cu-catalyzed hydroboration reactions: Topics by WorldWideScience.org

Sample records for cu-catalyzed hydroboration reactions

Spiro(phosphoamidite) ligand (SIPHOS)/Cu(OTf)2-catalyzed highly regio-and stereo-selective hydroborations of internal alkynes with diborane in water

Institute of Scientific and Technical Information of China (English)

Qing-Qing Xuan; Ya-Hui Wei; Qiu-Ling Song

2017-01-01

The highly regio-and stereoselective hydroborations of unactivated internal alkynes with diboron compound catalyzed by Cu(OTf)2 with spiro(phosphoamidite) as ligand in the presence of Cs2CO3 in water was developed.This protocol was applied efficiently in the aqueous synthesis of multi-substituted vinylboranes.
Vicinal Diboronates in High Enantiomeric Purity through Tandem Site-Selective NHC–Cu-Catalyzed Boron-Copper Additions to Terminal Alkynes

Science.gov (United States)

Lee, Yunmi; Jang, Hwanjong; Hoveyda, Amir H.

2009-01-01

A Cu-catalyzed protocol for conversion of terminal alkynes to enantiomerically enriched diboronates is reported. In a single vessel, a site-selective hydroboration of an alkyne leads to the corresponding terminal vinylboronate, which undergoes a second site-selective and enantioselective hydroboration. Reactions proceed in the presence of two equivalents of commercially available bis(pinacolato)diboron [B2(pin)2] and 5–7.5 mol % of a chiral bidentate imidazolinium salt, affording diboronates in 60–93% yield and up to 97.5:2.5 enantiomeric ratio (er). The enantiomerically enriched products can be functionalized to afford an assortment of versatile organic molecules. Enynes are converted to unsaturated diboronates with high chemo- (>98% reaction of alkyne; <2% at alkene) and enantioselectivity (e.g., 94.5:5.5 er). PMID:19968273
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.
A Proton-Switchable Bifunctional Ruthenium Complex That Catalyzes Nitrile Hydroboration.

Science.gov (United States)

Geri, Jacob B; Szymczak, Nathaniel K

2015-10-14

A new bifunctional pincer ligand framework bearing pendent proton-responsive hydroxyl groups was prepared and metalated with Ru(II) and subsequently isolated in four discrete protonation states. Stoichiometric reactions with H2 and HBPin showed facile E-H (E = H or BPin) activation across a Ru(II)-O bond, providing access to unusual Ru-H species with strong interactions with neighboring proton and boron atoms. These complexes were found to promote the catalytic hydroboration of ketones and nitriles under mild conditions, and the activity was highly dependent on the ligand's protonation state. Mechanistic experiments revealed a crucial role of the pendent hydroxyl groups for catalytic activity.
An efficient synthesis of isocoumarins via a CuI catalyzed cascade reaction process

Institute of Scientific and Technical Information of China (English)

无

2009-01-01

3-Alkyl isocoumarins are provided by CuI/amino acid-catalyzed Sonogashira coupling reaction of o-bromo benzoic acids and terminal alkynes and the subsequent additive cyclization. This cascade process allows synthesis of diverse isocoumarins by varying both coupling partners bearing a wide range of functional groups.
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.
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.
Selective coupling reaction between 2,6-diiodoanisoles and terminal alkynes catalyzed by Pd(PPh32Cl2 and CuI

Directory of Open Access Journals (Sweden)

Allan F. C. Rossini

2012-06-01

Full Text Available The cross-coupling reaction between aryl halides and terminal alkynes, catalyzed by palladium complexes and copper (I salts, consists in an efficient synthetic tool for the formation of C-C bonds, resulting in disubstituted acetylenic compounds. Accordingly, in this work we present our preliminary results involving the selective cross-coupling reaction between 2,6-diiodoanisoles and terminal alkynes, catalyzed by Pd(PPh32Cl2 and CuI, in the formation of 2-iodo-alkynylanisoles (scheme 1.
Development of Copper-Catalyzed Electrophilic Trifluoromethylation and Exploiting Cu/Cu2O Nanowires with Novel Catalytic Reactivity

KAUST Repository

Li, Huaifeng

2014-06-01

This thesis is based on research in Cu-catalyzed electrophilic trifluoromethylation and exploiting Cu/Cu2O nanowires with novel catalytic reactivity for developing of catalytic and greener synthetic methods. A large number of biological active pharmaceuticals and agrochemicals contain fluorine substituents (-F) or trifluoromethyl groups (-CF3) because these moieties often result in profound changes of their physical, chemical, and biological properties, such as metabolic stability and lipophilicity. For this reason, the introduction of fluorine or trifluoromethyl groups into organic molecules has attracted intensive attention. Among them, transition metal-catalyzed trifluoromethylation reactions has proved to be an efficient and reliable strategy to construct carbon-fluorine (C-F) and carbontrifluoromethyl (C-CF3) bond. We have developed a catalytic process for the first time for trifluoromethylation of terminal alkynes with Togni’s reagent, affording trifluoromethylated acetylenes in good to excellent yields. The reaction is conducted at room temperature and exhibits tolerance to a range of functional groups. Derived from this discovery, the extension of work of copper catalyzed electrophilic trifluoromethylation were investigated which include the electrophilic trifluoromethylation of arylsulfinate salts and electrophilic trifluoromethylation of organotrifluoroborates. Because of growing environmental concern, the development of greener synthetic methods has drawn much attention. Nano-sized catalysts are environment-friendly and an attractive green alternative to the conventional homogeneous catalysts. The nano-sized catalysts can be easily separated from the reaction mixture due to their insolubility and thus they can be used recycled. Notably, because of the high reactivities of nano-sized metal catalysts, the use of ligands can be avoided and the catalysts loadings can be reduced greatly. Moreover, the nano-sized catalysts can increase the exposed surface
Cu-catalyzed C(sp³)-H bond activation reaction for direct preparation of cycloallyl esters from cycloalkanes and aromatic aldehydes.

Science.gov (United States)

Zhao, Jincan; Fang, Hong; Han, Jianlin; Pan, Yi

2014-05-02

Cu-catalyzed dehydrogenation-olefination and esterification of C(sp(3))-H bonds of cycloalkanes with TBHP as an oxidant has been developed. The reaction involves four C-H bond activations and gives cycloallyl ester products directly from cycloalkanes and aromatic aldehydes.
Enantioselective Intramolecular CH-Insertions upon Cu-Catalyzed Decomposition of Phenyliodonium Ylides

Directory of Open Access Journals (Sweden)

Christelle BolÃƒÂ©a

2001-02-01

Full Text Available The Cu-catalyzed intramolecular CH insertion of phenyliodonium ylide 5b has been investigated at 0Ã‚Â° C in the presence of several chiral ligands. Enantioselectivities vary in the range of 38Ã¢Â€Â“72 %, and are higher than those resulting from reaction of the diazo compound 5c at 65Ã‚Â° C. The results are consistent with a carbenoid mechanism for Cu-catalyzed decomposition of phenyliodonium ylides.
Cu(I)/Diamine-catalyzed Aryl-alkyne Coupling Reactions

Institute of Scientific and Technical Information of China (English)

无

2005-01-01

CuI/ethylene diamine/K2CO3/dioxane is shown to be a useful system for the cross coupling reactions of various aryl iodides and bromides with aryl and alkyl alkynes. Compared to the conventional Sonogashira reactions, the new procedure is free of palladium and phosphines.
Theoretical insights into the sites and mechanisms for base catalyzed esterification and aldol condensation reactions over Cu.

Science.gov (United States)

Neurock, Matthew; Tao, Zhiyuan; Chemburkar, Ashwin; Hibbitts, David D; Iglesia, Enrique

2017-04-28

Condensation and esterification are important catalytic routes in the conversion of polyols and oxygenates derived from biomass to fuels and chemical intermediates. Previous experimental studies show that alkanal, alkanol and hydrogen mixtures equilibrate over Cu/SiO 2 and form surface alkoxides and alkanals that subsequently promote condensation and esterification reactions. First-principle density functional theory (DFT) calculations were carried out herein to elucidate the elementary paths and the corresponding energetics for the interconversion of propanal + H 2 to propanol and the subsequent C-C and C-O bond formation paths involved in aldol condensation and esterification of these mixtures over model Cu surfaces. Propanal and hydrogen readily equilibrate with propanol via C-H and O-H addition steps to form surface propoxide intermediates and equilibrated propanal/propanol mixtures. Surface propoxides readily form via low energy paths involving a hydrogen addition to the electrophilic carbon center of the carbonyl of propanal or via a proton transfer from an adsorbed propanol to a vicinal propanal. The resulting propoxide withdraws electron density from the surface and behaves as a base catalyzing the activation of propanal and subsequent esterification and condensation reactions. These basic propoxides can readily abstract the acidic C α -H of propanal to produce the CH 3 CH (-) CH 2 O* enolate, thus initiating aldol condensation. The enolate can subsequently react with a second adsorbed propanal to form a C-C bond and a β-alkoxide alkanal intermediate. The β-alkoxide alkanal can subsequently undergo facile hydride transfer to form the 2-formyl-3-pentanone intermediate that decarbonylates to give the 3-pentanone product. Cu is unique in that it rapidly catalyzes the decarbonylation of the C 2n intermediates to form C 2n-1 3-pentanone as the major product with very small yields of C 2n products. This is likely due to the absence of Brønsted acid sites
Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C-S Bond Cleavage: Reaction Development and Mechanism Study.

Science.gov (United States)

Du, Bingnan; Wang, Wenmin; Wang, Yang; Qi, Zhenghang; Tian, Jiaqi; Zhou, Jie; Wang, Xiaochen; Han, Jianlin; Ma, Jing; Pan, Yi

2018-02-16

A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C-S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated Cu II intermediate, O-O bond homolysis induced C-S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C-S bond cleavage and transformations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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 ...
Cu-catalyzed esterification reaction via aerobic oxygenation and C-C bond cleavage: an approach to α-ketoesters.

Science.gov (United States)

Zhang, Chun; Feng, Peng; Jiao, Ning

2013-10-09

The Cu-catalyzed novel aerobic oxidative esterification reaction of 1,3-diones for the synthesis of α-ketoesters has been developed. This method combines C-C σ-bond cleavage, dioxygen activation and oxidative C-H bond functionalization, as well as provides a practical, neutral, and mild synthetic approach to α-ketoesters which are important units in many biologically active compounds and useful precursors in a variety of functional group transformations. A plausible radical process is proposed on the basis of mechanistic studies.
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.
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.
Cyclic aldimines as superior electrophiles for Cu-catalyzed decarboxylative Mannich reaction of β-ketoacids with a broad scope and high enantioselectivity.

Science.gov (United States)

Zhang, Heng-Xia; Nie, Jing; Cai, Hua; Ma, Jun-An

2014-05-02

A novel Cu-catalyzed enantioselective decarboxylative Mannich reaction of cyclic aldimines with β-ketoacids is described. The cyclic structure of these aldimines, in which the C═N bond is constrained in the Z geometry, appears to be important, allowing Mannich condensation to proceed in high yields with excellent enantioselectivities. A chiral chroman-4-amine was synthesized from the decarboxylative Mannich product in several steps without loss of enantioselectivity.
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.

A Mechanistic Study of Hydroboration of 1-Octene with 1,3,2 ...

African Journals Online (AJOL)

NJD

... on hydroboration.9,10. Thaisrivongs et al.8 reported hydroboration of a range of alkenes ... low temperature, a good 65 % yield was obtained (Entry 7). Maintaining the ... method, borane-dimethyl sulphide complex reacted with an equimolar ...
Cu(II)-catalyzed esterification reaction via aerobic oxidative cleavage of C(CO)-C(alkyl) bonds.

Science.gov (United States)

Ma, Ran; He, Liang-Nian; Liu, An-Hua; Song, Qing-Wen

2016-02-04

A novel Cu(II)-catalyzed aerobic oxidative esterification of simple ketones for the synthesis of esters has been developed with wide functional group tolerance. This process is assumed to go through a tandem sequence consisting of α-oxygenation/esterification/nucleophilic addition/C-C bond cleavage and carbon dioxide is released as the only byproduct.
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
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…
Copper-catalyzed azide–alkyne cycloaddition (CuAAC) and beyond: new reactivity of copper(i) acetylides†

OpenAIRE

Hein, Jason E.; Fokin, Valery V.

2010-01-01

Copper-catalyzed azide–alkyne cycloaddition (CuAAC) is a widely utilized, reliable, and straightforward way for making covalent connections between building blocks containing various functional groups. It has been used in organic synthesis, medicinal chemistry, surface and polymer chemistry, and bioconjugation applications. Despite the apparent simplicity of the reaction, its mechanism involves multiple reversible steps involving coordination complexes of copper(i) acetylides of varying nucle...
Synthesis of Novel Aliphatic N-sulfonylamidino Thymine Derivatives by Cu(I)-catalyzed Three-component Coupling Reaction

OpenAIRE

Krstulović, Luka; Ismaili, Hamit; Višnjevac, Aleksandar; Glavaš-Obrovac, Ljubica; Žinić, Biserka

2012-01-01

A series of new aliphatic N-sulfonylamidino thymine derivatives containing nucleobase, N-sulfonyl and amidine pharmacophores in the structure were synthesized by Cu(I)-catalyzed threecomponent coupling of 1-propargyl thymine, benzenesulfonyl azides and amines or ammonium salts. Preliminary in vitro antitumor screening (human cervix adenocarcinoma -HeLa and leukemia cells - Jurkat) revealed promising activities of N,N-diethyl- (2) and N-4-cyanobenzyl- (6) derivatives of 4-acetamido...
Cu-catalyzed aerobic oxidative cyclizations of 3-N-hydroxyamino-1,2-propadienes with alcohols, thiols, and amines to form α-O-, S-, and N-substituted 4-methylquinoline derivatives.

Science.gov (United States)

Sharma, Pankaj; Liu, Rai-Shung

2015-03-16

A one-pot, two-step synthesis of α-O-, S-, and N-substituted 4-methylquinoline derivatives through Cu-catalyzed aerobic oxidations of N-hydroxyaminoallenes with alcohols, thiols, and amines is described. This reaction sequence involves an initial oxidation of N-hydroxyaminoallenes with NuH (Nu = OH, OR, NHR, and SR) to form 3-substituted 2-en-1-ones, followed by Brønsted acid catalyzed intramolecular cyclizations of the resulting products. Our mechanistic analysis suggests that the reactions proceed through a radical-type mechanism rather than a typical nitrone-intermediate route. The utility of this new Cu-catalyzed reaction is shown by its applicability to the synthesis of several 2-amino-4-methylquinoline derivatives, which are known to be key precursors to several bioactive molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Facile synthesis of dendritic Cu by electroless reaction of Cu-Al alloys in multiphase solution

Science.gov (United States)

Wang, Ying; Liang, Shuhua; Yang, Qing; Wang, Xianhui

2016-11-01

Two-dimensional nano- or micro-scale fractal dendritic coppers (FDCs) were synthesized by electroless immersing of Cu-Al alloys in hydrochloric acid solution containing copper chloride without any assistance of template or surfactant. The FDC size increases with the increase of Al content in Cu-Al alloys immersed in CuCl2 + HCl solution. Compared to Cu40Al60 and Cu45Al55 alloys, the FDC shows hierarchical distribution and homogeneous structures using Cu17Al83 alloy as the starting alloy. The growth direction of the FDC is , and all angles between the trunks and branches are 60°. Nanoscale Cu2O was found at the edge of FDC. Interestingly, nanoporous copper (NPC) can also be obtained through Cu17Al83 alloy. Studies showed that the formation of FDC depended on two key factors: the potential difference between CuAl2 intermetallic and α-Al phase of dual-phase Cu-Al alloys; a replacement reaction that usually occurs in multiphase solution. The electrochemical experiment further proved that the multi-branch dendritic structure is very beneficial to the proton transfer in the process of catalyzing methanol.
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
Facile synthesis of dendritic Cu by electroless reaction of Cu-Al alloys in multiphase solution

Energy Technology Data Exchange (ETDEWEB)

Wang, Ying; Liang, Shuhua, E-mail: liangxaut@gmail.com; Yang, Qing; Wang, Xianhui

2016-11-30

Highlights: • Nano- or micro-scale fractal dendritic copper (FDC) was synthesized by electroless immersing of Cu-Al alloys in CuCl{sub 2} + HCl. • FDC size increases with the increase of Al content in Cu-Al alloys immersed in CuCl{sub 2} + HCl solution. • Nanoscale Cu{sub 2}O was found at the edge of FDC. Nanoporous copper (NPC) can also be obtained by using Cu{sub 17}Al{sub 83} alloy. • The potential difference between CuAl{sub 2} and α-Al phase and the replacement reaction in multiphase solution are key factors. - Abstract: Two-dimensional nano- or micro-scale fractal dendritic coppers (FDCs) were synthesized by electroless immersing of Cu-Al alloys in hydrochloric acid solution containing copper chloride without any assistance of template or surfactant. The FDC size increases with the increase of Al content in Cu-Al alloys immersed in CuCl{sub 2} + HCl solution. Compared to Cu{sub 40}Al{sub 60} and Cu{sub 45}Al{sub 55} alloys, the FDC shows hierarchical distribution and homogeneous structures using Cu{sub 17}Al{sub 83} alloy as the starting alloy. The growth direction of the FDC is <110>, and all angles between the trunks and branches are 60°. Nanoscale Cu{sub 2}O was found at the edge of FDC. Interestingly, nanoporous copper (NPC) can also be obtained through Cu{sub 17}Al{sub 83} alloy. Studies showed that the formation of FDC depended on two key factors: the potential difference between CuAl{sub 2} intermetallic and α-Al phase of dual-phase Cu-Al alloys; a replacement reaction that usually occurs in multiphase solution. The electrochemical experiment further proved that the multi-branch dendritic structure is very beneficial to the proton transfer in the process of catalyzing methanol.
Supported Single-Site Ti(IV) on a Metal–Organic Framework for the Hydroboration of Carbonyl Compounds

Energy Technology Data Exchange (ETDEWEB)

Huang, Zhiyuan [College; amp, Molecular Sciences, Institute of Advanced Studies, Wuhan University, Wuhan 430072, PR China; Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Liu, Dong [College; amp, Molecular Sciences, Institute of Advanced Studies, Wuhan University, Wuhan 430072, PR China; Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Camacho-Bunquin, Jeffrey [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Zhang, Guanghui [Department; Yang, Dali [College; amp, Molecular Sciences, Institute of Advanced Studies, Wuhan University, Wuhan 430072, PR China; Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; López-Encarnación, Juan M. [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Department; Xu, Yunjie [Department; Ferrandon, Magali S. [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Niklas, Jens [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Poluektov, Oleg G. [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Jellinek, Julius [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Lei, Aiwen [College; amp, Molecular Sciences, Institute of Advanced Studies, Wuhan University, Wuhan 430072, PR China; Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Bunel, Emilio E. [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States; Delferro, Massimiliano [Chemical; amp, Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States

2017-10-10

ABSTRACT: A stable and structurally well-defined titanium alkoxide catalyst supported on a metal-organic-framework (MOF) of UiO-67 topology (ANL1-Ti(OiPr)2) was synthesized and fully characterized by a variety of analytical and spectroscopic techniques, including BET, TGA, PXRD, XAS, DRIFT, SEM, and DFT computations. The Ti-functionalized MOF was demonstrated active for the catalytic hydroboration of a wide range of aldehydes and ketones with HBpin as the boron source. Compared to traditional homogeneous and supported hydroboration catalysts, ANL1-Ti(OiPr)2 is completely recyclable and reusable, making it a promising hydroboration catalyst alternative for green and sustainable chemical synthesis. DFT calculations suggest that the catalytic hydroboration proceeds via a (1) hydride transfer between the active Ti-hydride species and a carbonyl moiety (rate determining step), and (2) alkoxide transfer (intramolecular σ-bond metathesis) to generate the boronate ester product.
Microwave Assisted Expeditious and Green Cu(II-Clay Catalyzed Domino One-Pot Three Component Synthesis of 2H-indazoles

Directory of Open Access Journals (Sweden)

Bashir Ahmad Dar

2018-01-01

How to Cite: Dar, B.A., Safvi, S.W., Rizvi, M.A. (2018. Microwave Assisted Expeditious and Green Cu(II-Clay Catalyzed Domino One-Pot Three Component Synthesis of 2H-indazoles. Bulletin of Chemical Reaction Engineering & Catalysis, 13 (1: 82-88 (doi:10.9767/bcrec.13.1.963.82-88
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.
Synthesis of Imidazopyridines via Copper-Catalyzed, Formal Aza-[3 + 2] Cycloaddition Reaction of Pyridine Derivatives with α-Diazo Oxime Ethers.

Science.gov (United States)

Park, Sangjune; Kim, Hyunseok; Son, Jeong-Yu; Um, Kyusik; Lee, Sooho; Baek, Yonghyeon; Seo, Boram; Lee, Phil Ho

2017-10-06

The Cu-catalyzed, formal aza-[3 + 2] cycloaddition reaction of pyridine derivatives with α-diazo oxime ethers in trifluoroethanol was used to synthesize imidazopyridines via the release of molecular nitrogen and elimination of alcohol. These methods enabled modular synthesis of a wide range of N-heterobicyclic compounds such as imidazopyridazines, imidazopyrimidines, and imidazopyrazines with an α-imino Cu-carbenoid generated from the α-diazo oxime ethers and copper.
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.
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.
Synthesis of Bioactive 2-(Arylaminothiazolo[5,4-f]-quinazolin-9-ones via the Hügershoff Reaction or Cu- Catalyzed Intramolecular C-S Bond Formation

Directory of Open Access Journals (Sweden)

Damien Hédou

2016-06-01

Full Text Available A library of thirty eight novel thiazolo[5,4-f]quinazolin-9(8H-one derivatives (series 8, 10, 14 and 17 was prepared via the Hügershoff reaction and a Cu catalyzed intramolecular C-S bond formation, helped by microwave-assisted technology when required. The efficient multistep synthesis of the key 6-amino-3-cyclopropylquinazolin-4(3H-one (3 has been reinvestigated and performed on a multigram scale from the starting 5-nitroanthranilic acid. The inhibitory potency of the final products was evaluated against five kinases involved in Alzheimer’s disease and showed that some molecules of the 17 series described in this paper are particularly promising for the development of novel multi-target inhibitors of kinases.
Cyclodextrin-Catalyzed Organic Synthesis: Reactions, Mechanisms, and Applications

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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.
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
Hydroboration of Graphene Oxide: Towards Stoichiometric Graphol and Hydroxygraphane

Czech Academy of Sciences Publication Activity Database

Poh, H. L.; Sofer, Z.; Šimek, P.; Tomandl, Ivo; Pumera, M.

2015-01-01

Roč. 21, č. 22 (2015), s. 8130-8136 ISSN 0947-6539 R&D Projects: GA ČR(CZ) GA15-09001S; GA MŠk LM2011019 Institutional support: RVO:61389005 Keywords : boranes * electrochemistry * graphene * hydroboration * synthetic methods Subject RIV: CA - Inorganic Chemistry Impact factor: 5.771, year: 2015

(E)-α,β-unsaturated amides from tertiary amines, olefins and CO via Pd/Cu-catalyzed aerobic oxidative N-dealkylation.

Science.gov (United States)

Shi, Renyi; Zhang, Hua; Lu, Lijun; Gan, Pei; Sha, Yuchen; Zhang, Heng; Liu, Qiang; Beller, Matthias; Lei, Aiwen

2015-02-21

A novel Pd/Cu-catalyzed chemoselective aerobic oxidative N-dealkylation/carbonylation reaction has been developed. Tertiary amines are utilized as a "reservoir" of "active" secondary amines in this transformation, which inhibits the formation of undesired by-products and the deactivation of the catalysts. This protocol allows for an efficient and straightforward construction of synthetically useful and bioactive (E)-α,β-unsaturated amide derivatives from easily available tertiary amines, olefins and CO.
Pyridine synthesis by reactions of allyl amines and alkynes proceeding through a Cu(OAc)2 oxidation and Rh(III)-catalyzed N-annulation sequence.

Science.gov (United States)

Kim, Dong-Su; Park, Jung-Woo; Jun, Chul-Ho

2012-11-28

A new methodology has been developed for the synthesis of pyridines from allyl amines and alkynes, which involves sequential Cu(II)-promoted dehydrogenation of the allylamine and Rh(III)-catalyzed N-annulation of the resulting α,β-unsaturated imine and alkyne.
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.
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.
Solvent effect on copper-catalyzed azide-alkyne cycloaddition (CuAAC): synthesis of novel triazolyl substituted quinolines as potential anticancer agents.

Science.gov (United States)

Ellanki, Amarender Reddy; Islam, Aminul; Rama, Veera Swamy; Pulipati, Ranga Prasad; Rambabu, D; Krishna, G Rama; Reddy, C Malla; Mukkanti, K; Vanaja, G R; Kalle, Arunasree M; Kumar, K Shiva; Pal, Manojit

2012-05-15

A regioselective route to novel mono triazolyl substituted quinolines has been developed via copper-catalyzed azide-alkyne cycloaddition (CuAAC) of 2,4-diazidoquinoline with terminal alkynes in DMF. The reaction provided bis triazolyl substituted quinolines when performed in water in the presence of Et(3)N. A number of the compounds synthesized showed promising anti-proliferative properties when tested in vitro especially against breast cancer cells. Copyright © 2012 Elsevier Ltd. All rights reserved.
Copper-catalyzed azide alkyne cycloaddition polymer networks

Science.gov (United States)

Alzahrani, Abeer Ahmed

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

Science.gov (United States)

Pekala, Katarzyna; Jurczakowski, Rafał; Lewera, Adam; Orlik, Marek

2007-05-10

The oscillatory oxidation of thiocyanate ions with hydrogen peroxide, catalyzed by Cu2+ ions in alkaline media, was so far observed as occurring simultaneously in the entire space of the batch or flow reactor. We performed this reaction for the first time in the thin-layer reactor and observed the spatiotemporal course of the above process, in the presence of luminol as the chemiluminescent indicator. A series of luminescent patterns periodically starting from the random reaction center and spreading throughout the entire solution layer was reported. For a batch-stirred system, the bursts of luminescence were found to correlate with the steep decreases of the oscillating Pt electrode potential. These novel results open possibilities for further experimental and theoretical investigations of those spatiotemporal patterns, including studies of the mechanism of this chemically complex process.
In Situ Imaging the Oxygen Reduction Reactions of Solid State Na-O2 Batteries with CuO Nanowires as the Air Cathode.

Science.gov (United States)

Liu, Qiunan; Yang, Tingting; Du, Congcong; Tang, Yongfu; Sun, Yong; Jia, Peng; Chen, Jingzhao; Ye, Hongjun; Shen, Tongde; Peng, Qiuming; Zhang, Liqiang; Huang, Jianyu

2018-05-14

We report real time imaging of the oxygen reduction reactions (ORRs) in all solid state sodium oxygen batteries (SOBs) with CuO nanowires (NWs) as the air cathode in an aberration-corrected environmental transmission electron microscope under an oxygen environment. The ORR occurred in a distinct two-step reaction, namely, a first conversion reaction followed by a second multiple ORR. In the former, CuO was first converted to Cu 2 O and then to Cu; in the latter, NaO 2 formed first, followed by its disproportionation to Na 2 O 2 and O 2 . Concurrent with the two distinct electrochemical reactions, the CuO NWs experienced multiple consecutive large volume expansions. It is evident that the freshly formed ultrafine-grained Cu in the conversion reaction catalyzed the latter one-electron-transfer ORR, leading to the formation of NaO 2 . Remarkably, no carbonate formation was detected in the oxygen cathode after cycling due to the absence of carbon source in the whole battery setup. These results provide fundamental understanding into the oxygen chemistry in the carbonless air cathode in all solid state Na-O 2 batteries.
A Mechanistic Study of Hydroboration of 1-Octene with 1,3,2 ...

African Journals Online (AJOL)

dithiaborinane in their ground states have been studied using density functional theory (DFT) at the B3LYP/3-21+G and B3LYP/6-31+G(d) levels. Hydroboration and disproportionation transition states have been determined and activation energies ...
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.
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.
Primary Alcohols from Terminal Olefins: Formal Anti-Markovnikov Hydration via Triple Relay Catalysis

KAUST Repository

Dong, G.

2011-09-15

Alcohol synthesis is critical to the chemical and pharmaceutical industries. The addition of water across olefins to form primary alcohols (anti-Markovnikov olefin hydration) would be a broadly useful reaction but has largely proven elusive; an indirect hydroboration/oxidation sequence requiring stoichiometric borane and oxidant is currently the most practical methodology. Here, we report a more direct approach with the use of a triple relay catalysis system that couples palladium-catalyzed oxidation, acid-catalyzed hydrolysis, and ruthenium-catalyzed reduction cycles. Aryl-substituted terminal olefins are converted to primary alcohols by net reaction with water in good yield and excellent regioselectivity.
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.
Selective C–C Coupling Reaction of Dimethylphenol to Tetramethyldiphenoquinone Using Molecular Oxygen Catalyzed by Cu Complexes Immobilized in Nanospaces of Structurally-Ordered Materials

Directory of Open Access Journals (Sweden)

Zen Maeno

2015-02-01

Full Text Available Two high-performance Cu catalysts were successfully developed by immobilization of Cu ions in the nanospaces of poly(propylene imine (PPI dendrimer and magadiite for the selective C–C coupling of 2,6-dimethylphenol (DMP to 3,3',5,5'-tetramethyldiphenoquinone (DPQ with O2 as a green oxidant. The PPI dendrimer encapsulated Cu ions in the internal nanovoids to form adjacent Cu species, which exhibited significantly high catalytic activity for the regioselective coupling reaction of DMP compared to previously reported enzyme and metal complex catalysts. The magadiite-immobilized Cu complex acted as a selective heterogeneous catalyst for the oxidative C–C coupling of DMP to DPQ. This heterogeneous catalyst was recoverable from the reaction mixture by simple filtration, reusable without loss of efficiency, and applicable to a continuous flow reactor system. Detailed characterization using ultraviolet-visible (UV-vis, Fourier transform infrared (FTIR, electronic spin resonance (ESR, and X-ray absorption fine structure (XAFS spectroscopies and the reaction mechanism investigation revealed that the high catalytic performances of these Cu catalysts were ascribed to the adjacent Cu species generated within the nanospaces of the PPI dendrimer and magadiite.
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.
Simple introduction of anion trapping site to polymer electrolytes through dehydrocoupling or hydroboration reaction using 9-borabicyclo[3.3.1]nonane

International Nuclear Information System (INIS)

Mizumo, Tomonobu; Sakamoto, Kenji; Matsumi, Noriyoshi; Ohno, Hiroyuki

2005-01-01

Organoboron-based anion trapping polymer electrolytes were synthesized through hydroboration or dehydrocoupling reaction between poly(propylene oxide) (PPO) oligomer (M n =400, 1200, 2000 and 4000) and 9-borabicyclo[3.3.1]nonane (9-BBN). Obtained oligomers were added various lithium salts (LiN(CF 3 SO 2 ) 2 , LiSO 3 CF 3 , LiCO 2 CF 3 or LiBr) to analyze the ionic conductivity and lithium ion transference number (t Li + ). The ionic conductivity of the oligomer in the presence of LiN(CF 3 SO 2 ) 2 showed higher ionic conductivity than other systems, however, the t Li + was less than 0.3. When LiSO 3 CF 3 or LiCO 2 CF 3 , was added high t Li + over 0.6 was obtained. Such difference in t Li + can be explained by HSAB principle. Since boron is a hard acid, soft (CF 3 SO 2 ) 2 N - anion can not be trapped effectively. High ionic conductivity of 1.3x10 -6 Scm -1 and high t Li + of 0.73 was obtained when PPO chain length was 2000. These values of facilely prepared polymer electrolytes are comparable to those of the PPOs having covalently bonded salt moieties on the chain ends

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.
CuI-catalyzed photochemical or thermal reactions of 3-(2-azidobenzylidene)lactams. Application to the synthesis of fused indoles.

