palladium-Catalyzed Heteroannulations

    Energy Technology Data Exchange (ETDEWEB)

    Rozhkov, Roman Vladimirovich [Iowa State Univ., Ames, IA (United States)

    2004-01-01

    Palladium-catalyzed heteroannulation of 1,3-dienes with 3-iodo-2-alkenols, and 2-iodo-2-alkenols, as well as their amino analogs, affords the corresponding cyclic ethers and amines respectively. The presence of a β-hydrogen in the vinylic halide results in β-hydride elimination giving the corresponding alkyne. The presence of a bulky group in the α-position of the vinylic halide results in failure or reduced amounts of annulation products. A chloride source, pyridine base and electron-rich phosphine are essential for this reaction.

  12. The atmospheric chemical vapour deposition of coatings on glass

    International Nuclear Information System (INIS)

    Sanderson, Kevin David

    1996-01-01

    The deposition of thin films of indium oxide, tin doped indium oxide (ITO) and titanium nitride for solar control applications have been investigated by Atmospheric Chemical Vapour Deposition (APCVD). Experimental details of the deposition system and the techniques used to characterise the films are presented. Results from investigations into the deposition parameters, the film microstructure and film material properties are discussed. A range of precursors were investigated for the deposition of indium oxide. The effect of pro-mixing the vaporised precursor with an oxidant source and the deposition temperature has been studied. Polycrystalline In 2 O 3 films with a resistivity of 1.1 - 3x10 -3 Ω cm were obtained with ln(thd) 3 , oxygen and nitrogen. The growth of ITO films from ln(thd) 3 , oxygen and a range of tin dopants is also presented. The effect of the dopant precursor, the doping concentration, deposition temperature and the effect of additives on film growth and microstructure is discussed. Control over the preferred orientation growth of ITO has been achieved by the addition of acetate species during film growth. Insitu infra-red spectroscopy has been used to identify the gas phase species and identify the species responsible for the film modification. ITO films with a resistivities of 1.5 - 4x10 -4 Ω cm have been achieved. The deposition of titanium nitride by the APCVD of Ti(NMe 2 ) 4 and a mixture of Ti(NMe 2 ) 4 and ammonia is reported. Contamination of the films and pro-reaction between the precursors in the gas phase is discussed, and the synthesis of new precursors for the deposition of titanium nitride is reported. New precursors have been synthesised under anaerobic conditions and characterised by infra-red spectroscopy, 1 H and 13 C NMR, mass spectrometry, thermal gravemetric analysis and three by single crystal X-ray diffraction. Deposition of titanium nitride utilising two new precursors is reported. (author)

  13. Development of melamine modified urea formaldehyde resins based o nstrong acidic pH catalyzed urea formaldehyde polymer

    Science.gov (United States)

    Chung-Yun Hse

    2009-01-01

    To upgrade the performance of urea-formaldehyde (UF) resin bonded particleboards, melamine modified urea-formaldehyde (MUF) resins based on strong acidic pH catalyzed UF polymers were investigated. The study was conducted in a series of two experiments: 1) formulation of MUF resins based on a UF polymer catalyzed with strong acidic pH and 2) determination of the...

  14. Pd(OAc)2/Ph3P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles.

    Science.gov (United States)

    Kellner, Dominik; Weger, Maximilian; Gini, Andrea; Mancheño, Olga García

    2017-01-01

    The palladium-catalyzed dimerization of isoprene is a practical approach of synthesizing monoterpenes. Though several highly selective methods have been reported, most of them still required pressure or costly ligands for attaining the active system and desired selectivity. Herein, we present a simple and economical procedure towards the tail-to-tail dimer using readily available Pd(OAc) 2 and inexpensive triphenylphosphine as ligand. Furthermore, simple screw cap vials are employed, allowing carrying out the reaction at low pressure. In addition, the potential of the dimer as a chemical platform for the preparation of heterocyclic terpenes by subsequent (hetero)-Diels-Alder or [4 + 1]-cycloadditions with nitrenes is also depicted.

  15. Scope and mechanism in palladium-catalyzed isomerizations of highly substituted allylic, homoallylic, and alkenyl alcohols.

    Science.gov (United States)

    Larionov, Evgeny; Lin, Luqing; Guénée, Laure; Mazet, Clément

    2014-12-03

    Herein we report the palladium-catalyzed isomerization of highly substituted allylic alcohols and alkenyl alcohols by means of a single catalytic system. The operationally simple reaction protocol is applicable to a broad range of substrates and displays a wide functional group tolerance, and the products are usually isolated in high chemical yield. Experimental and computational mechanistic investigations provide complementary and converging evidence for a chain-walking process consisting of repeated migratory insertion/β-H elimination sequences. Interestingly, the catalyst does not dissociate from the substrate in the isomerization of allylic alcohols, whereas it disengages during the isomerization of alkenyl alcohols when additional substituents are present on the alkyl chain.

  16. Carbon isotope fractionation of 1,1,1-trichloroethane during base-catalyzed persulfate treatment

    International Nuclear Information System (INIS)

    Marchesi, Massimo; Thomson, Neil R.; Aravena, Ramon; Sra, Kanwartej S.; Otero, Neus; Soler, Albert

    2013-01-01

    Highlights: • Treatability and C fractionation of 1,1,1-TCA by base-catalyzed S 2 O 8 2− was studied. • The rate of degradation of 1,1,1-TCA increased with a higher OH − :S 2 O 8 2− ratio. •Base-catalyzed S 2 O 8 2− can potentially treat recalcitrant compound like 1,1,1-TCA. • An enrichment factor of −7.0‰ independent of the OH − :S 2 O 8 2− ratio was obtained. • Carbon isotope can potentially be used to estimate the ISCO treatment efficacy. -- Abstract: The extent of carbon isotope fractionation during degradation of 1,1,1-trichloroethane (1,1,1-TCA) by a base-catalyzed persulfate (S 2 O 8 2− ) treatment system was investigated. Significant destruction of 1,1,1-TCA was observed at a pH of ∼12. An increase in the NaOH:S 2 O 8 2− molar ratio from 0.2:1 to 8:1 enhanced the reaction rate of 1,1,1-TCA by a factor of ∼5 to yield complete (>99.9%) destruction. An average carbon isotope enrichment fractionation factor which was independent of the NaOH:S 2 O 8 2− molar ratio of −7.0 ± 0.2‰ was obtained. This significant carbon isotope fractionation and the lack of dependence on changes in the NaOH:S 2 O 8 2− molar ratio demonstrates that carbon isotope analysis can potentially be used in situ as a performance assessment tool to estimate the degradation effectiveness of 1,1,1-TCA by a base-catalyzed persulfate system

  17. Comparison of Growth Rates of Aerobic Anoxygenic Phototrophic Bacteria and Other Bacterioplankton Groups in Coastal Mediterranean Waters

    Czech Academy of Sciences Publication Activity Database

    Ferrera, I.; Gasol, J.M.; Sebastian, M.; Hojerová, Eva; Koblížek, Michal

    2011-01-01

    Roč. 77, č. 21 (2011), s. 7451-7458 ISSN 0099-2240 R&D Projects: GA ČR GAP501/10/0221 Institutional research plan: CEZ:AV0Z50200510 Keywords : CATALYZED REPORTER DEPOSITION * NATURAL AQUATIC SYSTEMS * IN-SITU HYBRIDIZATION Subject RIV: EE - Microbiology, Virology Impact factor: 3.829, year: 2011

  18. Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

    Science.gov (United States)

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

    2013-05-01

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

  19. Electrochemical reduction of oxygen catalyzed by Pseudomonas aeruginosa

    Energy Technology Data Exchange (ETDEWEB)

    Cournet, Amandine [Universite de Toulouse, UPS, LU49, Adhesion bacterienne et formation de biofilms, 35 chemin des Maraichers, 31062 Toulouse Cedex 09 (France)] [Laboratoire de Genie Chimique CNRS UMR5503, 4 allee Emile Monso, BP 84234, 31432 Toulouse Cedex 04 (France); Berge, Mathieu; Roques, Christine [Universite de Toulouse, UPS, LU49, Adhesion bacterienne et formation de biofilms, 35 chemin des Maraichers, 31062 Toulouse Cedex 09 (France); Bergel, Alain [Laboratoire de Genie Chimique CNRS UMR5503, 4 allee Emile Monso, BP 84234, 31432 Toulouse Cedex 04 (France); Delia, Marie-Line, E-mail: marieline.delia@ensiacet.f [Laboratoire de Genie Chimique CNRS UMR5503, 4 allee Emile Monso, BP 84234, 31432 Toulouse Cedex 04 (France)

    2010-07-01

    Pseudomonas aeruginosa has already been shown to catalyze oxidation processes in the anode compartment of a microbial fuel cell. The present study focuses on the reverse capacity of the bacterium, i.e. reduction catalysis. Here we show that P. aeruginosa is able to catalyze the electrochemical reduction of oxygen. The use of cyclic voltammetry showed that, for a given range of potential values, the current generated in the presence of bacteria could reach up to four times the current obtained without bacteria. The adhesion of bacteria to the working electrode was necessary for the catalysis to be observed but was not sufficient. The electron transfer between the working electrode and the bacteria did not involve mediator metabolites like phenazines. The transfer was by direct contact. The catalysis required a certain contact duration between electrodes and live bacteria but after this delay, the metabolic activity of cells was no longer necessary. Membrane-bound proteins, like catalase, may be involved. Various strains of P. aeruginosa, including clinical isolates, were tested and all of them, even catalase-defective mutants, presented the same catalytic property. P. aeruginosa offers a new model for the analysis of reduction catalysis and the protocol designed here may provide a basis for developing an interesting tool in the field of bacterial adhesion.

  20. Radioactive mineral deposits of the Pembroke-Renfrew area

    International Nuclear Information System (INIS)

    Masson, S.L.; Gordon, J.B.

    1981-01-01

    This report deals with the geological features of all the reported uranium and thorium occurrences in the Pembroke-Renfrew area of southeastern Ontario. There are 118 radioactive occurrences within the study area of which 102 were examined by the authors during the summers of 1977 and 1978. The report consists of a comprehensive description of the geological association and mineral content of the deposits which were examined. In addition, an attempt has been made to determine their mode of origin in order to assess the potential for discovery of additional deposits and to provide guidelines for exploration

  1. Managing Distrust-Induced Risk with Deposit in Supply Chain Contract Decisions

    Directory of Open Access Journals (Sweden)

    Guanghua Han

    2014-01-01

    Full Text Available This paper studies the trust issue in a two-echelon supply chain information sharing process. In a supply chain, the retailer reports the forecasted demand to the supplier. Traditionally, the supplier’s trust in the retailer’s reported information is based on the retailer’s reputation. However, this paper considers that trust is random and is also affected by the reputation and the demand gap. The supplier and retailer have been shown to have different evaluations regarding the degree of trust. Furthermore, distrust is inherently linked to perceived risk. To mitigate perceived risk, a two-stage decision process with an unpayback deposit contract is proposed. At the first stage, the supplier and the retailer negotiate the deposit contract. At the second stage, a Stackelberg game is used to determine the retailer’s reported demand and the supplier’s production quantity. We show that the deposits from the retailer’s and supplier’s perspectives are different. When the retailer’s reported demand is equal to the supplier’s forecasted demand, the retailer’s evaluation of the deposit is more than that of supplier’s. When the retailer’s reported demand is equal to the retailer’s forecasted demand, the deposit from the retailer’s perspective is at the lowest level.

  2. Zn(OTf)2 catalyzed indolylation and pyrrolylation of isatins: Efficient ...

    Indian Academy of Sciences (India)

    praveenithya

    Zn(OTf)2 catalyzed indolylation and pyrrolylation of isatins: Efficient synthesis and biochemical assay of 3,3- di(heteroaryl)oxindoles. C PRAVEEN a. , S NARENDIRAN b. , P DHEENKUMAR a,c and P T PERUMAL a,. * a. Organic Chemistry Division, Central Leather Research Institute (CSIR), Adyar, Chennai. 600020 ...

  3. Ag-catalyzed InAs nanowires grown on transferable graphite flakes

    DEFF Research Database (Denmark)

    Meyer-Holdt, Jakob; Kanne, Thomas; Sestoft, Joachim E.

    2016-01-01

    on exfoliated graphite flakes by molecular beam epitaxy. Ag catalyzes the InAs nanowire growth selectively on the graphite flakes and not on the underlying InAs substrates. This allows for easy transfer of the flexible graphite flakes with as-grown nanowire ensembles to arbitrary substrates by a micro...

  4. Investigation of acetic acid-catalyzed hydrothermal pretreatment on corn stover

    DEFF Research Database (Denmark)

    Xu, Jian; Thomsen, Mette Hedegaard; Thomsen, Anne Belinda

    2010-01-01

    Acetic acid (AA)-catalyzed liquid hot water (LHW) pretreatments on raw corn stover (RCS) were carried out at 195 °C at 15 min with the acetic acid concentrations between 0 and 400 g/kg RCS. After pretreatment, the liquor fractions and water-insoluble solids (WIS) were collected separately...

  5. Microsomal UDP-glucuronyltransferase-catalyzed bilirubin diglucuronide formation in human liver

    NARCIS (Netherlands)

    Peters, W. H.; Jansen, P. L.