Science.gov (United States)

Shi, Zongjun; Ren, Yuwei; Li, Bing; Lu, Shenci; Zhang, Wei

2010-06-14

Photochemical or thermal reactions of 3-(2-azidobenzylidene)-lactams afforded fused indoles such as indolo[3,2-c]quinolin-6-ones, pyrido[4,3-b]indol-1-ones and other similar compounds in moderate to high yields via cyclization-ring expansion reactions. The photolytic process was much more facile than the thermal process and could be further improved by addition of CuI.
CuInSe2 nano-crystallite reaction kinetics using solid state reaction from Cu2Se and In2Se3 powders

International Nuclear Information System (INIS)

Hsiang, Hsing-I; Lu, Li-Hsin; Chang, Yu-Lun; Ray, Dahtong; Yen, Fu-Su

2011-01-01

Highlights: → CuInSe 2 phase increased gradually accompanied with a decrease in γ-In 2 Se 3 and no intermediate phase during calcination. → CuInSe 2 formation from Cu 2 Se and In 2 Se 3 powders follows a one-dimensional diffusion-controlled reaction with apparent activation energy of about 122.5 kJ/mol. → The solid reaction kinetics may be dominated by the diffusion of In 3+ ions. - Abstract: The reaction mechanism and CuInSe 2 formation kinetics using a solid state reaction from Cu 2 Se and In 2 Se 3 powders synthesized using a heating up process were investigated using X-ray diffractomy (XRD) and transmission electron microscopy (TEM). It was observed that the CuInSe 2 phase increased gradually, accompanied with a decrease in γ-In 2 Se 3 with no intermediate phase as the calcination temperature and soaking time were increased. The reaction kinetics was analyzed using the Avrami and polynomial kinetic model, suggesting that CuInSe 2 formation from Cu 2 Se and In 2 Se 3 powders follows a diffusion-controlled reaction with an apparent activation energy of about 122.5-182.3 kJ/mol. Cu 2 Se and In 2 Se 3 phases react and directly transform into CIS without the occurrence of any intermediate phase and the size of the newly formed CuInSe 2 crystallites was close to that of the Cu 2 Se reactant particle based on the TEM results, which indicated that the solid reaction kinetics may be dominated by the diffusion of In 3+ ions.
An Efficient and Practical Process for Pd/Cu Cocatalyzed Homocoupling Reaction of Terminal Alkynes Using Sodium Percarbonate as a Dual Reagent in Aqueous Media

Institute of Scientific and Technical Information of China (English)

ZHOU, Lei; ZHAN, Hai-Ying; LIU, Hai-Ling; JIANG, Huan-Feng

2007-01-01

A new process for the Pd/Cu co-catalyzed homocoupling reaction of terminal alkynes was developed. The reaction was carried out in aqueous media with sodium percarbonate as both a clean oxidant and a base. Meanwhile, a palladium complex immobilized on a synthetic PS-PEG400-PPh2 resin was used as the catalyst, which may be recovered by simple filtration and reused for several times with high activity.
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
Failure and Redemption of Statistical and Nonstatistical Rate Theories in the Hydroboration of Alkenes.

Science.gov (United States)

Bailey, Johnathan O; Singleton, Daniel A

2017-11-08

Our previous work found that canonical forms of transition state theory incorrectly predict the regioselectivity of the hydroboration of propene with BH 3 in solution. In response, it has been suggested that alternative statistical and nonstatistical rate theories can adequately account for the selectivity. This paper uses a combination of experimental and theoretical studies to critically evaluate the ability of these rate theories, as well as dynamic trajectories and newly developed localized statistical models, to predict quantitative selectivities and qualitative trends in hydroborations on a broader scale. The hydroboration of a series of terminally substituted alkenes with BH 3 was examined experimentally, and a classically unexpected trend is that the selectivity increases as the alkyl chain is lengthened far from the reactive centers. Conventional and variational transition state theories can predict neither the selectivities nor the trends. The canonical competitive nonstatistical model makes somewhat better predictions for some alkenes but fails to predict trends, and it performs poorly with an alkene chosen to test a specific prediction of the model. Added nonstatistical corrections to this model make the predictions worse. Parametrized Rice-Ramsperger-Kassel-Marcus (RRKM)-master equation calculations correctly predict the direction of the trend in selectivity versus alkene size but overpredict its magnitude, and the selectivity with large alkenes remains unpredictable with any parametrization. Trajectory studies in explicit solvent can predict selectivities without parametrization but are impractical for predicting small changes in selectivity. From a lifetime and energy analysis of the trajectories, "localized RRKM-ME" and "competitive localized noncanonical" rate models are suggested as steps toward a general model. These provide the best predictions of the experimental observations and insight into the selectivities.
Enzyme-catalyzed and binding reaction kinetics determined by titration calorimetry.

Science.gov (United States)

Hansen, Lee D; Transtrum, Mark K; Quinn, Colette; Demarse, Neil

2016-05-01

Isothermal calorimetry allows monitoring of reaction rates via direct measurement of the rate of heat produced by the reaction. Calorimetry is one of very few techniques that can be used to measure rates without taking a derivative of the primary data. Because heat is a universal indicator of chemical reactions, calorimetry can be used to measure kinetics in opaque solutions, suspensions, and multiple phase systems and does not require chemical labeling. The only significant limitation of calorimetry for kinetic measurements is that the time constant of the reaction must be greater than the time constant of the calorimeter which can range from a few seconds to a few minutes. Calorimetry has the unique ability to provide both kinetic and thermodynamic data. This article describes the calorimetric methodology for determining reaction kinetics and reviews examples from recent literature that demonstrate applications of titration calorimetry to determine kinetics of enzyme-catalyzed and ligand binding reactions. A complete model for the temperature dependence of enzyme activity is presented. A previous method commonly used for blank corrections in determinations of equilibrium constants and enthalpy changes for binding reactions is shown to be subject to significant systematic error. Methods for determination of the kinetics of enzyme-catalyzed reactions and for simultaneous determination of thermodynamics and kinetics of ligand binding reactions are reviewed. Copyright © 2015 Elsevier B.V. All rights reserved.
Rhodium-catalyzed asymmetric hydroboration of γ,δ-unsaturated amide derivatives: δ-borylated amides.

Science.gov (United States)

Hoang, G L; Zhang, S; Takacs, J M

2018-05-08

γ,δ-Unsaturated amides in which the alkene moiety bears an aryl or heteroaryl substituent undergo regioselective rhodium-catalyzed δ-borylation by pinacolborane to afford chiral secondary benzylic boronic esters. The results contrast the γ-borylation of γ,δ-unsaturated amides in which the disubstituted alkene moiety bears only alkyl substituents; the reversal in regiochemistry is coupled with a reversal in the sense of π-facial selectivity.
AuCu@Pt Nanoalloys for Catalytic Application in Reduction of 4-Nitrophenol

Directory of Open Access Journals (Sweden)

Sadia Mehmood

2016-01-01

Full Text Available To enhance and optimize nanocatalyst ability for nitrophenol (4-NP reduction reaction we look beyond Au-metal nanoparticles and describe a new class of Au nanoalloys with controlled composition for core of AuCu-metals and Pt-metal shell. The reduction of 4-NP was investigated in aqueous media spectroscopically on 7.8 nm Au nanospheres (AuNSs, 8.3 nm AuCuNSs, and 9.1 nm AuCu@Pt core-shell NSs in diameter. The rate constants of the catalyzed reaction at room temperature, activation energies, and entropies of activation of reactions catalyzed by the AuCu@Pt core-shell NSs are found to have different values to those of the pure metal NSs. The results strongly support the proposal that catalysis by nanoparticles is taking place efficiently on the surface of NSs. These core-shell nanocatalysts exhibited stability throughout the reduction reaction and proved that heterogonous type mechanisms are most likely to be dominant in nanoalloy based catalysis if the surface of the NSs is not defected upon shell incorporation.
Sonogashira Reaction of Aryl and Heteroaryl Halides with Terminal Alkynes Catalyzed by a Highly Efficient and Recyclable Nanosized MCM-41 Anchored Palladium Bipyridyl Complex

Directory of Open Access Journals (Sweden)

Chung-Yuan Mou

2010-12-01

Full Text Available A heterogeneous catalyst, nanosized MCM-41-Pd, was used to catalyze the Sonogashira coupling of aryl and heteroaryl halides with terminal alkynes in the presence of CuI and triphenylphosphine. The coupling products were obtained in high yields using low Pd loadings to 0.01 mol%, and the nanosized MCM-41-Pd catalyst was recovered by centrifugation of the reaction solution and re-used in further runs without significant loss of reactivity.
Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

DEFF Research Database (Denmark)

Beier, Matthias Josef

Heterogeneously catalyzed selective oxidation reactions have attracted a lot of attention in recent time. The first part of the present thesis provides an overview over heterogeneous copper and silver catalysts for selective oxidations in the liquid phase and compared the performance and catalytic...... that both copper and silver can function as complementary catalyst materials to gold showing different catalytic properties and being more suitable for hydrocarbon oxidation reactions. Potential opportunities for future research were outlined. In an experimental study, the potential of silver as a catalyst...... revealed that all catalysts were more active in combination with ceria nanoparticles and that under the tested reaction conditions silver was equally or even more efficient than the gold catalysts. Calcination at 900 °C of silver on silica prepared by impregnation afforded a catalyst which was used...
Stability and dynamics of reactors with heterogeneously catalyzed reactions

Energy Technology Data Exchange (ETDEWEB)

Eigenberger, G [BASF A.G., Ludwigshafen am Rhein (Germany, F.R.)

1978-12-01

Our knowledge of causes and consequences of problems arising from instability and dynamic effects in reactors with heterogeneously catalyzed reactions has increased remarkably in recent years. Especially thermal effects, caused by the self-acceleration of an exothermic reaction in combination with heat and mass transport, are now well understood. In addition, kinetic effects, i.e. phenomena which have to be explained by the kinetic peculiarities of surface reactions, have attracted increasing interest. For both cases the state of the art will be reviewed, highlighting the physical and chemical causes of the observed phenomena.
Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

Energy Technology Data Exchange (ETDEWEB)

Klobukowski, Erik [Iowa State Univ., Ames, IA (United States)

2011-01-01

This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system and
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.
Synthesis of E-Alkyl Alkenes from Terminal Alkynes via Ni-Catalyzed Cross-Coupling of Alkyl Halides with B-Alkenyl-9-borabicyclo[3.3.1]nonanes.

Science.gov (United States)

Di Franco, Thomas; Epenoy, Alexandre; Hu, Xile

2015-10-02

The first Ni-catalyzed Suzuki-Miyaura coupling of alkyl halides with alkenyl-(9-BBN) reagents is reported. Both primary and secondary alkyl halides including alkyl chlorides can be coupled. The coupling method can be combined with hydroboration of terminal alkynes, allowing the expedited synthesis of functionalized alkyl alkenes from readily available alkynes with complete (E)-selectivity in one pot. The method was applied to the total synthesis of (±)-Recifeiolide, a natural macrolide.
Synthesis, characterization and catalytic property of CuO and Ag/CuO nanoparticles for the epoxidation of styrene

Energy Technology Data Exchange (ETDEWEB)

Lashanizadegan, Maryam; Erfaninia, Nasrin [Alzahra University, Tehran (Iran, Islamic Republic of)

2013-11-15

CuO nanorodes, CuO nanoplates and Ag/CuO nanoparticles were synthesized in the presence of polyethylene glycol by depositional in alkaline environment. Oxide nanoparticles were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared absorption spectra (FT-IR). CuO and Ag/CuO nanoparticles show high catalytic activity for the selective epoxidation of styrene to styrene oxide by TBHP. Under the optimized reaction condition, the oxidation of styrene catalyzed by CuO nanorods gave 100% conversion with 60 and 35% styrene oxide and benzaldehyde, respectively. Ag/CuO gave 99% conversion and styrene oxide (71%) and benzaldehyde (12%) being the major product.
The chemisorption and reactions of formic acid on Cu films on ZnO (000 overline1)-O

Science.gov (United States)

Ludviksson, A.; Zhang, R.; Campbell, Charles T.; Griffiths, K.

1994-06-01

The adsorption and reactions of formic acid (HCOOD : HCOOH = 3:1) on the oxygen-terminated ZnO(0001¯)-O surface and on thin Cu films deposited on the ZnO(0001¯)-O surface have been studied with temperature programmed desorption (TPD) and XPS. Small amounts of formic acid dissociate at defect sites on clean ZnO(0001¯)-O to yield surface formate (HCOO). The acid D(H) from this dissociation does not reappear in TPD, and is lost to the ZnO bulk, as confirmed by nuclear reaction analysis. The surface HCOO decomposes to yield nearly simultaneous CO 2 (37%), CO (63%) and H 2 TPD peaks at 560 K. Substantial amounts of D (˜ 20%) are incorporated in this hydrogen TPD peak resulting from formate decomposition at ZnO defects, indicating that bulk D is readily accessible. Submonolayer and multilayer Cu films that are deposited at 130 K and partially cover the ZnO surface as 2D and 3D islands adsorb formic acid and decompose it into formate and hydrogen much like the Cu(110) surface. The surface formate from the Cu film decomposes at 470-500 K to give primarily CO 2 and H 2, also much like Cu(110), although atom-thin Cu islands also give ˜ 40% CO. Annealed Cu films give formate decomposition peaks at 25-50 K lower in temperature, attributed to thickening and ordering of the Cu islands to form Cu(111)-like sites. The acid D(H) atom from the formic acid is partially lost by hydrogen spillover from the Cu islands into the ZnO substrate, especially for thin Cu films. This effect partially desorbs and is enhanced upon preannealing the Cu layers, due to increased H diffusion rates across the annealed Cu islands, and/or the decrease in island size. Bulk D(H) is slowly removed as D 2, HD and H 2 above 400 K in diffusion-limited desorption, catalyzed by Cu.
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.
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.
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

Influence of hydroxylamine conformation on stereocontrol in Pd-catalyzed isoxazolidine-forming reactions.

Science.gov (United States)

Lemen, Georgia S; Giampietro, Natalie C; Hay, Michael B; Wolfe, John P

2009-03-20

Palladium-catalyzed carboamination reactions between N-Boc-O-(but-3-enyl)hydroxylamine derivatives and aryl or alkenyl bromides afford cis-3,5- and trans-4,5-disubstituted isoxazolidines in good yield with up to >20:1 dr. The diastereoselectivity observed in the formation of cis-3,5-disubstituted isoxazolidines is superior to selectivities typically obtained in other transformations, such as 1,3-dipolar cycloaddition reactions, that provide these products. In addition, the stereocontrol in the C-N bond-forming Pd-catalyzed carboamination reactions of N-Boc-O-(but-3-enyl)hydroxylamines is significantly higher than that of related C-O bond-forming carboetherification reactions of N-benzyl-N-(but-3-enyl)hydroxylamine derivatives. This is likely due to a stereoelectronic preference for cyclization via transition states in which the Boc group is placed in a perpendicular orientation relative to the plane of the developing ring, which derives from the conformational equilibria of substituted hydroxylamines.
Post Modification of Acetylene Functional Poly(oxindole biphenylylene) by Photoinduced CuAAC

KAUST Repository

Arslan, Mustafa; Cem Bicak, Tugrul; Pulido, Bruno; Nunes, Suzana Pereira; Yagci, Yusuf

2018-01-01

A novel strategy to obtain side chain modified poly(oxindole biphenylylene) (POXI) by photoinduced copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click reaction is described. In the first step, an alkyne-functionalized poly(oxindolebiphenylylene) (POXI-alkyne) is synthesized by superacid-catalyzed condensation of isatin with aromatic hydrocarbons. Subsequently, poly(ethylene glycol) methyl ether (Me-PEG), 1-pyrenemethanol (Py-OH) and 1,3-dibromopropane (DBP) are functionalized by azide groups via simple nucleophilic substitution reaction. Visible-light-induced CuAAC reaction between POXI-alkyne and the corresponding azide functionalized click components employing dibenzoyldiethylgermane (DBDEG) as photoactivator resulted in the formation of POXI-PEG, POXI-Py and insoluble network, respectively. Successful modification of POXI was confirmed by the spectral, (1H NMR, FT-IR, Fluorescence), chromatographic (GPC) and thermal (DSC) investigations.
Post Modification of Acetylene Functional Poly(oxindole biphenylylene) by Photoinduced CuAAC

KAUST Repository

Arslan, Mustafa

2018-02-08

A novel strategy to obtain side chain modified poly(oxindole biphenylylene) (POXI) by photoinduced copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click reaction is described. In the first step, an alkyne-functionalized poly(oxindolebiphenylylene) (POXI-alkyne) is synthesized by superacid-catalyzed condensation of isatin with aromatic hydrocarbons. Subsequently, poly(ethylene glycol) methyl ether (Me-PEG), 1-pyrenemethanol (Py-OH) and 1,3-dibromopropane (DBP) are functionalized by azide groups via simple nucleophilic substitution reaction. Visible-light-induced CuAAC reaction between POXI-alkyne and the corresponding azide functionalized click components employing dibenzoyldiethylgermane (DBDEG) as photoactivator resulted in the formation of POXI-PEG, POXI-Py and insoluble network, respectively. Successful modification of POXI was confirmed by the spectral, (1H NMR, FT-IR, Fluorescence), chromatographic (GPC) and thermal (DSC) investigations.
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...
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
Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration.

Science.gov (United States)

Grigg, R David; Van Hoveln, Ryan; Schomaker, Jennifer M

2012-10-03

A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring bromine or iodine from a sp(2) to a benzylic carbon with concomitant borylation of the Ar-X bond. The resulting benzyl halide can be reacted in the same vessel under a variety of conditions to form an additional carbon-heteroatom bond. Cross-over experiments using an isotopically enriched bromide source support intramolecular transfer of Br. The reaction is postulated to proceed via a Markovnikov hydrocupration of the o-halostyrene, oxidative addition of the resulting Cu(I) complex into the Ar-X bond, reductive elimination of the new sp(3) C-X bond, and final borylation of an Ar-Cu(I) species to turn over the catalytic cycle.
From ketones to esters by a Cu-catalyzed highly selective C(CO)-C(alkyl) bond cleavage: aerobic oxidation and oxygenation with air.

Science.gov (United States)

Huang, Xiaoqiang; Li, Xinyao; Zou, Miancheng; Song, Song; Tang, Conghui; Yuan, Yizhi; Jiao, Ning

2014-10-22

The Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. (18)O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process.
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...
Sequential Au(I-catalyzed reaction of water with o-acetylenyl-substituted phenyldiazoacetates

Directory of Open Access Journals (Sweden)

Jianbo Wang

2011-05-01

Full Text Available The gold(I-catalyzed reaction of water with o-acetylenyl-substituted phenyldiazoacetates provides 1H-isochromene derivatives in good yields. The reaction follows a catalytic sequence of gold carbene formation/water O–H insertion/alcohol-alkyne cyclization. The gold(I complex is the only catalyst in each of these steps.
Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature.

Science.gov (United States)

Kim, Jinho; Stahl, Shannon S

2013-07-05

An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4'- t Bu 2 bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one N -oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst is the turnover-limiting step of the reaction.
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...
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.
Palladium-catalyzed ring-opening reactions of cyclopropanated 7-oxabenzonorbornadiene with alcohols

Directory of Open Access Journals (Sweden)

Katrina Tait

2016-10-01

Full Text Available Palladium-catalyzed ring-opening reactions of cyclopropanated 7-oxabenzonorbornadiene derivatives using alcohol nucleophiles were investigated. The optimal conditions were found to be 10 mol % PdCl2(CH3CN2 in methanol, offering yields up to 92%. The reaction was successful using primary, secondary and tertiary alcohol nucleophiles and was compatible with a variety of substituents on cyclopropanated oxabenzonorbornadiene. With unsymmetrical C1-substituted cyclopropanated 7-oxabenzonorbornadienes, the regioselectivity of the reaction was excellent, forming only one regioisomer in all cases.
Synthesis of polystyrene with high melting temperature through BDE/CuCl catalyzed polymerization

Institute of Scientific and Technical Information of China (English)

WAN; Xiaolong

2001-01-01

［1］Ewen, J. A., Novel method for plastic production, Science (in Chinese), 1997, 9: 34.［2］Brintzinger, H. H., Fischer, D., Waymouth, R. M. et al., Stereospecific olefin polymerization with chiral metallocene catalysts, Angewandte Chemie International Edition in English, 1995, 34(11): 1143.［3］Matyjaszewski, K., Atom transfer radical polymerization, role of various components and reaction conditions, Polym. Prep., 1997, 38(2): 736.［4］Wang, J. S., Matyjaszewski, K., Controlled/"living" radical polymerization, atom transfer radical polymerization in the presence of transition-metal complex, J. Am. Soc., 1995, 117: 5614.［5］Wang, J. S., Matyjaszewski, K., Controlled/"living" radical polymerization, halogen atom transfer radical polymerization promoted by a Cu(I)/Cu(II) redox process, Macromolecules, 1995, 28: 7901.［6］Koto, M., Kamigaito, M., Sawamoto, M. et al., Polymerization of methyl methacrylate with the carbon tetrachloride/dichloro-tris(triphenyphosphine) ruthenium(II)/methylaluminum bis(2,6-di-tert-butylphenoxide) initiating system: possible of living radical polymerization, Macromolecules, 1995, 28: 1721.［7］Ando, T., Kato, M., Living radical polymerization of methyl methacrylate with Ruthenium complex: formation of polymers with controlled molecular weights and very narrow distributions, Macromolecules, 1996, 29: 1070.［8］Granel, C., Dubios, P., Jerome, R. et al., Controlled radical polymerization of methacrylic monomers in the presence of a bis(ortho-chelated) arylnickel(II) complex and different activated alkyl halides, Macromolecules, 1996, 29: 8576.［9］Granel, C., Moineau, G., Lecome, P. et al., (Meth)acrylates pseudo-living radical polymerization in the presence of transition metal complexes: the kharasch reaction revisited, Polym. Prep., 1997, 38(1): 450.［10］Ando, T., Kamigaito, M., Sawamoto, M., Iron(II) chloride complex for living radical polymerization of methyl methacrylate, Macromolecules, 1997, 30: 4507.［11�
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.
Redox reactions of Cu(II)-amine complexes in aqueous solutions

International Nuclear Information System (INIS)

Kumbhar, A.G.; Kishore, Kamal

2003-01-01

A number of amines can be employed for all volatile treatment (AVT) of steam generator (SG) systems of nuclear power reactors. These amines form complexes with Cu 2+ and Ni 2+ ions which come into water due to corrosion. The redox reactions of a number of Cu(II)-AVT amine complexes and the stability of the transient species formed have been studied by pulse radiolysis technique. Rate constants for the reaction of e aq - with a number of Cu(II)-amine complexes have been determined by following the decay of e aq - absorption. Stability of Cu(I)-amine complexes was studied by following the kinetics of the bleaching signal formed at the λ max of the Cu(II) amine complex. Except for Cu(I)-triethanolamine complex all other Cu(I)-amine complexes were found to be stable. One-electron oxidation of Cu(II) amine complexes was studied using azidyl radicals for the oxidation reaction as OH radicals react with the alcohol groups present in the amines used in this study. Cu(III)-amine complexes were found to be unstable and decayed by second-order kinetics
Scalable production of Cu@C composites for cross-coupling catalysis

Energy Technology Data Exchange (ETDEWEB)

Bu, Lijuan [Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education), College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081 (China); Ming, Hai, E-mail: lunaticmh@163.com [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China)

2015-10-15

Highlights: • Cu@C core–shell composite was prepared by reduction of [Cu(NH{sub 3}){sub 4}]{sup 2+} with glucose. • The carbon shell in Cu@C can be tuned to the different degree of carbonization. • The Cu@C composites were utilized to catalyze the C−N cross coupling reaction. • The catalytic ability of Cu@C depends on the degree of shell-carbonization. - Abstract: A novel Cu@C core–shell microstructure was prepared by reduction of [Cu(NH{sub 3}){sub 4}]{sup 2+} with glucose using a mild hydrothermal process. The carbon shell of such Cu@C composite can be tuned to different carbonization degrees just through varying the calcination conditions. The structural properties of as-prepared Cu@C were investigated in detail by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron micrographs (TEM) and Raman spectra. In addition, these Cu@C composites were firstly used to catalyze the C−N cross coupling of amines with iodobenzene. Among them, the catalytic ability of Cu@C composites increased as their surface carbon’s carburization degree improved.
Photonuclear spallation reactions in Cu

International Nuclear Information System (INIS)

Shibata, S.; Imamura, M.; Miyachi, T.

1986-06-01

Formation yields of 24 radioactive nuclides by the interaction of bremsstrahlung in the maximum end-point energies of 100 MeV - 1 GeV with Cu have been measured by direct γ-ray counting of irradiated targets. The yields in the mass range of 42 to 60 except for 60 Cu were analysed by non-linear least-squares fit to construct the mass yield and charge dispersion curves in spallation reactions. From the parameter values obtained, the energy dependence of the slope of the mass yield curve and the relationship between target N/Z and the most probable product N/Z were investigated in comparison with the results of proton, α and heavy ion-induced spallations of Cu. The characteristics of photon-induced spallations are discussed. (author)
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.
Synthesis of 2-vinylic indoles and derivatives via a Pd-catalyzed tandem coupling reaction.

Science.gov (United States)

Fayol, Aude; Fang, Yuan-Qing; Lautens, Mark

2006-09-14

A novel one-step synthesis of valuable 2-vinylic indoles and their tricycle derivatives is described. This reaction, which utilizes a gem-dibromovinyl unit as a readily available starting material, occurs via an efficient Pd-catalyzed tandem Buchwald-Hartwig/Heck reaction.

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...
Fully recoverable rigid shape memory foam based on copper-catalyzed azide-alkyne cycloaddition (CuAAC) using a salt leaching technique.

Science.gov (United States)

Alzahrani, Abeer A; Saed, Mohand; Yakacki, Christopher M; Song, Han Byul; Sowan, Nancy; Walston, Joshua J; Shah, Parag K; McBride, Matthew K; Stansbury, Jeffrey W; Bowman, Christopher N

2018-01-07

This study is the first to employ the use of the copper-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization to form a tough and stiff, porous material from a well-defined network possessing a high glass transition temperature. The effect of the network linkages formed as a product of the CuAAC reaction, i.e., the triazoles, on the mechanical behavior at high strain was evaluated by comparing the CuAAC foam to an epoxy-amine-based foam, which consisted of monomers with similar backbone structures and mechanical properties (i.e., T g of 115 °C and a rubbery modulus of 1.0 MPa for the CuAAC foam, T g of 125 °C and a rubbery modulus of 1.2 MPa for the epoxy-amine foam). When each foam was compressed uniformly to 80% strain at ambient temperature, the epoxy-amine foam was severely damaged after only reaching 70% strain in the first compression cycle with a toughness of 300 MJ/m 3 . In contrast, the CuAAC foam exhibited pronounced ductile behavior in the glassy state with three times higher toughness of 850 MJ/m 3 after the first cycle of compression to 80% strain. Additionally, when the CuAAC foam was heated above T g after each of five compression cycles to 80% strain at ambient temperature, the foam completely recovered its original shape while exhibiting a gradual decrease in mechanical performance over the multiple compression cycles. The foam demonstrated almost complete shape fixity and recovery ratios even through five successive cycles, indicative of "reversible plasticity", making it highly desirable as a glassy shape memory foams.
Mechanism and the origins of stereospecificity in copper-catalyzed ring expansion of vinyl oxiranes: a traceless dual transition-metal-mediated process.

Science.gov (United States)

Mustard, Thomas J L; Mack, Daniel J; Njardarson, Jon T; Cheong, Paul Ha-Yeon

2013-01-30

Density functional theory computations of the Cu-catalyzed ring expansion of vinyloxiranes is mediated by a traceless dual Cu(I)-catalyst mechanism. Overall, the reaction involves a monomeric Cu(I)-catalyst, but a single key step, the Cu migration, requires two Cu(I)-catalysts for the transformation. This dual-Cu step is found to be a true double Cu(I) transition state rather than a single Cu(I) transition state in the presence of an adventitious, spectator Cu(I). Both Cu(I) catalysts are involved in the bond forming and breaking process. The single Cu(I) transition state is not a stationary point on the potential energy surface. Interestingly, the reductive elimination is rate-determining for the major diastereomeric product, while the Cu(I) migration step is rate-determining for the minor. Thus, while the reaction requires dual Cu(I) activation to proceed, kinetically, the presence of the dual-Cu(I) step is untraceable. The diastereospecificity of this reaction is controlled by the Cu migration step. Suprafacial migration is favored over antarafacial migration due to the distorted Cu π-allyl in the latter.
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
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.
Pd-catalyzed ethylene methoxycarbonylation with Brønsted acid ionic liquids as promoter and phase-separable reaction media

DEFF Research Database (Denmark)

Garcia-Suarez, Eduardo J.; Khokarale, Santosh Govind; Nguyen van Buu, Olivier

2014-01-01

Brønsted acid ionic liquids (BAILs) were prepared and applied as combined acid promoters and reaction media in Pd–phosphine catalyzed methoxycarbonylation of ethylene to produce methyl propionate. The BAILs served as alternatives to common mineral acids required for the reaction, e.g. methanesulf......Brønsted acid ionic liquids (BAILs) were prepared and applied as combined acid promoters and reaction media in Pd–phosphine catalyzed methoxycarbonylation of ethylene to produce methyl propionate. The BAILs served as alternatives to common mineral acids required for the reaction, e...
Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature

OpenAIRE

Kim, Jinho; Stahl, Shannon S.

2013-01-01

An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4′-tBu2bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one N-oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst...
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
Mechanistic Insights into Solvent and Ligand Dependency in Cu(I)-Catalyzed Allylic Alkylation with gem-Diborylalkanes.

Science.gov (United States)

Zhang, Qi; Wang, Bing; Liu, Jia-Qin; Fu, Yao; Wu, Yu-Cheng

2018-01-19

The recent Cu-catalyzed allylic substitution reaction between gem-diboryalkane and allyl electrophiles shows intriguing solvent and ligand-controlled regioselectivity. The α-alkylation product was obtained in DMF solvent, while γ-alkylation product was obtained in dioxane solvent and the dioxane and NHC ligand situation. In the present study, density functional theory calculations have been used to investigate the reaction mechanism and origin of the regioselectivity. For both dioxane and DMF, γ-alkylation undergoes successive oxidative addition (CH 2 Bpin trans to leaving group) and direct Cγ-C reductive elimination. The α-alkylation is found to undergo oxidative addition (CH 2 Bpin trans to leaving group), isomerization, and Cα-C reductive elimination rather than the previously proposed oxidative addition (-CH 2 Bpin cis to the leaving group) and Cα-C reductive elimination. The γ-alkylation and α-alkylation is, respectively, favorable for dioxane and DMF solvent, which is consistent with the γ- and α-selectivity in experiment. The solvent interferes the isomerization step, thereby affects the relative facility of the α- and γ-alkylation. Further investigation shows that η 1 -intermediate formation promoted by solvent is the rate-determining step of the isomerization. The stronger electron-donating ability of DMF than dioxane facilitates the η 1 -intermediate formation and finally results in the easier isomerization in DMF. For dioxane and NHC situation, in the presence of neutral NHC ligand, the -PO 4 Et 2 group tightly coordinates with the Cu center after the oxidative addition, preventing the isomerization process. The regioselectivity is determined by the relative facility of the oxidative addition step. Therefore, the favorable oxidative addition (in which -CH 2 Bpin trans to the leaving group) results in the facility of γ-alkylation.
Beyond benzyl grignards: facile generation of benzyl carbanions from styrenes.

Science.gov (United States)

Grigg, R David; Rigoli, Jared W; Van Hoveln, Ryan; Neale, Samuel; Schomaker, Jennifer M

2012-07-23

Benzylic functionalization is a convenient approach towards the conversion of readily available aromatic hydrocarbon feedstocks into more useful molecules. However, the formation of carbanionic benzyl species from benzyl halides or similar precursors is far from trivial. An alternative approach is the direct reaction of a styrene with a suitable coupling partner, but these reactions often involve the use of precious-metal transition-metal catalysts. Herein, we report the facile and convenient generation of reactive benzyl anionic species from styrenes. A Cu(I)-catalyzed Markovnikov hydroboration of the styrenic double bond by using a bulky pinacol borane source is followed by treatment with KOtBu to facilitate a sterically induced cleavage of the C-B bond to produce a benzylic carbanion. Quenching this intermediate with a variety of electrophiles, including CO(2), CS(2), isocyanates, and isothiocyanates, promotes C-C bond formation at the benzylic carbon atom. The utility of this methodology was demonstrated in a three-step, two-pot synthesis of the nonsteroidal anti-inflammatory drug (±)-flurbiprofen. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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 �
Reaction pathways of furfural, furfuryl alcohol and 2-methylfuran on Cu(111) and NiCu bimetallic surfaces

Science.gov (United States)

Xiong, Ke; Wan, Weiming; Chen, Jingguang G.

2016-10-01

Hydrodeoxygenation (HDO) is an important reaction for converting biomass-derived furfural to value-added 2-methylfuran, which is a promising fuel additive. In this work, the HDO of furfural to produce 2-methylfuran occurred on the NiCu bimetallic surfaces prepared on either Ni(111) or Cu(111). The reaction pathways of furfural were investigated on Cu(111) and Ni/Cu(111) surfaces using density functional theory (DFT) calculations, temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) experiments. These studies provided mechanistic insights into the effects of bimetallic formation on enhancing the HDO activity. Specifically, furfural weakly adsorbed on Cu(111), while it strongly adsorbed on Ni/Cu(111) through an η2(C,O) configuration, which led to the HDO of furfural on Ni/Cu(111). The ability to dissociate H2 on Ni/Cu(111) is also an important factor for enhancing the HDO activity over Cu(111).
Asymmetric Brønsted acid-catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene

Directory of Open Access Journals (Sweden)

Magnus Rueping

2012-10-01

Full Text Available A new chiral Brønsted acid-catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene has been developed. The reaction provides optically active aza-tetracycles in good yields with high diastereo- and enantioselectivities under mild reaction conditions.
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
Copper-Catalyzed Chan-Lam Cyclopropylation of Phenols and Azaheterocycles.

Science.gov (United States)

Derosa, Joseph; O'Duill, Miriam L; Holcomb, Matthew; Boulous, Mark N; Patman, Ryan L; Wang, Fen; Tran-Dubé, Michelle; McAlpine, Indrawan; Engle, Keary M

2018-04-06

Small molecules containing cyclopropane-heteroatom linkages are commonly needed in medicinal chemistry campaigns yet are problematic to prepare using existing methods. To address this issue, a scalable Chan-Lam cyclopropylation reaction using potassium cyclopropyl trifluoroborate has been developed. With phenol nucleophiles, the reaction effects O-cyclopropylation, whereas with 2-pyridones, 2-hydroxybenzimidazoles, and 2-aminopyridines the reaction brings about N-cyclopropylation. The transformation is catalyzed by Cu(OAc) 2 and 1,10-phenanthroline and employs 1 atm of O 2 as the terminal oxidant. This method is operationally convenient to perform and provides a simple, strategic disconnection toward the synthesis of cyclopropyl aryl ethers and cyclopropyl amine derivatives bearing an array of functional groups.
Reactions of green and black teas with Cu(II).

Science.gov (United States)

Goodman, B A; Ferreira Severino, J; Pirker, K F

2012-04-01

Electron paramagnetic resonance (EPR) measurements of the products of reactions between Cu(II) and samples of green and black teas showed spectral components from at least six different Cu(II) complexes with both tea types. Several of these complexes were common to both teas in spite of major differences in their polyphenol compositions. The pH range observed for complex formation, and the total signal intensity in the pH range 4-8, were greatly different from those for the reactions of Cu(II) with (-)-epigallocatechin gallate and gallic acid, the main polyphenols responsible for the free radical signals observed during oxidation of these beverages. Components with spectral parameters similar to those of Cu(II) complexes with theanine, the major amino acid in tea, may contribute to two of the spectra recorded under acidic conditions. However, the initial complexes formed at the lowest pH values investigated are still unidentified. EPR spectra with parameters consistent with Cu(II) polyphenol complexes were only observed under alkaline conditions, thus suggesting that components of tea other than polyphenols might be more important in reactions with copper, and possibly other transition metals, in solutions under physiological conditions. This journal is © The Royal Society of Chemistry 2012
The Manganese-Catalyzed Cross-Coupling Reaction and the Influence of Trace Metals

DEFF Research Database (Denmark)

Santilli, Carola; Beigbaghlou, Somayyeh Sarvi; Ahlburg, Andreas

2017-01-01

The substrate scope of the MnCl2-catalyzed cross-coupling between aryl halides and Grignard reagents has been extended to several methyl-substituted aryl iodides by performing the reaction at elevated temperature in a microwave oven. A radical clock experiment revealed the presence of an aryl...
Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: A review.

Science.gov (United States)

He, Jie; Yang, Xiaofang; Men, Bin; Wang, Dongsheng

2016-01-01

The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals (OH) from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH. Hence, it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology. Due to the complex reaction system, the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating, and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies. Iron-based materials usually possess high catalytic activity, low cost, negligible toxicity and easy recovery, and are a superior type of heterogeneous Fenton catalysts. Therefore, this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials. OH, hydroperoxyl radicals/superoxide anions (HO2/O2(-)) and high-valent iron are the three main types of reactive oxygen species (ROS), with different oxidation reactivity and selectivity. Based on the mechanisms of ROS generation, the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron, the heterogeneous catalysis mechanism, and the heterogeneous reaction-induced homogeneous mechanism. Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed. Finally, related future research directions are also suggested. Copyright © 2015. Published by Elsevier B.V.
Lewis acid catalysis of a Diels-Alder reaction in water

NARCIS (Netherlands)

Otto, S; Bertoncin, F; Engberts, JBFN

1996-01-01

Here we report the first detailed study of a Diels-Alder (DA) reaction that is catalyzed by Lewis acids in water. The effect of Co2+, Ni2+, Cu2+ and Zn2+ ions as Lewis acid catalysts on the rate and endo-exo selectivity of the DA reaction between the bidentate dienophiles
Solvent-free copper-catalyzed click chemistry for the synthesis of N-heterocyclic hybrids based on quinoline and 1,2,3-triazole

Directory of Open Access Journals (Sweden)

Martina Tireli

2017-11-01

Full Text Available Copper-catalyzed mechanochemical click reactions using Cu(II, Cu(I and Cu(0 catalysts have been successfully implemented to provide novel 6-phenyl-2-(trifluoromethylquinolines with a phenyl-1,2,3-triazole moiety at O-4 of the quinoline core. Milling procedures proved to be significantly more efficient than the corresponding solution reactions, with up to a 15-fold gain in yield. Efficiency of both solution and milling procedures depended on the p-substituent in the azide reactant, resulting in H < Cl < Br < I reactivity bias. Solid-state catalysis using Cu(II and Cu(I catalysts entailed the direct involvement of the copper species in the reaction and generation of highly luminescent compounds which hindered in situ monitoring by Raman spectroscopy. However, in situ monitoring of the milling processes was enabled by using Cu(0 catalysts in the form of brass milling media which offered a direct insight into the reaction pathway of mechanochemical CuAAC reactions, indicating that the catalysis is most likely conducted on the surface of milling balls. Electron spin resonance spectroscopy was used to determine the oxidation and spin states of the respective copper catalysts in bulk products obtained by milling procedures.

Diversification of indoles via microwave-assisted ligand-free copper-catalyzed N-arylation

Energy Technology Data Exchange (ETDEWEB)

Kwon, Jae Kwan; Lee, Jin Hee; Kim, Tae Sung; Yum, Eul Kgun [Dept. of Chemistry, Chu ngnam National University, Daejon (Korea, Republic of); Park, Jee Jung [Western Seoul Center Korea Basic Science Institute, Seoul (Korea, Republic of)

2016-12-15

A simple, efficient Cu{sub 2}O catalyst system under microwave irradiation was developed for N-arylation of various indoles without ligands and additives. Diverse N-heteroarylated indoles were prepared by coupling indoles with various heteroaryl halides within 1 h. The selective reactivity of bromoindole with aryl iodide provided N-aryl bromoindoles, which could be useful intermediates for palladium-catalyzed Heck and Suzuki coupling reactions.
Amorphization reaction in thin films of elemental Cu and Y

Science.gov (United States)

Johnson, R. W.; Ahn, C. C.; Ratner, E. R.

1989-10-01

Compositionally modulated thin films of Cu and Y were prepared in an ultrahigh-vacuum dc ion-beam deposition chamber. The amorphization reaction was monitored by in situ x-ray-diffraction measurements. Growth of amorphous Cu1-xYx is observed at room temperature with the initial formation of a Cu-rich amorphous phase. Further annealing in the presence of unreacted Y leads to Y enrichment of the amorphous phase. Growth of crystalline CuY is observed for T=469 K. Transmission-electron-microscopy measurements provide real-space imaging of the amorphous interlayer and growth morphology. Models are developed, incorporating metastable interfacial and bulk free-energy diagrams, for the early stage of the amorphization reaction.
Preparation of Cu@Cu2O Nanocatalysts by Reduction of HKUST-1 for Oxidation Reaction of Catechol

Directory of Open Access Journals (Sweden)

Seongwan Jang

2016-11-01

Full Text Available HKUST-1, a copper-based metal organic framework (MOF, has been investigated as a catalyst in various reactions. However, the HKUST-1 shows low catalytic activity in the oxidation of catechol. Therefore, we synthesized Fe3O4@HKUST-1 by layer-by layer assembly strategy and Cu@Cu2O by reduction of HKUST-1 for enhancement of catalytic activity. Cu@Cu2O nanoparticles exhibited highly effective catalytic activity in oxidation of 3,5-di-tert-butylcatechol. Through this method, MOF can maintain the original core-shell structure and be used in various other reactions with enhanced catalytic activity.
Insights into the formation of carlactone from in-depth analysis of the CCD8-catalyzed reactions

KAUST Repository

Bruno, Mark; Vermathen, Martina; Alder, Adrian; Wü st, Florian; Schaub, Patrick; van der Steen, Rob; Beyer, Peter; Ghisla, Sandro; Al-Babili, Salim

2017-01-01

Strigolactones (SLs) are a new class of phytohormones synthesized from carotenoids via carlactone. The complex structure of carlactone is not easily deducible from its precursor, a cis-configured β-carotene cleavage product, and is thus formed via a poorly understood series of reactions and molecular rearrangements, all catalyzed by only one enzyme, the carotenoid cleavage dioxygenase 8 (CCD8). Moreover, the reactions leading to carlactone are expected to form a second, yet unidentified product. In this study, we used (13) C and (18) O-labelling to shed light on the reactions catalyzed by CCD8. The characterization of the resulting carlactone by LC-MS and NMR, and the identification of the assumed, less accessible second product allowed us to formulate a minimal reaction mechanism for carlactone generation. This article is protected by copyright. All rights reserved.
Insights into the formation of carlactone from in-depth analysis of the CCD8-catalyzed reactions

KAUST Repository

Bruno, Mark

2017-02-10

Strigolactones (SLs) are a new class of phytohormones synthesized from carotenoids via carlactone. The complex structure of carlactone is not easily deducible from its precursor, a cis-configured β-carotene cleavage product, and is thus formed via a poorly understood series of reactions and molecular rearrangements, all catalyzed by only one enzyme, the carotenoid cleavage dioxygenase 8 (CCD8). Moreover, the reactions leading to carlactone are expected to form a second, yet unidentified product. In this study, we used (13) C and (18) O-labelling to shed light on the reactions catalyzed by CCD8. The characterization of the resulting carlactone by LC-MS and NMR, and the identification of the assumed, less accessible second product allowed us to formulate a minimal reaction mechanism for carlactone generation. This article is protected by copyright. All rights reserved.
Reaction of hydroborate anions with liquid hydrogen fluoride

International Nuclear Information System (INIS)

Volkov, V.V.; Myakishev, K.G.

1978-01-01

The reaction of anhydrous liquid HF with salts of the decahydro-closodecarborate (2) ion B 10 H 10 2- at room temperature or a decreased temperature leads to the formation of complex mixtures of high-molecular boranes with yields of 88 to 92 %. This solid, yellow, nonvolatile product contains traces of B 10 H 14 and B 18 H 22 . The average molecular masses of the borane mixtures obtained are in the range of 438 - 992. The complex composition of the mixtures was confirmed by thin-layer chromatography on silica gel. The IR and NMR spectra of the products are presented. The possible mechanism of the reaction between HF and B 10 H 10 2- with the formation of higher boron hydrides is discussed. Salts of B 12 H 10 2- and B 10 Cl 10 2- do not react with HF; KBF 4 and CsB 9 H 14 are decomposed by HF with the formation of MBF 4
The Role of Solvent Polarity on Low-Temperature Methanol Synthesis Catalyzed by Cu Nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Ahoba-Sam, Christian [Department of Process, Energy and Environmental Technology, University College of Southeast Norway, Porsgrunn (Norway); Olsbye, Unni [Department of Chemistry, University of Oslo, Oslo (Norway); Jens, Klaus-Joachim, E-mail: Klaus.J.Jens@usn.no [Department of Process, Energy and Environmental Technology, University College of Southeast Norway, Porsgrunn (Norway)

2017-07-14

Methanol syntheses at low temperature in a liquid medium present an opportunity for full syngas conversion per pass. The aim of this work was to study the role of solvents polarity on low-temperature methanol synthesis reaction using eight different aprotic polar solvents. A “once through” catalytic system, which is composed of Cu nanoparticles and sodium methoxide, was used for methanol synthesis at 100°C and 20 bar syngas pressure. Solvent polarity rather than the 7–10 nm Cu (and 30 nm Cu on SiO{sub 2}) catalyst used dictated trend of syngas conversion. Diglyme with a dielectric constant (ε) = 7.2 gave the highest syngas conversion among the eight different solvents used. Methanol formation decreased with either increasing or decreasing solvent ε value of diglyme (ε = 7.2). To probe the observed trend, possible side reactions of methyl formate (MF), the main intermediate in the process, were studied. MF was observed to undergo two main reactions; (i) decarbonylation to form CO and MeOH and (ii) a nucleophilic substitution to form dimethyl ether and sodium formate. Decreasing polarity favored the decarbonylation side reaction while increasing polarity favored the nucleophilic substitution reaction. In conclusion, our results show that moderate polarity solvents, e.g., diglyme, favor MF hydrogenolysis and, hence, methanol formation, by retarding the other two possible side reactions.
A facile copper(I)-catalyzed homocoupling of terminal alkynes to 1,3-diynes with diaziridinone under mild conditions

OpenAIRE

Zhu, Yingguang; Shi, Yian

2013-01-01

A novel and efficient Cu(I)-catalyzed oxidative homocoupling of terminal alkynes with diaziridinone as oxidant is described. Various terminal alkynes can be transformed into the corresponding 1,3-diynes in good yields. The reaction process is base-free, operationally simple, and amenable to gram scale.
Correction: A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

Science.gov (United States)

Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

2016-12-22

Correction for 'A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide' by Chee Koon Ng et al., Chem. Commun., 2016, 52, 11842-11845.
Triosephosphate isomerase: energetics of the reaction catalyzed by the yeast enzyme expressed in Escherichia coli

International Nuclear Information System (INIS)

Nickbarg, E.B.; Knowles, J.R.

1988-01-01

Triosephosphate isomerase from bakers' yeast, expressed in Escherichia coli strain DF502(p12), has been purified to homogeneity. The kinetics of the reaction in each direction have been determined at pH 7.5 and 30 degrees C. Deuterium substitution at the C-2 position of substrate (R)-glyceraldehyde phosphate and at the 1-pro-R position of substrate dihydroxyacetone phosphate results in kinetic isotope effects on kcat of 1.6 and 3.4, respectively. The extent of transfer of tritium from [1(R)- 3 H]dihydroxyacetone phosphate to product (R)-glyceraldehyde phosphate during the catalyzed reaction is only 3% after 66% conversion to product, indicating that the enzymic base that mediates proton transfer is in rapid exchange with solvent protons. When the isomerase-catalyzed reaction is run in tritiated water in each direction, radioactivity is incorporated both into the remaining substrate and into the product. In the exchange-conversion experiment with dihydroxyacetone phosphate as substrate, the specific radioactivity of remaining dihydroxyacetone phosphate rises as a function of the extent of reaction with a slope of about 0.3, while the specific radioactivity of the products is 54% that of the solvent. In the reverse direction with (R)-glyceraldehyde phosphate as substrate, the specific radioactivity of the product formed is only 11% that of the solvent, while the radioactivity incorporated into the remaining substrate (R)-glyceraldehyde phosphate also rises as a function of the extent of reaction with a slope of 0.3. These results have been analyzed according to the protocol described earlier to yield the free energy profile of the reaction catalyzed by the yeast isomerase
Silver-catalyzed formal inverse electron-demand Diels-Alder reaction of 1,2-diazines and siloxy alkynes.

Science.gov (United States)

Türkmen, Yunus E; Montavon, Timothy J; Kozmin, Sergey A; Rawal, Viresh H

2012-06-06

A highly effective silver-catalyzed formal inverse electron-demand Diels-Alder reaction of 1,2-diazines and siloxy alkynes has been developed. The reactions provide ready access to a wide range of siloxy naphthalenes and anthracenes, which are formed in good to high yields, under mild reaction conditions, using low catalyst loadings.
Synthesis of heterocycles through transition-metal-catalyzed isomerization reactions

DEFF Research Database (Denmark)

Ishøy, Mette; Nielsen, Thomas Eiland

2014-01-01

of structurally complex and diverse heterocycles. In this Concept article, we attempt to cover this area of research through a selection of recent versatile examples. A sea of opportunities! Transition-metal-catalyzed isomerization of N- and O-allylic compounds provides a mild, selective and synthetically...... versatile method to form iminium and oxocarbenium ions. Given the number of reactions involving these highly electrophilic intermediates, this concept provides a sea of opportunities for heterocycle synthesis, (see scheme; Nu=nucleophile). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim....
Interfacial Reaction of Sn-Ag-Cu Lead-Free Solder Alloy on Cu: A Review

Directory of Open Access Journals (Sweden)

Liu Mei Lee

2013-01-01

Full Text Available This paper reviews the function and importance of Sn-Ag-Cu solder alloys in electronics industry and the interfacial reaction of Sn-Ag-Cu/Cu solder joint at various solder forms and solder reflow conditions. The Sn-Ag-Cu solder alloys are examined in bulk and in thin film. It then examines the effect of soldering conditions to the formation of intermetallic compounds such as Cu substrate selection, structural phases, morphology evolution, the growth kinetics, temperature and time is also discussed. Sn-Ag-Cu lead-free solder alloys are the most promising candidate for the replacement of Sn-Pb solders in modern microelectronic technology. Sn-Ag-Cu solders could possibly be considered and adapted in miniaturization technologies. Therefore, this paper should be of great interest to a large selection of electronics interconnect materials, reliability, processes, and assembly community.
Palladium(II-catalyzed Heck reaction of aryl halides and arylboronic acids with olefins under mild conditions

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Tanveer Mahamadali Shaikh

2013-08-01

Full Text Available A series of general and selective Pd(II-catalyzed Heck reactions were investigated under mild reaction conditions. The first protocol has been developed employing an imidazole-based secondary phosphine oxide (SPO ligated palladium complex (6 as a precatalyst. The catalytic coupling of aryl halides and olefins led to the formation of the corresponding coupled products in excellent yields. A variety of substrates, both electron-rich and electron-poor olefins, were converted smoothly to the targeted products in high yields. Compared with the existing approaches employing SPO–Pd complexes in a Heck reaction, the current strategy features mild reaction conditions and broad substrate scope. Furthermore, we described the coupling of arylboronic acids with olefins, which were catalyzed by Pd(OAc2 and employed N-bromosuccinimide as an additive under ambient conditions. The resulted biaryls have been obtained in moderate to good yields.
A facile copper(I)-catalyzed homocoupling of terminal alkynes to 1,3-diynes with diaziridinone under mild conditions.

Science.gov (United States)

Zhu, Yingguang; Shi, Yian

2013-11-21

A novel and efficient Cu(I)-catalyzed oxidative homocoupling of terminal alkynes with diaziridinone as an oxidant is described. Various terminal alkynes can be transformed into the corresponding 1,3-diynes in good yields. The reaction process is base-free, operationally simple, and amenable to the gram scale.
Copper-Catalyzed Sulfonyl Azide-Alkyne Cycloaddition Reactions: Simultaneous Generation and Trapping of Copper-Triazoles and -Ketenimines for the Synthesis of Triazolopyrimidines.

Science.gov (United States)

Nallagangula, Madhu; Namitharan, Kayambu

2017-07-07

First simultaneous generation and utilization of both copper-triazole and -ketenimine intermediates in copper-catalyzed sulfonyl azide-alkyne cycloaddition reactions is achieved for the one-pot synthesis of triazolopyrimidines via a novel copper-catalyzed multicomponent cascade of sulfonyl azides, alkynes, and azirines. Significantly, the reaction proceeds under very mild conditions in good yields.
DNA-based catalytic enantioselective intermolecular oxa-Michael addition reactions

NARCIS (Netherlands)

Megens, Rik P.; Roelfes, Gerard

2012-01-01

Using the DNA-based catalysis concept, a novel Cu(II) catalyzed enantioselective oxa-Michael addition of alcohols to enones is reported. Enantioselectivities of up to 86% were obtained. The presence of water is important for the reactivity, possibly by reverting unwanted side reactions such as
S,O-Ligand-Promoted Palladium-Catalyzed C-H Functionalization Reactions of Nondirected Arenes

NARCIS (Netherlands)

Naksomboon, K.; Valderas, C.; Gomez-Martinez, M.; Alvarez-Casao, Y.; Fernández Ibáñez, M.A.

Pd(II)-catalyzed C-H functionalization of non directed arenes has been realized using an inexpensive and easily accessible type of bidentate S,O-ligand. The catalytic system shows high efficiency in the C-H olefination reaction of electron-rich and electron-poor arenes. This methodology is
Interfacial reactions in the Sb–Sn/(Cu, Ni) systems: Wetting experiments

International Nuclear Information System (INIS)

Novakovic, R.; Lanata, T.; Delsante, S.; Borzone, G.

2012-01-01

Interfacial reactions in the Sb–Sn/Cu and Sb–Sn/Ni systems have been investigated by means of wetting experiments. The wetting behaviour of two lead-free alloys, namely, Sb 2.5 Sn 97.5 and Sb 14.5 Sn 85.5 (at.%), in contact with Cu and Ni-substrates has been studied in view of possible applications as high-temperature solders in the electronics industry. The contact angle measurements on Cu and Ni plates were performed by using a sessile drop apparatus. The solder/substrate interface was characterised by the SEM-EDS analyses. -- Highlights: ► Sb–Sn alloys are used as high temperature lead-free solders. ► Sb–Sn alloys have good wetting properties on Cu and Ni substrates. ► Interfacial reactions and products are important for joint properties. ► Interfacial reactions/products data can be used to study the phase diagrams.
On the Effect of Microwave Energy on Lipase-Catalyzed Polycondensation Reactions

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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.

The three transglycosylation reactions catalyzed by cyclodextrin glycosyltransferase from Bacillus circulans (strain 251) proceed via different kinetic mechanisms

NARCIS (Netherlands)

Veen, Bart A. van der; Alebeek, Gert-Jan W.M. van; Uitdehaag, Joost C.M.; Dijkstra, Bauke W.; Dijkhuizen, Lubbert

Cyclodextrin glycosyltransferase (CGTase) catalyzes three transglycosylation reactions via a double displacement mechanism involving a covalent enzyme-intermediate complex (substituted-enzyme intermediate). Characterization of the three transglycosylation reactions, however, revealed that they
Synthesis of the C(18)-C(34) fragment of amphidinolide C and the C(18)-C(29) fragment of amphidinolide F.

Science.gov (United States)

Roy, Sudeshna; Spilling, Christopher D

2010-11-19

A convergent synthesis of the C(18)-C(34) fragment of amphidinolide C and the C(18)-C(29) fragment of amphidinolide F is reported. The approach involves the synthesis of the common intermediate tetrahydrofuranyl-β-ketophosphonate via cross metathesis, Pd(0)-catalyzed cyclization, and hydroboration-oxidation. The β-ketophosphonate was coupled to three side chain aldehydes using a Horner-Wadsworth-Emmons (HWE) olefination reaction to give dienones, which were reduced with l-selectride to give the fragments of amphidinolide C and F.
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.
Novel Role of Carbon Dioxide as a Selective Agent in Palladium-Catalyzed Cyclotrimerization of Alkynes

Institute of Scientific and Technical Information of China (English)

李金恒; 谢叶香

2004-01-01

Carbon dioxide was found as a selective agent to promote the palladium-catalyzed cyclotrimerization of alkynes in water. Both aryl and alkylacetylenes afforded the corresponding cyclotrimerization products regioselectively in high yields using PdCl2, CuCl2, and CO2 as the catalytic system. However, tert-butylacetylene bearing a bulky group gave a dimerization product. Mechanism of this reaction was also discussed.
CuX2络合物催化甲基丙烯酸甲酯的氧化聚合%CuX2 COMPLEX-CATALYZED OXIDATIVE POLYMERIZATIONS OF METHYL METHACRYLATE

Institute of Scientific and Technical Information of China (English)

孙燕; 孙晋; 宋瑾; 黄文艳; 蒋必彪; 翟光群

2011-01-01

Oxidative polymerizations of methyl methacrylate ( MMA) catalyzed by complexes of transition metal halides in high oxidation states were investigated. First, CuBr2/2, 2'-bipyridine ( bPy)-catalyzed oxidative polymerizations of MMA in the presence of poly (2-( N, iV-dimethylamino) ethyl methacrylate) were performed in different solvents. When cyclohexanone was used as a solvent, only poly ( methyl methacrylate) ( PMMA) was obtained, suggesting redox initiation between CuBr2/bPy and tertiary amines in cyclohexanone is negligible. Second, oxidative polymerizations of MMA catalyzed by different complexes were carried out. Complexes of CuCl2 ,CuBr2 or FeCl3 with bPy,N,N,/V',N",/V"-pentamethyldiethylenetriamine or N,N,N',N'-tetramethylethylenediamine can catalyze oxidative polymerizations of MMA, and polymerization rates increased with the increase of the catalyst concentration. Molecular weight of PMMA increases with monomer conversions initially and maintains constant later. Last,atom transfer radical polymerization ( ATRP) chain extension using PMMA from the oxidative polymerizations at different conversions was performed. The results show the C-X functionality of PMMA chains at low conversion was also 100% ,and it decreased sharply with conversions. Two different mechanisms were conceived to contribute to the oxidative polymerization of MMA: (1) the complexes form ATRP initiators and catalysts with MMA via monomer addition, and then ATRP proceeds to give rise to PMMA chains with C-X terminal groups; (2) the complexes catalyze/initiate conventional free radical polymerizations of MMA.%研究了高氧化态过渡金属卤化物络合物催化甲基丙烯酸甲酯(MMA)的氧化聚合.首先在叔胺类聚合物存在条件下以CuBr2/2,2′-联吡啶(bPy)络合物催化MMA在不同溶剂中的氧化聚合,结果在环己酮中得到PMMA均聚物,CuBr2/bPy同叔胺的氧化还原引发可以忽略.随后在环己酮中分别以不同络合物催化MMA的氧化聚合.结果发现,Cu
Mechanistic Implications for the Ni(I-Catalyzed Kumada Cross-Coupling Reaction

Directory of Open Access Journals (Sweden)

Linda Iffland

2017-11-01

Full Text Available Herein we report on the cross-coupling reaction of phenylmagnesium bromide with aryl halides using the well-defined tetrahedral Ni(I complex, [(TriphosNiICl] (Triphos = 1,1,1-tris(diphenylphosphinomethylethane. In the presence of 0.5 mol % [(TriphosNiICl], good to excellent yields (75–97% of the respective coupling products within a reaction time of only 2.5 h at room temperature were achieved. Likewise, the tripodal Ni(IIcomplexes [(κ2-TriphosNiIICl2] and [(κ3-TriphosNiIICl](X (X = ClO4, BF4 were tested as potential pre-catalysts for the Kumada cross-coupling reaction. While the Ni(II complexes also afford the coupling products in comparable yields, mechanistic investigations by UV/Vis and electron paramagnetic resonance (EPR spectroscopy indicate a Ni(I intermediate as the catalytically active species in the Kumada cross-coupling reaction. Based on experimental findings and density functional theory (DFT calculations, a plausible Ni(I-catalyzed reaction mechanism for the Kumada cross-coupling reaction is presented.
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.
Platinum-Catalyzed, Terminal-Selective C(sp(3))-H Oxidation of Aliphatic Amines.