    1986-01-01

    Human liver microsomal bilirubin UDP-glucuronyltransferase catalyzes formation of bilirubin mono- and diglucuronide. KmUDPGA and Vmax of the enzyme are 0.6 mM and 1.69 nmol/mg protein X min. In vitro, bilirubin readily dissolves in the microsomal lipid phase. Taking this into account a Kmbilirubin

  6. A 11-Steps Total Synthesis of Magellanine through a Gold(I)-Catalyzed Dehydro Diels-Alder Reaction.

    Science.gov (United States)

    McGee, Philippe; Bétournay, Geneviève; Barabé, Francis; Barriault, Louis

    2017-05-22

    We have developed an innovative strategy for the formation of angular carbocycles via a gold(I)-catalyzed dehydro Diels-Alder reaction. This transformation provides rapid access to a variety of complex angular cores in excellent diastereoselectivities and high yields. The usefulness of this Au I -catalyzed cycloaddition was further demonstrated by accomplishing a 11-steps total synthesis of (±)-magellanine. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Quantitative measurement of aerosol deposition on skin, hair and clothing for dosimetric assessment. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Fogh, C.L.; Byrne, M.A.; Andersson, K.G.; Bell, K.F.; Roed, J.; Goddard, A.J.H.; Vollmair, D.V.; Hotchkiss, S.A.M

    1999-06-01

    In the past, very little thought has been given to the processes and implications of deposition of potentially hazardous aerosol directly onto humans. This state of unpreparedness is unsatisfactory and suitable protocols have been developed and validated for tracer experiments to investigate the deposition and subsequent fate of contaminant aerosol on skin, hair and clothing. The main technique applied involves the release and subsequent deposition on volunteers in test rooms of particles of different sizes labelled with neutron activatable rare earth tracers. Experiments indicate that the deposition velocity to skin increases linearly with the particle size. A wind tunnel experiment simulating outdoor conditions showed a dependence on skin deposition velocity of wind speed, indicating that outdoor deposition velocities may be great. Both in vivo and in vitro experiments were conducted, and the influence of various factors, such as surface type, air flow, heating and electrostatics were examined. The dynamics of particle removal from human skin were studied by fluorescence scanning. This technique was also applied to estimate the fraction of aerosol dust transferred to skin by contact with a contaminated surface. The various parameters determined were applied to establish a model for calculation of radiation doses received from deposition of airborne radioactive aerosol on human body surfaces. It was found that the gamma doses from deposition on skin may be expected to be of the same order of magnitude as the gamma doses received over the first year from contamination on outdoor surfaces. According to the calculations, beta doses from skin deposition to individuals in areas of Russia, where dry deposition of Chernobyl fallout led to very high levels of contamination, may have amounted to several Sievert and may thus be responsible for a significant cancer risk. (au)

  8. 2017 Report for New LANL Physical Vapor Deposition Capability

    Energy Technology Data Exchange (ETDEWEB)

    Roman, Audrey Rae [Los Alamos National Laboratory; Zhao, Xinxin [Los Alamos National Laboratory; Bond, Evelyn M. [Los Alamos National Laboratory; Gooden, Matthew Edgell [Los Alamos National Laboratory; Rundberg, Robert S. [Los Alamos National Laboratory; Bredeweg, Todd Allen [Los Alamos National Laboratory

    2017-10-03

    There is an urgent need at LANL to achieve uniform, thin film actinide targets that are essential for nuclear physics experiments. The target preparation work is currently performed externally by Professor Walter Loveland at Oregon State University, who has made various evaporated actinide targets such as Th and U for use on several nuclear physics measurements at LANSCE. We are developing a vapor deposition capability, with the goal of evaporating Th and U in the Actinide Research Facility (ARF) at TA-48. In the future we plan to expand this work to evaporating transuranic elements, such as Pu. The ARF is the optimal location for evaporating actinides because this lab is specifically dedicated to actinide research. There are numerous instruments in the ARF that can be used to provide detailed characterization of the evaporated thin films such as: Table top Scanning Electron Microscope, In-situ X-Ray Diffraction, and 3D Raman spectroscopy. These techniques have the ability to determine the uniformity, surface characterization, and composition of the deposits.

  9. Calcium(ii)-catalyzed enantioselective conjugate additions of amines.

    Science.gov (United States)

    Uno, Brice E; Dicken, Rachel D; Redfern, Louis R; Stern, Charlotte M; Krzywicki, Greg G; Scheidt, Karl A

    2018-02-14

    The direct enantioselective chiral calcium(ii)·phosphate complex (Ca[CPA] 2 )-catalyzed conjugate addition of unprotected alkyl amines to maleimides was developed. This mild catalytic system represents a significant advance towards the general convergent asymmetric amination of α,β-unsaturated electrophiles, providing medicinally relevant chiral aminosuccinimide products in high yields and enantioselectivities. Furthermore, the catalyst can be reused directly from a previously chromatographed reaction and still maintain both high yield and selectivity.

  10. Beckmann rearrangement of aldoximes catalyzed by transition metal salts: mechanical aspects

    NARCIS (Netherlands)

    Leusink, A.J.; Meerbeek, T.G.; Noltes, J.G.

    1977-01-01

    The Beckmann rearrangement of aldoximes catalyzed by transition metal salts like palladium and nickel acetylacetonates is shown to be a dehydration‐hydration reaction in which the anti‐oxime is converted into nitrile and the nitrile is converted into amide.

  11. Regional aerosol deposition in human upper airways: Progress report, June 1, 1988--February 28, 1989

    International Nuclear Information System (INIS)

    Swift, D.L.

    1989-01-01

    The objective of this research program is to elucidate important factors which influence overall and local deposition of aerosols in the human airways above the trachea, including nasal airways, oral passage, pharynx and larynx. The intent is to develop information which can be used for exposure models for radon from unattached radon progeny (/approximately/1nm) up to 10 μm. Special emphasis is upon flow rate and airway dimensions as influenced by age and respiratory condition, as no experimental data presently exist for age-related deposition. Because of ethical and practical considerations associated with measuring aerosol deposition in children and difficulties of measuring local deposition in vivo, our experimental approach is to construct faithful replicate models of the airways for several ages of humans in which detailed studies of deposition can be carried out with well-characterized aerosols. Initial studies of overall deposition of ultrafine aerosols in an adult model have been carried out using replicate nasal passage models provided from this laboratory. These studies demonstrate a significant deposition percent for particle sizes approaching that of unattached radon progeny (40--50%), decreasing as particle size approaches 0.1 μm. Studies of the effect of flow rate indicate that higher deposition percent is realized at lower flow rate over the range from 4--60 lmin -1

  12. A Highly Stereocontrolled, One-Pot Approach toward Pyrrolobenzoxazinones and Pyrroloquinazolinones through a Lewis Acid-Catalyzed [3 + 2]-Cycloannulation Process.

    Science.gov (United States)

    Boomhoff, Michael; Ukis, Rostyslav; Schneider, Christoph

    2015-08-21

    We report herein a stereocontrolled [3 + 2]-cycloheteroannulation of bis-silyl dienediolate 1 with 2-aminobenzoic acid- and 2-aminobenzamide-derived imines to furnish highly substituted pyrrolo[1,2-a]benzoxazinones 3 and pyrrolo[1,2-a]quinazolinones 4, respectively, in good overall yields. This one-pot process rapidly generates molecular complexity and comprises a Lewis acid-catalyzed, vinylogous Mannich reaction of 1 followed by an intramolecular N,O-acetal- and N,N-aminal formation, respectively, which proceeds with good to excellent stereocontrol.

  13. Esterification of Oleic Acid for Biodiesel Production Catalyzed by SnCl2: A Kinetic Investigation

    Directory of Open Access Journals (Sweden)

    Marcio J. da Silva

    2008-09-01

    Full Text Available The production of biodiesel from low-cost raw materials which generally contain high amounts of free fatty acids (FFAs is a valuable alternative that would make their production costs more competitive than petroleum-derived fuel. Currently, the production of biodiesel from this kind of raw materials comprises a two-stage process, which requires an initial acid-catalyzed esterification of the FFA, followed by a basecatalyzed transesterification of the triglycerides. Commonly, the acid H2SO4 is the catalyst on the first step of this process. It must be said, however, that major drawbacks such as substantial reactor corrosion and the great generation of wastes, including the salts formed due to neutralization of the mineral acid, are negative and virtually unsurmountable aspects of this protocol. In this paper, tin(II chloride dihydrate (SnCl2·2H2O, an inexpensive Lewis acid, was evaluated as catalyst on the ethanolysis of oleic acid, which is the major component of several fat and vegetable oils feedstocks. Tin chloride efficiently promoted the conversion of oleic acid into ethyl oleate in ethanol solution and in soybean oil samples, under mild reaction conditions. The SnCl2 catalyst was shown to be as active as the mineral acid H2SO4. Its use has relevant advantages in comparison to mineral acids catalysts, such as less corrosion of the reactors and as well as avoiding the unnecessary neutralization of products. Herein, the effect of the principal parameters of reaction on the yield and rate of ethyl oleate production has been investigated. Kinetic measurements revealed that the esterification of oleic acid catalyzed by SnCl2·2H2O is first-order in relation to both FFAs and catalyst concentration. Experimentally, it was verified that the energy of activation of the esterification reaction of oleic acid catalyzed by SnCl2 was very close those reported for H2SO4.

  14. Gold-catalyzed heterocyclizations in alkynyl- and allenyl-β-lactams

    Directory of Open Access Journals (Sweden)

    Pedro Almendros

    2011-05-01

    Full Text Available New gold-catalyzed methods using the β-lactam scaffold have been recently developed for the synthesis of different sized heterocycles. This overview focuses on heterocyclization reactions of allenic and alkynic β-lactams which rely on the activation of the allene and alkyne component. The mechanism as well as the regio- and stereoselectivity of the cyclizations are also discussed.

  15. Interlayers Applied to CVD Diamond Deposition on Steel Substrate: A Review

    Directory of Open Access Journals (Sweden)

    Djoille Denner Damm

    2017-09-01

    Full Text Available Academics and industry have sought after combining the exceptional properties of diamonds with the toughness of steel. Since the early 1990s several partial solutions have been found but chemical vapor deposition (CVD diamond deposition on steel substrate continues to be a persistent problem. The main drawbacks are the high carbon diffusion from gas phase into substrate, the transition metals on the material surface that catalyze sp2 bond formation, instead of sp3 bonds, and the high thermal expansion coefficient (TEC mismatch between diamond and steels. An intermediate layer has been found necessary to increase diamond adhesion. Literature has proposed many efficient intermediate layers as a diffusion barrier for both, carbon and iron, but most intermediate layers shown have not solved TEC mismatch. In this review, we briefly discuss the solutions that exclusively work as diffusion barrier and discuss in a broader way the ones that also solve, or may potentially solve, the TEC mismatch problem. We examine some multilayers, the iron borides, the chromium carbides, and vanadium carbides. We go through the most relevant results of the last two and a half decades, including recent advances in our group. Vanadium carbide looks promising since it has shown excellent diffusion barrier properties, its TEC is intermediary between diamond and steel and, it has been thickened to manage thermal stress relief. We also review a new deposition technique to set up intermediate layers: laser cladding. It is promising because of its versatility in mixing different materials and fusing and/or sintering them on a steel surface. We conclude by remarking on new perspectives.

  16. A case of regression of atypical dense deposit disease without C3 deposition in a child.

    Science.gov (United States)

    Kim, Min Sun; Hwang, Pyoung Han; Kang, Mung Jae; Lee, Dae-Yeol

    2010-07-01

    Dense deposit disease (DDD) is a rare disorder characterized by the deposition of abnormal electron-dense material within the glomerular basement membrane of the kidneys. The diagnosis is made in most patients between 5 and 15 years of age, and within 10 years, approximately half of the affected patients progress to end-stage renal disease. We report a rare case of regressive DDD without C3 deposition after steroid therapy in an 11-year-old boy. The patient presented with edema, gross hematuria, and nephrotic-range proteinuria. Laboratory testing revealed a serum creatinine level of 1.17 mg/dL, albumin level of 2.3 g/dL, and serum C3 level of 125 mg/dL (range 90-180 mg/dL). The results of the renal biopsy were consistent with DDD without C3 deposition. After 6 weeks of steroid therapy, the nephrotic syndrome completely resolved. The follow-up renal biopsy showed a significant reduction in mesangial proliferation and disappearance of electron-dense deposits in the GBM.

  17. Mild and Efficient Nickel-Catalyzed Heck Reactions with Electron-Rich Olefins

    DEFF Research Database (Denmark)

    Gøgsig, Thomas; Kleimark, Jonatan; Lill, Sten O. Nilsson

    2012-01-01

    proved compatible, and the corresponding aryl methyl ketone could be secured after hydrolysis in yields approaching quantitative. Good functional group tolerance was observed matching the characteristics of the analogous Pd-catalyzed Heck reaction. The high levels of catalytic activity were explained...

  18. Heterogeneously catalyzed reactive extraction for biomass valorization into chemicals and fuels

    NARCIS (Netherlands)

    Ordomskiy, V.; Khodakov, A.Y.; Nijhuis, T.A.; Schouten, J.C.