Science.gov (United States)

Lee, Melissa; Sanford, Melanie S

2015-10-14

This Communication describes the terminal-selective, Pt-catalyzed C(sp(3))-H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol%. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (iii) it electronically deactivates the C-H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp(3))-H oxidation of a variety of primary, secondary, and tertiary amines.
Controlled Synthesis of Heterostructured SnO2-CuO Composite Hollow Microspheres as Efficient Cu-Based Catalysts for the Rochow Reaction

Directory of Open Access Journals (Sweden)

Hezhi Liu

2018-04-01

Full Text Available In this work, we report the design and synthesis of a series of heterostructured SnO2-CuO hollow microspherical catalysts (H-SnO2(x-CuO, x is the weight ratio of Sn/Cu for the Rochow reaction. The microspherical catalysts with nanosheets and nanoparticles as building blocks were prepared by a facile one-pot hydrothermal method coupled with calcination. When tested for the Rochow reaction, the prepared H-SnO2(0.2-CuO composite exhibited higher dimethyldichlorosilane selectivity (88.2% and Si conversion (36.7% than the solid CuO, hollow CuO and other H-SnO2(x-CuO microspherical samples, because in the former there is a stronger synergistic interaction between CuO and SnO2.
Influence of CuO nanoparticle on palm oil based alkyd resin preparation and its antimicrobial activity

Science.gov (United States)

Ruey Ong, Huei; Maksudur Rahman Khan, Md.; Ramli, Ridzuan; Shein Hong, Chi; Yunus, Rosli Mohd

2018-03-01

An alkyd resin has been synthesized from palm oil that reacted with glycerol and phthalic anhydride by alcoholysis-polyesterification process and co-catalyzed by CuO nanoparticle. The CuO nanoparticle was pre-prepared in the glycerol via sol gel method, which creates a new reaction condition for resin preparation. The resins were characterized by fourier transform infrared spectroscopy (FTIR), where a new ester linkage bond (C-O-C) was noticed for resin sample. The antimicrobial activity and the curing behaviour of the resin were determined by Kirby-Bauer and differential scanning calorimeter technique. It was found that, the addition of CuO speeded up the reaction rate and played antimicrobial role. Moreover, it shortens the reaction time of alcoholysis and polyesterification process.
Sequential Condensation and Hydrodeoxygenation Reaction of Furfural-Acetone Adduct over Mix Catalysts Ni/SiO2 and Cu/SiO2 in Water

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Siti Mariyah Ulfa

2018-05-01

Full Text Available Sequential condensation and hydrodeoxygenation reaction were perform using autoclave batch reactor in the presence of water as a solvent. The condensation of furfural and acetone was performed using MgO catalyst followed by hydrodeoxygenation using mix catalyst Ni/SiO2 and Cu/SiO2. The catalyst was prepared by wet-impregnation method and analyzed by XRD, SEM-EDX as well as BET surface. Condensation of furfural and acetone in 1:2 mol ratio was carried out by reflux gave 4-(2-furyl-3-buten-2-one and 1,5-bis-(2-furanyl-1,4-pentadien-3-one. The condensation product was then subjected for hydrodeoxygenation using batch reactor, catalyzed by mixed Ni/SiO2 and Cu/SiO2 at 150 and 180 °C for 2 h. The product identified as alkane derivatives with the conversion at 38.83 and 50.35%, respectively. The selectivity of hydrocarbon is 61.39% at 150 °C and 16.55% at 180 °C. Increasing the reaction temperature to 200 °C did not give any products except the recovery of the precursor. It showed that higher temperature enhanced the catalyst activity but the selectivity is controlled by low reaction temperature.
Cu2O/CuO Bilayered Composite as a High-Efficiency Photocathode for Photoelectrochemical Hydrogen Evolution Reaction

Science.gov (United States)

Yang, Yang; Xu, Di; Wu, Qingyong; Diao, Peng

2016-10-01

Solar powered hydrogen evolution reaction (HER) is one of the key reactions in solar-to-chemical energy conversion. It is desirable to develop photocathodic materials that exhibit high activity toward photoelectrochemical (PEC) HER at more positive potentials because a higher potential means a lower overpotential for HER. In this work, the Cu2O/CuO bilayered composites were prepared by a facile method that involved an electrodeposition and a subsequent thermal oxidation. The resulting Cu2O/CuO bilayered composites exhibited a surprisingly high activity and good stability toward PEC HER, expecially at high potentials in alkaline solution. The photocurrent density for HER was 3.15 mA·cm-2 at the potential of 0.40 V vs. RHE, which was one of the two highest reported at the same potential on copper-oxide-based photocathode. The high photoactivity of the bilayered composite was ascribed to the following three advantages of the Cu2O/CuO heterojunction: (1) the broadened light absorption band that made more efficient use of solar energy, (2) the large space-charge-region potential that enabled a high efficiency for electron-hole separation, and (3) the high majority carrier density that ensured a faster charge transportation rate. This work reveals the potential of the Cu2O/CuO bilayered composite as a promising photocathodic material for solar water splitting.
Mechanism of Cytochrome P450 17A1-Catalyzed Hydroxylase and Lyase Reactions

DEFF Research Database (Denmark)

Bonomo, Silvia; Jorgensen, Flemming Steen; Olsen, Lars

2017-01-01

Cytochrome P450 17A1 (CYP17A1) catalyzes C17 hydroxylation of pregnenolone and progesterone and the subsequent C17–C20 bond cleavage (lyase reaction) to form androgen precursors. Compound I (Cpd I) and peroxo anion (POA) are the heme-reactive species underlying the two reactions. We have characte...... the concept that the selectivity of the steroidogenic CYPs is ruled by direct interactions with the enzyme, in contrast to the selectivity of drug-metabolizing CYPs, where the reactivity of the substrates dominates....... characterized the reaction path for both the hydroxylase and lyase reactions using density functional theory (DFT) calculations and the enzyme–substrate interactions by molecular dynamics (MD) simulations. Activation barriers for positions subject to hydroxylase reaction have values close to each other and span...
CuO and Ag2O/CuO Catalyzed Oxidation of Aldehydes to the Corresponding Carboxylic Acids by Molecular Oxygen

Directory of Open Access Journals (Sweden)

Yaowu Sha

2008-04-01

Full Text Available Furfural was oxidized to furoic acid by molecular oxygen under catalysis by 150nm-sized Ag2O/CuO (92% or simply CuO (86.6%. When 30 nm-size catalyst was used,the main product was a furfural Diels-Alder adduct. Detailed reaction conditions andregeneration of catalysts were investigated. Under optimal conditions, a series of aromaticand aliphatic aldehydes were oxidized to the corresponding acids in good yields.
Crystal structure of a trapped phosphate intermediate in vanadium apochloroperoxidase catalyzing a dephosphorylation reaction

NARCIS (Netherlands)

de Macedo-Ribeiro, S.; Renirie, R.; Wever, R.; Messerschmidt, A.

2008-01-01

The crystal structure of the apo form of vanadium chloroperoxidase from Curvularia inaequalis reacted with para-nitrophenylphosphate was determined at a resolution of 1.5 Å. The aim of this study was to solve structural details of the dephosphorylation reaction catalyzed by this enzyme. Since the
Synthesis of the C(18)–C(34) Fragment of Amphidinolide C and the C(18)–C(29) Fragment of Amphidinolide F

Science.gov (United States)

Roy, Sudeshna; Spilling, Christopher D.

2010-01-01

A convergent synthesis of the C(18)–C(34) fragment of amphidinolide C and the C(18)–C(29) fragment of amphidinolide F is reported. The approach involves the synthesis of the common intermediate tetrahydrofuranyl-β-ketophosphonate via cross metathesis, Pd(0)-catalyzed cyclization and hydroboration-oxidation. The β-ketophosphonate was coupled to three side chain aldehydes using a Horner-Wadsworth-Emmons (HWE) olefination reaction to give dienones, which were reduced with L-selectride to give the fragments of amphidinolide C and F. PMID:21028791
Efficient Synthesis of Spirobarbiturates and Spirothiobarbiturates Bearing Cyclopropane Rings by Rhodium(II)-Catalyzed Reactions of Cyclic Diazo Compounds

International Nuclear Information System (INIS)

Wang, Xue; Lee, Yong Rok

2013-01-01

Rhodium(II)-catalyzed reactions of cyclic diazo compounds derived from barbituric acid and thiobarbituric acid with a variety of styrene moieties were examined. These reactions provide rapid synthetic routes to the preparations of spirobarbiturates and spirothiobarbiturates bearing cyclopropane rings
Efficient Synthesis of Spirobarbiturates and Spirothiobarbiturates Bearing Cyclopropane Rings by Rhodium(II)-Catalyzed Reactions of Cyclic Diazo Compounds

Energy Technology Data Exchange (ETDEWEB)

Wang, Xue; Lee, Yong Rok [Yeungnam Univ., Gyeongsan (Korea, Republic of)

2013-06-15

Rhodium(II)-catalyzed reactions of cyclic diazo compounds derived from barbituric acid and thiobarbituric acid with a variety of styrene moieties were examined. These reactions provide rapid synthetic routes to the preparations of spirobarbiturates and spirothiobarbiturates bearing cyclopropane rings.
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.
Preparation of Cu@Cu2O Nanocatalysts by Reduction of HKUST-1 for Oxidation Reaction of Catechol

OpenAIRE

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

2016-01-01

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

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.
Alumina nanowire growth by water decomposition and the peritectic reaction of decagonal Al{sub 65}Cu{sub 15}Co{sub 20} quasicrystals

Energy Technology Data Exchange (ETDEWEB)

Téllez-Vázquez, J.O., E-mail: oswald.tellez@gmail.com [Instituto de Investigaciones en Metalurgia y Materiales, UMSNH, Edificio U, Ciudad Universitaria, CP 58060 Morelia Michoacán, México (Mexico); Patiño-Carachure, C., E-mail: cpatino@pampano.unacar.mx [Facultad de Ingeniería, Universidad Autónoma del Carmen, Campus III, Avenida Central S/N, Esq. Con Fracc. Mundo Maya, C.P. 24115 Ciudad del Carmen, Campeche, México (Mexico); Rosas, G., E-mail: grtrejo@yahoo07.com.mx [Instituto de Investigaciones en Metalurgia y Materiales, UMSNH, Edificio U, Ciudad Universitaria, CP 58060 Morelia Michoacán, México (Mexico)

2016-02-15

In this paper, the results of the Al{sub 2}O{sub 3} nanowires' growth through a chemical reaction between Al and water vapor at 1050 °C are presented. Our approach is based on two primary considerations. First, at room temperature, the Al{sub 65}Cu{sub 15}Co{sub 20} alloy is affected by the following mechanism: 2Al (s) + 3H{sub 2}O (g) → Al{sub 2}O{sub 3} (s) + H{sub 2} (g). In this reaction, the released hydrogen induces cleavage fracture of the material to form small particles. Second, the Al{sub 65}Cu{sub 15}Co{sub 20} quasicrystalline phase is transformed on heating to liquid + Al (Cu, Co) cubic phase through a peritectic reaction at 1050 °C. The Al-rich liquid then reacts with water vapor, forming Al{sub 2}O{sub 3} nanowires. X-ray diffraction (XRD) analysis shows that the formed nanowires have a hexagonal structure, and infrared analysis further confirms the presence of α-Al{sub 2}O{sub 3} phase in the final products. Transmission electron microscopy observations show that nanoparticles are present at the end of nanowires, suggesting the VLS growth mechanism. Elemental analysis by energy dispersive spectroscopy (EDS) indicates that the particles at the tip of the nanowires are mainly formed by Co and Cu alloying elements and small amounts of Al. Electron microscopy observations showed nanowires with diameters ranging from 20 to 70 nm; the average diameter was 37 nm and the nanowire lengths were up to several micrometers. - Highlights: • Hexagonal alumina nanowires are grown at 1050 °C through the VLS process. • Alumina nanowires are obtained by the decomposition of decagonal quasicrystalline phase. • The decagonal phase decomposition follows a peritectic reaction at 1030 °C. • Nanoparticles are obtained by hydrogen embrittlement mechanism. • The nanoparticles catalyze the water decomposition to form wires.
FeCl3- and GaCl3-Catalyzed Dehydrative Coupling Reaction of Chromone-Derived Morita-Baylis-Hillman Alcohols with Terminal Alkynes%FeCl3- and GaCl3-Catalyzed Dehydrative Coupling Reaction of Chromone-Derived Morita-Baylis-Hillman Alcohols with Terminal Alkynes

Institute of Scientific and Technical Information of China (English)

武陈; 曾皓; 刘哲; 刘利; 王东; 陈拥军

2011-01-01

FeCl3- and GaCl3-catalyzed dehydrative coupling reactions of chromone-derived Morita-Baylis-Hillman （MBH） alcohols with terminal alkynes were developed. The reactions provided exclusively a-regioselective and acetylene-substituted products in good yields.
Effect of Barium-Precursors on Reaction Kinetics in Y-Ba-Cu-O System

Institute of Scientific and Technical Information of China (English)

无

2001-01-01

The reactions of stoichiometric Y2O3, CuO, and different Ba salts or oxides (BaCO3, Ba(NO3)2, BaO2, BaCuO2) for forming various compounds in the Y-Ba-Cu-O system (i.e., YBa2Cu3O7-δ, BaCuO2, Y2BaCuO5 and Y2Cu2O5) were systematically investigated by thermal analysis and X-ray diffractometry. The relevant activation energies were calculated from thermogravimetric data. It is found that the reaction pathway significantly depends on the thermal stability of the Ba precursors. Binary BaO-CuO phases form at low temperature (650～700 ℃) when in presence of easy-to-decompose Ba precursors, and then slowly transform to ternary compounds. On the contrary, when Ba ions are released at temperature higher than 900 ℃, ternary phases form directly from the components.
Dependence of CuO particle size and diameter of reaction tubing on tritium recovery for tritium safety operation

Energy Technology Data Exchange (ETDEWEB)

Hu, Cui, E-mail: cdxohc10000@163.com [Shizuoka University, 836 Ohya, Suruga-ku Shizuoka 422-8529 (Japan); Uemura, Yuki; Yuyama, Kenta; Fujita, Hiroe; Sakurada, Shodai; Azuma, Keisuke [Shizuoka University, 836 Ohya, Suruga-ku Shizuoka 422-8529 (Japan); Taguchi, Akira; Hara, Masanori; Hatano, Yuji [University of Toyama, 3190 Gofuku, Toyama 939-8555 (Japan); Chikada, Takumi; Oya, Yasuhisa [Shizuoka University, 836 Ohya, Suruga-ku Shizuoka 422-8529 (Japan)

2016-12-15

Highlights: • Influence of CuO particle size and diameter of reaction tubing on the tritium recovery was evaluated. • Reaction rate constant of tritium with CuO particle has been calculated by the combination of experimental results and a simulation code. • Dependence of reaction tubing length on tritium conversion ratio has been explored. - Abstract: Usage of CuO and water bubbler is one of the conventional and convenient methods for tritium recovery. In present work, influence of CuO particle size and diameter of reaction tubing on the tritium recovery was evaluated. Reaction rate constant of tritium with CuO particle has been calculated by the combination of experimental results and a simulation code. Then, these results were applied for exploring the dependence of reaction tubing length on tritium conversion ratio. The results showed that the surface area of CuO has a great influence on the oxidation rate constant. The frequency factor of the reaction would be approximately doubled by reducing the CuO particle size from 1.0 mm to 0.2 mm. Cross section of reaction tubing mainly affected on the duration of tritium at the temperature below 600 K. Reaction tubing with length of 1 m at temperature of 600 K would be suitable for keeping the tritium conversion ratio above 99.9%. The length of reaction tubing can be reduced by using the smaller CuO particle or increasing the CuO temperature.
Possibilities and scope of the double isotope effect method in the elucidation of mechanisms of enzyme catalyzed reactions

Energy Technology Data Exchange (ETDEWEB)

Schmidt, H L; Medina, R [Technische Univ. Muenchen, Freising (Germany, F.R.). Lehrstuhl fuer Allgemeine Chemie und Biochemie

1991-01-01

Kinetic isotope effects on enzyme catalyzed reactions are indicative for the first irreversible in a sequence of individual steps. Hints on the relative velocities of other steps can only be obtained from the partitioning factor R and its dependence on external reaction conditions. In general, the experimental data needed are obtained from isotope abundance measurements in a defined position of the substrate or product as a function of turnover. This method does not reveal events dealing with neighbour atoms or preceding the main isotope sensitive step. In the method presented here, the analytical measurement is extended to the second atom involved in a bond fission of formation (Double Isotope Effect Method). It is shown that the additional results obtained support the identification of the main isotopically sensitive step and its relative contribution to the overall reaction rate, the identification of other kinetically significant steps and the differentiation between stepwise and concerted reaction mechanisms. The method and its advantages are demonstrated on reactions comprising C-N-bond splitting (urease and arginase reaction), C-C-bound fission (reactions catalyzed by pyruvate-dehydrogenase, pyruvate-formiate-lyase and lactate-oxidase), C-O-bound formation (ribulose-bisphosphate-oxygenase reaction), and N-O-bond fission (nitrate- and nitrite-reductase reactions). (orig.).
Platinum-Catalyzed Terminal-Selective C(sp3)–H Oxidation of Aliphatic Amines

Science.gov (United States)

Lee, Melissa; Sanford, Melanie S.

2016-01-01

This paper describes the terminal-selective Pt-catalyzed C(sp3)–H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol %. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (ii) it electronically deactivates the C–H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp3)–H oxidation of a variety of primary, secondary and tertiary amines. PMID:26439251
Combined cross-linked enzyme aggregates of horseradish peroxidase and glucose oxidase for catalyzing cascade chemical reactions.

Science.gov (United States)

Nguyen, Le Truc; Yang, Kun-Lin

2017-05-01

Cascade reactions involved unstable intermediates are often encountered in biological systems. In this study, we developed combined cross-linked enzyme aggregates (combi-CLEA) to catalyze a cascade reaction which involves unstable hydrogen peroxide as an intermediate. The combi-CLEA contains two enzymes̶ glucose oxidase (GOx) and horseradish peroxidase (HRP) which are cross-linked together as solid aggregates. The first enzyme GOx catalyzes the oxidation of glucose and produces hydrogen peroxide, which is used by the second enzyme HRP to oxidize 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS). The apparent reaction rate of the cascade reaction reaches 10.5±0.5μM/min when the enzyme ratio is 150:1 (GOx:HRP). Interestingly, even in the presence of catalase, an enzyme that quickly decomposes hydrogen peroxide, the reaction rate only decreases by 18.7% to 8.3±0.3μM/min. This result suggests that the intermediate hydrogen peroxide is not decomposed by catalase due to a short diffusion distance between GOx and HRP in the combi-CLEA. Scanning electron microscopy images suggest that combi-CLEA particles are hollow spheres and have an average diameter around 250nm. Because of their size, combi-CLEA particles can be entrapped inside a nylon membrane for detecting glucose by using the cascade reaction. Copyright © 2017 Elsevier Inc. All rights reserved.
Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework.

Science.gov (United States)

Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei; Sanchez-Sanchez, Maricruz; Ortuño, Manuel A; Pahls, Dale R; Fulton, John L; Camaioni, Donald M; Li, Zhanyong; Ray, Debmalya; Mehdi, B Layla; Browning, Nigel D; Farha, Omar K; Hupp, Joseph T; Cramer, Christopher J; Gagliardi, Laura; Lercher, Johannes A

2017-08-02

Copper oxide clusters synthesized via atomic layer deposition on the nodes of the metal-organic framework (MOF) NU-1000 are active for oxidation of methane to methanol under mild reaction conditions. Analysis of chemical reactivity, in situ X-ray absorption spectroscopy, and density functional theory calculations are used to determine structure/activity relations in the Cu-NU-1000 catalytic system. The Cu-loaded MOF contained Cu-oxo clusters of a few Cu atoms. The Cu was present under ambient conditions as a mixture of ∼15% Cu + and ∼85% Cu 2+ . The oxidation of methane on Cu-NU-1000 was accompanied by the reduction of 9% of the Cu in the catalyst from Cu 2+ to Cu + . The products, methanol, dimethyl ether, and CO 2 , were desorbed with the passage of 10% water/He at 135 °C, giving a carbon selectivity for methane to methanol of 45-60%. Cu oxo clusters stabilized in NU-1000 provide an active, first generation MOF-based, selective methane oxidation catalyst.
Investigations Of Surface-Catalyzed Reactions In A Mars Mixture

Science.gov (United States)

Dougherty, Max; Owens, W.; Meyers, J.; Fletcher, D. G.

2011-05-01

In the design of a thermal protection system (TPS) for a planetary entry vehicle, accurate modeling of the trajectory aero-heating poses a significant challenge owing to large uncertainties in chemical processes taking place at the surface. Even for surface-catalyzed reactions, which have been investigated extensively, there is no consensus on how they should be modeled; or, in some cases, on which reactions are likely to occur. Current TPS designs for Mars missions rely on a super-catalytic boundary condition, which assumes that all dissociated species recombine to the free stream composition.While this is recognized to be the the most conservative approach, discrepancies in aero-heating measurements in ground test facilities preclude less conservative design options, resulting in an increased TPS mass at the expense of scientific pay- load.Using two-photon absorption laser induced fluorescence in a 30 kW inductively coupled plasma torch facility, preliminary studies have been performed to obtain spatially-resolved measurements of the dominant species in a plasma boundary layer for a Martian atmosphere mixture over catalytic and non-catalytic surfaces.
Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides

Science.gov (United States)

Strieter, Eric R.; Bhayana, Brijesh; Buchwald, Stephen L.

2009-01-01

The copper-catalyzed N-arylation of amides, i.e., the Goldberg reaction, is an efficient method for the construction of products relevant to both industry and academic settings. Herein, we present mechanistic details concerning the catalytic and stoichiometric N-arylation of amides. In the context of the catalytic reaction, our findings reveal the importance of chelating diamine ligands in controlling the concentration of the active catalytic species. The consistency between the catalytic and stoichiometric results suggest that the activation of aryl halides occurs through a 1,2-diamine-ligated copper(I) amidate complex. Kinetic studies on the stoichiometric N-arylation of aryl iodides using 1,2-diamine ligated Cu(I) amidates also provide insights into the mechanism of aryl halide activation. PMID:19072233
Negative resists for i-line lithography utilizing acid-catalyzed intramolecular dehydration reaction

Science.gov (United States)

Ueno, Takumi; Uchino, Shou-ichi; Hattori, Keiko T.; Onozuka, Toshihiko; Shirai, Seiichiro; Moriuchi, Noboru; Hashimoto, Michiaki; Koibuchi, S.

1994-05-01

Chemical amplification negative resist system composed of a novolak resin, a carbinol and an acid generator is investigated for i-line phase-shift lithography. The reaction in this resist is based on an acid-catalyzed intramolecular dehydration reaction. The dehydration products act as aqueous-base dissolution inhibitors, and carbinol compounds in unexposed areas work as dissolution promoters. The resist composed of a novolak resin, 1,4-bis((alpha) -hydroxyisopropyl) benzene (DIOL-1) and 2- naphthoylmethyltetramethylenesulfonium triflate (PAG-2) gives the best lithographic performance in terms of sensitivity and resolution. Line-and-space patterns of 0.275 micrometers are obtained using an i-line stepper (NA:0.45) in conjunction with a phase shifting mask.
Palladium-catalyzed domino C,N-coupling/carbonylation/Suzuki coupling reaction: an efficient synthesis of 2-aroyl-/heteroaroylindoles.

Science.gov (United States)

Arthuis, Martin; Pontikis, Renée; Florent, Jean-Claude

2009-10-15

A convenient one-pot synthesis of 2-aroylindoles using a domino palladium-catalyzed C,N-coupling/carbonylation/C,C-coupling sequence is described. The reaction involved easily prepared 2-gem-dibromovinylanilines and boronic acids under carbon monoxide. Optimized reaction conditions allowed the construction of a wide variety of highly functionalized 2-aroyl-/heteroaroylindoles in satisfactory yields.
Titanocene(III)-Catalyzed Three-Component Reaction of Secondary Amides, Aldehydes, and Electrophilic Alkenes.

Science.gov (United States)

Zheng, Xiao; He, Jiang; Li, Heng-Hui; Wang, Ao; Dai, Xi-Jie; Wang, Ai-E; Huang, Pei-Qiang

2015-11-09

An umpolung Mannich-type reaction of secondary amides, aliphatic aldehydes, and electrophilic alkenes has been disclosed. This reaction features the one-pot formation of C-N and C-C bonds by a titanocene-catalyzed radical coupling of the condensation products, from secondary amides and aldehydes, with electrophilic alkenes. N-substituted γ-amido-acid derivatives and γ-amido ketones can be efficiently prepared by the current method. Extension to the reaction between ketoamides and electrophilic alkenes allows rapid assembly of piperidine skeletons with α-amino quaternary carbon centers. Its synthetic utility has been demonstrated by a facile construction of the tricyclic core of marine alkaloids such as cylindricine C and polycitorol A. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Ruthenium-catalyzed reactions--a treasure trove of atom-economic transformations.

Science.gov (United States)

Trost, Barry M; Frederiksen, Mathias U; Rudd, Michael T

2005-10-21

The demand for new chemicals spanning the fields of health care to materials science combined with the pressure to produce these substances in an environmentally benign fashion pose great challenges to the synthetic chemical community. The maximization of synthetic efficiency by the conversion of simple building blocks into complex targets remains a fundamental goal. In this context, ruthenium complexes catalyze a number of non-metathesis conversions and allow the rapid assembly of complex molecules with high selectivity and atom economy. These complexes often exhibit unusual reactivity. Careful consideration of the mechanistic underpinnings of the transformations can lead to the design of new reactions and the discovery of new reactivity.
A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

Science.gov (United States)

Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

2016-09-27

Binary catalyst systems comprising a cationic Ru-CNC pincer complex and an alkali metal salt were developed for selective hydroboration of CO 2 utilizing pinacolborane at r.t. and 1 atm CO 2 , with the combination of [Ru(CNC Bn )(CO) 2 (H)][PF 6 ] and KOCO 2 t Bu producing formoxyborane in 76% yield. A bicyclic catalytic mechanism was proposed and discussed.
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.
CLC in packed beds using syngas and CuO/Al2O3: Model description and experimental validation

International Nuclear Information System (INIS)

Hamers, H.P.; Gallucci, F.; Cobden, P.D.; Kimball, E.; Sint Annaland, M. van

2014-01-01

Highlights: • CLC with CuO/Al 2 O 3 and syngas and air has been demonstrated experimentally. • Model predicts accurately only if kinetics describe the complete solid reduction. • CuO/Al 2 O 3 is proven to catalyze the reversed water gas shift reaction. • H 2 O is more effective to suppress carbon deposition on CuO/Al 2 O 3 than CO 2 . • The OC reaction rate is not permanently affected by exposure to H 2 S. - Abstract: The objective of this work is to study the performance of the oxygen carrier in a packed bed with periodic switching between oxidizing and reducing conditions. In this paper the performance of CuO/Al 2 O 3 as the oxygen carrier in a packed bed reactor with syngas as the fuel are investigated, while also studying the (possible) carbon deposition and the effect of sulphur impurities on the stability of the carrier. Both experiments and simulations are used in this work. Cyclic experiments (oxidation with air and reduction with syngas) have been carried out in a lab scale packed bed reactor with 13 wt% CuO/Al 2 O 3 . The experimental results were well described by a 1D reactor model, provided that critical attention was given to the reaction rate for the complete reduction reaction, including a dramatic decrease in reaction rate at high solid conversions. Feeding syngas (p H2 = p CO = 0.1 bar) resulted in 1.1% carbon deposition of the feed. Steam was proven to be more effective in reducing carbon deposition than CO 2 . Moreover, it has been found that CuO/Al 2 O 3 catalyzed the water gas shift reaction and the reaction rate was not permanently affected by exposure to H 2 S, two key factors for CLC operation. The results of this work imply that CuO/Al 2 O 3 is an effective oxygen carrier as the first packed bed reactor in a TSCLC process and that the developed model is able to describe the performance at larger scales accurately
An Efficient Synthesis of Substituted Quinolines via Indium(III) Chloride Catalyzed Reaction of Imines with Alkynes

International Nuclear Information System (INIS)

Zhu, Mei; Fu, Weijun; Xun, Chen; Zou, Guanglong

2012-01-01

An efficient synthetic method for the preparation of quinolines through indium(III) chloride-catalyzed tandem addition-cyclization-oxidation reactions of imines with alkynes was developed. The processes can provide a diverse range of quinoline derivatives in good yields from simple imines and alkynes
Ab initio molecular dynamics study of thermite reaction at Al and CuO nano-interfaces at different temperatures

Science.gov (United States)

Tang, Cui-Ming; Chen, Xiao-Xu; Cheng, Xin-Lu; Zhang, Chao-Yang; Lu, Zhi-Peng

2018-05-01

The thermite reaction at Al/CuO nano-interfaces is investigated with ab initio molecular dynamics calculations in canonical ensemble at 500 K, 800 K, 1200 K and 1500 K, respectively. The reaction process and reaction products are analyzed in terms of chemical bonds, average charge, time constants and total potential energy. The activity of the reactants enhances with increasing temperature, which induces a faster thermite reaction. The alloy reaction obviously expands outward at Cu-rich interface of Al/CuO system, and the reaction between Al and O atoms obviously expands outward at O-rich interface as temperature increases. Different reaction products are found at the outermost layer of different interfaces in the Al/CuO system. In generally, the average charge of the outer layer aluminum atoms (i.e., Al1, Al2, Al5 and Al6) increases with temperature. The potential energy of Al/CuO system decreases significantly, which indicates that drastic exothermic reaction occurs at the Al/CuO system. This research enhances fundamental understanding in temperature effect on the thermite reaction at atomic level, which can potentially open new possibilities for its industrial application.

The Reaction Mechanism and Rate Constants in the Radiolysis of Fe2+-Cu2+ Solutions

DEFF Research Database (Denmark)

Bjergbakke, Erling; Sehested, Knud; Rasmussen, O. Lang

1976-01-01

Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some ...... 10^{8}$ and $1.3\\times 10^{8}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$ in pH 2.1 H2 SO4 and HClO4, respectively.......Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some...... of the reactions have been determined at different pH's. $k_{{\\rm Cu}^{+}+{\\rm O}_{2}}=4.6\\times 10^{5}$ and $1.0\\times 10^{6}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$, $k_{{\\rm Cu}^{+}+{\\rm Fe}^{3+}}=5.5\\times 10^{6}$ and $1.3\\times 10^{7}\\ {\\rm mol}^{-1}\\ {\\rm sec}^{-1}$, $k_{{\\rm Cu}({\\rm III)}+{\\rm Fe}^{2+}}=3.3\\times...
Palladium-catalyzed three-component reaction of N-tosyl hydrazones, isonitriles and amines leading to amidines.

Science.gov (United States)

Dai, Qiang; Jiang, Yan; Yu, Jin-Tao; Cheng, Jiang

2015-12-04

A palladium-catalyzed three-component reaction between N-tosyl hydrazones, aryl isonitriles and amines was developed, leading to amidines in moderate to good yields. This procedure features the rapid construction of amidine frameworks with high diversity and complexity. Ketenimines serve as intermediates, which encounter nucleophilic attack by amines to produce amidines.
Rhodium-Catalyzed Insertion Reaction of PhP Group of Pentaphenylcyclopentaphosphine with Acyclic and Cyclic Disulfides.

Science.gov (United States)

Arisawa, Mieko; Sawahata, Kyosuke; Yamada, Tomoki; Sarkar, Debayan; Yamaguchi, Masahiko

2018-02-16

Organophosphorus compounds with a phosphorus atom attached to a phenyl group and two organothio/organoseleno groups were synthesized using the rhodium-catalyzed insertion reaction of the PhP group of pentaphenylcyclopentaphosphine (PhP) 5 with acyclic disulfides and diselenides. The method was applied to the synthesis of heterocyclic compounds containing the S-P-S group by the reaction of (PhP) 5 and cyclic disulfides such as 1,2-dithietes, 1,2-dithiocane, 1,4,5-dithiopane, and 1,2-dithiolanes.
Gold-catalyzed tandem hydroamination/formal aza-Diels-Alder reaction of homopropargyl amino esters: a combined computational and experimental mechanistic study.

Science.gov (United States)

Miró, Javier; Sánchez-Roselló, María; González, Javier; del Pozo, Carlos; Fustero, Santos

2015-03-27

A tandem gold-catalyzed hydroamination/formal aza-Diels-Alder reaction is described. This process, which employs quaternary homopropargyl amino ester substrates, leads to the formation of an intrincate tetracyclic framework and involves the generation of four bonds and five stereocenters in a highly diastereoselective manner. Theoretical calculations have allowed us to propose a suitable mechanistic rationalization for the tandem protocol. Additionally, by studying the influence of the ligands on the rate of the gold-catalyzed reactions, it was possible to establish optimum conditions in which to perform the process with a variety of substituents on the amino ester substrates. Notably, the asymmetric version of the tandem reaction was also evaluated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Kinetic and mechanism formation reaction of complex compound Cu with di-n-buthildithiocarbamate (dbdtc) ligand

Science.gov (United States)

Haryani, S.; Kurniawan, C.; Kasmui

2018-04-01

Synthesis of complex compound is one field of research which intensively studied. Metal-dithiocarbamate complexes find wide-ranging applications in nanomaterial and metal separation science, and have potential use as chemotherapeutic, pesticides, and as additives to lubricants. However, the information about is reaction kinetic and mechanism are very much lacking. The research and analyzes results show that reaction synthesis ligand DBDTC and complex compounds Cu-DBDTC. Optimum reaction condition of formation of complex compounds Cu with DBDTC at pH=3, [DBDTC] = 4.10-3 M, and the time of reaction 5 minutes. Based the analysis varian reaction of complex compounds at pH 3 and 4, diffrence significance at the other pH: 5; 5,5; 6; 6,5 ; 7; and 8. The various of mole with reactants comosition difference sigbificance, those the time reaction for 5 and 6 minutes diffrence by significance with the other time, it is 3,4,8, and 10 minutes. The great product to at condition pH 6, the time optimum at 5 minutes and molar ratio of logam: ligand = 1:2. The reaction kinetic equation of complex compound Cu with chelathing ligand DBDTC is V=0.917106 [Cu2+]0.87921 [DBDTC]2.03021. Based on the kinetic data, and formed complex compounds estimation, the mechanism explaining by 2 stages. In the first stage formation of [Cu(DBDTC)], and then [Cu(DBDTC)2] with the last structure geomethry planar rectangle. The result of this research will be more useful if an effort is being done in reaction mechanism by chemical computation method for obtain intermediate, and for constant “k” in same stage, k1.k2. and compound complex constanta (β).
Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO2 and H2O

Science.gov (United States)

Chen, S.G.; Yang, R.T.

1997-01-01

From molecular orbital calculations, a unified mechanism is proposed for the gasification reactions of graphite by CO2 and H2O, both uncatalyzed and catalyzed by alkali and alkaline earth catalysts. In this mechanism, there are two types of oxygen intermediates that are bonded to the active edge carbon atoms: an in-plane semiquinone type, Cf(O), and an off-plane oxygen bonded to two saturated carbon atoms that are adjacent to the semiquinone species, C(O)Cf(O). The rate-limiting step is the decomposition of these intermediates by breaking the C-C bonds that are connected to Cf(O). A new rate equation is derived for the uncatalyzed reactions, and that for the catalyzed reactions is readily available from the proposed mechanism. The proposed mechanism can account for several unresolved experimental observations: TPD and TK (transient kinetics) desorption results of the catalyzed systems, the similar activation energies for the uncatalyzed and catalyzed reactions, and the relative activities of the alkali and alkaline earth elements. The net charge of the edge carbon active site is substantially changed by gaining electron density from the alkali or alkaline earth element (by forming C-O-M, where M stands for metal). The relative catalytic activities of these elements can be correlated with their abilities of donating electrons and changing the net charge of the edge carbon atom. As shown previously (Chen, S. G.; Yang, R. T. J. Catal. 1993, 141, 102), only clusters of the alkali compounds are active. This derives from the ability of the clusters to dissociate CO2 and H2O to form O atoms and the mobility of the dissociated O atoms facilitated by the clusters.
Transition metal-catalyzed carboxylation reactions with carbon dioxide.

Science.gov (United States)

Martin, Ruben; Tortajada, Andreu; Juliá-Hernández, Francisco; Borjesson, Marino; Moragas, Toni

2018-05-03

Driven by the inherent synthetic potential of CO2 as an abundant, inexpensive and renewable C1 chemical feedstock, the recent years have witnessed renewed interest in devising catalytic CO2 fixations into organic matter. Although the formation of C-C bonds via catalytic CO2 fixation remained rather limited for a long period of time, a close look into the recent literature data indicates that catalytic carboxylation reactions have entered a new era of exponential growth, evolving into a mature discipline that allows for streamlining the synthesis of carboxylic acids, building blocks of utmost relevance in industrial endeavours. These strategies have generally proven broadly applicability and convenient to perform. However, substantial challenges still need to be addressed reinforcing the need to cover metal-catalyzed carboxylation arena in a conceptual and concise manner, delineating the underlying new principles that are slowly emerging in this vibrant area of expertise. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
[Study of ATP-independent stages of reaction catalyzed by phage T4 RNA-ligase].

Science.gov (United States)

Zagrebel'nyĭ, S N; Zernov, Iu P

1986-01-01

The isotope exchange between [5'-32P]pAP and A(5')ppAp catalyzed by enzyme was shown not to take place in the absence of the acceptor; i. e. the necessity of the acceptor presence during the second step of the process was demonstrated. The isotope exchange reaction between [5'32P]pAp and (pA)5p was studied. It was demonstrated that acceptor (pA)4, slightly whereas the acceptor (pU)4 completely inhibits the isotope reaction. The isotope reaction exchange between [5'-32P]pAp and (pU)4pAp does not take place. The question of existence of adenylated donor elimination mechanism in the presence of "poor" acceptors is considered on the basis of the data obtained.
Pd-catalyzed versus uncatalyzed, PhI(OAc)2-mediated cyclization reactions of N6-([1,1'-biaryl]-2-yl)adenine nucleosides.

Science.gov (United States)

Satishkumar, Sakilam; Poudapally, Suresh; Vuram, Prasanna K; Gurram, Venkateshwarlu; Pottabathini, Narender; Sebastian, Dellamol; Yang, Lijia; Pradhan, Padmanava; Lakshman, Mahesh K

2017-11-09

In this work we have assessed reactions of N 6 -([1,1'-biaryl]-2-yl)adenine nucleosides with Pd(OAc) 2 and PhI(OAc) 2 , via a Pd II /Pd IV redox cycle. The substrates are readily obtained by Pd/Xantphos-catalyzed reaction of adenine nucleosides with 2-bromo-1,1'-biaryls. In PhMe, the N 6 -biarylyl nucleosides gave C6-carbazolyl nucleoside analogues by C-N bond formation with the exocyclic N 6 nitrogen atom. In the solvent screening for the Pd-catalyzed reactions, an uncatalyzed process was found to be operational. It was observed that the carbazolyl products could also be obtained in the absence of a metal catalyst by reaction with PhI(OAc) 2 in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP). Thus, under Pd catalysis and in HFIP, reactions proceed to provide carbazolyl nucleoside analogues, with some differences. If reactions of N 6 -biarylyl nucleoside substrates were conducted in MeCN, formation of aryl benzimidazopurinyl nucleoside derivatives was observed in many cases by C-N bond formation with the N 1 ring nitrogen atom of the purine (carbazole and benzimidazole isomers are readily separated by chromatography). Whereas Pd II /Pd IV redox is responsible for carbazole formation under the metal-catalyzed conditions, in HFIP and MeCN radical cations and/or nitrenium ions can be intermediates. An extensive set of radical inhibition experiments was conducted and the data are presented.
Efficient Destruction of Pollutants in Water by a Dual-Reaction-Center Fenton-like Process over Carbon Nitride Compounds-Complexed Cu(II)-CuAlO2.

Science.gov (United States)

Lyu, Lai; Yan, Dengbiao; Yu, Guangfei; Cao, Wenrui; Hu, Chun

2018-04-03

Carbon nitride compounds (CN) complexed with the in-situ-produced Cu(II) on the surface of CuAlO 2 substrate (CN-Cu(II)-CuAlO 2 ) is prepared via a surface growth process for the first time and exhibits exceptionally high activity and efficiency for the degradation of the refractory pollutants in water through a Fenton-like process in a wide pH range. The reaction rate for bisphenol A removal is ∼25 times higher than that of the CuAlO 2 . According to the characterization, Cu(II) generation on the surface of CuAlO 2 during the surface growth process results in the marked decrease of the surface oxygen vacancies and the formation of the C-O-Cu bridges between CN and Cu(II)-CuAlO 2 in the catalyst. The electron paramagnetic resonance (EPR) analysis and density functional theory (DFT) calculations demonstrate that the dual reaction centers are produced around the Cu and C sites due to the cation-π interactions through the C-O-Cu bridges in CN-Cu(II)-CuAlO 2 . During the Fenton-like reactions, the electron-rich center around Cu is responsible for the efficient reduction of H 2 O 2 to • OH, and the electron-poor center around C captures electrons from H 2 O 2 or pollutants and diverts them to the electron-rich area via the C-O-Cu bridge. Thus, the catalyst exhibits excellent catalytic performance for the refractory pollutant degradation. This study can deepen our understanding on the enhanced Fenton reactivity for water purification through functionalizing with organic solid-phase ligands on the catalyst surface.
The investigation on electrochemical reaction mechanism of CuF2 thin film with lithium

International Nuclear Information System (INIS)

Cui Yanhua; Xue Mingzhe; Zhou Yongning; Peng Shuming; Wang Xiaolin; Fu Zhengwen

2011-01-01

Crystalline CuF 2 thin films were prepared by pulsed laser deposition under room temperature. The physical and electrochemical properties of the as-deposited thin films have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic cycling and cyclic voltammetry (CV). Reversible capacity of 544 mAh g -1 was achieved in the potential range of 1.0-4.0 V. A reversible couple of redox peaks at 3.0 V and 3.7 V was firstly observed. By using ex situ XRD and TEM techniques, an insertion process followed by a fully conversion reaction to Cu and LiF was revealed in the lithium electrochemical reaction of CuF 2 thin film electrode. The reversible insertion reaction above 2.8 V could provide a capacity of about 125 mAh g -1 , which makes CuF 2 a potential cathode material for rechargeable lithium batteries.
NHC-Copper(I) Halide-Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Water

KAUST Repository

Czerwiński, Paweł

2016-05-04

An efficient and easily scalable NHC-copper(I) halide-catalyzed addition of terminal alkynes to 1,1,1-trifluoromethyl ketones, carried out on water for the first time, is reported. A series of addition reactions were performed with as little as 0.1-2.0mol% of [(NHC)CuX] (X=Cl, Br, I, OAc, OTf) complexes, providing tertiary propargylic trifluoromethyl alcohols in high yields and with excellent chemoselectivity from a broad range of aryl- and more challenging alkyl-substituted trifluoromethyl ketones (TFMKs). DFT calculations were performed to rationalize the correlation between the yield of catalytic alkynylation and the sterics of N-heterocyclic carbenes (NHCs), expressed as buried volume (%VBur), indicating that steric effects dominate the yield of the reaction. Additional DFT calculations shed some light on the differential reactivity of [(NHC)CuX] complexes in the alkynylation of TFMKs. The first enantioselective version of a direct alkynylation in the presence of C1-symmetric NHC-copper(I) complexes is also presented. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Solvent- and ligand-induced switch of selectivity in gold(I-catalyzed tandem reactions of 3-propargylindoles

Directory of Open Access Journals (Sweden)

Roberto Sanz

2011-06-01

Full Text Available The selectivity of our previously described gold-catalyzed tandem reaction, 1,2-indole migration followed by aura-iso-Nazarov cyclization, of 3-propargylindoles bearing (heteroaromatic substituents at both the propargylic and terminal positions, was reversed by the proper choice of the catalyst and the reaction conditions. Thus, 3-(inden-2-ylindoles, derived from an aura-Nazarov cyclization (instead of an aura-iso-Nazarov cyclization, were obtained in moderate to good yields from a variety of 3-propargylindoles.
Remediation of Cu metal-induced accelerated Fenton reaction by potato peels bio-sorbent.

Science.gov (United States)

Azmat, Rafia; Moin, Sumeira; Saleem, Ailyan

2016-12-01

This article has allied exposure to Ecological Particulate Matter (EPM) and its remediation using potato peel surface (PPC) bio-sorbent on two important edible crops Spinacia oleracea and Luffa acutangula. Fenton reaction acceleration was one of the major stress oxidation reactions as a consequence of iron and copper toxicity, which involve in the formation of hydroxyl radical (OH) through EPM. Results showed that the oxidative stress encouraged by Cu in both species that recruits the degradation of photosynthetic pigments, initiating decline in growth, reduced leaf area and degrade proteins. The plants were cultivated in natural environmental condition in three pots with three replicates like (a) control, (b) Cu treated and (c) treated water. Oxidative stress initiated by metal activity in Cu accumulated plant (b) were controlled, through bio-sorption of metal from contaminated water using PPC; arranged at laboratory scale. The acceleration of Fenton reaction was verified in terms of OH radical generation. These radicals were tested in aqueous extract of leaves of three types of plants via benzoic acid. The benzoic acid acts as a scavenger of OH radical due to which the decarboxylation of benzoic acid cured. Observation on (b) showed more rapid decarboxylation as compared to other plants which showed that Cu activity was much higher in (b) as compared to (a) and (c). The rapid decarboxylation of benzoic acid and lower chlorophyll contents in (b) suggest that Fenton reaction system was much enhanced by Cu-O and Fe-O chemistry that was successfully controlled by PPC which results in restoring the metabolic pathway and nullifying oxidative stress in (c).
Mechanisms of reactions of organoaluminium compounds with alkenes and alkynes catalyzed by Zr complexes

International Nuclear Information System (INIS)

Parfenova, L V; Khalilov, Leonard M; Dzhemilev, Usein M

2012-01-01

The results of studies dealing with mechanisms of hydro-, carbo- and cycloalumination of alkenes and alkynes catalyzed by zirconium complexes are generalized and systematized for the first time. Data about the structures of intermediates responsible for the formation of the target compounds are presented and the available data on the effect of the structure of organoaluminium compounds and the electronic and steric factors determining the catalytic activity of metal complexes in these reactions are considered in detail. Much attention is paid to studies of the influence of reaction conditions on the chemo-, regio- and stereoselectivity of the Zr-containing complex catalysts. The bibliography includes 217 references.
Cu(II)-catalyzed oxidation of dopamine in aqueous solutions: mechanism and kinetics.

Science.gov (United States)

Pham, A Ninh; Waite, T David

2014-08-01

Spontaneous oxidation of dopamine (DA) and the resultant formation of free radical species within dopamine neurons of the substantia nigra (SN) is thought to bestow a considerable oxidative load upon these neurons and may contribute to their vulnerability to degeneration in Parkinson's disease (PD). An understanding of DA oxidation under physiological conditions is thus critical to understanding the relatively selective vulnerability of these dopaminergic neurons in PD and may support the development of novel neuro-protective approaches for this disorder. In this study, the oxidation of dopamine (0.2-10μM) was investigated both in the absence and the presence of copper (0.01-0.4μM), a redox active metal that is present at considerable concentrations in the SN, over a range of background chloride concentrations (0.01-0.7M), different oxygen concentrations and at physiological pH7.4. DA was observed to oxidize extremely slowly in the absence of copper and at moderate rates only in the presence of copper but without chloride. The oxidation of DA however was significantly enhanced in the presence of both copper and chloride with the rate of DA oxidation greatest at intermediate chloride concentrations (0.05-0.2M). The variability of the catalytic effect of Cu(II) on DA oxidation at different chloride concentrations can be explained and successfully modeled by appropriate consideration of the reaction of Cu(II) species with DA and the conversion of Cu(I) to Cu(II) through oxygenation. This model suggests that the speciation of Cu(II) and Cu(I) is critically important to the kinetics of DA oxidation and thus the vulnerability to degradation of dopaminergic neuron in the brain milieu. Copyright © 2014 Elsevier Inc. All rights reserved.
Mechanism insight of pollutant degradation and bromate inhibition by Fe-Cu-MCM-41 catalyzed ozonation.

Science.gov (United States)

Chen, Weirui; Li, Xukai; Tang, Yiming; Zhou, Jialu; Wu, Dan; Wu, Yin; Li, Laisheng

2018-03-15

A flexible catalyst, Fe-Cu-MCM-41, was employed to enhance diclofenac (DCF) mineralization and inhibit bromate formation in catalytic ozonation process. Greater TOC removal was achieved in Fe-Cu-MCM-41/O 3 process (78%) than those in Fe-MCM-41/O 3 (65%), Cu-MCM-41/O 3 (73%) and sole ozonation (42%). But it was interesting that both Cu-MCM-41/O 3 and Fe-MCM-41/O 3 achieved 93% bromate inhibition efficiency, only 71% inhibition efficiency was observed in Fe-Cu-MCM-41/O 3 . Influence of pH, TBA/NaHSO 3 and detection of by-products were conducted to explore the mechanism. By Pyridine adsorption-IR and XPS, a relationship was found among activity of catalysts, Lewis acid sites and electron transfer effect between Fe (II/III) and Cu (I/II). Fe-Cu-MCM-41 promoted ozone decomposition to generate OH, which accounted for enhanced DCF mineralization. The consumption of aqueous O 3 also suppressed the oxidative of Br - and HBrO/Br - . More HBrO/BrO - accumulated in catalytic ozonation process and less bromate generated. Bromate formation in Fe-Cu-MCM-41/O 3 process was sensitive with pH value, the acidic condition was not favor for bromate formation. Both DCF mineralization and bromate inhibition were influenced by surface reaction. Moreover, Fe-Cu-MCM-41 showed excellent catalytic performance in suppressing the accumulation of carboxylic acid, especially for oxalic acid. Nearly no oxalic acid was detected during Fe-Cu-MCM-41/O 3 process. Copyright © 2017 Elsevier B.V. All rights reserved.
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)
Al-Si/Al2O3 in situ composite prepared by displacement reaction of CuO/Al system

Directory of Open Access Journals (Sweden)

Zhang Jing

2010-02-01

Full Text Available Al2O3 particle-reinforced ZL109 composite was prepared by in situ reaction between CuO and Al. The microstructure was observed by means of OM, SEM and TEM. The Al2O3 particles in sub-micron sizes distribute uniformly in the matrix, and the Cu displaced from the in situ reaction forms net-like alloy phases with other alloy elements. The hardness and the tensile strength of the composites at room temperature have a slight increase as compared to that of the matrix. However, the tensile strength at 350 ℃ has reached 90.23 MPa, or 16.92 MPa higher than that of the matrix. The mechanism of the reaction in the CuO/Al system was studied by using of differential scanning calorimetry(DSC and thermodynamic calculation. The reaction between CuO and Al involves two steps. First, CuO reacts with Al to form Cu2O and Al2O3 at the melting temperature of the matrix alloy, and second, Cu2O reacts with Al to form Cu and Al2O3 at a higher temperature. At ZL109 casting temperature of 750–780 ℃, the second step can also take place because of the effect of exothermic reaction of the first step.
Synthesis of chitosan-PEO hydrogels via mesylation and regioselective Cu(I)-catalyzed cycloaddition.

Science.gov (United States)

Tirino, Pasquale; Laurino, Rosaria; Maglio, Giovanni; Malinconico, Mario; d'Ayala, Giovanna Gomez; Laurienzo, Paola

2014-11-04

In this work, a well-defined hydrogel was developed by coupling chitosan with PEO through "click chemistry". Azide functionalities were introduced onto chitosan, through mesylation of C-6 hydroxyl groups, and reacted with a di-alkyne PEO by a regioselective Cu(I)-catalyzed cycloaddition. This synthetic approach allowed us to obtain a hydrogel with a controlled crosslinking degree. In fact, the extent of coupling is strictly dependent on the amount of azido groups on chitosan, which in turn can be easily modulated. The obtained hydrogel, with a crosslinking degree of around 90%, showed interesting swelling properties. With respect to chitosan hydrogels reported in literature, a considerably higher equilibrium uptake was reached (940%). The possibility to control the crosslinking degree of hydrogel and its capability to rapidly absorb high amounts of water make this material suitable for several applications, such as controlled drug release and wound healing. Copyright © 2014. Published by Elsevier Ltd.

The Triple Roles of Glutathione for a DNA-Cleaving DNAzyme and Development of a Fluorescent Glutathione/Cu2+-Dependent DNAzyme Sensor for Detection of Cu2+ in Drinking Water.

Science.gov (United States)

Wang, Shijin; Liu, Chengcheng; Li, Guiying; Sheng, Yongjie; Sun, Yanhong; Rui, Hongyue; Zhang, Jin; Xu, Jiacui; Jiang, Dazhi

2017-03-24

Pistol-like DNAzyme (PLDz) is an oxidative DNA-cleaving catalytic DNA with ascorbic acid as cofactor. Herein, glutathione was induced into the reaction system to maintain reduced ascorbic acid levels for higher efficient cleavage. However, data indicated that glutathione played triple roles in PLDz-catalyzed reactions. Glutathione alone had no effect on PLDz, and showed inhibitory effect on ascorbic acid-induced PLDz catalysis, but exhibited stimulating effect on Cu 2+ -promoted self-cleavage of PLDz. Further analysis of the effect of glutathione/Cu 2+ on PLDz indicated that H 2 O 2 played a key role in PLDz catalysis. Finally, we developed a fluorescent Cu 2+ sensor (PL-Cu 1.0) based on the relationship between glutathione/Cu 2+ and catalytic activity of PLDz. The fluorescent intensity showed a linear response toward the logarithm concentration of Cu 2+ over the range from 80 nM to 30 μM, with a detection limit of 21.1 nM. PL-Cu 1.0 provided only detection of Cu 2+ over other divalent metal ions. Ca 2+ and Mg 2+ could not interfere with Cu 2+ detection even at a 1000-fold concentration. We further applied PL-Cu 1.0 for Cu 2+ detection in tap and bottled water. Water stored in copper taps overnight had relatively high Cu 2+ concentrations, with a maximum 22.3 μM. Trace Cu 2+ (52.2 nM) in deep spring was detected among the tested bottled water. Therefore, PL-Cu 1.0 is feasible to detect Cu 2+ in drinking water, with a practical application.
Tandem Cu-catalyzed ketenimine formation and intramolecular nucleophile capture: Synthesis of 1,2-dihydro-2-iminoquinolines from 1-(o-acetamidophenyl)propargyl alcohols

Science.gov (United States)

Kant, Ruchir

2014-01-01

Summary The copper-catalyzed ketenimine formation reaction of 1-(o-acetamidophenyl)propargyl alcohols with various sulfonyl azides is found to undergo a concomitant intramolecular nucleophile attack to generate 1,2-dihydro-2-iminoquinolines after aromatization (via elimination of acetyl and hydroxy groups) and tautomerization. The reaction produces 4-substituted and 3,4-unsubstituted title compounds in moderate to good yields under mild reaction conditions. PMID:24991276
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...
CuAAC-Based Click Chemistry in Self-Healing Polymers.

Science.gov (United States)

Döhler, Diana; Michael, Philipp; Binder, Wolfgang H

2017-10-17

Click chemistry has emerged as a significant tool for materials science, organic chemistry, and bioscience. Based on the initial concept of Barry Sharpless in 2001, the copper(I)-catalyzed azide/alkyne cycloaddition (CuAAC) reaction has triggered a plethora of chemical concepts for linking molecules and building blocks under ambient conditions, forming the basis for applications in autonomous cross-linking materials. Self-healing systems on the other hand are often based on mild cross-linking chemistries that are able to react either autonomously or upon an external trigger. In the ideal case, self-healing takes place efficiently at low temperatures, independent of the substrate(s) used, by forming strong and stable networks, binding to the newly generated (cracked) interfaces to restore the original material properties. The use of the CuAAC in self-healing systems, most of all the careful design of copper-based catalysts linked to additives as well as the chemical diversity of substrates, has led to an enormous potential of applications of this singular reaction. The implementation of click-based strategies in self-healing systems therefore is highly attractive, as here chemical (and physical) concepts of molecular reactivity, molecular design, and even metal catalysis are connected to aspects of materials science. In this Account, we will show how CuAAC reactions of multivalent components can be used as a tool for self-healing materials, achieving cross-linking at low temperatures (exploiting concepts of autocatalysis or internal chelation within the bulk CuAAC and systematic optimization of the efficiency of the used Cu(I) catalysts). Encapsulation strategies to separate the click components by micro- and nanoencapsulation are required in this context. Consequently, the examples reported here describe chemical concepts to realize more efficient and faster click reactions in self-healing polymeric materials. Thus, enhanced chain diffusion in (hyper
Flavin-N5 Covalent Intermediate in a Nonredox Dehalogenation Reaction Catalyzed by an Atypical Flavoenzyme.

Science.gov (United States)

Dai, Yumin; Kizjakina, Karina; Campbell, Ashley C; Korasick, David A; Tanner, John J; Sobrado, Pablo

2018-01-04

The flavin-dependent enzyme 2-haloacrylate hydratase (2-HAH) catalyzes the conversion of 2-chloroacrylate, a major component in the manufacture of acrylic polymers, to pyruvate. The enzyme was expressed in Escherichia coli, purified, and characterized. 2-HAH was shown to be monomeric in solution and contained a non-covalent, yet tightly bound, flavin adenine dinucleotide (FAD). Although the catalyzed reaction was redox-neutral, 2-HAH was active only in the reduced state. A covalent flavin-substrate intermediate, consistent with the flavin-acrylate iminium ion, was trapped with cyanoborohydride and characterized by mass spectrometry. Small-angle X-ray scattering was consistent with 2-HAH belonging to the succinate dehydrogenase/fumarate reductase family of flavoproteins. These studies establish 2-HAH as a novel noncanonical flavoenzyme. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Rhodium(III)-catalyzed three-component reaction of imines, alkynes, and aldehydes through C-H activation.

Science.gov (United States)

Huang, Ji-Rong; Song, Qiang; Zhu, Yu-Qin; Qin, Liu; Qian, Zhi-Yong; Dong, Lin

2014-12-15

An efficient rhodium(III)-catalyzed tandem three-component reaction of imines, alkynes and aldehydes through CH activation has been developed. High stereo- and regioselectivity, as well as good yields were obtained in most cases. The simple and atom-economical approach offers a broad scope of substrates, providing polycyclic skeletons with potential biological properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Kinetics and optimization on discoloration of dyeing wastewater by schorl-catalyzed fenton-like reaction

Directory of Open Access Journals (Sweden)

Xu Huan-Yan

2014-01-01

Full Text Available Kinetics and optimization on the discoloration of an active commercial dye, Argazol Blue BFBR (ABB by heterogeneous Fenton-like reaction catalyzed by natural schorl were investigated in this study. Kinetic investigations revealed that the first-order kinetic model was more favorable to describe the discoloration of ABB at different reaction conditions than the second-order and Behnajady-Modirshahla-Ghanbery models. The relationship between the reaction rate constant k and reaction temperature T followed the Arrhenius equation, with the apparent activation energy Ea of 51.31kJ•mol-1. The central composite design under the response surface methodology was employed for the experimental design and optimization of the ABB discoloration process. The significance of a second order polynomial model for predicting the optimal values of ABB discoloration was evaluated by the analysis of variance and 3D response surface plots for the interactions between two variables were constructed. Then, the optimum conditions were determined.
Preparation of carrier-free 67Cu by the 68Zn(γ,p) reaction

International Nuclear Information System (INIS)

Yagi, M.; Kondo, K.

1978-01-01

The preparation of pure, carrier-free 67 Cu using the 68 Zn(γ, p) reaction with an isotopically enriched 68 Zn(98.97%) target is described. The production rates of 67 Cu and contaminants were determined as a function of the maximum bremsstrahlung energies between 30 and 60 MeV. The chemical separation of the carrier-free 67 Cu and the recovery of the 68 Zn target were also studied. (author)
Electromigration-induced cracks in Cu/Sn3.5Ag/Cu solder reaction couple at room temperature

International Nuclear Information System (INIS)

He Hongwen; Xu Guangchen; Guo Fu

2009-01-01

Electromigration (EM) behavior of Cu/Sn 3.5 Ag/Cu solder reaction couple was investigated with a high current density of 5 x 10 3 A/cm 2 at room temperature. One dimensional structure, copper wire/solder ball/copper wire SRC was designed and fabricated to dissipate the Joule heating induced by the current flow. In addition, thermomigration effect was excluded due to the symmetrical structure of the SRC. The experimental results indicated that micro-cracks initially appeared near the cathode interface between solder matrix and copper substrate after 474 h current stressing. With current stressing time increased, the cracks propagated and extended along the cathode interface. It should be noted that the continuous Cu 6 Sn 5 intermetallic compounds (IMCs) layer both at the anode and at the cathode remained their sizes. Interestingly, tiny cracks appeared at the root of some long column-type Cu 6 Sn 5 at the cathode interface due to the thermal stress.
Phosphoramidite accelerated copper(I)-catalyzed [3+2] cycloadditions of azides and alkynes

NARCIS (Netherlands)

Campbell-Verduyn, Lachlan S.; Mirfeizi, Leila; Dierckx, Rudi A.; Elsinga, Philip H.; Feringa, Ben L.