    2015-01-01

    This paper focuses on the heterogeneously catalyzed reactive extraction and separation in reaction steps in organic and aqueous phases during the transformation of biomass derived products. Two approaches are demonstrated for decomposing and preserving routes for biomass transformation into valuable

  19. Enantioselective Evans-Tishchenko Reduction of b-Hydroxyketone Catalyzed by Lithium Binaphtholate

    Directory of Open Access Journals (Sweden)

    Makoto Nakajima

    2011-06-01

    Full Text Available Lithium diphenylbinaphtholate catalyzed the enantioselective Evans-Tishchenko reduction of achiral b-hydroxyketones to afford monoacyl-protected 1,3-diols with high stereoselectivities. In the reaction of racemic b-hydroxyketones, kinetic optical resolution occurred in a highly stereoselective manner.

  20. Muon-catalyzed fusion revisited

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    1984-12-15

    A negative muon can induce nuclear fusion in the reaction of deuteron and triton nuclei giving a helium nucleus, a neutron and an emerging negative muon. The muon forms a tightlybound deuteron-triton-muon molecule and fusion follows in about 10{sup -12}s. Then the muon is free again to induce further reactions. Thus the muon can serve as a catalyst for nuclear fusion, which can proceed without the need for the high temperatures which are needed in the confinement and inertial fusion schemes. At room temperature, up to 80 fusions per muon have recently been observed at the LAMPF machine at Los Alamos, and it is clear that this number can be exceeded. These and other results were presented at a summer Workshop on Muon-Catalyzed Fusion held in Jackson, Wyoming. Approximately fifty scientists attended from Austria, Canada, India, Italy, Japan, South Africa, West Germany, and the United States. The Workshop itself is symbolic of the revival of interest in this subject.

  1. Synthesis of trifluoromethylated acetylenes via copper-catalyzed trifluoromethylation of alkynyltrifluoroborates

    KAUST Repository

    Zheng, Huidong

    2012-12-01

    A new method for the synthesis of trifluoromethylated acetylenes is developed which involves the copper-catalyzed trifluoromethylation of alkynyltrifluoroborates with an electrophilic trifluoromethylating reagent. This method offers significant advantages such as efficiency and mild and base-free reaction conditions. A plausible mechanism is proposed. © 2012 Elsevier Ltd. All rights reserved.

  2. Ruthenium-Catalyzed Transformations of Alcohols: Mechanistic Investigations and Methodology Development

    DEFF Research Database (Denmark)

    Makarov, Ilya; Madsen, Robert; Fristrup, Peter

    with dimethoxyisopropylidene and pyridilidene ligands could be more active than RuCl2(IiPr)(p-cymene) used in the mechanistic investigation. Two analogs of the calculated complexes were synthesized but were not isolated in a pure form. The amidation reaction catalyzed by a mixture containing the N-ethyl pyridilidene...

  3. Synthesis of trifluoromethylated acetylenes via copper-catalyzed trifluoromethylation of alkynyltrifluoroborates

    KAUST Repository

    Zheng, Huidong; Huang, Yuanyuan; Wang, Zhiwei; Li, Huaifeng; Huang, Kuo-Wei; Yuan, Yaofeng; Weng, Zhiqiang

    2012-01-01

    A new method for the synthesis of trifluoromethylated acetylenes is developed which involves the copper-catalyzed trifluoromethylation of alkynyltrifluoroborates with an electrophilic trifluoromethylating reagent. This method offers significant advantages such as efficiency and mild and base-free reaction conditions. A plausible mechanism is proposed. © 2012 Elsevier Ltd. All rights reserved.

  4. Electrical and optical performance of transparent conducting oxide films deposited by electrostatic spray assisted vapour deposition.

    Science.gov (United States)

    Hou, Xianghui; Choy, Kwang-Leong; Liu, Jun-Peng

    2011-09-01

    Transparent conducting oxide (TCO) films have the remarkable combination of high electrical conductivity and optical transparency. There is always a strong motivation to produce TCO films with good performance at low cost. Electrostatic Spray Assisted Vapor Deposition (ESAVD), as a variant of chemical vapour deposition (CVD), is a non-vacuum and low-cost deposition method. Several types of TCO films have been deposited using ESAVD process, including indium tin oxide (ITO), antimony-doped tin oxide (ATO), and fluorine doped tin oxide (FTO). This paper reports the electrical and optical properties of TCO films produced by ESAVD methods, as well as the effects of post treatment by plasma hydrogenation on these TCO films. The possible mechanisms involved during plasma hydrogenation of TCO films are also discussed. Reduction and etching effect during plasma hydrogenation are the most important factors which determine the optical and electrical performance of TCO films.

  5. Flexible CIGS solar cells on large area polymer foils with in-line deposition methods and application of alternative back contacts - Final report

    Energy Technology Data Exchange (ETDEWEB)

    Tiwari, A. N.

    2009-08-15

    This illustrated report for the Swiss Federal Office of Energy (SFOE) summarises the work performed within this project and also reports on synergies with other projects that helped to make a significant contribution to the development of CIGS thin film solar cells on flexible substrates such as polymer foils. The project's aims were to learn more about up-scaling issues and to demonstrate the abilities required for the processing of layers on large area polyimide foils for flexible CIGS solar cells. Custom-built evaporators that were designed and constructed in-house are described. A CIGS system for in-line deposition was also modified for roll-to-roll deposition and alternative electrical back contacts to conventional ones were evaluated on flexible polyimide foils. The objectives of the project and the results obtained are looked at and commented on in detail.

  6. Aerial electrostatic spray deposition and canopy penetration in cotton

    Science.gov (United States)

    Spray deposition on abaxial and adaxial leaf surfaces along with canopy penetration are essential for insect control and foliage defoliation in cotton production agriculture. Researchers have reported that electrostatically charged sprays have increased spray deposit onto these surfaces under widel...

  7. Carbon isotope fractionation of 1,1,1-trichloroethane during base-catalyzed persulfate treatment

    Energy Technology Data Exchange (ETDEWEB)

    Marchesi, Massimo, E-mail: m2marche@uwaterloo.ca [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Department of Earth and Environmental Sciences, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Thomson, Neil R. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Aravena, Ramon [Department of Earth and Environmental Sciences, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Sra, Kanwartej S. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Golder Associates Inc, Toronto, Ontario, Canada L5N 5Z7 (Canada); Otero, Neus; Soler, Albert [Departament de Cristal.lographia, Mineralogia i Diposits Minerals, Facultat de Geologia, Universitat de Barcelona, Barcelona, Spain 08028 (Spain)

    2013-09-15

    Highlights: • Treatability and C fractionation of 1,1,1-TCA by base-catalyzed S{sub 2}O{sub 8}{sup 2−} was studied. • The rate of degradation of 1,1,1-TCA increased with a higher OH{sup −}:S{sub 2}O{sub 8}{sup 2−} ratio. •Base-catalyzed S{sub 2}O{sub 8}{sup 2−} can potentially treat recalcitrant compound like 1,1,1-TCA. • An enrichment factor of −7.0‰ independent of the OH{sup −}:S{sub 2}O{sub 8}{sup 2−} ratio was obtained. • Carbon isotope can potentially be used to estimate the ISCO treatment efficacy. -- Abstract: The extent of carbon isotope fractionation during degradation of 1,1,1-trichloroethane (1,1,1-TCA) by a base-catalyzed persulfate (S{sub 2}O{sub 8}{sup 2−}) treatment system was investigated. Significant destruction of 1,1,1-TCA was observed at a pH of ∼12. An increase in the NaOH:S{sub 2}O{sub 8}{sup 2−} molar ratio from 0.2:1 to 8:1 enhanced the reaction rate of 1,1,1-TCA by a factor of ∼5 to yield complete (>99.9%) destruction. An average carbon isotope enrichment fractionation factor which was independent of the NaOH:S{sub 2}O{sub 8}{sup 2−} molar ratio of −7.0 ± 0.2‰ was obtained. This significant carbon isotope fractionation and the lack of dependence on changes in the NaOH:S{sub 2}O{sub 8}{sup 2−} molar ratio demonstrates that carbon isotope analysis can potentially be used in situ as a performance assessment tool to estimate the degradation effectiveness of 1,1,1-TCA by a base-catalyzed persulfate system.

  8. Competition Between Self-birth and Catalyzed Death in Aggregation Growth with Catalysis Injection

    International Nuclear Information System (INIS)

    Chen Dan; Lin Zhenquan; Sun Yunfei; Ke Jianhong

    2009-01-01

    We propose two irreversible aggregation growth models of aggregates of two distinct species (A and B) to study the interactions between virus aggregates and medicine efficacy aggregates in the virus-medicine cooperative evolution system. The A-species aggregates evolve driven by self monomer birth and B-species aggregate-catalyzed monomer death in model I and by self birth, catalyzed death, and self monomer exchange reactions in model II, while the catalyst B-species aggregates are assumed to be injected into the system sustainedly or at a periodic time-dependent rate. The kinetic behaviors of the A-species aggregates are investigated by the rate equation approach based on the mean-field theory with the self birth rate kernel I A (k) = Ik, catalyzed death rate kernel J AB (k) = Jk and self exchange rate kernel K A (k, l) = Kkl. The kinetic behaviors of the A-species aggregates are mainly dominated by the competition between the two effects of the self birth (with the effective rate I) and the catalyzed death (with the effective rate JB 0 ), while the effects of the self exchanges of the A-species aggregates which appear in an effective rate KA 0 play important roles in the cases of I > JB 0 and I = JB 0 . The evolution behaviors of the total mass M A 1 (t) and the total aggregate number M A 0 (t) are obtained, and the aggregate size distribution α k (t) of species A is found to approach a generalized scaling form in the case of I ≥ JB 0 and a special modified scaling form in the case of I 0 . The periodical evolution of the B-monomers concentration plays an exponential form of the periodic modulation. (interdisciplinary physics and related areas of science and technology)

  9. The mechanism of the phosphine-free palladium-catalyzed hydroarylation of alkynes

    DEFF Research Database (Denmark)

    Ahlquist, Mårten Sten Gösta; Fabrizi, G.; Cacchi, S.

    2006-01-01

    The mechanism of the Pd-catalyzed hydroarylation and hydrovinylation reaction of alkynes has been studied by a combination of experimental and theoretical methods (B3LYP), with an emphasis on the phosphine-free version. The regioselectivity of the hydroarylation and hydrovinylation shows unexpected...

  10. Geology and recognition criteria for uraniferous humate deposits, Grants Uranium Region, New Mexico. Final report

    International Nuclear Information System (INIS)

    Adams, S.S.; Saucier, A.E.

    1981-01-01

    The geology of the uraniferous humate uranium deposits of the Grants Uranium Region, northwestern New Mexico, is summarized. The most important conclusions of this study are enumerated. Although the geologic characteristics of the uraniferous humate deposits of the Grants Uranium Region are obviously not common in the world, neither are they bizarre or coincidental. The source of the uranium in the deposits of the Grants Uranium Region is not known with certainty. The depositional environment of the host sediments was apparently the mid and distal portions of a wet alluvial fan system. The influence of structural control on the location and accumulation of the host sediments is now supported by considerable data. The host sediments possess numerous important characteristics which influenced the formation of uraniferous humate deposits. Ilmenite-magnetite distribution within potential host sandstones is believed to be the simplest and most useful regional alteration pattern related to this type of uranium deposit. A method is presented for organizing geologic observations into what is referred to as recognition criteria. The potential of the United States for new districts similar to the Grants Uranium Region is judged to be low based upon presently available geologic information. Continuing studies on uraniferous humate deposits are desirable in three particular areas

  11. Dermal Titanium Dioxide Deposition Associated With Intralesional Triamcinolone Injection.

    Science.gov (United States)

    Cohen, Brandon E; Bashey, Sameer; Cole, Christine; Abraham, Jerrold L; Ragsdale, Bruce; Ngo, Binh

    2016-12-01

    Cutaneous discoloration secondary to dermal deposition of titanium dioxide (TiO2) particles is recognized but seldom reported in the literature. In this report, the authors describe the case of a 61-year-old gentleman, with a long history of alopecia areata, who presented with numerous, discrete dark blue macules on the scalp. Scanning electron microscopy with energy dispersive x-ray spectroscopy analysis ultimately identified the macules as deposits of TiO2. The patient had a history of intralesional triamcinolone injections for management of alopecia areata. A sample of generic 0.1% triamcinolone acetonide paste was analyzed and found to contain many TiO2 particles analogous to those seen in the patient's biopsy sample. To the authors' knowledge, this is the first reported case of TiO2 deposition in the dermis likely resulting from topical combined with intralesional triamcinolone injection.

  12. Oxidative Esterification of Aldehydes with Urea Hydrogen Peroxide Catalyzed by Aluminum Chloride Hexahydrate

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sin-Ae; Kim, Yoon Mi; Lee, Jong Chan [Chung-Ang University, Seoul (Korea, Republic of)

    2016-08-15

    We have developed a new, environmentally benign and highly efficient oxidative preparation of methyl esters by the reaction of various aldehydes with UHP in methanol catalyzed by readily accessible aluminum(III) chloride hexahydrate. This new greener and cost effective direct esterification method can serve as a useful alternative to existing protocols. Esters are some of the most important functional groups in organic chemistry and have been found in the sub-structure of a variety of natural products, industrial chemicals, and pharmaceuticals. Numerous methods have been reported for the preparation of various esters. In particular, this method gives low yields for both aldehydes containing electron donating substituents in aromatic rings and heterocyclic aldehydes. Therefore, development of a more general, efficient, and greener protocol for the esterification of aldehydes with readily available catalyst is still desirable.