2009-01-01

Monodentate phosphoramidite ligands are used to accelerate the copper(I)-catalyzed 1,3-dipolar cycloaddition of azides and alkynes (CuAAC) rapidly yielding a wide variety of functionalized 1,4-disubstituted-1,2,3-triazoles; Cu(I) and Cu(II) salts both function as the copper source in aqueous
Metallurgically prepared NiCu alloys as cathode materials for hydrogen evolution reaction

International Nuclear Information System (INIS)

Wang, Kunchan; Xia, Ming; Xiao, Tao; Lei, Ting; Yan, Weishan

2017-01-01

Ni−Cu bimetallic alloys with Cu content of 5, 10, 20, 30 and 50 wt% are prepared by powder metallurgy method, which consisted of powder mixing, pressing and sintering processes. The X-ray diffraction (XRD) measurement confirms that all the five Ni−Cu alloys possess the f.c.c. structure. The hydrogen evolution reaction (HER) activity of the prepared Ni−Cu alloy electrodes was studied in 6 M KOH solution by cathodic current-potential curves and electrochemical impedance spectroscopy (EIS) techniques. It was found that the electrocatalytic activity for the HER depended on the composition of Ni−Cu alloys, where Ni−10Cu alloy exhibited considerably higher HER activity than Ni plate and other Ni−Cu alloys, indicative of its chemical composition related intrinsic activity. - Highlights: • Ni−Cu alloys with various Cu contents were prepared by powder metallurgy method. • Ni−Cu alloy exhibits chemical composition related synergistic effect for HER activity. • Ni−10Cu alloy electrode presents a most efficient activity for HER. • Two time constants are observed in Nyquist curve and both of them related to the kinetics of HER.
Metallurgically prepared NiCu alloys as cathode materials for hydrogen evolution reaction

Energy Technology Data Exchange (ETDEWEB)

Wang, Kunchan; Xia, Ming [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Xiao, Tao [2nd Xiangya Hospital, Central South University, Changsha 410011 (China); Lei, Ting, E-mail: tlei@mail.csu.edu.cn [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Yan, Weishan [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China)

2017-01-15

Ni−Cu bimetallic alloys with Cu content of 5, 10, 20, 30 and 50 wt% are prepared by powder metallurgy method, which consisted of powder mixing, pressing and sintering processes. The X-ray diffraction (XRD) measurement confirms that all the five Ni−Cu alloys possess the f.c.c. structure. The hydrogen evolution reaction (HER) activity of the prepared Ni−Cu alloy electrodes was studied in 6 M KOH solution by cathodic current-potential curves and electrochemical impedance spectroscopy (EIS) techniques. It was found that the electrocatalytic activity for the HER depended on the composition of Ni−Cu alloys, where Ni−10Cu alloy exhibited considerably higher HER activity than Ni plate and other Ni−Cu alloys, indicative of its chemical composition related intrinsic activity. - Highlights: • Ni−Cu alloys with various Cu contents were prepared by powder metallurgy method. • Ni−Cu alloy exhibits chemical composition related synergistic effect for HER activity. • Ni−10Cu alloy electrode presents a most efficient activity for HER. • Two time constants are observed in Nyquist curve and both of them related to the kinetics of HER.
Kinetic study of the annealing reactions in Cu-Ni-Fe alloys

International Nuclear Information System (INIS)

Donoso, E.

2014-01-01

The thermal aging of a Cu-45Ni-4Fe, Cu-34Ni-11Fe and Cu-33Ni-22Fe alloys tempered from 1173 K have been studied from Differential Scanning Calorimetry (DSC) and microhardness measurements. The analysis of DSC curves, from room temperature to 950 K, shows the presence of one exothermic reaction associated to the formation of FeNi 3 phase nucleating from a modulate structure, and one endothermic peak attributed to dissolution of this phase. Kinetic parameters were obtained using the usual Avrami-Erofeev equation, modified Kissinger method and integrated kinetic functions. Microhardness measurements confirmed the formation and dissolution of the FeNi 3 phase. (Author)
Synthesis of 1,1-Diborylalkenes through a Bronsted Base Catalyzed Reaction between Terminal Alkynes and Bis(pinacolato)diboron

OpenAIRE

Morinaga, Akira; Nagao, Kazunori; Ohmiya, Hirohisa; Sawamura, Masaya

2015-01-01

A method for the synthesis of 1,1-diborylalkenes through a Bronsted base catalyzed reaction between terminal alkynes and bis(pinacolato)diboron has been developed. The procedure allows direct synthesis of functionalized 1,1-diborylalkenes from various terminal alkynes including propiolates, propiolamides, and 2-ethynylazoles.
Gold-Catalyzed Cyclization of Furan-Ynes bearing a Propargyl Carbonate Group: Intramolecular Diels-Alder Reaction with In Situ Generated Allenes.

Science.gov (United States)

Sun, Ning; Xie, Xin; Chen, Haoyi; Liu, Yuanhong

2016-09-26

Gold-catalyzed cyclization of various furan-ynes with a propargyl carbonate or ester moiety results in the formation of a series of polycyclic aromatic ring systems. The reactions can be rationalized through a tandem gold-catalyzed 3,3-rearrangement of the propargyl carboxylate moiety in furan-yne substrates to form an allenic intermediate, which is followed by an intramolecular Diels-Alder reaction of furan and subsequent ring-opening of the oxa-bridged cycloadduct. It was found that the steric and electronic properties of phosphine ligands on the gold catalyst had a significant impact on the reaction outcome. In the case of 1,5-furan-yne, the cleavage of the oxa-bridge in the cycloadduct with concomitant 1,2-migration of the R(1) group occurs to furnish anthracen-1(2H)-ones bearing a quaternary carbon center. For 1,4-furan-yne, a facile aromatization of the cycloadduct takes place to give 9-oxygenated anthracene derivatives. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
CuI/Pd0 cooperative dual catalysis: tunable stereoselective construction of tetra-substituted alkenes.

Science.gov (United States)

Vercruysse, Sébastien; Cornelissen, Loïc; Nahra, Fady; Collard, Laurent; Riant, Olivier

2014-02-10

This paper describes a tunable and stereoselective dual catalytic system that uses copper and palladium reagents. This cooperative silylcupration and palladium-catalyzed allylation readily affords trisubstituted alkenylsilanes. Fine-tuning the reaction conditions allows selective access to one stereoisomer over the other. This new methodology tolerates different substituents on both coupling partners with high levels of stereoselectivity. The one-pot reaction involving a Cu(I)/Pd(0) cooperative dual catalyst directly addresses the need to develop more time-efficient and less-wasteful synthetic pathways. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
N-Heterocyclic Carbene-Catalyzed Vinylogous Mukaiyama Aldol Reaction of α-Keto Esters and α-Trifluoromethyl Ketones

KAUST Repository

Du, Guang-Fen; Wang, Ying; Xing, Fen; Xue, Mei; Guo, Xu-Hong; Huang, Kuo-Wei; Dai, Bin

2015-01-01

© Georg Thieme Verlag Stuttgart · New York · Synthesis 2016. N-Heterocyclic carbene (NHC)-catalyzed vinylogous Mukaiyama aldol reaction of ketones was developed. Under the catalysis of 5 mol% NHC, α-keto esters and α-trifluoromethyl ketones reacted with 2-(trimethysilyloxy)furan efficiently to produce γ-substituted butenolides containing adjacent quaternary and tertiary carbon centers in high yields with good diastereoselectivities.
Experimental study of peripheral reactions in the 16O +63,65 Cu systems

International Nuclear Information System (INIS)

Razeto, G.R.

1987-01-01

In this work elastic scattering and ( 16 O,N) ( 16 O,C) transfer reaction data are presented for the 16 O + 63,65 Cu systems at the incident energy range of 40 to 64MeV. The data was analized with the Optical Model, and the total reaction cross section was compared with the fusion cross section data available from a previus work. Furthermore correlation was made between transfer processes with the different optical potential parameters for these systems. The Frahnand Venter fenomelogical modelo and DWBA calculations were employed for analysis of the transfer reaction data. For the 16 O + 63 Cu system beside the threshold anomaly, an atypical angles (θ cm > 140 0 ). The Regge poles ressonances formalism was used to explain it. (author) [pt
MOF-derived Cu/nanoporous carbon composite and its application for electro-catalysis of hydrogen evolution reaction

International Nuclear Information System (INIS)

Raoof, Jahan-Bakhsh; Hosseini, Sayed Reza; Ojani, Reza; Mandegarzad, Sakineh

2015-01-01

In this work, metal-organic framework Cu_3(BTC)_2 [BTC = 1,3,5-benzenetricarboxylate] (commonly known as MOF-199 or HKUST-1), is used as porous template for preparation of a Cu/nanoporous carbon composite. The MOF-derived Cu/nanoporous carbon composite (Cu/NPC composite) is synthesized by direct carbonization of the MOF-199 without any carbon precursor additive. The physical characterization of the solid catalyst is achieved by using a variety of different techniques, including XRD (X-ray powder diffraction), scanning electron microscopy, thermo-gravimetric analysis, and nitrogen physisorption measurements. The electrochemical results have shown that the Cu/NPC composite modified glassy carbon electrode (Cu/NPC/GCE) as a non-platinum electrocatalyst exhibited favorable catalytic activity for hydrogen evolution reaction, in spite of high resistance to faradic process. This behavior can be attributed to existence of Cu metal confirmed by XRD and/or high effective pore surface area (1025 m"2 g"−"1) in the Cu/NPC composite. The electron transfer coefficient and exchange current density for the Cu/NPC/GCE is calculated by Tafel plot at about 0.34 and 1.2 × 0"−"3 mAcm"−"2, respectively. - Graphical abstract: Metal organic framework-derived Cu/nanoporous carbon composite (Cu/NPC composite) was prepared by direct carbonization of MOF-199 without addition of any carbon source at 900 °C. The Cu/NPC/GCE demonstrated an excellent electrocatalytic activity towards hydrogen evolution reaction compared with bare GCE. - Highlights: • MDNPC (MOF-199 derived nanoporous carbon) is prepared by direct carbonization. • MOF-199 is utilized as a template without addition of carbon resource. • The MDNPC has a good electrocatalytic activity in hydrogen evolution reaction. • High BET surface area and hydrogen adsorption property improved catalyst activity.
Synthesis and characterization of Cu-MFI catalyst for the direct medium temperature range NO decomposition

Directory of Open Access Journals (Sweden)

Valkaj Karolina Maduna

2016-03-01

Full Text Available In this study the physico-chemical and catalytic properties of copper bearing MFI zeolites (Cu-MFI with different Si/Al and Si/Cu ratios were investigated. Two different methods for incorporation of metal ions into the zeolite framework were used: the ion exchange from the solution of copper acetate and the direct hydrothermal synthesis. Direct synthesis of a zeolite in the presence of copper-phosphate complexes was expected to generate more active copper species necessary for the desired reaction than the conventional ion exchange method. Direct decomposition of NO was used as a model reaction, because this reaction still offers a very attractive approach to NOX removal. The catalytic properties of zeolite samples were studied using techniques, such as XRD, SEM, EPR and nitrogen adsorption/desorption measurements at 77 K. Results of the kinetic investigation revealed that both methods are applicable for the preparation of the catalysts with active sites capable of catalyzing the NO decomposition. It was found out that Cu-MFI zeolites obtained through direct synthesis are promising catalysts for NO decomposition, especially at lower reaction temperatures. The efﬁciency of the catalysts prepared by both methods is compared and discussed.

Determination of k{sub 0} for {sup 63}Cu(n,γ){sup 64}Cu reaction with covariance analysis

Energy Technology Data Exchange (ETDEWEB)

Barros, Livia F.; Dias, Mauro S.; Koskinas, Marina F.; Yamazaki, Ione M.; Semmler, Renato, E-mail: lfbarros@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2015-07-01

Nowadays the k{sub 0} Method is one of the most used procedures on Neutron Activation Analysis (NAA). For an element of interest, the parameter k{sub 0} can be used to determine its mass concentration. The recommended nuclear data has been investigated, and the measurement of this parameter for {sup 63}Cu(n,γ){sup 64}Cu reaction was motivated by some discrepancies that were observed in the literature. The irradiations were performed near the core of the IEA-R1 4.5 MW nuclear research reactor of the Nuclear and Energy Research Institute – IPEN-CNEN/SP, in São Paulo, Brazil. Two irradiations were carried out in sequence, using two sets of samples: the first one with a cadmium cover around the samples and the second one without it. The activity measurements were carried out in a previously calibrated HPGe gamma-ray spectrometer. Standard sources of {sup 152}Eu, {sup 133}Ba, {sup 60}Co and {sup 13}'7Cs supplied by the IAEA with gamma transitions ranging from 121 keV to 1408 keV were used in order to obtain the HPGe gamma-ray peak efficiency as a function of the energy. The covariance matrix methodology was applied to all uncertainties involved. The resulting value of k{sub 0} for {sup 63}Cu(n,γ){sup 64}Cu reaction for the gamma transition energy of the formed isotope {sup 64}Cu 1345.77 keV was 4.99 x 10{sup -4} (78).This final value for k{sub 0} has been compared with the literature. (author)
Linking Metal Ions via Inorganic Click (iClick) Reactions

Energy Technology Data Exchange (ETDEWEB)

Veige, Adam [Univ. of Florida, Gainesville, FL (United States)

2015-11-17

This final report discusses the major objectives of the project, a discussion of the objectives achieved, a discussion of the objectives that failed, and finally, a discussion of future directions given the new knowledge obtained. This one-year seed project (with one year no-cost extension) contained three objectives: A) Expand the scope of iClick synthesis beyond AuI/AuI reactions. B) Elucidate a CuI-catalyzed iClick reaction. C) Synthesize and characterize tri- and tetra-metallic complexes as models for metallopolymers. Objectives A and C were achieved, whereas only parts of objective B were achieved.
Modeling the reactions catalyzed by coenzyme B12-dependent enzymes.

Science.gov (United States)

Sandala, Gregory M; Smith, David M; Radom, Leo

2010-05-18

Enzymes accelerate chemical reactions with an exceptional selectivity that makes life itself possible. Understanding the factors responsible for this efficient catalysis is of utmost importance in our quest to harness the tremendous power of enzymes. Computational chemistry has emerged as an important adjunct to experimental chemistry and biochemistry in this regard, because it provides detailed insights into the relationship between structure and function in a systematic and straightforward manner. In this Account, we highlight our recent high-level theoretical investigations toward this end in studying the radical-based reactions catalyzed by enzymes dependent on coenzyme B(12) (or adenosylcobalamin, AdoCbl). In addition to their fundamental position in biology, the AdoCbl-dependent enzymes represent a valuable framework within which to understand Nature's method of efficiently handling high-energy species to execute very specific reactions. The AdoCbl-mediated reactions are characterized by the interchange of a hydrogen atom and a functional group on adjacent carbon atoms. Our calculations are consistent with the conclusion that the main role of AdoCbl is to provide a source of radicals, thus moving the 1,2-rearrangements onto the radical potential energy surface. Our studies also show that the radical rearrangement step is facilitated by partial proton transfer involving the substrate. Specifically, we observe that the energy requirements for radical rearrangement are reduced dramatically with appropriate partial protonation or partial deprotonation or sometimes (synergistically) both. Such interactions are particularly relevant to enzyme catalysis, because it is likely that the local amino acid environment in the active site of an enzyme can function in this capacity through hydrogen bonding. Finally, our calculations indicate that the intervention of a very stable radical along the reaction pathway may inactivate the enzyme, demonstrating that sustained
Regio-, Diastereo-, and Enantioselective Nitroso-Diels-Alder Reaction of 1,3-Diene-1-carbamates Catalyzed by Chiral Phosphoric Acids.

Science.gov (United States)

Pous, Jonathan; Courant, Thibaut; Bernadat, Guillaume; Iorga, Bogdan I; Blanchard, Florent; Masson, Géraldine

2015-09-23

Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.
Investigation of the complex reaction coordinate of acid catalyzed amide hydrolysis from molecular dynamics simulations

International Nuclear Information System (INIS)

Zahn, Dirk

2004-01-01

The rate-determining step of acid catalyzed peptide hydrolysis is the nucleophilic attack of a water molecule to the carbon atom of the amide group. Therein the addition of the hydroxyl group to the amide carbon atom involves the association of a water molecule transferring one of its protons to an adjacent water molecule. The protonation of the amide nitrogen atom follows as a separate reaction step. Since the nucleophilic attack involves the breaking and formation of several bonds, the underlying reaction coordinate is rather complex. We investigate this reaction step from path sampling Car-Parrinello molecular dynamics simulations. This approach does not require the predefinition of reaction coordinates and is thus particularly suited for investigating reaction mechanisms. From our simulations the most relevant components of the reaction coordinate are elaborated. Though the C···O distance of the oxygen atom of the water molecule performing the nucleophilic attack and the corresponding amide carbon atom is a descriptor of the reaction progress, a complete picture of the reaction coordinate must include all three molecules taking part in the reaction. Moreover, the proton transfer is found to depend on favorable solvent configurations. Thus, also the arrangement of non-reacting, i.e. solvent water molecules needs to be considered in the reaction coordinate
Kinetic and thermodynamic study of the reaction catalyzed by glucose-6-phosphate dehydrogenase with nicotinamide adenine dinucleotide

International Nuclear Information System (INIS)

Martin del Campo, Julia S.; Patino, Rodrigo

2011-01-01

Research highlights: → The reaction catalyzed by one enzyme of the pentose phosphate pathway was studied. → A spectrophotometric method is proposed for kinetic and thermodynamic analysis. → The pH and the temperature influences are reported on physical chemical properties. → Relative concentrations of substrates are also important in the catalytic process. - Abstract: The enzyme glucose-6-phosphate dehydrogenase (G6PD, EC 1.1.1.49) from Leuconostoc mesenteroides has a dual coenzyme specificity with oxidized nicotinamide adenine dinucleotide (NAD ox ) and oxidized nicotinamide adenine dinucleotide phosphate as electron acceptors. The G6PD coenzyme selection is determined by the metabolic cellular prevailing conditions. In this study a kinetic and thermodynamic analysis is presented for the reaction catalyzed by G6PD from L. mesenteroides with NAD ox as coenzyme in phosphate buffer. For this work, an in situ spectrophotometric technique was employed based on the detection of one product of the reaction. Substrate and coenzyme concentrations as well as temperature and pH effects were evaluated. The apparent equilibrium constant, the Michaelis constant, and the turnover number were determined as a function of each experimental condition. The standard transformed Gibbs energy of reaction was determined from equilibrium constants at different initial conditions. For the product 6-phospho-D-glucono-1,5-lactone, a value of the standard Gibbs energy of formation is proposed, Δ f G o = -1784 ± 5 kJ mol -1 .
Kinetic and thermodynamic study of the reaction catalyzed by glucose-6-phosphate dehydrogenase with nicotinamide adenine dinucleotide

Energy Technology Data Exchange (ETDEWEB)

Martin del Campo, Julia S. [Departamento de Fisica Aplicada, Centro de Investigacion y de Estudios Avanzados - Unidad Merida, Carretera antigua a Progreso Km. 6, A.P. 73 Cordemex, 97310, Merida, Yucatan (Mexico); Patino, Rodrigo, E-mail: rtarkus@mda.cinvestav.mx [Departamento de Fisica Aplicada, Centro de Investigacion y de Estudios Avanzados - Unidad Merida, Carretera antigua a Progreso Km. 6, A.P. 73 Cordemex, 97310, Merida, Yucatan (Mexico)

2011-04-20

Research highlights: {yields} The reaction catalyzed by one enzyme of the pentose phosphate pathway was studied. {yields} A spectrophotometric method is proposed for kinetic and thermodynamic analysis. {yields} The pH and the temperature influences are reported on physical chemical properties. {yields} Relative concentrations of substrates are also important in the catalytic process. - Abstract: The enzyme glucose-6-phosphate dehydrogenase (G6PD, EC 1.1.1.49) from Leuconostoc mesenteroides has a dual coenzyme specificity with oxidized nicotinamide adenine dinucleotide (NAD{sub ox}) and oxidized nicotinamide adenine dinucleotide phosphate as electron acceptors. The G6PD coenzyme selection is determined by the metabolic cellular prevailing conditions. In this study a kinetic and thermodynamic analysis is presented for the reaction catalyzed by G6PD from L. mesenteroides with NAD{sub ox} as coenzyme in phosphate buffer. For this work, an in situ spectrophotometric technique was employed based on the detection of one product of the reaction. Substrate and coenzyme concentrations as well as temperature and pH effects were evaluated. The apparent equilibrium constant, the Michaelis constant, and the turnover number were determined as a function of each experimental condition. The standard transformed Gibbs energy of reaction was determined from equilibrium constants at different initial conditions. For the product 6-phospho-D-glucono-1,5-lactone, a value of the standard Gibbs energy of formation is proposed, {Delta}{sub f}G{sup o} = -1784 {+-} 5 kJ mol{sup -1}.
Palladium-catalyzed cyclization reactions of 2-vinylthiiranes with heterocumulenes. Regioselective and enantioselective formation of thiazolidine, oxathiolane, and dithiolane derivatives.

Science.gov (United States)

Larksarp, C; Sellier, O; Alper, H

2001-05-18

The first palladium-catalyzed ring-expansion reaction of 2-vinylthiiranes with heterocumulenes to form sulfur-containing five-membered-ring heterocycles is described. This regioselective reaction requires 5 mol % of Pd(2)(dba)(3).CHCl(3) and 10 mol % of bidendate phosphine ligand (dppp, BINAP), at 50-80 degrees C, in THF. The reaction of 2-vinylthiiranes with carbodiimides, isocyanates, and ketenimines affords 1,3-thiazolidine derivatives, whereas the reaction with diphenylketene or isothiocyanates results in the formation of 1,3-oxathiolane or 1,3-dithiolane compounds in good to excellent isolated yields and in up to 78% ee.
Synthesis of Cu-coated Graphite Powders Using a Chemical Reaction Process

Energy Technology Data Exchange (ETDEWEB)

Jang, Jun-Ho; Park, Hyun-Kuk; Oh, Ik-Hyun [Korea Institute of Industrial Technology (KITECH), Gwangju (Korea, Republic of); Lim, Jae-Won [Chonbuk National University, Jeonju (Korea, Republic of)

2017-05-15

In this paper, Cu-coated graphite powders for a low thermal expansion coefficient and a high thermal conductivity are fabricated using a chemical reaction process. The Cu particles adhere to the irregular graphite powders and they homogeneously disperse in the graphite matrix. Cu-coated graphite powders are coarser at approximately 3-4 μm than the initial graphite powders; furthermore, their XRD patterns exhibit a low intensity in the oxide peak with low Zn powder content. For the passivation powders, the transposition solvent content has low values, and the XRD pattern of the oxide peaks is almost non-existent, but the high transposition solvent content does not exhibit a difference to the non-passivation treated powders.
Effects of Ag addition on solid–state interfacial reactions between Sn–Ag–Cu solder and Cu substrate

International Nuclear Information System (INIS)

Yang, Ming; Ko, Yong-Ho; Bang, Junghwan; Kim, Taek-Soo; Lee, Chang-Woo; Li, Mingyu

2017-01-01

Low–Ag–content Sn–Ag–Cu (SAC) solders have attracted much recent attention in electronic packaging for their low cost. To reasonably reduce the Ag content in Pb–free solders, a deep understanding of the basic influence of Ag on the SAC solder/Cu substrate interfacial reaction is essential. Previous studies have discussed the influence of Ag on the interfacial intermetallic compound (IMC) thickness. However, because IMC growth is the joint result of multiple factors, such characterizations do not reveal the actual role of Ag. In this study, changes in interfacial IMCs after Ag introduction were systemically and quantitatively characterized in terms of coarsening behaviors, orientation evolution, and growth kinetics. The results show that Ag in the solder alloy affects the coarsening behavior, accelerates the orientation concentration, and inhibits the growth of interfacial IMCs during solid–state aging. The inhibition mechanism was quantitatively discussed considering the individual diffusion behaviors of Cu and Sn atoms, revealing that Ag inhibits interfacial IMC growth primarily by slowing the diffusion of Cu atoms through the interface. - Highlights: •Role of Ag in IMC formation during Sn–Ag–Cu soldering was investigated. •Ag affects coarsening, crystallographic orientation, and IMC growth. •Diffusion pathways of Sn and Cu are affected differently by Ag. •Ag slows Cu diffusion to inhibit IMC growth at solder/substrate interface.
Effects of Ag addition on solid–state interfacial reactions between Sn–Ag–Cu solder and Cu substrate

Energy Technology Data Exchange (ETDEWEB)

Yang, Ming [Micro-Joining Center, Korea Institute of Industrial Technology (KITECH), Incheon 21999 (Korea, Republic of); Ko, Yong-Ho [Micro-Joining Center, Korea Institute of Industrial Technology (KITECH), Incheon 21999 (Korea, Republic of); Department of Mechanical Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291, Daehak-ro, Yuseong-gu, Daejeon 34141 (Korea, Republic of); Bang, Junghwan [Micro-Joining Center, Korea Institute of Industrial Technology (KITECH), Incheon 21999 (Korea, Republic of); Kim, Taek-Soo [Department of Mechanical Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291, Daehak-ro, Yuseong-gu, Daejeon 34141 (Korea, Republic of); Lee, Chang-Woo, E-mail: cwlee@kitech.re.kr [Micro-Joining Center, Korea Institute of Industrial Technology (KITECH), Incheon 21999 (Korea, Republic of); Li, Mingyu, E-mail: myli@hit.edu.cn [Shenzhen Key Laboratory of Advanced Materials, Harbin Institute of Technology Shenzhen Graduate School, Shenzhen 518055 (China)

2017-02-15

Low–Ag–content Sn–Ag–Cu (SAC) solders have attracted much recent attention in electronic packaging for their low cost. To reasonably reduce the Ag content in Pb–free solders, a deep understanding of the basic influence of Ag on the SAC solder/Cu substrate interfacial reaction is essential. Previous studies have discussed the influence of Ag on the interfacial intermetallic compound (IMC) thickness. However, because IMC growth is the joint result of multiple factors, such characterizations do not reveal the actual role of Ag. In this study, changes in interfacial IMCs after Ag introduction were systemically and quantitatively characterized in terms of coarsening behaviors, orientation evolution, and growth kinetics. The results show that Ag in the solder alloy affects the coarsening behavior, accelerates the orientation concentration, and inhibits the growth of interfacial IMCs during solid–state aging. The inhibition mechanism was quantitatively discussed considering the individual diffusion behaviors of Cu and Sn atoms, revealing that Ag inhibits interfacial IMC growth primarily by slowing the diffusion of Cu atoms through the interface. - Highlights: •Role of Ag in IMC formation during Sn–Ag–Cu soldering was investigated. •Ag affects coarsening, crystallographic orientation, and IMC growth. •Diffusion pathways of Sn and Cu are affected differently by Ag. •Ag slows Cu diffusion to inhibit IMC growth at solder/substrate interface.
Enhanced removal of aqueous acetaminophen by a laccase-catalyzed oxidative coupling reaction under a dual-pH optimization strategy.

Science.gov (United States)

Wang, Kaidong; Huang, Ke; Jiang, Guoqiang

2018-03-01

Acetaminophen is one kind of pharmaceutical contaminant that has been detected in municipal water and is hard to digest. A laccase-catalyzed oxidative coupling reaction is a potential method of removing acetaminophen from water. In the present study, the kinetics of radical polymerization combined with precipitation was studied, and the dual-pH optimization strategy (the enzyme solution at pH7.4 being added to the substrate solution at pH4.2) was proposed to enhance the removal efficiency of acetaminophen. The reaction kinetics that consisted of the laccase-catalyzed oxidation, radical polymerization and precipitation were studied by UV in situ, LC-MS and DLS (dynamic light scattering) in situ. The results showed that the laccase-catalyzed oxidation is the rate-limiting step in the whole process. The higher rate of enzyme-catalyzed oxidation under a dual-pH optimization strategy led to much faster formation of the dimer, trimer and tetramer. Similarly, the formation of polymerized products that could precipitate naturally from water was faster. Under the dual-pH optimization strategy, the initial laccase activity was increased approximately 2.9-fold, and the activity remained higher for >250s, during which approximately 63.7% of the total acetaminophen was transformed into biologically inactive polymerized products, and part of these polymerized products precipitated from the water. Laccase belongs to the family of multi-copper oxidases, and the present study provides a universal method to improve the activity of multi-copper oxidases for the high-performance removal of phenol and its derivatives. Copyright © 2017 Elsevier B.V. All rights reserved.
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
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.
Formation of bromate and halogenated disinfection byproducts during chlorination of bromide-containing waters in the presence of dissolved organic matter and CuO

KAUST Repository

Liu, Chao; Croue, Jean-Philippe

2015-01-01

Previous studies showed that significant bromate (BrO3-) can be formed via the CuO-catalyzed disproportionation of hypobromous acid (HOBr) pathway. In this study, the influence of CuO on the formation of BrO3- and halogenated disinfection byproducts (DBPs) (e.g., trihalomethanes, THMs and haloacetic acids, HAAs) during chlorination of six dissolved organic matter (DOM) isolates was investigated. Only in the presence of slow reacting DOM (from treated Colorado River water, i.e., CRW-BF-HPO), significant BrO3- formation is observed, which competes with bromination of DOM (i.e., THM and HAA formation). Reactions between HOBr and 12 model compounds in the presence of CuO indicates that CuO-catalyzed HOBr disproportionation is completely inhibited by fast reacting phenols, while it predominates in the presence of practically unreactive compounds (acetone, butanol, propionic, and butyric acids). In the presence of slow reacting di- and tri-carboxylic acids (oxalic, malonic, succinic, and citric acids), BrO3- formation varies, depending on its competition with bromoform and dibromoacetic acid formation (i.e., bromination pathway). The latter pathway can be enhanced by CuO due to the activation of HOBr. Therefore, increasing CuO dose (0-0.2 g L-1) in a reaction system containing chlorine, bromide, and CRW-BF-HPO enhances the formation of BrO3-, total THMs and HAAs. Factors including pH and initial reactant concentrations influence the DBP formation. These novel findings have implications for elevated DBP formation during transportation of chlorinated waters in copper-containing distribution systems.
Formation of bromate and halogenated disinfection byproducts during chlorination of bromide-containing waters in the presence of dissolved organic matter and CuO

KAUST Repository

Liu, Chao

2015-12-02

Previous studies showed that significant bromate (BrO3-) can be formed via the CuO-catalyzed disproportionation of hypobromous acid (HOBr) pathway. In this study, the influence of CuO on the formation of BrO3- and halogenated disinfection byproducts (DBPs) (e.g., trihalomethanes, THMs and haloacetic acids, HAAs) during chlorination of six dissolved organic matter (DOM) isolates was investigated. Only in the presence of slow reacting DOM (from treated Colorado River water, i.e., CRW-BF-HPO), significant BrO3- formation is observed, which competes with bromination of DOM (i.e., THM and HAA formation). Reactions between HOBr and 12 model compounds in the presence of CuO indicates that CuO-catalyzed HOBr disproportionation is completely inhibited by fast reacting phenols, while it predominates in the presence of practically unreactive compounds (acetone, butanol, propionic, and butyric acids). In the presence of slow reacting di- and tri-carboxylic acids (oxalic, malonic, succinic, and citric acids), BrO3- formation varies, depending on its competition with bromoform and dibromoacetic acid formation (i.e., bromination pathway). The latter pathway can be enhanced by CuO due to the activation of HOBr. Therefore, increasing CuO dose (0-0.2 g L-1) in a reaction system containing chlorine, bromide, and CRW-BF-HPO enhances the formation of BrO3-, total THMs and HAAs. Factors including pH and initial reactant concentrations influence the DBP formation. These novel findings have implications for elevated DBP formation during transportation of chlorinated waters in copper-containing distribution systems.
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.
Advanced Precursor Reaction Processing for Cu(InGa)(SeS)2 Solar Cells

Energy Technology Data Exchange (ETDEWEB)

Shafarman, William N. [Univ. of Delaware, Newark, DE (United States)

2015-10-12

This project “Advanced Precursor Reaction Processing for Cu(InGa)(SeS)2 Solar Cells”, completed by the Institute of Energy Conversion (IEC) at the University of Delaware in collaboration with the Department of Chemical Engineering at the University of Florida, developed the fundamental understanding and technology to increase module efficiency and improve the manufacturability of Cu(InGa)(SeS)2 films using the precursor reaction approach currently being developed by a number of companies. Key results included: (1) development of a three-step H2Se/Ar/H2S reaction process to control Ga distribution through the film and minimizes back contact MoSe2 formation; (2) Ag-alloying to improve precursor homogeneity by avoiding In phase agglomeration, faster reaction and improved adhesion to allow wider reaction process window; (3) addition of Sb, Bi, and Te interlayers at the Mo/precursor junction to produce more uniform precursor morphology and improve adhesion with reduced void formation in reacted films; (4) a precursor structure containing Se and a reaction process to reduce processing time to 5 minutes and eliminate H2Se usage, thereby increasing throughput and reducing costs. All these results were supported by detailed characterization of the film growth, reaction pathways, thermodynamic assessment and device behavior.
Site-specific bioconjugation of a murine dihydrofolate reductase enzyme by copper(I-catalyzed azide-alkyne cycloaddition with retained activity.

Directory of Open Access Journals (Sweden)

Sung In Lim

Full Text Available Cu(I-catalyzed azide-alkyne cycloaddition (CuAAC is an efficient reaction linking an azido and an alkynyl group in the presence of copper catalyst. Incorporation of a non-natural amino acid (NAA containing either an azido or an alkynyl group into a protein allows site-specific bioconjugation in mild conditions via CuAAC. Despite its great potential, bioconjugation of an enzyme has been hampered by several issues including low yield, poor solubility of a ligand, and protein structural/functional perturbation by CuAAC components. In the present study, we incorporated an alkyne-bearing NAA into an enzyme, murine dihydrofolate reductase (mDHFR, in high cell density cultivation of Escherichia coli, and performed CuAAC conjugation with fluorescent azide dyes to evaluate enzyme compatibility of various CuAAC conditions comprising combination of commercially available Cu(I-chelating ligands and reductants. The condensed culture improves the protein yield 19-fold based on the same amount of non-natural amino acid, and the enzyme incubation under the optimized reaction condition did not lead to any activity loss but allowed a fast and high-yield bioconjugation. Using the established conditions, a biotin-azide spacer was efficiently conjugated to mDHFR with retained activity leading to the site-specific immobilization of the biotin-conjugated mDHFR on a streptavidin-coated plate. These results demonstrate that the combination of reactive non-natural amino acid incorporation and the optimized CuAAC can be used to bioconjugate enzymes with retained enzymatic activity.
A sensitive fluorescence biosensor for alkaline phosphatase activity based on the Cu(II)-dependent DNAzyme

Energy Technology Data Exchange (ETDEWEB)

Zhao, Mengmeng; Guo, Yajuan; Wang, Lixu [College of Chemistry, Fuzhou University, Fuzhou, Fujian 350116 (China); Luo, Fang, E-mail: luofang0812@163.com [College of Biological Science and Technology, Fuzhou University, Fuzhou, Fujian 350116 (China); Lin, Cuiying, E-mail: lcuiying@fzu.edu.cn [College of Chemistry, Fuzhou University, Fuzhou, Fujian 350116 (China); Lin, Zhenyu; Chen, Guonan [College of Chemistry, Fuzhou University, Fuzhou, Fujian 350116 (China)

2016-12-15

Alkaline phosphatase (ALP) plays an important role in phosphate metabolism processes; deviation from its normal level may indicate different kinds of diseases, so it is highly necessary to develop some simple and sensitive methods to monitor the ALP level. In this study, a simple, high selective, and sensitive fluorescent biosensor has been proposed for ALP activity determination. The Cu(II)-dependent DNAzyme (Cu-Enzyme) are divided into two parts: Cu-Enzyme 1 and Cu-Enzyme 2, and labelled with alkyne and azido groups, respectively. The Cu-substrate (Cu-Sub) is labelled with a FAM fluorophore (6-carboxyfluorescein) at the 3′-end and an additional quencher (BHQ1) at the 5′-end. The 5′-end of Cu-Enzyme 1 is labelled with BHQ1 as well. The hybridization of the Cu-Enzyme 1 and Cu-Enzyme 2 with Cu-Sub strand results in the low background fluorescence signal because the fluorescence from FAM is quenched. The addition of ALP can hydrolyze AA-P into AA, which can reduce Cu(II) into Cu(I) and in turn catalyze the cycloaddition of Cu-Enzyme 1 and Cu-Enzyme 2 to form a modified Cu-Enzyme. Then the modified Cu-Enzyme catalyzes the cleavage of the Cu-Sub strands into two pieces. One piece containing FAM fluorophore can easily diffuse into solution and give off a strong fluorescence signal. The enhanced fluorescent intensity has a linear relationship with the ALP concentration in the range of 0.36–54.55 U L{sup −1} with the detection limit of 0.14 U L{sup −1} (S/N = 3). The proposed biosensor has been successfully applied to detect ALP in serum samples with satisfied results. - Highlights: • We have proposed a simple, high selective and sensitive fluorescent biosensor for ALP. • The biosensor combines the high selectivity and the click reaction and the high sensitivity of the fluorescence detection. • The biosensor has been successfully applied to detect ALP in serum samples with satisfied results.

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...
Longitudinally Controlled Modification of Cylindrical and Conical Track-Etched Poly(ethylene terephthalate) Pores Using an Electrochemically Assisted Click Reaction

International Nuclear Information System (INIS)

Coceancigh, Herman; Tran-Ba, Khanh-Hoa; Columbia University, New York, NY; Siepser, Natasha; Baker, Lane A.; Ito, Takashi

2017-01-01

Here in this study, the longitudinally controlled modification of the inner surfaces of poly(ethylene terephthalate) (PET) track-etched pores was explored using an electrochemically assisted Cu(I)-catalyzed azide–alkyne cycloaddition (CuAAC) click reaction. Cylindrical or conical PET track-etched pores were first decorated with ethynyl groups via the amidation of surface -COOH groups, filled with a solution containing Cu(II) and azide-tagged fluorescent dye, and then sandwiched between comb-shaped and planar gold electrodes. Cu(I) was produced at the comb-shaped working electrode by the reduction of Cu(II); it diffused along the pores toward the other electrode and catalyzed CuAAC between an azide-tagged fluorescent dye and a pore-tethered ethynyl group. The modification efficiency of cylindrical pores (ca. 1 μm in diameter) was assessed from planar and cross-sectional fluorescence microscope images of modified membranes. Planar images showed that pore modification took place only above the teeth of the comb-shaped electrode with a higher reaction yield for longer Cu(II) reduction times. Cross-sectional images revealed micrometer-scale gradient modification along the pore axis, which reflected a Cu(I) concentration profile within the pores, as supported by finite-element computer simulations. The reported approach was applicable to the asymmetric modification of cylindrical pores with two different fluorescent dyes in the opposite directions and also for the selective visualization of the tip and base openings of conical pores (ca. 3.5 μm in base diameter and ca. 1 μm in tip diameter). Lastly, the method based on electrochemically assisted CuAAC provides a controlled means to fabricate asymmetrically modified nanoporous membranes and, in the future, will be applicable for chemical separations and the development of sequential catalytic reactors.
1,2-Ferrocenediylazaphosphinines 3: a new class of planar chiral ligands for Cu-catalyzed cyclopropanation

Energy Technology Data Exchange (ETDEWEB)

Paek, Seung Hwan; Co, Thanh Thien; Lee, Dong Ho; Park, Yu Chul; Kim, Tae Jeong [Kyungpook National Univ., Daegu (Korea, Republic of)

2002-12-01

The synthesis and catalytic application of a new class of planar chiral ferrocenes, 1,2-ferrocenediylazaphos-phinines (1 and 2) are described. They are powerful ligands for the copper(I)-catalyzed asymmetric cyclopropanation of a range of alkenes with diazo esters to exhibit an exceptionally high degree of diastereoselectivity ({approx}100%) in favor of trans isomers, regardless the structure of the olefins and the diazo compounds. Comparative studies between 1 and 2 reveal that the former works better in terms of diastereocontrol. In contrast, however, enantioselectivity is low with both 1 and 2 as a whole although, in certain cases with a proper combination of the olefin and the diazo ester, high optical yields (up to 100% ee) can be achieved. Other reaction parameters such as the reaction temperature and the structure of the ligand do exhibit some influence, although infinitesimal, on both chemical and optical yields.
1,2-Ferrocenediylazaphosphinines 3: a new class of planar chiral ligands for Cu-catalyzed cyclopropanation

International Nuclear Information System (INIS)

Paek, Seung Hwan; Co, Thanh Thien; Lee, Dong Ho; Park, Yu Chul; Kim, Tae Jeong

2002-01-01

The synthesis and catalytic application of a new class of planar chiral ferrocenes, 1,2-ferrocenediylazaphos-phinines (1 and 2) are described. They are powerful ligands for the copper(I)-catalyzed asymmetric cyclopropanation of a range of alkenes with diazo esters to exhibit an exceptionally high degree of diastereoselectivity (∼100%) in favor of trans isomers, regardless the structure of the olefins and the diazo compounds. Comparative studies between 1 and 2 reveal that the former works better in terms of diastereocontrol. In contrast, however, enantioselectivity is low with both 1 and 2 as a whole although, in certain cases with a proper combination of the olefin and the diazo ester, high optical yields (up to 100% ee) can be achieved. Other reaction parameters such as the reaction temperature and the structure of the ligand do exhibit some influence, although infinitesimal, on both chemical and optical yields
Label-Free and Ultrasensitive Biomolecule Detection Based on Aggregation Induced Emission Fluorogen via Target-Triggered Hemin/G-Quadruplex-Catalyzed Oxidation Reaction.

Science.gov (United States)

Li, Haiyin; Chang, Jiafu; Gai, Panpan; Li, Feng

2018-02-07

Fluorescence biosensing strategy has drawn substantial attention due to their advantages of simplicity, convenience, sensitivity, and selectivity, but unsatisfactory structure stability, low fluorescence quantum yield, high cost of labeling, and strict reaction conditions associated with current fluorescence methods severely prohibit their potential application. To address these challenges, we herein propose an ultrasensitive label-free fluorescence biosensor by integrating hemin/G-quadruplex-catalyzed oxidation reaction with aggregation induced emission (AIE) fluorogen-based system. l-Cysteine/TPE-M, which is carefully and elaborately designed and developed, obviously contributes to strong fluorescence emission. In the presence of G-rich DNA along with K + and hemin, efficient destruction of l-cysteine occurs due to hemin/G-quadruplex-catalyzed oxidation reactions. As a result, highly sensitive fluorescence detection of G-rich DNA is readily realized, with a detection limit down to 33 pM. As a validation for the further development of the proposed strategy, we also successfully construct ultrasensitive platforms for microRNA by incorporating the l-cysteine/TPE-M system with target-triggered cyclic amplification reaction. Thus, this proposed strategy is anticipated to find use in basic biochemical research and clinical diagnosis.
A polymer supported Cu(I) catalyst for the 'click reaction' in aqueous media.

Science.gov (United States)

Ul Islam, Rafique; Taher, Abu; Choudhary, Meenakshi; Witcomb, Michael J; Mallick, Kaushik

2015-01-21

Polymer stabilized monovalent copper has been synthesized using an in situ chemical transformation route and was characterized by means of different microscopic, optical and surface characterization techniques, which offered information about the chemical structure of the polymer and the morphology of the complex. The supramolecular material, Cu(i)-poly(2-aminobenzoic acid), denoted Cu(i)-pABA, showed catalytic activity for the cycloaddition reaction between terminal alkynes and azides to synthesize 1,2,3-triazoles with excellent yields. The catalyst was recovered from the reaction mixture and recycled several times without an appreciable loss of catalytic activity. The whole strategy was done under ambient conditions and in the presence of water as a solvent.
The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

KAUST Repository

Ebner, Davidâ C.; Bagdanoff, Jeffreyâ T.; Ferreira, Ericâ M.; McFadden, Ryanâ M.; Caspi, Danielâ D.; Trend, Raissaâ M.; Stoltz, Brianâ M.

2009-01-01

The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.
The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

KAUST Repository

Ebner, Davidâ C.

2009-12-07

The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.
Degradation of Perfluorooctanoic Acid and Perfluoroctane Sulfonate by Enzyme Catalyzed Oxidative Humification Reactions

Science.gov (United States)

Huang, Q.

2016-12-01

Poly- and perfluoroalkyl substances (PFASs) are alkyl based chemicals having multiple or all hydrogens replaced by fluorine atoms, and thus exhibit high thermal and chemical stability and other unusual characteristics. PFASs have been widely used in a wide variety of industrial and consumer products, and tend to be environmentally persistent. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are two representative PFASs that have drawn particular attention because of their ubiquitous presence in the environment, resistance to degradation and toxicity to animals. This study examined the decomposition of PFOA and PFOS in enzyme catalyzed oxidative humification reactions (ECOHR), a class of reactions that are ubiquitous in the environment involved in natural organic humification. Reaction rates and influential factors were examined, and high-resolution mass spectrometry was used to identify possible products. Fluorides and partially fluorinated compounds were identified as likely products from PFOA and PFOS degradation, which were possibly formed via a combination of free radical decomposition, rearrangements and coupling processes. The findings suggest that PFOA and PFOS may be transformed during humification, and ECOHR can potentially be used for the remediation of these chemicals.
Kinetic Studies on Enzyme-Catalyzed Reactions: Oxidation of Glucose, Decomposition of Hydrogen Peroxide and Their Combination

Science.gov (United States)

Tao, Zhimin; Raffel, Ryan A.; Souid, Abdul-Kader; Goodisman, Jerry

2009-01-01

The kinetics of the glucose oxidase-catalyzed reaction of glucose with O2, which produces gluconic acid and hydrogen peroxide, and the catalase-assisted breakdown of hydrogen peroxide to generate oxygen, have been measured via the rate of O2 depletion or production. The O2 concentrations in air-saturated phosphate-buffered salt solutions were monitored by measuring the decay of phosphorescence from a Pd phosphor in solution; the decay rate was obtained by fitting the tail of the phosphorescence intensity profile to an exponential. For glucose oxidation in the presence of glucose oxidase, the rate constant determined for the rate-limiting step was k = (3.0 ± 0.7) ×104 M−1s−1 at 37°C. For catalase-catalyzed H2O2 breakdown, the reaction order in [H2O2] was somewhat greater than unity at 37°C and well above unity at 25°C, suggesting different temperature dependences of the rate constants for various steps in the reaction. The two reactions were combined in a single experiment: addition of glucose oxidase to glucose-rich cell-free media caused a rapid drop in [O2], and subsequent addition of catalase caused [O2] to rise and then decrease to zero. The best fit of [O2] to a kinetic model is obtained with the rate constants for glucose oxidation and peroxide decomposition equal to 0.116 s−1 and 0.090 s−1 respectively. Cellular respiration in the presence of glucose was found to be three times as rapid as that in glucose-deprived cells. Added NaCN inhibited O2 consumption completely, confirming that oxidation occurred in the cellular mitochondrial respiratory chain. PMID:19348778
Transition Metal Catalyzed Reactions of Carbohydrates: a Nonoxidative Approach to Oxygenated Organics

Energy Technology Data Exchange (ETDEWEB)

Andrews, Mark

1997-01-08

There is a critical need for new environmentally friendly processes in the United States chemical industry as legislative and economic pressures push the industry to zero-waste and cradle-to-grave responsibility for the products they produce. Carbohydrates represent a plentiful, renewable resource, which for some processes might economically replace fossil feedstocks. While the conversion of biomass to fuels, is still not generally economical, the selective synthesis of a commodity or fine chemical, however, could compete effectively if appropriate catalytic conversion systems can be found. Oxygenated organics, found in a variety of products such as nylon and polyester, are particularly attractive targets. We believe that with concerted research efforts, homogeneous transition metal catalyzed reactions could play a significant role in bringing about this future green chemistry technology.
One-pot synthesis of 2H-pyrans by indium(III) chloride-catalyzed reactions. efficient synthesis of pyranocoumarins, pyranophenalenones, and pyranoquinolinones

International Nuclear Information System (INIS)

Lee, Yong Rok; Kim, Do Hoon; Shim, Jae Jin; Kim, Seog K.; Park, Jung Hag; Cha, Jin Soon; Lee, Chong Soon

2002-01-01

An efficient synthesis of 2H-pyrans is achieved by indium (III) chloride-catalyzed reactions of 1,3-dicarbonyl compounds with a variety of α.β-unsaturated aldehydes in moderates yields. This method has been applied to the synthesis of pyranocoumarins, pyranophenaleneones, and pyranoquinolinone alkaloids
One-pot synthesis of 2H-pyrans by indium(III) chloride-catalyzed reactions. efficient synthesis of pyranocoumarins, pyranophenalenones, and pyranoquinolinones

Energy Technology Data Exchange (ETDEWEB)

Lee, Yong Rok; Kim, Do Hoon; Shim, Jae Jin; Kim, Seog K.; Park, Jung Hag; Cha, Jin Soon; Lee, Chong Soon [Yeungnam Univ., Kyongsan (Korea, Republic of)

2002-08-01

An efficient synthesis of 2H-pyrans is achieved by indium (III) chloride-catalyzed reactions of 1,3-dicarbonyl compounds with a variety of {alpha}.{beta}-unsaturated aldehydes in moderates yields. This method has been applied to the synthesis of pyranocoumarins, pyranophenaleneones, and pyranoquinolinone alkaloids.
Morphology-Dependent Properties of Cu/CeO2 Catalysts for the Water-Gas Shift Reaction

Directory of Open Access Journals (Sweden)

Zhibo Ren

2017-02-01

Full Text Available CeO2 nanooctahedrons, nanorods, and nanocubes were prepared by the hydrothermal method and were then used as supports of Cu-based catalysts for the water-gas shift (WGS reaction. The chemical and physical properties of these catalysts were characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, N2 adsorption/desorption, UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS, hydrogen temperature-programmed reduction (H2-TPR and in situ diffuse reflectance infra-red fourier transform spectroscopy (DRIFTS techniques. Characterization results indicate that the morphology of the CeO2 supports, originating from the selective exposure of different crystal planes, has a distinct impact on the dispersion of Cu and the catalytic properties. The nanooctahedron CeO2 catalyst (Cu-CeO2-O showed the best dispersion of Cu, the largest amount of moderate copper oxide, and the strongest Cu-support interaction. Consequently, the Cu-CeO2-O catalyst exhibited the highest CO conversion at the temperature range of 150–250 °C when compared with the nanocube and nanorod Cu-CeO2 catalysts. The optimized Cu content of the Cu-CeO2-O catalysts is 10 wt % and the CO conversion reaches 91.3% at 300 °C. A distinctive profile assigned to the evolution of different types of carbonate species was observed in the 1000–1800 cm−1 region of the in situ DRIFTS spectra and a particular type of carbonate species was identified as a potential key reaction intermediate at low temperature.
Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts.

Science.gov (United States)

Sad, María E; Neurock, Matthew; Iglesia, Enrique

2011-12-21

This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H(2) and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO(2) through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H(2)O using H(2) added or formed in situ from CO/H(2)O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H(2) equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H(2), propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the α-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions. © 2011 American Chemical Society
Diversity-Oriented Syntheses by Combining CuAAC and Stereoselective INCIC Reactions with Peptides

DEFF Research Database (Denmark)

Wang, Yuanyuan; Madsen, Anders; Diness, Frederik

2017-01-01

Cascade reactions proceeding through peptide-derived N-carbamoyl iminium ions are reported. Two new reactions of N-carbamoyl iminium ions are described, including a stereoselective double cyclization generating N,N′-aminals and an acid-promoted auto-oxidation. Mechanistic investigations revealed...... that the N,N′-aminal formation is reversible under strongly acidic conditions. Both of these new reactions proved to be completely orthogonal to subsequent CuAAC chemistry. The reactions were performed in solution and on solid support. The robustness and high stereoselectivity of the methodology holds great...
Hydrogen-deuterium exchange reaction of 2-methylpyridine catalyzed by several fatty acids

International Nuclear Information System (INIS)

Hirata, Hirohumi; Fukuzumi, Kazuo.

1976-01-01

Hydrogen-deuterium exchange reaction of 2-methylpyridine has been studied by using several fatty acids as catalysts. The reaction was carried out in a sealed pyrex tube at 120 0 C, and the contents of the products were determined by mass spectrometry. Reaction of 2-methylpyridine with monodeuteroacetic acid (1 : 1, mol/mol) arrived at a equilibrium (d 0 reversible d 1 reversible d 2 reversible d 3 ) in 2 hr (d 0 41%, d 1 42%, d 2 15%, d 3 2%). No exchange was observed for the reaction of pyridine with monodeuteroacetic acid. The conversion-time curves of typical series reactions (d 0 → d 1 → d 2 → d 3 ) were obtained for the fatty acid catalyzed exchange in deuterium oxide. The effect of the fatty acid RCO 2 H (substrate : fatty acid : D 2 O=1 : 0.86 : 27.6, mol/mol/mol) on the conversion was in the order of R; C 1 --C 3 4 --C 10 , where the reaction mixtures were homogeneous in the case of C 1 --C 3 and were heterogeneous in the case of C 4 --C 10 . The effects of the initial concentration of the substrates and the catalysts (RCO 2 H) on the total conversion were studied by using some fatty acids (R; C 2 , C 4 and C 9 ) in deuterium oxide (for 2 hr). The total conversion of the substrate increases with increasing the concentration of the acids. The total conversion decreases in the case of R=C 9 , but, increases in the case of R=C 2 with increasing the concentration of the substrate. In the case of reactions with low concentrations of the substrate, the reactivity was in the order of C 9 >C 4 >C 2 , while with high concentrations, the reactivity was in the order of C 4 >C 2 >C 9 and C 9 >C 4 >C 2 with high and low concentrations of the acids, respectively. A possible reaction mechanism was proposed and discussed. (auth.)
Palladium-catalyzed coupling reactions

CERN Document Server

Molnár, Árpád

2013-01-01

This handbook and ready reference brings together all significant issues of practical importance for interested readers in one single volume. While covering homogeneous and heterogeneous catalysis, the text is unique in focusing on such important aspects as using different reaction media, microwave techniques or catalyst recycling. It also provides a comprehensive treatment of modern-day coupling reactions and emphasizes those topics that show potential for future development, such as continuous flow systems, water as a reaction medium, and catalyst immobilization, among others. With i
One-Pot Synthesis of Novel Chiral β-Amino Acid Derivatives by Enantioselective Mannich Reactions Catalyzed by Squaramide Cinchona Alkaloids

Directory of Open Access Journals (Sweden)

Kankan Zhang

2013-05-01

Full Text Available An efﬁcient one-pot synthesis of novel β-amino acid derivatives containing a thiadiazole moiety was developed using a chiral squaramide cinchona alkaloid as organocatalyst. The reactions afforded chiral β-amino acid derivatives in moderate yields and with moderate to excellent enantioselectivities. The present study demonstrated for the first time the use of a Mannich reaction catalyzed by a chiral bifunctional organocatalyst for the one-pot synthesis of novel β-amino acid derivatives bearing a 1,3,4-thiadiazole moiety on nitrogen.
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.

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
Metal-catalyzed asymmetric aldol reactions

Energy Technology Data Exchange (ETDEWEB)

Dias, Luiz C.; Lucca Junior, Emilio C. de; Ferreira, Marco A. B.; Polo, Ellen C., E-mail: ldias@iqm.unicamp.br [Universidade de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica

2012-12-15

The aldol reaction is one of the most powerful and versatile methods for the construction of C-C bonds. Traditionally, this reaction was developed in a stoichiometric version; however, great efforts in the development of chiral catalysts for aldol reactions were performed in recent years. Thus, in this review article, the development of metal-mediated chiral catalysts in Mukaiyama-type aldol reaction, reductive aldol reaction and direct aldol reaction are discussed. Moreover, the application of these catalysts in the total synthesis of complex molecules is discussed. (author)
Bicyclic Guanidine Catalyzed Asymmetric Tandem Isomerization Intramolecular-Diels-Alder Reaction: The First Catalytic Enantioselective Total Synthesis of (+)-alpha-Yohimbine.

Science.gov (United States)

Feng, Wei; Jiang, Danfeng; Kee, Choon-Wee; Liu, Hongjun; Tan, Choon-Hong

2016-02-04

Hydroisoquinoline derivatives were prepared in moderate to good enantioselectivities via a bicyclic guanidine-catalyzed tandem isomerization intramolecular-Diels-Alder (IMDA) reaction of alkynes. With this synthetic method, the first enantioselective synthesis of (+)-alpha-yohimbine was completed in 9 steps from the IMDA products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Synthesis of DOTA-conjugated multimeric [Tyr3]octreotide peptides via a combination of Cu(I)-catalyzed "click" cycloaddition and thio acid/sulfonyl azide "sulfo-click" amidation and their in vivo evaluation.

NARCIS (Netherlands)

Yim, C.B.; Dijkgraaf, I.; Merkx, R.; Versluis, C.; Eek, A.; Mulder, G.E.; Rijkers, D.T.; Boerman, O.C.; Liskamp, R.M.

2010-01-01

Herein, we describe the design, synthesis, and biological evaluation of a series of DOTA-conjugated monomeric, dimeric, and tetrameric [Tyr(3)]octreotide-based analogues as a tool for tumor imaging and/or radionuclide therapy. These compounds were synthesized using a Cu(I)-catalyzed 1,3-dipolar
Asymmetric Formal Aza-Diels-Alder Reaction of Trifluoromethyl Hemiaminals with Enones Catalyzed by Primary Amines.

Science.gov (United States)

Zhang, Sheng; Cha, Lide; Li, Lijun; Hu, Yanbin; Li, Yanan; Zha, Zhenggen; Wang, Zhiyong

2016-04-15

A primary amine-catalyzed asymmetric formal aza-Diels-Alder reaction of trifluoromethyl hemiaminals with enones was developed via a chiral gem-diamine intermediate. This novel protocol allowed facile access to structurally diverse trifluoromethyl-substituted piperidine scaffolds with high stereoselectivity. The utility of this method was further demonstrated through a concise approach to biologically active 4-hydroxypiperidine. More importantly, a stepwise mechanism involving an asymmetric induction process was proposed to rationalize the positive correlation between the chirality of the gem-diamine intermediate and the formal aza-Diels-Alder product.
Solvent-dependent reactions for the synthesis of β-keto-benzo-δ-sultone scaffolds via DBU-catalyzed O-sulfonylation/intramolecular Baylis-Hillman/1,3-H shift or dehydration tandem sequences.

Science.gov (United States)

Ghandi, Mehdi; Bozcheloei, Abolfazl Hasani; Nazari, Seyed Hadi; Sadeghzadeh, Masoud

2011-12-16

We have developed a solvent-dependent method for the synthesis of novel benzo-δ-sultone scaffolds. A variety of benzylbenzo[e][1,2]oxathiin-4(3H)-one-2,2-dioxides were obtained in high yields in DMF using a one-pot, DBU-catalyzed condensation of 2-hydroxybenzaldehydes with a number of (E)-2-phenylethenesulfonyl chlorides. On the other hand, the initially prepared 2-formylphenyl-(E)-2-phenylethenesulfonate derivatives underwent DBU-catalyzed reactions to a series of 3-[methoxy(phenyl)methyl]benzo[e][1,2]oxathiine-2,2-dioxides in moderate to good yields in MeOH. These reactions presumably proceed via DBU-catalyzed O-sulfonylation/intramolecular Baylis-Hillman/1,3-H shift or dehydration tandem sequences, respectively.
Amine-Controlled Divergent Reaction: Iminolactonization and Olefination in the Presence of a Cu(I) Catalyst.

Science.gov (United States)

Nishikata, Takashi; Itonaga, Kohei; Yamaguchi, Norihiro; Sumimoto, Michinori

2017-05-19

α-Bromoamides and styrenes underwent iminolactonization reactions (carbooxygenation), in which simultaneous C-C and C-O formation occurred in the presence of a copper catalyst with triethylamine as the base. Conversely, olefination reactions occurred in the presence of a Cu catalyst with piperidine as the base. The selectivities in those reactions were very high.
Visible-light photoredox catalyzed synthesis of pyrroloisoquinolines via organocatalytic oxidation/[3 + 2] cycloaddition/oxidative aromatization reaction cascade with Rose Bengal

Directory of Open Access Journals (Sweden)

Carlos Vila

2014-05-01

Full Text Available Pyrrolo[2,1-a]isoquinoline alkaloids have been prepared via a visible light photoredox catalyzed oxidation/[3 + 2] cycloaddition/oxidative aromatization cascade using Rose Bengal as an organo-photocatalyst. A variety of pyrroloisoquinolines have been obtained in good yields under mild and metal-free reaction conditions.
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.
New syntheses of No-carrier-added 123I-labeled agents via organoborane chemistry

International Nuclear Information System (INIS)

Kabalka, G.W.

1985-01-01

No-carrier-added 123 I-labeled agents are readily prepared via the reaction of organoboranes with sodium iodide- 123 I in the presence of mild oxidizing agents. The reactions are rapid and regiospecific, and they produce excellent yields of the labeled products. The organoboranes are readily prepared from alkenes and alkynes via the hydroboration reaction. A wide variety of functional groups are tolerated by the hydroboration-iodination sequence. The sequence has been utilized to prepare 123 I-labeled steroids and fatty acids, as well as a number of labeled esters, and aromatic derivatives
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
Structural analysis of CuO / CeO2-based catalytic materials intended for PROX reaction: Part I

International Nuclear Information System (INIS)

Neiva, L.S.; Simoes, A.N.; Bispo, A.; Ribeiro, M.A.; Gama, L.

2011-01-01

This work relates the synthesis process of CuO/CeO 2 catalytic materials by a combustion reaction method as well as it introduces a structural analysis of the developed material, this structural analysis had as main focus to evaluate the influence of the doping substance (CuO) when being incorporated in the hostess matrix structure that is CeO 2 . The CuO/CeO catalytic materials developed in this work are destined to preferential oxidation of CO reaction (PROX). The developed materials were characterized by XRD, SEM and textural complete analysis by the BET method. According to the results, the CuO incorporation changed crystallinity of the structure of the catalytic materials. On the other hand, the morphologic and textural characteristics did not showed significant differences regarding the presence of the doping substance (CuO) in the structure of the developed materials. The porosity of the structures of the developed catalytic materials belongs to the type macroporous. (author)
Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products

Energy Technology Data Exchange (ETDEWEB)

Ji, Yuefei [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Kong, Deyang [Nanjing Institute of Environmental Science, Ministry of Environmental Protection of PRC, Nanjing 210042 (China); Lu, Junhe, E-mail: jhlu@njau.edu.cn [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Jin, Hao; Kang, Fuxing; Yin, Xiaoming; Zhou, Quansuo [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China)

2016-08-05

Highlights: • Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A. • Phenolic moiety was the reactive site for sulfate radical attack. • Pathways include β-scission, oxidation, debromination and coupling reactions. • Brominated disinfection by-products were found during TBBPA degradation. • Humic acid inhibited TBBPA degradation but promoted DBPs formation. - Abstract: Degradation of tetrabromobisphenol A (TBBPA), a flame retardant widely spread in the environment, in Co(II) catalyzed peroxymonosulfate (PMS) oxidation process was systematically explored. The second-order-rate constant for reaction of sulfate radical (SO{sub 4}{sup ·−}) with TBBPA was determined to be 5.27 × 10{sup 10} M{sup −1} s{sup −1}. Apparently, degradation of TBBPA showed first-order kinetics to the concentrations of both Co(II) and PMS. The presence of humic acid (HA) and bicarbonate inhibited TBBPA degradation, most likely due to their competition for SO{sub 4}{sup ·−}. Degradation of TBBPA was initiated by an electron abstraction from one of the phenolic rings. Detailed transformation pathways were proposed, including β-scission of isopropyl bridge, phenolic ring oxidation, debromination and coupling reactions. Further oxidative degradation of intermediates in Co(II)/PMS process yielded brominated disinfection by-products (Br-DBPs) such as bromoform and brominated acetic acids. Evolution profile of Br-DBPs showed an initially increasing and then decreasing pattern with maximum concentrations occurring around 6–10 h. The presence of HA enhanced the formation of Br-DBPs significantly. These findings reveal potentially important, but previously unrecognized, formation of Br-DBPs during sulfate radical-based oxidation of bromide-containing organic compounds that may pose toxicological risks to human health.
A Recyclable Cu-MOF-74 Catalyst for the Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol.