  13. Highly enantioselective rhodium(I)-catalyzed carbonyl carboacylations initiated by C-C bond activation.

    Science.gov (United States)

    Souillart, Laetitia; Cramer, Nicolai

    2014-09-01

    The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom-economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of CC bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)-catalyzed transformation is induced by an enantiotopic CC bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Rubber muscle actuation with pressurized CO2 from enzyme-catalyzed urea hydrolysis

    Science.gov (United States)

    Sutter, Thomas M.; Dickerson, Matthew B.; Creasy, Terry S.; Justice, Ryan S.

    2013-09-01

    A biologically inspired pneumatic pressure source was designed and sized to supply high pressure CO2(g) to power a rubber muscle actuator. The enzyme urease served to catalyze the hydrolysis of urea, producing CO2(g) that flowed into the actuator. The actuator’s power envelope was quantified by testing actuator response on a custom-built linear-motion rig. Reaction kinetics and available work density were determined by replacing the actuator with a double-action piston and measuring volumetric gas generation against a fixed pressure on the opposing piston. Under the conditions investigated, urease catalyzed the generation of up to 0.81 MPa (117 psi) of CO2(g) in the reactor headspace within 18 min, and the evolved gas produced a maximum work density of 0.65 J ml-1.

  15. Rubber muscle actuation with pressurized CO2 from enzyme-catalyzed urea hydrolysis

    International Nuclear Information System (INIS)

    Sutter, Thomas M; Dickerson, Matthew B; Creasy, Terry S; Justice, Ryan S

    2013-01-01

    A biologically inspired pneumatic pressure source was designed and sized to supply high pressure CO 2(g) to power a rubber muscle actuator. The enzyme urease served to catalyze the hydrolysis of urea, producing CO 2(g) that flowed into the actuator. The actuator’s power envelope was quantified by testing actuator response on a custom-built linear-motion rig. Reaction kinetics and available work density were determined by replacing the actuator with a double-action piston and measuring volumetric gas generation against a fixed pressure on the opposing piston. Under the conditions investigated, urease catalyzed the generation of up to 0.81 MPa (117 psi) of CO 2(g) in the reactor headspace within 18 min, and the evolved gas produced a maximum work density of 0.65 J ml −1 . (paper)

  16. Synthesis of Arylthiopyrimidines by Copper-catalyzed Aerobic Oxidative C-S Cross-coupling

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ok Suk; Kim, Hyeji; Sohn, Jeong-Hun [Chungnam National University, Daejeon (Korea, Republic of); Lee, Hee-Seung [KAIST, Daejeon (Korea, Republic of); Shin, Hyunik [Yonsung Fine Chemicals R and D Center, Suwon (Korea, Republic of)

    2016-02-15

    Copper-catalyzed C–S cross-coupling reactions have been considered as powerful tools in synthetic chemistry and utilized for diverse heterocycle syntheses. In the reactions, the aspects of no need of ligands has been particular advantage over other metal catalysis. We have developed a Cu-catalyzed cascade reaction for the synthesis of fully substituted 2-arylthiopyrimidines from 3,4-dihydropyrimidine-2(1H)-thiones (DHPMs) under aerobic conditions. This cascade reaction of DHPM with aryl iodide proceeds presumably via sequential tautomerization, C–S cross-coupling, and oxidative dehydrogenation (oxidation followed by elimination). Considering that DHPM substrates were easily synthesized by Biginelli three component coupling reaction of aryl aldehyde, β-ketoester, and thiourea, the present method provides a direct access toward diverse 2-arylthiopyrimidines which have been used as a prominent substructure of drug molecules.

  17. Tyrosyl-DNA Phosphodiesterase I Catalytic Mutants Reveal an Alternative Nucleophile That Can Catalyze Substrate Cleavage*

    Science.gov (United States)

    Comeaux, Evan Q.; Cuya, Selma M.; Kojima, Kyoko; Jafari, Nauzanene; Wanzeck, Keith C.; Mobley, James A.; Bjornsti, Mary-Ann; van Waardenburg, Robert C. A. M.

    2015-01-01

    Tyrosyl-DNA phosphodiesterase I (Tdp1) catalyzes the repair of 3′-DNA adducts, such as the 3′-phosphotyrosyl linkage of DNA topoisomerase I to DNA. Tdp1 contains two conserved catalytic histidines: a nucleophilic His (Hisnuc) that attacks DNA adducts to form a covalent 3′-phosphohistidyl intermediate and a general acid/base His (Hisgab), which resolves the Tdp1-DNA linkage. A Hisnuc to Ala mutant protein is reportedly inactive, whereas the autosomal recessive neurodegenerative disease SCAN1 has been attributed to the enhanced stability of the Tdp1-DNA intermediate induced by mutation of Hisgab to Arg. However, here we report that expression of the yeast HisnucAla (H182A) mutant actually induced topoisomerase I-dependent cytotoxicity and further enhanced the cytotoxicity of Tdp1 Hisgab mutants, including H432N and the SCAN1-related H432R. Moreover, the HisnucAla mutant was catalytically active in vitro, albeit at levels 85-fold less than that observed with wild type Tdp1. In contrast, the HisnucPhe mutant was catalytically inactive and suppressed Hisgab mutant-induced toxicity. These data suggest that the activity of another nucleophile when Hisnuc is replaced with residues containing a small side chain (Ala, Asn, and Gln), but not with a bulky side chain. Indeed, genetic, biochemical, and mass spectrometry analyses show that a highly conserved His, immediately N-terminal to Hisnuc, can act as a nucleophile to catalyze the formation of a covalent Tdp1-DNA intermediate. These findings suggest that the flexibility of Tdp1 active site residues may impair the resolution of mutant Tdp1 covalent phosphohistidyl intermediates and provide the rationale for developing chemotherapeutics that stabilize the covalent Tdp1-DNA intermediate. PMID:25609251

  18. Genetic effects from internally deposited radionuclides

    International Nuclear Information System (INIS)

    Anon.

    1987-01-01

    It was learned in the late 1920's that ionizing radiation could produce genetic effects such as gene mutations and chromosome aberrations. However, at least until 1945, the focus on interest in radiation protection was primarily on somatic effects manifested in the individual exposed. Studies of the genetic effects of radiation using drosophila, however, refocused attention on effects transmitted to the exposed individuals offspring and concern over fallout in the 1950's resulted in efforts to estimate the genetic effects from exposure of human populations to internally deposited radionuclides. No human populations have been identified with burdens of internally deposited radioactive materials which have been shown to produce evidence of transmissible genetic damage. As a result, the research approach has been one in which macromolecular, cellular, and whole animal genetic studies have been combined to estimate genetic effects on humans following the deposition of radioactive materials in the body. The purpose of this report is to update the information available from animal and cellular experiments that relates genetic effects to deposited activity and dose from internally deposited radioactive materials

  19. Chemical vapour deposition of carbon nanotubes

    CSIR Research Space (South Africa)

    Arendse, CJ

    2006-02-01

    Full Text Available , effective, more versatile and easily scalable to large substrate sizes. In this paper, we present a design of the hot-wire CVD system constructed at the CSIR for the deposition of CNTs. Additionally, we will report on the structure of CNTs deposited... exhibit exceptional chemical and physical properties related to toughness, chemical inertness, magnetism, and electrical and thermal conductivity. A variety of preparation methods to synthesise CNTs are known, e.g. carbon-arc discharge, laser ablation...

  20. Rhodium catalyzed regioselective arene homologation of aryl urea via double C-H bond activation and migratory insertion of alkyne

    Institute of Scientific and Technical Information of China (English)

    Yan Wang; Hao Zhou; Ke Xu; Mei-Hua Shen; Hua-Dong Xu

    2017-01-01

    A convenient rhodium catalyzed oxidative arene homologation of aniline derivatives with symmetrical or unsymmetrical alkynes using Cu(OAc)2 as oxidant is described.Urea group is shown to be effective as a directing group for initial ortho C-H activation.Two migratory insertion events of alkyne into Rh-C bond occur successively,both with complete regioselectivity.This method is particularly useful for synthesis of polyarenes with different substituents,which has not been reported with conventional protocol.A mechanism has been proposed to explain the observed data.

  1. Enzyme catalyzed oxidative gelation of sugar beet pectin: Kinetics and rheology

    DEFF Research Database (Denmark)

    Abang Zaidel, Dayang Norulfairuz; Chronakis, Ioannis S.; Meyer, Anne S.

    2012-01-01

    Sugar beet pectin (SBP) is a marginally utilized co-processing product from sugar production from sugar beets. In this study, the kinetics of oxidative gelation of SBP, taking place via enzyme catalyzed cross-linking of ferulic acid moieties (FA), was studied using small angle oscillatory...

  2. Copper-catalyzed trifluoromethylation of arylsulfinate salts using an electrophilic trifluoromethylation reagent

    KAUST Repository

    Lin, Xiaoxi

    2013-03-01

    A copper-catalyzed method for the trifluoromethylation of arylsulfinates with Togni\\'s reagent has been developed, affording aryltrifluoromethylsulfones in moderate to good yields. A wide range of functional groups in arylsulfinates are compatible with the reaction conditions. © 2013 Elsevier Ltd. All rights reserved.

  3. Rhodium enalcarbenoids: direct synthesis of indoles by rhodium(II)-catalyzed [4+2] benzannulation of pyrroles.

    Science.gov (United States)

    Dawande, Sudam Ganpat; Kanchupalli, Vinaykumar; Kalepu, Jagadeesh; Chennamsetti, Haribabu; Lad, Bapurao Sudam; Katukojvala, Sreenivas

    2014-04-14

    Disclosed herein is the design of an unprecedented electrophilic rhodium enalcarbenoid which results from rhodium(II)-catalyzed decomposition of a new class of enaldiazo compounds. The synthetic utility of these enalcarbenoids has been successfully demonstrated in the first transition-metal-catalyzed [4+2] benzannulation of pyrroles, thus leading to substituted indoles. The new benzannulation has been applied to the efficient synthesis of the natural product leiocarpone as well as a potent adipocyte fatty-acid binding protein inhibitor. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Cu(OAc)2 catalyzed Sonogashira cross-coupling reaction in amines

    Institute of Scientific and Technical Information of China (English)

    Sheng Mei Guo; Chen Liang Deng; Jin Heng Li

    2007-01-01

    A simple Cu(OAc)2 catalyzed Sonogashira coupling protocol is presented. It was found that the couplings of a variety of aryl halides with terminal alkynes were conducted smoothly to afford the corresponding desired products in moderate to excellent yields, using Cu(OAc)2 as the catalyst and Et3N as the solvent.

  5. Regional aerosol deposition in human upper airways

    International Nuclear Information System (INIS)

    Swift, D.L.

    1991-01-01

    During the current report experimental studies of upper respiratory deposition of radon progeny aerosols and stimulant aerosols were carried out in replicate casts of nasal and oral passages of adults and children. Additionally, preliminary studies of nasal passage deposition of unattached Po 218 particles was carried out in four human subjects. Data on nasal inspiratory deposition in replicate models of adults and infants from three collaborating laboratories were compared and a best-fit curve of deposition efficiency for both attached and unattached particles was obtained, showing excellent inter-laboratory agreement. This curve demonstrates that nasal inspiratory deposition of radon progeny is weakly dependent upon flow rate over physiologically realistic ranges of flow, does not show a significant age effect, and is relatively independent of nasal passage dimensions for a given age range. Improved replicate models of the human adult oral passage extending to the mid-trachea were constructed for medium and higher flow mouth breathing states; these models were used to assess the deposition of unattached Po 218 particles during oronasal breathing in the oral passage and demonstrated lower deposition efficiency than the nasal passage. Measurements of both Po 218 particle and attached fraction particle size deposition were performed in replicate nasal passage of a four week old infant. 5 refs., 1 fig

  6. New Insights into the Origins of Sb-Induced Effects on Self-Catalyzed GaAsSb Nanowire Arrays.

    Science.gov (United States)

    Ren, Dingding; Dheeraj, Dasa L; Jin, Chengjun; Nilsen, Julie S; Huh, Junghwan; Reinertsen, Johannes F; Munshi, A Mazid; Gustafsson, Anders; van Helvoort, Antonius T J; Weman, Helge; Fimland, Bjørn-Ove

    2016-02-10

    Ternary semiconductor nanowire arrays enable scalable fabrication of nano-optoelectronic devices with tunable bandgap. However, the lack of insight into the effects of the incorporation of Vy element results in lack of control on the growth of ternary III-V(1-y)Vy nanowires and hinders the development of high-performance nanowire devices based on such ternaries. Here, we report on the origins of Sb-induced effects affecting the morphology and crystal structure of self-catalyzed GaAsSb nanowire arrays. The nanowire growth by molecular beam epitaxy is changed both kinetically and thermodynamically by the introduction of Sb. An anomalous decrease of the axial growth rate with increased Sb2 flux is found to be due to both the indirect kinetic influence via the Ga adatom diffusion induced catalyst geometry evolution and the direct composition modulation. From the fundamental growth analyses and the crystal phase evolution mechanism proposed in this Letter, the phase transition/stability in catalyst-assisted ternary III-V-V nanowire growth can be well explained. Wavelength tunability with good homogeneity of the optical emission from the self-catalyzed GaAsSb nanowire arrays with high crystal phase purity is demonstrated by only adjusting the Sb2 flux.

  7. An enzyme-catalyzed multistep DNA refolding mechanism in hairpin telomere formation.

    Directory of Open Access Journals (Sweden)

    Ke Shi

    Full Text Available Hairpin telomeres of bacterial linear chromosomes are generated by a DNA cutting-rejoining enzyme protelomerase. Protelomerase resolves a concatenated dimer of chromosomes as the last step of chromosome replication, converting a palindromic DNA sequence at the junctions between chromosomes into covalently closed hairpins. The mechanism by which protelomerase transforms a duplex DNA substrate into the hairpin telomeres remains largely unknown. We report here a series of crystal structures of the protelomerase TelA bound to DNA that represent distinct stages along the reaction pathway. The structures suggest that TelA converts a linear duplex substrate into hairpin turns via a transient strand-refolding intermediate that involves DNA-base flipping and wobble base-pairs. The extremely compact di-nucleotide hairpin structure of the product is fully stabilized by TelA prior to strand ligation, which drives the reaction to completion. The enzyme-catalyzed, multistep strand refolding is a novel mechanism in DNA rearrangement reactions.

  8. On the Effect of Microwave Energy on Lipase-Catalyzed Polycondensation Reactions

    Directory of Open Access Journals (Sweden)

    Alessandro Pellis

    2016-09-01

    Full Text Available Microwave energy (MWe is, nowadays, widely used as a clean synthesis tool to improve several chemical reactions, such as drug molecule synthesis, carbohydrate conversion and biomass pyrolysis. On the other hand, its exploitation in enzymatic reactions has only been fleetingly investigated and, hence, further study of MWe is required to reach a precise understanding of its potential in this field. Starting from the authors’ experience in clean synthesis and biocatalyzed reactions, this study sheds light on the possibility of using MWe for enhancing enzyme-catalyzed polycondensation reactions and pre-polymer formation. Several systems and set ups were investigated involving bulk and organic media (solution phase reactions, different enzymatic preparations and various starting bio-based monomers. Results show that MWe enables the biocatalyzed synthesis of polyesters and pre-polymers in a similar way to that reported using conventional heating with an oil bath, but in a few cases, notably bulk phase polycondensations under intense microwave irradiation, MWe leads to a rapid enzyme deactivation.

  9. Direct Synthesis of Protoberberine Alkaloids by Rh-Catalyzed C-H Bond Activation as the Key Step.

    Science.gov (United States)

    Jayakumar, Jayachandran; Cheng, Chien-Hong

    2016-01-26

    A one-pot reaction of substituted benzaldehydes with alkyne-amines by a Rh-catalyzed C-H activation and annulation to afford various natural and unnatural protoberberine alkaloids is reported. This reaction provides a convenient route for the generation of a compound library of protoberberine salts, which recently have attracted great attention because of their diverse biological activities. In addition, pyridinium salt derivatives can also be formed in good yields from α,β-unsaturated aldehydes and amino-alkynes. This reaction proceeds with excellent regioselectivity and good functional group compatibility under mild reaction conditions by using O2 as the oxidant. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Heterocycles by Transition Metals Catalyzed Intramolecular Cyclization of Acetylene Compounds

    International Nuclear Information System (INIS)

    Vizer, S.A.; Yerzhanov, K.B.; Dedeshko, E.C.

    2003-01-01

    Review shows the new strategies in the synthesis of heterocycles, having nitrogen, oxygen and sulfur atoms, via transition metals catalyzed intramolecular cyclization of acetylenic compounds on the data published at the last 30 years, Unsaturated heterocyclic compounds (pyrroles and pyrroline, furans, dihydro furans and benzofurans, indoles and iso-indoles, isoquinolines and isoquinolinones, aurones, iso coumarins and oxazolinone, lactams and lactones with various substitutes in heterocycles) are formed by transition metals, those salts [PdCl 2 , Pd(OAc) 2 , HgCl 2 , Hg(OAc) 2 , Hg(OCOCF 3 ) 2 , AuCl 3 ·2H 2 O, NaAuCl 4 ·2H 2 O, CuI, CuCl], oxides (HgO) and complexes [Pd(OAc) 2 (PPh 3 )2, Pd(PPh 3 ) 4 , PdCl 2 (MeCN) 2 , Pd(OAc ) 2 /TPPTS] catalyzed intramolecular cyclization of acetylenic amines, amides, ethers, alcohols, acids, ketones and βdiketones. More complex hetero polycyclic systems typical for natural alkaloids can to obtain similar. Proposed mechanisms of pyrroles, isoquinolines, iso indoles and indoles, benzofurans and iso coumarins, thiazolopyrimidinones formation are considered. (author)

  11. Quantitative proteomics reveals the kinetics of trypsin-catalyzed protein digestion.

    Science.gov (United States)

    Pan, Yanbo; Cheng, Kai; Mao, Jiawei; Liu, Fangjie; Liu, Jing; Ye, Mingliang; Zou, Hanfa

    2014-10-01

    Trypsin is the popular protease to digest proteins into peptides in shotgun proteomics, but few studies have attempted to systematically investigate the kinetics of trypsin-catalyzed protein digestion in proteome samples. In this study, we applied quantitative proteomics via triplex stable isotope dimethyl labeling to investigate the kinetics of trypsin-catalyzed cleavage. It was found that trypsin cleaves the C-terminal to lysine (K) and arginine (R) residues with higher rates for R. And the cleavage sites surrounded by neutral residues could be quickly cut, while those with neighboring charged residues (D/E/K/R) or proline residue (P) could be slowly cut. In a proteome sample, a huge number of proteins with different physical chemical properties coexists. If any type of protein could be preferably digested, then limited digestion could be applied to reduce the sample complexity. However, we found that protein abundance and other physicochemical properties, such as molecular weight (Mw), grand average of hydropathicity (GRAVY), aliphatic index, and isoelectric point (pI) have no notable correlation with digestion priority of proteins.

  12. Support Effects in the Gold-Catalyzed Preferential Oxidation of CO

    KAUST Repository

    Ivanova, S.

    2010-04-08

    The study of support effects on the gold-catalyzed preferential oxidation of carbon monoxide in the presence of hydrogen (PROX reaction) is possible only with careful control of the gold particle size, which is facilitated by the application of the direct anionic exchange method. Catalytic evaluation of thermally stable gold nanoparticles, with an average size of around 3 nm on a variety of supports (alumina, titania, zirconia, or ceria), clearly shows that the influence of the support on the CO oxidation rate is of primary importance under CO+O 2 conditions and that this influence becomes secondary in the presence of hydrogen. The impact of the support surface structure on the oxidation rates, catalyst selectivity, and catalyst activation/deactivation is investigated in terms of oxygen vacancies, oxygen mobility, OH groups, and surface area on the oxidation rates, catalyst selectivity and catalyst activation/deactivation. It allows the identification of key morphological and structural features of the support to ensure high activity and selectivity in the gold-catalyzed PROX reaction. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Pd(OAc2/Ph3P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles

    Directory of Open Access Journals (Sweden)

    Dominik Kellner

    2017-08-01

    Full Text Available The palladium-catalyzed dimerization of isoprene is a practical approach of synthesizing monoterpenes. Though several highly selective methods have been reported, most of them still required pressure or costly ligands for attaining the active system and desired selectivity. Herein, we present a simple and economical procedure towards the tail-to-tail dimer using readily available Pd(OAc2 and inexpensive triphenylphosphine as ligand. Furthermore, simple screw cap vials are employed, allowing carrying out the reaction at low pressure. In addition, the potential of the dimer as a chemical platform for the preparation of heterocyclic terpenes by subsequent (hetero-Diels–Alder or [4 + 1]-cycloadditions with nitrenes is also depicted.

  14. High mobility n-type organic thin-film transistors deposited at room temperature by supersonic molecular beam deposition

    Energy Technology Data Exchange (ETDEWEB)

    Chiarella, F., E-mail: fabio.chiarella@spin.cnr.it; Barra, M.; Ciccullo, F.; Cassinese, A. [CNR-SPIN and Physics Department, University of Naples, Piazzale Tecchio 80, I-80125 Naples (Italy); Toccoli, T.; Aversa, L.; Tatti, R.; Verucchi, R. [IMEM-CNR-FBK Division of Trento, Via alla Cascata 56/C, I-38123 Povo (Italy); Iannotta, S. [IMEM-CNR, Parco Area delle Scienze 37/A, I-43124 Parma (Italy)

    2014-04-07

    In this paper, we report on the fabrication of N,N′-1H,1H-perfluorobutil dicyanoperylenediimide (PDIF-CN{sub 2}) organic thin-film transistors by Supersonic Molecular Beam Deposition. The devices exhibit mobility up to 0.2 cm{sup 2}/V s even if the substrate is kept at room temperature during the organic film growth, exceeding by three orders of magnitude the electrical performance of those grown at the same temperature by conventional Organic Molecular Beam Deposition. The possibility to get high-mobility n-type transistors avoiding thermal treatments during or after the deposition could significantly extend the number of substrates suitable to the fabrication of flexible high-performance complementary circuits by using this compound.

  15. External quality-assurance project report for the National Atmospheric Deposition Program/National Trends Network and Mercury Deposition Network, 2009-2010

    Science.gov (United States)

    Wetherbee, Gregory A.; Martin, RoseAnn; Rhodes, Mark F.; Chesney, Tanya A.

    2014-01-01

    The U.S. Geological Survey operated six distinct programs to provide external quality-assurance monitoring for the National Atmospheric Deposition Program/National Trends Network (NTN) and Mercury Deposition Network (MDN) during 2009–2010. The field-audit program assessed the effects of onsite exposure, sample handling, and shipping on the chemistry of NTN samples; a system-blank program assessed the same effects for MDN. Two interlaboratory-comparison programs assessed the bias and variability of the chemical analysis data from the Central Analytical Laboratory (CAL) and Mercury (Hg) Analytical Laboratory (HAL). The blind-audit program was also implemented for the MDN to evaluate analytical bias in total Hg concentration data produced by the HAL. The co-located-sampler program was used to identify and quantify potential shifts in NADP data resulting from replacement of original network instrumentation with new electronic recording rain gages (E-gages) and precipitation collectors that use optical sensors. The results indicate that NADP data continue to be of sufficient quality for the analysis of spatial distributions and time trends of chemical constituents in wet deposition across the United States. Results also suggest that retrofit of the NADP networks with the new precipitation collectors could cause –8 to +14 percent shifts in NADP annual precipitation-weighted mean concentrations and total deposition values for ammonium, nitrate, sulfate, and hydrogen ion, and larger shifts (+13 to +74 percent) for calcium, magnesium, sodium, potassium, and chloride. The prototype N-CON Systems bucket collector is more efficient in the catch of precipitation in winter than Aerochem Metrics Model 301 collector, especially for light snowfall.

  16. Graphene oxide directed in-situ deposition of electroactive silver nanoparticles and its electrochemical sensing application for DNA analysis

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Ningning [College of Chemistry and Environment, Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology, Minnan Normal University, Zhangzhou, 363000 (China); Gao, Feng, E-mail: fgao1981@mnnu.edu.cn [College of Chemistry and Environment, Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology, Minnan Normal University, Zhangzhou, 363000 (China); Department of Chemistry, Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue, Shimane, 690-8504 (Japan); He, Suyu; Zhu, Qionghua; Huang, Jiafu [College of Chemistry and Environment, Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology, Minnan Normal University, Zhangzhou, 363000 (China); Tanaka, Hidekazu [Department of Chemistry, Graduate School of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue, Shimane, 690-8504 (Japan); Wang, Qingxiang, E-mail: axiang236@126.com [College of Chemistry and Environment, Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology, Minnan Normal University, Zhangzhou, 363000 (China)

    2017-01-25

    The development of high-performance biosensing platform is heavily dependent on the recognition property of the sensing layer and the output intensity of the signal probe. Herein, we present a simple and highly sensitive biosensing interface for DNA detection on the basis of graphene oxide nanosheets (GONs) directed in-situ deposition of silver nanoparticles (AgNPs). The fabrication process and electrochemical properties of the biosensing interface were probed by electrochemical techniques and scanning electron microscopy. The results indicate that GONs can specifically adsorb at the single-stranded DNA probe surface, and induces the deposition of highly electroactive AgNPs. Upon hybridization with complementary oligonucleotides to generate the duplex DNA on the electrode surface, the GONs with the deposited AgNPs will be liberated from the sensing interface due to the inferior affinity of GONs and duplex DNA, resulting in the reduction of the electrochemical signal. Such a strategy combines the superior recognition of GONs toward single-stranded DNA and double-stranded DNA, and the strong electrochemical response of in-situ deposited AgNPs. Under optimal conditions, the biosensor can detect target DNA over a wide range from 10 fM to 10 nM with a detection limit of 7.6 fM. Also, the developed biosensor shows outstanding discriminating ability toward oligonucleotides with different mismatching degrees. - Highlights: • An novel DNA biosensor was constructed based on GONs with deposited AgNPs. • GONs catalyze the in-situ deposition of AgNPs on the sensing interface. • Unique π-stacking of GONs with probe DNA contributes high selectivity of the biosensor. • High electroactivity of AgNPs leads to low detection limit (7.6 fM) for target DNA.

  17. Regional aerosol deposition in human upper airways

    International Nuclear Information System (INIS)

    Swift, D.L.

    1989-01-01

    During the report period significant progress on the quantitative understanding of regional upper airway deposition of airborne particle has been realized. Replicate models of the human upper airways obtained from post-mortem casting of the nasal, oral, pharyngeal, laryngeal and upper tracheal regions and in vivo magnetic resonance imaging (MRI) of the same regions of adults and children have been employed to determine the overall and local deposition characteristics of aerosols in the ultrafine (1--100 μm diameter) and fine (0.8--12 μm diameter) region. Studies have been carried out for both nasal and oral breathing during inspiratory and expiratory flow at constant flow rates representative of rest and states of exercise. The results of these investigations indicate that particles in the size range of ''unattached'' radon progeny (1--3 nm) are deposited in both the nasal and oral passages with high efficiency (60--80%) for both inspiration and expiration, with the nasal deposition being somewhat greater (5--10%) than oral deposition. The effect of flow rate on upper airway deposition for both pathways is not great; data analysis indicates that the deposition for all flow rates from 4--50 liters/minute can be grouped by plotting deposition vs Q- 1/8 , where Q is flow rate, a far weaker dependency than observed for inertial deposition. Diffusional transport is the primary mechanism of deposition, and size dependence can be accounted for by plotting, deposition percent vs D n where D is particle diffusion coefficient and n ranges from 0.5--0.66. 2 refs

  18. Ruthenium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

    DEFF Research Database (Denmark)

    Mazziotta, Andrea; Madsen, Robert

    2017-01-01

    Dehydrogenative decarbonylation of a primary alcohol involves the release of both dihydrogen and carbon monoxide to afford the one-carbon shorter product. The transformation has now been achieved with a ruthenium-catalyzed protocol by using the complex Ru(COD)Cl2 and the hindered monodentate ligand...... P(o-tolyl)3 in refluxing p-cymene. The reaction can be applied to both benzylic and long chain linear aliphatic alcohols. The intermediate aldehyde can be observed during the transformation, which is therefore believed to proceed through two separate catalytic cycles involving first dehydrogenation...... of the alcohol and then decarbonylation of the resulting aldehyde....

  19. Silver-Catalyzed Aldehyde Olefination Using Siloxy Alkynes.

    Science.gov (United States)

    Sun, Jianwei; Keller, Valerie A; Meyer, S Todd; Kozmin, Sergey A

    2010-03-20

    We describe the development of a silver-catalyzed carbonyl olefination employing electron rich siloxy alkynes. This process constitutes an efficient synthesis of trisubstituted unsaturated esters, and represents an alternative to the widely utilized Horner-Wadsworth-Emmons reaction. Excellent diastereoselectivities are observed for a range of aldehydes using either 1-siloxy-1-propyne or 1-siloxy-1-hexyne. This mild catalytic process also enables chemoselective olefination of aldehydes in the presence of either ester or ketone functionality. Furthermore, since no by-products are generated, this catalytic process is perfectly suited for development of sequential reactions that can be carried out in a single flask.

  20. Homocoupling of benzyl halides catalyzed by POCOP-nickel pincer complexes

    KAUST Repository

    Chen, Tao

    2012-08-01

    Two types of POCOP-nickel(II) pincer complexes were prepared by mixing POCOP pincer ligands and NiX 2 in toluene at reflux. The resulting nickel complexes efficiently catalyze the homocoupling reactions of benzyl halides in the presence of zinc. The coupled products were obtained in excellent to quantitative yields. © 2012 Elsevier Ltd. All rights reserved.

  1. A novel mechanism of sulfur transfer catalyzed by O-acetylhomoserine sulfhydrylase in the methionine-biosynthetic pathway of Wolinella succinogenes

    Energy Technology Data Exchange (ETDEWEB)

    Tran, Timothy H. [Cornell University, Ithaca, New York 14853-1301 (United States); Krishnamoorthy, Kalyanaraman; Begley, Tadhg P., E-mail: begley@tamu.edu [Texas A& M University, College Station, TX 77842 (United States); Ealick, Steven E., E-mail: begley@tamu.edu [Cornell University, Ithaca, New York 14853-1301 (United States)

    2011-10-01

    MetY is the first reported structure of an O-acetylhomoserine sulfhydrylase that utilizes a protein thiocarboxylate intermediate as the sulfur source in a novel methionine-biosynthetic pathway instead of catalyzing a direct sulfhydrylation reaction. O-Acetylhomoserine sulfhydrylase (OAHS) is a pyridoxal 5′-phosphate (PLP) dependent sulfide-utilizing enzyme in the l-cysteine and l-methionine biosynthetic pathways of various enteric bacteria and fungi. OAHS catalyzes the conversion of O-acetylhomoserine to homocysteine using sulfide in a process known as direct sulfhydrylation. However, the source of the sulfur has not been identified and no structures of OAHS have been reported in the literature. Here, the crystal structure of Wolinella succinogenes OAHS (MetY) determined at 2.2 Å resolution is reported. MetY crystallized in space group C2 with two monomers in the asymmetric unit. Size-exclusion chromatography, dynamic light scattering and crystal packing indicate that the biological unit is a tetramer in solution. This is further supported by the crystal structure, in which a tetramer is formed using a combination of noncrystallographic and crystallographic twofold axes. A search for structurally homologous proteins revealed that MetY has the same fold as cystathionine γ-lyase and methionine γ-lyase. The active sites of these enzymes, which are also PLP-dependent, share a high degree of structural similarity, suggesting that MetY belongs to the γ-elimination subclass of the Cys/Met metabolism PLP-dependent family of enzymes. The structure of MetY, together with biochemical data, provides insight into the mechanism of sulfur transfer to a small molecule via a protein thiocarboxylate intermediate.

  2. Copper-catalyzed one-pot synthesis of 1,2,4-triazoles from nitriles and hydroxylamine.

    Science.gov (United States)

    Xu, Hao; Ma, Shuang; Xu, Yuanqing; Bian, Longxiang; Ding, Tao; Fang, Xiaomin; Zhang, Wenkai; Ren, Yanrong

    2015-02-06

    A simple and efficient copper-catalyzed one-pot synthesis of substituted 1,2,4-triazoles through reactions of two nitriles with hydroxylamine has been developed. The protocol uses simple and readily available nitriles and hydroxylamine hydrochloride as the starting materials and inexpensive Cu(OAc)2 as the catalyst, and the corresponding 1,2,4-triazole derivatives are obtained in moderate to good yields. The reactions include sequential intermolecular addition of hydroxylamine to one nitrile to provide amidoxime, copper-catalyzed treatment of the amidoxime with another nitrile, and intramolecular dehydration/cyclization. This finding provides a new and useful strategy for synthesis of 1,2,4-triazole derivatives.

  3. The fluid mechanics of deposition - how it gets there and why lattice-bar supports are deposition resistant

    International Nuclear Information System (INIS)

    Schneider, B.; Aly, K.

    2012-01-01

    Much analysis, research and inspection has gone into the understanding of deposition within steam generators. All of that work notwithstanding, it still remains a mystery in many respects - particularly regarding the fluid mechanics of deposition. This presentation tracks corrosion product transport (CPT) ingress to an SG and the approximate distribution of the resultant deposition. It also investigates deposition of the small but highly problematic amount of CPT which ends up on the tube-supports (TSPs). CPT ingress during full-power operation of modern well-run steam generators (SGs) represents as reported elsewhere at this conference, a very small amount of material. Unfortunately operation has not always achieved such standards. Plants with a few decades operation may have significant deposition – a condition which may well be accompanied by severe tube and tube-support deposition and the consequent blockage of the TSPs. CPT ingress to a steam generator may, in very rough numbers, distribute as follows; i) removal by blow-down ~ 15% (i.e. - most of what comes in stays in the SG); ii) deposition to the SG tube surface ~ 50% (plated out thinly over the 1 to 2 acres of SG tube surface); iii) tube-sheet sludge pile ~ 25% (bad news for tube life, but easy to inspect and water-lance); iv) TSP deposition <~5% (a small but highly problematic amount of material). Deposition as it turns out is exacerbated by the fluid-mechanics at square-cornered contractions which may exist at the entrance to flow passages of some types of tube-supports. High local velocities will occur at such corners – resulting in a significant local static-pressure depression – which causes flash-evaporation – which can leave behind CPT materials particularly in areas of moderately high bulk quality. All of that results counter-intuitively, in the initiation of deposition right at the -corner of the tube support. This type of inlet-corner deposition was first seen about three decades ago at

  4. Selectivity control in pd-catalyzed c-h functionalization reactions

    OpenAIRE

    Flores Gaspar, Areli

    2013-01-01

    Benzocyclobutenones are an intriguing four-membered ring ketone. In the present thesis, we have developed a new protocol for selectively preparing benzocyclobutenones through intramolecular acylation of aryl bromides via palladium catalyzed C-H bond functionalization reactions based on rac-BINAP ligand. We also found that a subtle modification on the ligand backbone lead to a new catalytic manifold for preparing configurationally-pure styrene derivatives, when using dcpp (bis-dicyclohexylphos...

  5. 1H NMR studies of substrate hydrogen exchange reactions catalyzed by L-methionine gamma-lyase

    International Nuclear Information System (INIS)

    Esaki, N.; Nakayama, T.; Sawada, S.; Tanaka, H.; Soda, K.

    1985-01-01

    Hydrogen exchange reactions of various L-amino acids catalyzed by L-methionine gamma-lyase (EC 4.4.1.11) have been studied. The enzyme catalyzes the rapid exchange of the alpha- and beta-hydrogens of L-methionine and S-methyl-L-cysteine with deuterium from the solvent. The rate of alpha-hydrogen exchange was about 40 times faster than that of the enzymatic elimination reaction of the sulfur-containing amino acids. The enzyme also catalyzes the exchange reaction of alpha- and beta-hydrogens of the straight-chain L-amino acids which are not susceptible to elimination. The exchange rates of the alpha-hydrogen and the total beta-hydrogens of L-alanine and L-alpha-aminobutyrate with deuterium followed first-order kinetics. For L-norvaline, L-norleucine, S-methyl-L-cysteine, and L-methionine, the rate of alpha-hydrogen exchange followed first-order kinetics, but the rate of total beta-hydrogen exchange decreased due to a primary isotope effect at the alpha-position. L-Phenylalanine and L-tryptophan slowly underwent alpha-hydrogen exchange. The pro-R hydrogen of glycine was deuterated stereospecifically

  6. Glymes as benign co-solvents for CaO-catalyzed transesterification of soybean oil to biodiesel.

    Science.gov (United States)

    Tang, Shaokun; Zhao, Hua; Song, Zhiyan; Olubajo, Olarongbe

    2013-07-01

    The base (such as CaO)-catalyzed heterogeneous preparation of biodiesel encounters a number of obstacles including the need for CaO pretreatment and the reactions being incomplete (typically 90-95% yields). In this study, a number of glymes were investigated as benign solvents for the CaO-catalyzed transesterification of soybean oil into biodiesel with a high substrate loading (typically soybean oil >50% v/v). The triglyceride-dissolving capability of glymes led to a much faster reaction rate (>98% conversions in 4h) than in methanol alone (typically 24h) and minimized the saponification reaction when catalyzed by anhydrous CaO or commercial lime without pre-activation. The use of glyme (e.g. P2) as co-solvent also activates commercial lime to become an effective catalyst without calcination pretreatment. The SEM images suggest a dissolution-agglomeration process of CaO surface in the presence of P2, which could remove the CaCO3 and Ca(OH)2 layer coated on the surface of lime. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. Ru(III) catalyzed permanganate oxidation of aniline at environmentally relevant pH.

    Science.gov (United States)

    Zhang, Jing; Zhang, Ying; Wang, Hui; Guan, Xiaohong

    2014-07-01

    Ru(III) was employed as catalyst for aniline oxidation by permanganate at environmentally relevant pH for the first time. Ru(III) could significantly improve the oxidation rate of aniline by 5-24 times with its concentration increasing from 2.5 to 15 μmol/L. The reaction of Ru(III) catalyzed permanganate oxidation of aniline was first-order with respect to aniline, permanganate and Ru(III), respectively. Thus the oxidation kinetics can be described by a third-order rate law. Aniline degradation by Ru(III) catalyzed permanganate oxidation was markedly influenced by pH, and the second-order rate constant (ktapp) decreased from 643.20 to 2.67 (mol/L)⁻¹sec⁻¹ with increasing pH from 4.0 to 9.0, which was possibly due to the decrease of permanganate oxidation potential with increasing pH. In both the uncatalytic and catalytic permanganate oxidation, six byproducts of aniline were identified in UPLC-MS/MS analysis. Ru(III), as an electron shuttle, was oxidized by permanganate to Ru(VI) and Ru(VII), which acted the co-oxidants for decomposition of aniline. Although Ru(III) could catalyze permanganate oxidation of aniline effectively, dosing homogeneous Ru(III) into water would lead to a second pollution. Therefore, efforts would be made to investigate the catalytic performance of supported Ru(III) toward permanganate oxidation in our future study. Copyright © 2014. Published by Elsevier B.V.

  8. Investigation on radioactivity of deposition

    International Nuclear Information System (INIS)

    Vaas, L.H.; Smetsers, R.C.G.M.; Mattern, F.C.M.; Drost, R.M.S. van; Ockhuizen, A.; Glastra, P.; Koolwijk, A.C.

    1990-04-01

    This report of the Dutch National Institute of Public Health and Environmental Protection (RIVM) summarizes the results of measurements of radionuclides deposited in the Netherlands in 1988. The samples of deposition were taken at Bilthoven, located near the center of the country. In 1988 measurements were carried out to determine the activities of γ-emitters, where 7 Be, 40 K, 134 Cs and 137 Cs were identified, and those of 3 H, 210 Pb and 210 Po. Also the gross α-, gross β- and gross γ-activities were determined. (author). 10 refs.; 7 figs.; 6 tabs

  9. Recent advances in transition metal-catalyzed Csp2-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

    Directory of Open Access Journals (Sweden)

    Grégory Landelle

    2013-11-01

    Full Text Available In the last few years, transition metal-mediated reactions have joined the toolbox of chemists working in the field of fluorination for Life-Science oriented research. The successful execution of transition metal-catalyzed carbon–fluorine bond formation has become a landmark achievement in fluorine chemistry. This rapidly growing research field has been the subject of some excellent reviews. Our approach focuses exclusively on transition metal-catalyzed reactions that allow the introduction of –CFH2, –CF2H, –CnF2n+1 and –SCF3 groups onto sp² carbon atoms. Transformations are discussed according to the reaction-type and the metal employed. The review will not extend to conventional non-transition metal methods to these fluorinated groups.

  10. Self-Catalyzed Growth and Characterization of In(As)P Nanowires on InP(111)B Using Metal-Organic Chemical Vapor Deposition.

    Science.gov (United States)

    Park, Jeung Hun; Pozuelo, Marta; Setiawan, Bunga P D; Chung, Choong-Heui

    2016-12-01

    We report the growth of vertical -oriented InAs x P1-x (0.11 ≤ x ≤ 0.27) nanowires via metal-organic chemical vapor deposition in the presence of indium droplets as catalysts on InP(111)B substrates at 375 °C. Trimethylindium, tertiarybutylphosphine, and tertiarybutylarsine are used as the precursors, corresponding to P/In and As/In molar ratios of 29 and 0.01, respectively. The as-grown nanowire growth morphologies, crystallinity, composition, and optical characteristics are determined using a combination of scanning and transmission electron microscopies, electron diffraction, and X-ray photoelectron, energy dispersive X-ray, and Raman spectroscopies. We find that the InAs x P1-x nanowires are tapered with narrow tops, wider bases, and In-rich In-As alloy tips, characteristic of vapor-liquid-solid process. The wires exhibit a mixture of zinc blende and wurtzite crystal structures and a high density of structural defects such as stacking faults and twins. Our results suggest that the incorporation of As into InP wires decreases with increasing substrate temperature. The Raman spectra obtained from the In(As)P nanowires reveal a red-shift and lower intensity of longitudinal optical mode relative to both InP nanowires and InP(111)B bulk, due to the incorporation of As into the InP matrix.

  11. An Efficient Green Synthesis of 3-Amino-1 H -chromenes Catalyzed ...

    African Journals Online (AJOL)

    An Efficient Green Synthesis of 3-Amino-1 H -chromenes Catalyzed by ZnO Nanoparticles Thin-film. ... South African Journal of Chemistry ... The mild reaction conditions, reusability of the catalyst, easy work-up and high yields of products make the present protocol sustainable and advantageous compared to conventional ...

  12. Room-temperature base-free copper-catalyzed trifluoromethylation of organotrifluoroborates to trifluoromethylarenes

    KAUST Repository

    Huang, Yuanyuan; Fang, Xin; Lin, Xiaoxi; Li, Huaifeng; He, Weiming; Huang, Kuo-Wei; Yuan, Yaofeng; Weng, Zhiqiang

    2012-01-01

    An efficient room temperature copper-catalyzed trifluoromethylation of organotrifluoroborates under the base free condition using an electrophilic trifluoromethylating reagent is demonstrated. The corresponding trifluoromethylarenes were obtained in good to excellent yields and the reaction tolerates a wide range of functional groups. © 2012 Elsevier Ltd. All rights reserved.

  13. Room-temperature base-free copper-catalyzed trifluoromethylation of organotrifluoroborates to trifluoromethylarenes

    KAUST Repository

    Huang, Yuanyuan

    2012-12-01

    An efficient room temperature copper-catalyzed trifluoromethylation of organotrifluoroborates under the base free condition using an electrophilic trifluoromethylating reagent is demonstrated. The corresponding trifluoromethylarenes were obtained in good to excellent yields and the reaction tolerates a wide range of functional groups. © 2012 Elsevier Ltd. All rights reserved.

  14. 20 CFR 703.306 - Kinds of negotiable securities that may be deposited; conditions of deposit; acceptance of deposits.

    Science.gov (United States)

    2010-04-01

    ... the Act in the amount fixed by the Office under the regulations in this part shall deposit any... deposited; conditions of deposit; acceptance of deposits. 703.306 Section 703.306 Employees' Benefits... negotiable securities that may be deposited; conditions of deposit; acceptance of deposits. A self-insurer or...

  15. Petrology, mineralogy and geochemistry of surficial uranium deposits

    International Nuclear Information System (INIS)

    Pagel, M.

    1984-01-01

    A comprehensive understanding of the petrology, mineralogy, and geochemistry of surficial uranium ore deposits is important for developing prospecting and evaluation strategies. Carnotite is the main uranium mineral and is found in those deposits that have the greatest potential uranium resources. The following uranium-bearing minerals have been reported to occur in surficial deposits: carnotite, tyuyamunite, soddyite, weeksite, haiweeite, uranophane, betauranophane, metaankoleite, torbernite, autunite, phosphuranylite, schroeckingerite, Pb-V-U hydroxide (unnamed mineral), uraninite and organourano complexes. The interrelationships between some of the minerals of the host rocks (especially the clays) are not well understood. (author)

  16. Transition metal-catalyzed carbocyclization of nitrogen and oxygen-tethered 1,n-enynes and diynes: synthesis of five or six-membered heterocyclic compounds.

    Science.gov (United States)

    Zhang, Di-Han; Zhang, Zhen; Shi, Min

    2012-10-25

    Cycloisomerization of 1,n-enynes and diynes is a powerful method in organic synthesis to access heterocyclic compounds and has drawn increasing attention from organic chemists. In this paper, we attempted to summarize our recent results on the transition metal-catalyzed cycloisomerization to synthesize five or six-membered heterocyclic compounds using 1,n-enynes and diynes having a propargylic ester moiety. First, we will describe the synthesis of 2,3-disubstituted 3-pyrrolines via gold catalyzed cycloisomerization of 1,6-diynes. In addition, we will also disclose a novel silver catalyzed tandem 1,3-acyloxy migration/Mannich-type addition/elimination of the sulfonyl group of N-sulfonylhydrazone-propargylic esters to 5,6-dihydropyridazin-4-one derivatives. Furthermore, we will introduce three interesting examples of the synthesis of bicyclic compounds via titanium or rhodium catalyzed carbocyclization of enynes. In this context, we have presented that 1,n-enynes and diynes containing propargylic esters are highly reactive and useful starting materials for the cycloisomerization catalyzed by a transition metal catalyst.

  17. Stochastic simulation of enzyme-catalyzed reactions with disparate timescales.

    Science.gov (United States)

    Barik, Debashis; Paul, Mark R; Baumann, William T; Cao, Yang; Tyson, John J

    2008-10-01

    Many physiological characteristics of living cells are regulated by protein interaction networks. Because the total numbers of these protein species can be small, molecular noise can have significant effects on the dynamical properties of a regulatory network. Computing these stochastic effects is made difficult by the large timescale separations typical of protein interactions (e.g., complex formation may occur in fractions of a second, whereas catalytic conversions may take minutes). Exact stochastic simulation may be very inefficient under these circumstances, and methods for speeding up the simulation without sacrificing accuracy have been widely studied. We show that the "total quasi-steady-state approximation" for enzyme-catalyzed reactions provides a useful framework for efficient and accurate stochastic simulations. The method is applied to three examples: a simple enzyme-catalyzed reaction where enzyme and substrate have comparable abundances, a Goldbeter-Koshland switch, where a kinase and phosphatase regulate the phosphorylation state of a common substrate, and coupled Goldbeter-Koshland switches that exhibit bistability. Simulations based on the total quasi-steady-state approximation accurately capture the steady-state probability distributions of all components of these reaction networks. In many respects, the approximation also faithfully reproduces time-dependent aspects of the fluctuations. The method is accurate even under conditions of poor timescale separation.

  18. Mutually catalyzed birth of population and assets in exchange-driven growth

    Science.gov (United States)

    Lin, Zhenquan; Ke, Jianhong; Ye, Gaoxiang

    2006-10-01

    We propose an exchange-driven aggregation growth model of population and assets with mutually catalyzed birth to study the interaction between the population and assets in their exchange-driven processes. In this model, monomer (or equivalently, individual) exchange occurs between any pair of aggregates of the same species (population or assets). The rate kernels of the exchanges of population and assets are K(k,l)=Kkl and L(k,l)=Lkl , respectively, at which one monomer migrates from an aggregate of size k to another of size l . Meanwhile, an aggregate of one species can yield a new monomer by the catalysis of an arbitrary aggregate of the other species. The rate kernel of asset-catalyzed population birth is I(k,l)=Iklμ [and that of population-catalyzed asset birth is J(k,l)=Jklν ], at which an aggregate of size k gains a monomer birth when it meets a catalyst aggregate of size l . The kinetic behaviors of the population and asset aggregates are solved based on the rate equations. The evolution of the aggregate size distributions of population and assets is found to fall into one of three categories for different parameters μ and ν : (i) population (asset) aggregates evolve according to the conventional scaling form in the case of μ⩽0 (ν⩽0) , (ii) population (asset) aggregates evolve according to a modified scaling form in the case of ν=0 and μ>0 ( μ=0 and ν>0 ), and (iii) both population and asset aggregates undergo gelation transitions at a finite time in the case of μ=ν>0 .

  19. Tsunami deposits

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2013-08-15

    The NSC (the Nuclear Safety Commission of Japan) demand to survey on tsunami deposits by use of various technical methods (Dec. 2011), because tsunami deposits have useful information on tsunami activity, tsunami source etc. However, there are no guidelines on tsunami deposit survey in JAPAN. In order to prepare the guideline of tsunami deposits survey and evaluation and to develop the method of tsunami source estimation on the basis of tsunami deposits, JNES carried out the following issues; (1) organizing information of paleoseismological record and tsunami deposit by literature research, (2) field survey on tsunami deposit, and (3) designing the analysis code of sediment transport due to tsunami. As to (1), we organize the information gained about tsunami deposits in the database. As to (2), we consolidate methods for surveying and identifying tsunami deposits in the lake based on results of the field survey in Fukui Pref., carried out by JNES. In addition, as to (3), we design the experimental instrument for hydraulic experiment on sediment transport and sedimentation due to tsunamis. These results are reflected in the guideline on the tsunami deposits survey and evaluation. (author)

  20. Tsunami deposits

    International Nuclear Information System (INIS)

    2013-01-01

    The NSC (the Nuclear Safety Commission of Japan) demand to survey on tsunami deposits by use of various technical methods (Dec. 2011), because tsunami deposits have useful information on tsunami activity, tsunami source etc. However, there are no guidelines on tsunami deposit survey in JAPAN. In order to prepare the guideline of tsunami deposits survey and evaluation and to develop the method of tsunami source estimation on the basis of tsunami deposits, JNES carried out the following issues; (1) organizing information of paleoseismological record and tsunami deposit by literature research, (2) field survey on tsunami deposit, and (3) designing the analysis code of sediment transport due to tsunami. As to (1), we organize the information gained about tsunami deposits in the database. As to (2), we consolidate methods for surveying and identifying tsunami deposits in the lake based on results of the field survey in Fukui Pref., carried out by JNES. In addition, as to (3), we design the experimental instrument for hydraulic experiment on sediment transport and sedimentation due to tsunamis. These results are reflected in the guideline on the tsunami deposits survey and evaluation. (author)

  1. Some thoughts on the muon catalyzed fusion reactor

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, H.

    1986-01-01

    The design of the muon catalyzed fusion reactor is discussed. Some of the engineering challenges and critical research areas such as ..pi../sup -/ meson transport, beam entry single crystal window and coherent x-ray for stripping the muon from ..cap alpha.. particle, are considered. In order to reduce the tritium inventory and neutron wall loading, use of the laser technique for manipulating the d-t mixture is considered. The heterogeneous d-t mixture using the droplet or jet is discussed. 39 refs., 6 figs.

  2. Indium-Catalyzed Reductive Dithioacetalization of Carboxylic Acids with Dithiols: Scope, Limitations, and Application to Oxidative Desulfurization.

    Science.gov (United States)

    Nishino, Kota; Minato, Kohei; Miyazaki, Takahiro; Ogiwara, Yohei; Sakai, Norio

    2017-04-07

    In this study an InI 3 -TMDS (1,1,3,3-tetramethyldisiloxane) reducing system effectively catalyzed the reductive dithioacetalization of a variety of aromatic and aliphatic carboxylic acids with 1,2-ethanedithiol or 1,3-propanedithiol leading to the one-pot preparation of either 1,3-dithiolane derivatives or a 1,3-dithiane derivative. Also, the intact indium catalyst continuously catalyzed the subsequent oxidative desulfurization of an in situ formed 1,3-dithiolane derivative, which led to the preparation of the corresponding aldehydes.

  3. Effects of grazing, phosphorus and light on the growth rates of major bacterioplankton taxa in the coastal NW Mediterranean

    Czech Academy of Sciences Publication Activity Database

    Sánchez, O.; Koblížek, Michal; Gasol, J.M.; Ferrera, I.

    2017-01-01

    Roč. 9, č. 3 (2017), s. 300-309 ISSN 1758-2229 R&D Projects: GA ČR GA13-11281S; GA MŠk(CZ) LO1416 Institutional support: RVO:61388971 Keywords : AEROBIC ANOXYGENIC PHOTOTROPHS * CATALYZED REPORTER DEPOSITION * NATURAL PLANKTONIC BACTERIA Subject RIV: EE - Microbiology , Virology OBOR OECD: Microbiology Impact factor: 3.363, year: 2016

  4. Regional aerosol deposition in human upper airways

    Energy Technology Data Exchange (ETDEWEB)

    Swift, D.L.

    1991-11-01

    During the current report experimental studies of upper respiratory deposition of radon progeny aerosols and stimulant aerosols were carried out in replicate casts of nasal and oral passages of adults and children. Additionally, preliminary studies of nasal passage deposition of unattached Po{sup 218} particles was carried out in four human subjects. Data on nasal inspiratory deposition in replicate models of adults and infants from three collaborating laboratories were compared and a best-fit curve of deposition efficiency for both attached and unattached particles was obtained, showing excellent inter-laboratory agreement. This curve demonstrates that nasal inspiratory deposition of radon progeny is weakly dependent upon flow rate over physiologically realistic ranges of flow, does not show a significant age effect, and is relatively independent of nasal passage dimensions for a given age range. Improved replicate models of the human adult oral passage extending to the mid-trachea were constructed for medium and higher flow mouth breathing states; these models were used to assess the deposition of unattached Po{sup 218} particles during oronasal breathing in the oral passage and demonstrated lower deposition efficiency than the nasal passage. Measurements of both Po{sup 218} particle and attached fraction particle size deposition were performed in replicate nasal passage of a four week old infant. 5 refs., 1 fig.

  5. Solid Acid-Catalyzed Cellulose Hydrolysis Monitored by In Situ ATR-IR Spectroscopy

    NARCIS (Netherlands)

    Zakzeski, J.; Grisel, R.J.H.; Smit, A.T.; Weckhuysen, B.M.

    2012-01-01

    The solid acid-catalyzed hydrolysis of cellulose was studied under elevated temperatures and autogenous pressures using in situ ATR-IR spectroscopy. Standards of cellulose and pure reaction products, which include glucose, fructose, hydroxymethylfurfural (HMF), levulinic acid (LA), formic acid, and

  6. Preparation of fluorinated biaryls through direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates

    KAUST Repository

    Fang, Xin; Huang, Yuanyuan; Chen, Xiaoqing; Lin, Xiaoxi; Bai, Zhengshuai; Huang, Kuo-Wei; Yuan, Yaofeng; Weng, Zhiqiang

    2013-01-01

    The direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates gave the desired products of fluorinated biaryls in good to excellent yields. A diverse set of important functional groups including methoxy, aldehyde, ester

  7. Coupled Ferredoxin and Crotonyl Coenzyme A (CoA) Reduction with NADH Catalyzed by the Butyryl-CoA Dehydrogenase/Etf Complex from Clostridium kluyveri▿ †

    Science.gov (United States)

    Li, Fuli; Hinderberger, Julia; Seedorf, Henning; Zhang, Jin; Buckel, Wolfgang; Thauer, Rudolf K.

    2008-01-01

    Cell extracts of butyrate-forming clostridia have been shown to catalyze acetyl-coenzyme A (acetyl-CoA)- and ferredoxin-dependent formation of H2 from NADH. It has been proposed that these bacteria contain an NADH:ferredoxin oxidoreductase which is allosterically regulated by acetyl-CoA. We report here that ferredoxin reduction with NADH in cell extracts from Clostridium kluyveri is catalyzed by the butyryl-CoA dehydrogenase/Etf complex and that the acetyl-CoA dependence previously observed is due to the fact that the cell extracts catalyze the reduction of acetyl-CoA with NADH via crotonyl-CoA to butyryl-CoA. The cytoplasmic butyryl-CoA dehydrogenase complex was purified and is shown to couple the endergonic reduction of ferredoxin (E0′ = −410 mV) with NADH (E0′ = −320 mV) to the exergonic reduction of crotonyl-CoA to butyryl-CoA (E0′ = −10 mV) with NADH. The stoichiometry of the fully coupled reaction is extrapolated to be as follows: 2 NADH + 1 oxidized ferredoxin + 1 crotonyl-CoA = 2 NAD+ + 1 ferredoxin reduced by two electrons + 1 butyryl-CoA. The implications of this finding for the energy metabolism of butyrate-forming anaerobes are discussed in the accompanying paper. PMID:17993531

  8. Amino acid-catalyzed conversion of citral : cis-trans isomerization and its conversion into 6-methyl-5-hepten-2-one and acetaldehyde

    NARCIS (Netherlands)

    Wolken, W.A.M.; Have, R. ten; Werf, M.J. van der

    2000-01-01

    Under alkaline conditions, amino acids or proteins catalyze the deacetylation of citral, a major aroma component, resulting in methylheptenone and acetaldehyde formation. 3-Hydroxycitronellal is an intermediate in this reaction. Amino acids also catalyze the cis-trans isomerization of the pure

  9. Kinetic Investigations on Pd(II) Catalyzed Oxidation of Some Amino ...

    African Journals Online (AJOL)

    Kinetic investigations on Pd(II) catalyzed oxidation of dl-serine and dl-threonine by acidic solution of potassium bromate in the presence of mercuric acetate, as a scavenger have been made in the temperature range of 30–45°C. The rate shows zero order kinetics in bromate [BrO3‾] and order of reaction is one with respect ...

  10. γ-Alumina Nanoparticle Catalyzed Efficient Synthesis of Highly Substituted Imidazoles

    Directory of Open Access Journals (Sweden)

    Bandapalli Palakshi Reddy

    2015-10-01

    Full Text Available γ-Alumina nano particle catalyzed multi component reaction of benzil, arylaldehyde and aryl amines afforded the highly substituted 1,2,4,5-tetraaryl imidazoles with good to excellent yield in less reaction time under the sonication as well as the conventional methods. Convenient operational simplicity, mild conditions and the reusability of catalyst were the other advantages of this developed protocol.

  11. Rhodium-Catalyzed Linear Codimerization and Cycloaddition of Ketenes with Alkynes

    Directory of Open Access Journals (Sweden)

    Teruyuki Kondo

    2010-06-01

    Full Text Available A novel rhodium-catalyzed linear codimerization of alkyl phenyl ketenes with internal alkynes to dienones and a novel synthesis of furans by an unusual cycloaddition of diaryl ketenes with internal alkynes have been developed. These reactions proceed smoothly with the same rhodium catalyst, RhCl(PPh33, and are highly dependent on the structure and reactivity of the starting ketenes.

  12. Base catalyzed synthesis of bicyclo[3.2.1]octane scaffolds.

    Science.gov (United States)

    Boehringer, Régis; Geoffroy, Philippe; Miesch, Michel

    2015-07-07

    The base-catalyzed reaction of achiral 1,3-cyclopentanediones tethered to activated olefins afforded in high yields bicyclo[3.2.1]octane-6,8-dione or bicyclo[3.2.1]octane-6-carboxylate derivatives bearing respectively three or five stereogenic centers. The course of the reaction is closely related to the reaction time and to the base involved in the reaction.

  13. Cobalt-catalyzed C-H olefination of aromatics with unactivated alkenes.

    Science.gov (United States)

    Manoharan, Ramasamy; Sivakumar, Ganesan; Jeganmohan, Masilamani

    2016-08-18

    A cobalt-catalyzed C-H olefination of aromatic and heteroaromatic amides with unactivated alkenes, allyl acetates and allyl alcohols is described. This method offers an efficient route for the synthesis of vinyl and allyl benzamides in a highly stereoselective manner. It is observed that the ortho substituent on the benzamide moiety is crucial for the observation of allylated products in unactivated alkenes.

  14. Radiolytic and photochemical reduction of carbon dioxide in solution catalyzed by transition metal complexes with some selected macrocycles

    International Nuclear Information System (INIS)

    Grodkowski, J.

    2004-01-01

    The main goal of the work presented in this report is an explanation of the mechanism of carbon dioxide (CO 2 ) reduction catalyzed by transition metal complexes with some selected macrocycles. The catalytic function of two electron exchange centers in the reduction of CO 2 , an inner metal and a macrocycle ring, was defined. Catalytic effects of rhodium, iron and cobalt porphyrins, cobalt and iron phthalocyanines and corroles as well as cobalt corrins have been investigated. CO 2 reduction by iron ions without presence of macrocycles and also in presence of copper compounds in aqueous solutions have been studied as well

  15. Reaction Acceleration in Thin Films with Continuous Product Deposition for Organic Synthesis.

    Science.gov (United States)

    Wei, Zhenwei; Wleklinski, Michael; Ferreira, Christina; Cooks, R Graham

    2017-08-01

    Thin film formats are used to study the Claisen-Schmidt base-catalyzed condensation of 6-hydroxy-1-indanone with substituted benzaldehydes and to compare the reaction acceleration relative to the bulk. Relative acceleration factors initially exceeded 10 3 and were on the order of 10 2 at steady state, although the confined volume reaction was not electrostatically driven. Substituent effects were muted compared to those in the corresponding bulk and microdroplet reactions and it is concluded that the rate-limiting step at steady state is reagent transport to the interface. Conditions were found that allowed product deposition from the thin film to occur continuously as the reaction mixture was added and as the solvent evaporated. Yields of 74 % and production rates of 98 mg h -1 were reached in a very simple experimental system that could be multiplexed to greater scales. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Developmentally Regulated Post-translational Modification of Nucleoplasmin Controls Histone Sequestration and Deposition

    Directory of Open Access Journals (Sweden)

    Takashi Onikubo

    2015-03-01

    Full Text Available Nucleoplasmin (Npm is an abundant histone chaperone in vertebrate oocytes and embryos. During embryogenesis, regulation of Npm histone binding is critical for its function in storing and releasing maternal histones to establish and maintain the zygotic epigenome. Here, we demonstrate that Xenopus laevis Npm post-translational modifications (PTMs specific to the oocyte and egg promote either histone deposition or sequestration, respectively. Mass spectrometry and Npm phosphomimetic mutations used in chromatin assembly assays identified hyperphosphorylation on the N-terminal tail as a critical regulator for sequestration. C-terminal tail phosphorylation and PRMT5-catalyzed arginine methylation enhance nucleosome assembly by promoting histone interaction with the second acidic tract of Npm. Electron microscopy reconstructions of Npm and TTLL4 activity toward the C-terminal tail demonstrate that oocyte- and egg-specific PTMs cause Npm conformational changes. Our results reveal that PTMs regulate Npm chaperoning activity by modulating Npm conformation and Npm-histone interaction, leading to histone sequestration in the egg.

  17. Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

    Science.gov (United States)

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

  18. The gravitino-stau scenario after catalyzed big bang nucleosynthesis

    Science.gov (United States)

    Kersten, Jörn; Schmidt-Hoberg, Kai

    2008-01-01

    We consider the impact of catalyzed big bang nucleosynthesis on theories with a gravitino lightest superparticle and a charged slepton next-to-lightest superparticle. In models where the gravitino to gaugino mass ratio is bounded from below, such as gaugino-mediated supersymmetry breaking, we derive a lower bound on the gaugino mass parameter m1/2. As a concrete example, we determine the parameter space of gaugino mediation that is compatible with all cosmological constraints.

  19. The gravitino–stau scenario after catalyzed big bang nucleosynthesis

    International Nuclear Information System (INIS)

    Kersten, Jörn; Schmidt-Hoberg, Kai

    2008-01-01

    We consider the impact of catalyzed big bang nucleosynthesis on theories with a gravitino lightest superparticle and a charged slepton next-to-lightest superparticle. In models where the gravitino to gaugino mass ratio is bounded from below, such as gaugino-mediated supersymmetry breaking, we derive a lower bound on the gaugino mass parameter m 1/2 . As a concrete example, we determine the parameter space of gaugino mediation that is compatible with all cosmological constraints

  20. The Extension Storyteller: Using Stories to Enhance Meaning and Catalyze Change

    Science.gov (United States)

    Franz, Nancy

    2016-01-01

    Many cultures share and pass on norms through storytelling. Extension as a culture also creates and shares stories to pass on history, provide information about Extension work and experiences, and develop the organization. However, Extension as a culture less frequently uses storytelling to enhance meaning and catalyze related change. This article…