Science.gov (United States)

Leo, Pedro; Orcajo, Gisela; Briones, David; Calleja, Guillermo; Sánchez-Sánchez, Manuel; Martínez, Fernando

2017-06-16

The activity and recyclability of Cu-MOF-74 as a catalyst was studied for the ligand-free C-O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by having unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration, and basic agent (type and concentration) were evaluated. High conversions were achieved at 120 °C, 5 mol % of catalyst, NB/Ph ratio of 1:2, DMF as solvent, and 1 equivalent of K₂CO₃ base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst. The catalytic advantages of using nanostructured Cu-MOF-74 catalyst were also proven.
Kinetics and mechanics of photo-polymerized triazole-containing thermosetting composites via the copper(I)-catalyzed azide-alkyne cycloaddition.

Science.gov (United States)

Song, Han Byul; Wang, Xiance; Patton, James R; Stansbury, Jeffrey W; Bowman, Christopher N

2017-06-01

Several features necessary for polymer composite materials in practical applications such as dental restorative materials were investigated in photo-curable CuAAC (copper(I)-catalyzed azide-alkyne cycloaddition) thermosetting resin-based composites with varying filler loadings and compared to a conventional BisGMA/TEGDMA based composite. Tri-functional alkyne and di-functional azide monomers were synthesized for CuAAC resins and incorporated with alkyne-functionalized glass microfillers for CuAAC composites. Polymerization kinetics, in situ temperature change, and shrinkage stress were monitored simultaneously with a tensometer coupled with FTIR spectroscopy and a data-logging thermocouple. The glass transition temperature was analyzed by dynamic mechanical analysis. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine. The photo-CuAAC polymerization of composites containing between 0 and 60wt% microfiller achieved ∼99% conversion with a dramatic reduction in the maximum heat of reaction (∼20°C decrease) for the 60wt% filled CuAAC composites as compared with the unfilled CuAAC resin. CuAAC composites with 60wt% microfiller generated more than twice lower shrinkage stress of 0.43±0.01MPa, equivalent flexural modulus of 6.1±0.7GPa, equivalent flexural strength of 107±9MPa, and more than 10 times higher energy absorption of 10±1MJm -3 when strained to 11% relative to BisGMA-based composites at equivalent filler loadings. Mechanically robust and highly tough, photo-polymerized CuAAC composites with reduced shrinkage stress and a modest reaction exotherm were generated and resulted in essentially complete conversion. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
Crystal growth of YBa2Cu3O(7-x) and reaction of gold crucible with Ba-Cu-rich flux

Science.gov (United States)

Tao, Y. K.; Chen, H. C.; Martini, L.; Bechtold, J.; Huang, Z. J.; Hor, P. H.

1991-01-01

YBa2Cu3O(7-x) crystals are grown in a gold crucible by a self-flux method. The flux moves along the gold surface due to surface wetting and leaves Y123 crystals behind. The obtained crystals are clean and have a size up to two millimeters and a Tc is greater than 90 K. In an effort to recycle the used crucibles, it is found that the used gold is contaminated by copper. A CuO thin film is easily formed on the surface of the crucible that is made of the used gold. This film provides good surface wetting and a buffer layer, which reduces the reaction between gold and the Y-Ba-Cu-oxide melt.
New Cu-based catalysts supported on TiO2 films for Ullmann SnAr-type C-O coupling reactions

NARCIS (Netherlands)

Benaskar, F.; Engels, V.; Rebrov, E.; Patil, N.G.; Meuldijk, J.; Thuene, P.C.; Magusin, P.C.M.M.; Mezari, B.; Hessel, V.; Hulshof, L.A.; Hensen, E.J.M.; Wheatley, A.E.H.; Schouten, J.C.

2012-01-01

New routes for the preparation of highly active TiO2-supported Cu and CuZn catalysts have been developed for CO coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles,
Characterization and optimization of carboxylesterase-catalyzed esterification between capric acid and glycerol for the production of 1-monocaprin in reversed micellar system.

Science.gov (United States)

Park, Kyung Min; Kwon, Oh Taek; Ahn, Seon Min; Lee, JaeHwan; Chang, Pahn-Shick

2010-02-28

Calotropis procera R. Br. carboxylesterase (EC 3.1.1.1) solubilized in reversed micellar glycerol droplets containing a very small amount of water (less than 5ppm) and stabilized by a surfactant effectively catalyzed the esterification between glycerol and capric acid to produce 1-monocaprin. Reaction variables including surfactant types, organic solvent media, reaction time, G-value ([glycerol]/[capric acid]), R-value ([water]/[surfactant]), pH, temperature, and types of metal ion inhibitors on the carboxylesterase-catalyzed esterification were characterized and optimized to efficiently produce 1-monocaprin. Bis(2-ethylhexyl) sodium sulfosuccinate (AOT) and isooctane were the most effective surfactant and organic solvent medium, respectively, for 1-monocaprin formation in reversed micelles. The optimum G- and R-values were 3.0 and 0.05, respectively, and the optimum pH and temperature were determined to be 10.0 and 60 degrees C, respectively. K(m,app.) and V(max,app.) were calculated from a Hanes-Woolf plot, and the values were 9.64 mM and 2.45 microM/min mg protein, respectively. Among various metal ions, Cu(2+) and Fe(2+) severely inhibited carboxylesterase-catalyzed esterification activity (less than 6.0% of relative activity). Copyright 2009 Elsevier B.V. All rights reserved.
Rapid syntheses of dehydrodiferulates via biomimetic radical coupling reactions of ethyl ferulate.

Science.gov (United States)

Lu, Fachuang; Wei, Liping; Azarpira, Ali; Ralph, John

2012-08-29

Dehydrodimerization of ferulates in grass cell walls provides a pathway toward cross-linking polysaccharide chains limiting the digestibility of carbohydrates by ruminant bacteria and in general affecting the utilization of grass as a renewable bioresource. Analysis of dehydrodiferulates (henceforth termed diferulates) in plant cell walls is useful in the evaluation of the quality of dairy forages as animal feeds. Therefore, there has been considerable demand for quantities of diferulates as standards for such analyses. Described here are syntheses of diferulates from ethyl ferulate via biomimetic radical coupling reactions using the copper(II)-tetramethylethylenediamine [CuCl(OH)-TMEDA] complex as oxidant or catalyst. Although CuCl(OH)-TMEDA oxidation of ethyl ferulate in acetonitrile produced mixtures composed of 8-O-4-, 8-5-, 8-8- (cyclic and noncyclic), and 5-5-coupled diferulates, a catalyzed oxidation using CuCl(OH)-TMEDA as catalyst and oxygen as an oxidant resulted in better overall yields of such diferulates. Flash chromatographic fractionation allowed isolation of 8-8- and 5-5-coupled diferulates. 8-5-Diferulate coeluted with 8-O-4-diferulate but was separated from it via crystallization; the 8-O-4 diferulate left in the mother solution was isolated by rechromatography following a simple tetrabutylammonium fluoride treatment that converted 8-5-diferulate to another useful diferulate, 8-5-(noncyclic) diferulate. Therefore, six of the nine (5-5, 8-O-4, 8-5-c, 8-5-nc, 8-5-dc, 8-8-c, 8-8-nc, 8-8-THF, 4-O-5) diferulic acids that have to date been found in the alkaline hydrolysates of plant cell walls can be readily synthesized by the CuCl(OH)-TMEDA catalyzed aerobic oxidative coupling reaction and subsequent saponification described here.
Chiral Nickel(II) Complex Catalyzed Enantioselective Doyle-Kirmse Reaction of α-Diazo Pyrazoleamides.

Science.gov (United States)

Lin, Xiaobin; Tang, Yu; Yang, Wei; Tan, Fei; Lin, Lili; Liu, Xiaohua; Feng, Xiaoming

2018-03-07

Although high enantioselectivity of [2,3]-sigmatropic rearrangement of sulfonium ylides (Doyle-Kirmse reaction) has proven surprisingly elusive using classic chiral Rh(II) and Cu(I) catalysts, in principle it is due to the difficulty in fine discrimination of the heterotopic lone pairs of sulfur and chirality inversion at sulfur of sulfonium ylides. Here, we show that the synergistic merger of new α-diazo pyrazoleamides and a chiral N, N'-dioxide-nickel(II) complex catalyst enables a highly enantioselective Doyle-Kirmse reaction. The pyrazoleamide substituent serves as both an activating and a directing group for the ready formation of a metal-carbene- and Lewis-acid-bonded ylide intermediate in the assistance of a dual-tasking nickel(II) complex. An alternative chiral Lewis-acid-bonded ylide pathway greatly improves the product enantiopurity even for the reaction of a symmetric diallylsulfane. The majority of transformations over a series of aryl- or vinyl-substituted α-diazo pyrazoleamindes and sulfides proceed rapidly (within 5-20 min in most cases) with excellent results (up to 99% yield and 96% ee), providing a breakthrough in enantioselective Doyle-Kirmse reaction.

Synthesis of 1,3,5-triazines via Cu(OAc)2-catalyzed aerobic oxidative coupling of alcohols and amidine hydrochlorides.

Science.gov (United States)

You, Qing; Wang, Fei; Wu, Chaoting; Shi, Tianchao; Min, Dewen; Chen, Huajun; Zhang, Wu

2015-06-28

Cu(OAc)2 was found to be an efficient catalyst for dehydrogenative synthesis of 1,3,5-triazine derivatives via oxidative coupling reaction of amidine hydrochlorides and alcohols in air. Both aromatic and aliphatic alcohols can be involved in the reaction and thirty-three products were obtained with good to excellent yields. Moreover, the use of a ligand, strong base and organic oxidant is unnecessary.
Redox reactions of the α-synuclein-Cu(2+) complex and their effects on neuronal cell viability.

Science.gov (United States)

Wang, Chengshan; Liu, Lin; Zhang, Lin; Peng, Yong; Zhou, Feimeng

2010-09-21

α-Synuclein (α-syn), a presynaptic protein believed to play an important role in neuropathology in Parkinson's disease (PD), is known to bind Cu(2+). Cu(2+) has been shown to accelerate the aggregation of α-syn to form various toxic aggregates in vitro. Copper is also a redox-active metal whose complexes with amyloidogenic proteins/peptides have been linked to oxidative stress in major neurodegenerative diseases. In this work, the formation of the Cu(2+) complex with α-syn or with an N-terminal peptide, α-syn(1-19), was confirmed with electrospray-mass spectrometry (ES-MS). The redox potentials of the Cu(2+) complex with α-syn (α-syn-Cu(2+)) and α-syn(1-19) were determined to be 0.018 and 0.053 V, respectively. Furthermore, the Cu(2+) center(s) can be readily reduced to Cu(+), and possible reactions of α-syn-Cu(2+) with cellular species (e.g., O(2), ascorbic acid, and dopamine) were investigated. The occurrence of a redox reaction can be rationalized by comparing the redox potential of the α-syn-Cu(2+) complex to that of the specific cellular species. For example, ascorbic acid can directly reduce α-syn-Cu(2+) to α-syn-Cu(+), setting up a redox cycle in which O(2) is reduced to H(2)O(2) and cellular redox species is continuously exhausted. In addition, the H(2)O(2) generated was demonstrated to reduce viability of the neuroblastoma SY-HY5Y cells. Although our results ruled out the direct oxidation of dopamine by α-syn-Cu(2+), the H(2)O(2) generated in the presence of α-syn-Cu(2+) can oxidize dopamine. Our results suggest that oxidative stress is at least partially responsible for the loss of dopaminergic cells in PD brain and reveal the multifaceted role of the α-syn-Cu(2+) complex in oxidative stress associated with PD symptoms.
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.
Theoretical investigation of the Friedlander reaction catalysed by CuBTC: Concerted effect of the adjacent Cu2+ sites

Czech Academy of Sciences Publication Activity Database

Položij, M.; Pérez-Mayoral, E.; Čejka, Jiří; Hermann, J.; Nachtigall, P.

2013-01-01

Roč. 204, APR 2013 (2013), s. 101-107 ISSN 0920-5861 R&D Projects: GA ČR GBP106/12/G015 Grant - others:European Commission(XE) FP7/2007-2013, contract 228862 Institutional support: RVO:61388955 Keywords : Friedlander reaction * Metal Organic Framework (MOF) * CuBTC Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.309, year: 2013
Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature.

Science.gov (United States)

Do, Hien-Quang; Bachman, Shoshana; Bissember, Alex C; Peters, Jonas C; Fu, Gregory C

2014-02-05

The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for SN2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C-N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper-amidate complex, followed by electron transfer to form an alkyl radical.
High Catalysis Activity of Cu₂O Microcrystals to the Electrochemiluminesence of Luminol and H₂O₂

DEFF Research Database (Denmark)

Zhang, Ling; Xu, Guobao; Zhang, Jingdong

Cuprous oxide (Cu2O) is a classical p-type semiconductor with a direct band gap of 2.17 eV, which is wildly used for solar energy conversion, CO oxidation, and photo catalytic water splitting for the low cost and environmental friendliness. For the energy band positions are favorable to the hydro......Cuprous oxide (Cu2O) is a classical p-type semiconductor with a direct band gap of 2.17 eV, which is wildly used for solar energy conversion, CO oxidation, and photo catalytic water splitting for the low cost and environmental friendliness. For the energy band positions are favorable...... to the hydrogen evolution and oxygen evolution potentials, Cu2O materials also catalyze the reduction of hydrogen peroxide (H2O2), which is an critical molecule in the bodies’ metabolism processes or the industrial catalysis reactions. To improve detection sensitivity of H2O2, people have composed Cu2O materials...... that Cu2O semiconductor microcrystal possess the good catalytic performance to this ECL reaction, which is important to develop the high-efficient and lowcost biosensors....
Supercritical CO2 as a reaction medium for synthesis of capsaicin analogues by lipase-catalyzed transacylation of capsaicin.

Science.gov (United States)

Kobata, Kenji; Kobayashi, Mamiko; Kinpara, Sachiyo; Watanabe, Tatsuo

2003-09-01

Capsaicin analogues having different acyl moiety were synthesized by lipase-catalyzed transacylation of capsaicin with a corresponding acyl donor in supercritical CO2 as a reaction medium. Transacylation with methyl tetradecanoate using Novozym 435 as a catalyst gave vanillyl tetradecanamide in a 54% yield at 80 degrees C and 19 MPa over 72 h. Vanillyl (Z)-9-octadecenamide, olvanil, was synthesized from triolein in a 21% yield over 7 d.
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 ...
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–Mn^V$=$O). Based on the ability of fluoride ion to decelerate the oxygen rebound step, we envisaged that a relatively long-lived substrate radical could be trapped by a Mn–F fluorine source, effecting carbon–fluorine bond
State of the art and prospective of lipase-catalyzed transesterification reaction for biodiesel production

International Nuclear Information System (INIS)

Amini, Zeynab; Ilham, Zul; Ong, Hwai Chyuan; Mazaheri, Hoora; Chen, Wei-Hsin

2017-01-01

Highlights: • Enzymatic transesterification process is less energy intensive and robust. • Nano-materials are promising immobilization supports for lipase. • Packed-bed reactors are appropriate for scale-up use. • Potential recombinant, whole cell and recombinant whole cell lipases were enlisted. • Genetic engineering is a promising prospect in biodiesel area. - Abstract: The world demand for fuel as energy sources have arisen the need for generating alternatives such as biofuel. Biodiesel is a renewable fuel used particularly in diesel engines. Currently, biodiesel is mainly produced through transesterification reactions catalyzed by chemical catalysts, which produces higher fatty acid alkyl esters in shorter reaction time. Although extensive investigations on enzymatic transesterification by downstream processing were carried out, enzymatic transesterification has yet to be used in scale-up since commercial lipases are chiefly limited to the cost as well as long reaction time. While numerous lipases were studied and proven to have the high catalytic capacity, still enzymatic reaction requires more investigation. To fill this gap, finding optimal conditions for the reaction such as alcohol and oil choice, water content, reaction time and temperature through proper reaction modelling and simulations as well as the appropriate design and use of reactors for large scale production are crucial issues that need to be accurately addressed. Furthermore, lipase concentration, alternative lipase resources through whole cell technology and genetic engineering, recent immobilizing materials including nanoparticles, and the capacity of enzyme to be reused are important criteria to be neatly investigated. The present work reviews the current biodiesel feedstock, catalysis, general and novel immobilizing materials, bioreactors for enzymatic transesterification, potential lipase resources, intensification technics, and process modelling for enzymatic
Visible-light-induced, Ir-catalyzed reactions of N-methyl-N-((trimethylsilylmethylaniline with cyclic α,β-unsaturated carbonyl compounds

Directory of Open Access Journals (Sweden)

Dominik Lenhart

2014-04-01

Full Text Available N-Methyl-N-((trimethylsilylmethylaniline was employed as reagent in visible-light-induced, iridium-catalyzed addition reactions to cyclic α,β-unsaturated carbonyl compounds. Typical reaction conditions included the use of one equivalent of the reaction substrate, 1.5 equivalents of the aniline and 2.5 mol % (in MeOH or 1.0 mol % (in CH2Cl2 [Ir(ppy2(dtbbpy]BF4 as the catalyst. Two major reaction products were obtained in combined yields of 30–67%. One product resulted from aminomethyl radical addition, the other product was a tricyclic compound, which is likely formed by attack of the intermediately formed α-carbonyl radical at the phenyl ring. For five-membered α,β-unsaturated lactone and lactam substrates, the latter products were the only products isolated. For the six-membered lactones and lactams and for cyclopentenone the simple addition products prevailed.
Investigation of Radioiodination of Meta-Iodobenzylguanidine Compound with 131I Isotope in Solid Phase Using Cu Catalyzer

International Nuclear Information System (INIS)

Davarpanah, M. R.; Attar Nosrati, S.; Khoshhosn, H.; Kazemi Boudani, M.; Fazlali, M.; Ghannadi Maragheh, M.

2012-01-01

In this study the radioiodination process of meta-iodobenzylguanidine with 131 I isotope in presence of ammonium sulphate and Cu(II) Catalyzer was investigated. In order to optimize the process, the influence of different parameters on labeling yield was studied. The results of experiments showed that the use of oil bath with temperature of 160 d egree C is necessary. After the labeling process, purification step of the final product was carried out using Dowex-1 x 8 resin. The mean labeling yield was 97.2 p ercent . In this method radiolabelling of MIBG with 131 I (185 MBq for diagnostic dose and 3330 MBq for therapeutic dose) is quite simple and it complies with the requirements of routine production of 13 1I-MIBG radiopharmaceutical for diagnostic and therapeutic purposes. This paper is a narration of industrial scale production of 131 I-MIBG radiopharmaceutical.
Structural characterization of tartrate dehydrogenase: a versatile enzyme catalyzing multiple reactions

International Nuclear Information System (INIS)

Malik, Radhika; Viola, Ronald E.

2010-01-01

The first structure of an NAD-dependent tartrate dehydrogenase (TDH) has been solved to 2 (angstrom) resolution by single anomalous diffraction (SAD) phasing as a complex with the intermediate analog oxalate, Mg 2+ and NADH. This TDH structure from Pseudomonas putida has a similar overall fold and domain organization to other structurally characterized members of the hydroxy-acid dehydrogenase family. However, there are considerable differences between TDH and these functionally related enzymes in the regions connecting the core secondary structure and in the relative positioning of important loops and helices. The active site in these complexes is highly ordered, allowing the identification of the substrate-binding and cofactor-binding groups and the ligands to the metal ions. Residues from the adjacent subunit are involved in both the substrate and divalent metal ion binding sites, establishing a dimer as the functional unit and providing structural support for an alternating-site reaction mechanism. The divalent metal ion plays a prominent role in substrate binding and orientation, together with several active-site arginines. Functional groups from both subunits form the cofactor-binding site and the ammonium ion aids in the orientation of the nicotinamide ring of the cofactor. A lysyl amino group (Lys192) is the base responsible for the water-mediated proton abstraction from the C2 hydroxyl group of the substrate that begins the catalytic reaction, followed by hydride transfer to NAD. A tyrosyl hydroxyl group (Tyr141) functions as a general acid to protonate the enolate intermediate. Each substrate undergoes the initial hydride transfer, but differences in substrate orientation are proposed to account for the different reactions catalyzed by TDH.
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.
Theoretical study of stability and reaction mechanism of CuO supported on ZrO{sub 2} during chemical looping combustion

Energy Technology Data Exchange (ETDEWEB)

Wang, Minjun; Liu, Jing, E-mail: liujing27@mail.hust.edu.cn; Shen, Fenghua; Cheng, Hao; Dai, Jinxin; Long, Yan

2016-03-30

Graphical abstract: - Highlights: • The stability and reaction mechanism of CuO supported on ZrO{sub 2} were studied by DFT. • ZrO{sub 2} provides a high resistance to CuO sintering. • ZrO{sub 2} promotes the activity of CuO for CO oxidation in fuel reactor. • The energy barriers are low enough for CuO/ZrO{sub 2} oxidation reaction in air reactor. - Abstract: The addition of inert support is important for the Cu-based oxygen carrier used in chemical looping combustion (CLC). The effects of the ZrO{sub 2} support on the stability and reactivity of Cu-based oxygen carrier were investigated using the density functional theory (DFT). First, the sintering inhibition mechanism of ZrO{sub 2} that support active CuO was investigated. The optimized Cu{sub 4}O{sub 4}/ZrO{sub 2} structure showed a strong interaction occurred between the Cu{sub 4}O{sub 4} cluster and ZrO{sub 2}(1 0 1) surface. The interaction prevented the migration and agglomeration of CuO. Next, the adsorption of CO on Cu{sub 4}O{sub 4}/ZrO{sub 2} and the mechanism of the CuO/ZrO{sub 2} reduction by CO were studied. CO mainly chemisorbed on the Cu site and ZrO{sub 2} acted as an electron donor in the adsorption system. The energy barrier of CuO/ZrO{sub 2} reduction by CO (0.79 eV) was much lower than that of the pure CuO cluster (1.44 eV), indicating that ZrO{sub 2} had a positive effect on CuO/ZrO{sub 2} reduction by CO. After CO was oxidized in the fuel reactor, the CuO was reduced into Cu. The adsorption of O{sub 2} on Cu{sub 2}/ZrO{sub 2} and the most likely pathway of Cu{sub 2}/ZrO{sub 2} oxidation by O{sub 2} were investigated. The adsorption of O{sub 2} was found a strong chemisorption behavior. The energy barriers were low enough for the Cu-based oxygen carrier oxidation reaction.
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...
Preparation of Cu@Cu₂O Nanocatalysts by Reduction of HKUST-1 for Oxidation Reaction of Catechol.

Science.gov (United States)

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

2016-11-02

HKUST-1, a copper-based metal organic framework (MOF), has been investigated as a catalyst in various reactions. However, the HKUST-1 shows low catalytic activity in the oxidation of catechol. Therefore, we synthesized Fe₃O₄@HKUST-1 by layer-by layer assembly strategy and Cu@Cu₂O by reduction of HKUST-1 for enhancement of catalytic activity. Cu@Cu₂O nanoparticles exhibited highly effective catalytic activity in oxidation of 3,5-di- tert -butylcatechol. Through this method, MOF can maintain the original core-shell structure and be used in various other reactions with enhanced catalytic activity.
Visible-Light Photoredox-Catalyzed Giese Reaction: Decarboxylative Addition of Amino Acid Derived α-Amino Radicals to Electron-Deficient Olefins

KAUST Repository

Millet, Anthony

2016-06-20

A tin- and halide-free, visible-light photoredox-catalyzed Giese reaction was developed. Primary and secondary α-amino radicals were generated readily from amino acids in the presence of catalytic amounts of an iridium photocatalyst. The reactivity of the α-amino radicals has been evaluated for the functionalization of a variety of activated olefins. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Visible-Light Photoredox-Catalyzed Giese Reaction: Decarboxylative Addition of Amino Acid Derived α-Amino Radicals to Electron-Deficient Olefins

KAUST Repository

Millet, Anthony; Lefebvre, Quentin; Rueping, Magnus

2016-01-01

A tin- and halide-free, visible-light photoredox-catalyzed Giese reaction was developed. Primary and secondary α-amino radicals were generated readily from amino acids in the presence of catalytic amounts of an iridium photocatalyst. The reactivity of the α-amino radicals has been evaluated for the functionalization of a variety of activated olefins. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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.

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.
NO oxidation on Zeolite Supported Cu Catalysts: Formation and Reactivity of Surface Nitrates

Energy Technology Data Exchange (ETDEWEB)

Chen, Hai-Ying; Wei, Zhehao; Kollar, Marton; Gao, Feng; Wang, Yilin; Szanyi, Janos; Peden, Charles HF

2016-04-18

The comparative activities of a small-pore Cu-CHA and a large-pore Cu-BEA catalyst for the selective catalytic reduction (SCR) of NOx with NH3, and for the oxidation of NO to NO2 and the subsequent formation of surface nitrates were investigated. Although both catalysts are highly active in SCR reactions, they exhibit very low NO oxidation activity. Furthermore, Cu-CHA is even less active than Cu-BEA in catalyzing NO oxidation but is clearly more active for SCR reactions. Temperature-programed desorption (TPD) experiments following the adsorption of (NO2 + NO + O2) with different NO2:NO ratios reveal that the poor NO oxidation activity of the two catalysts is not due to the formation of stable surface nitrates. On the contrary, NO is found to reduce and decompose the surface nitrates on both catalysts. To monitor the reaction pathways, isotope exchange experiments were conducted by using 15NO to react with 14N-nitrate covered catalyst surfaces. The evolution of FTIR spectra during the isotope exchange process demonstrates that 14N-nitrates are simply displaced with no formation of 15N-nitrates on the Cu-CHA sample, which is clearly different from that observed on the Cu-BEA sample where formation of 15N-nitrates is apparent. The results suggest that the formal oxidation state of N during the NO oxidation on Cu-CHA mainly proceeds from its original +2 to a +3 oxidation state, whereas reaching a higher oxidation state for N, such as +4 or +5, is possible on Cu-BEA. The authors at PNNL gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.
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.
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
Lecithin-cholesterol acyltransferase (LCAT) catalyzes transacylation of intact cholesteryl esters. Evidence for the partial reversal of the forward LCAT reaction

International Nuclear Information System (INIS)

Sorci-Thomas, M.; Babiak, J.; Rudel, L.L.

1990-01-01

Lecithin-cholesterol acyltransferase (LCAT) catalyzes the intravascular synthesis of lipoprotein cholesteryl esters by converting cholesterol and lecithin to cholesteryl ester and lysolecithin. LCAT is unique in that it catalyzes sequential reactions within a single polypeptide sequence. In this report we find that LCAT mediates a partial reverse reaction, the transacylation of lipoprotein cholesteryl oleate, in whole plasma and in a purified, reconstituted system. As a result of the reverse transacylation reaction, a linear accumulation of [3H]cholesterol occurred during incubations of plasma containing high density lipoprotein labeled with [3H]cholesteryl oleate. When high density lipoprotein labeled with cholesteryl [14C]oleate was also included in the incubation the labeled fatty acyl moiety remained in the cholesteryl [14C]oleate pool showing that the formation of labeled cholesterol did not result from hydrolysis of the doubly labeled cholesteryl esters. The rate of release of [3H]cholesterol was only about 10% of the forward rate of esterification of cholesterol using partially purified human LCAT and was approximately 7% in whole monkey plasma. Therefore, net production of cholesterol via the reverse LCAT reaction would not occur. [3H]Cholesterol production from [3H]cholesteryl oleate was almost completely inhibited by a final concentration of 1.4 mM 5,5'-dithiobis(nitrobenzoic acid) during incubation with either purified LCAT or whole plasma. Addition of excess lysolecithin to the incubation system did not result in the formation of [14C]oleate-labeled lecithin, showing that the reverse reaction found here for LCAT was limited to the last step of the reaction. To explain these results we hypothesize that LCAT forms a [14C]oleate enzyme thioester intermediate after its attack on the cholesteryl oleate molecule
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...
The catalytic cycle of nitrous oxide reductase - The enzyme that catalyzes the last step of denitrification.

Science.gov (United States)

Carreira, Cíntia; Pauleta, Sofia R; Moura, Isabel

2017-12-01

The reduction of the potent greenhouse gas nitrous oxide requires a catalyst to overcome the large activation energy barrier of this reaction. Its biological decomposition to the inert dinitrogen can be accomplished by denitrifiers through nitrous oxide reductase, the enzyme that catalyzes the last step of the denitrification, a pathway of the biogeochemical nitrogen cycle. Nitrous oxide reductase is a multicopper enzyme containing a mixed valence CuA center that can accept electrons from small electron shuttle proteins, triggering electron flow to the catalytic sulfide-bridged tetranuclear copper "CuZ center". This enzyme has been isolated with its catalytic center in two forms, CuZ*(4Cu1S) and CuZ(4Cu2S), proven to be spectroscopic and structurally different. In the last decades, it has been a challenge to characterize the properties of this complex enzyme, due to the different oxidation states observed for each of its centers and the heterogeneity of its preparations. The substrate binding site in those two "CuZ center" forms and which is the active form of the enzyme is still a matter of debate. However, in the last years the application of different spectroscopies, together with theoretical calculations have been useful in answering these questions and in identifying intermediate species of the catalytic cycle. An overview of the spectroscopic, kinetics and structural properties of the two forms of the catalytic "CuZ center" is given here, together with the current knowledge on nitrous oxide reduction mechanism by nitrous oxide reductase and its intermediate species. Copyright © 2017 Elsevier Inc. All rights reserved.
Reaction products between Bi-Sr-Ca-Cu-oxide thick films and alumina substrates

International Nuclear Information System (INIS)

Alarco, J.A.; Ilushechkin, A.; Yamashita, T.; Bhargava, A.; Barry, J.; Mackinnon, I.D.R.

1997-01-01

The structure and composition of reaction products between Bi-Sr-Ca-Cu-oxide (BSCCO) thick films and alumina substrates have been characterized using a combination of electron diffraction, scanning electron microscopy and energy dispersive X-ray spectrometry (EDX). Sr and Ca are found to be the most reactive cations with alumina. Sr 4 Al 6 O 12 SO 4 is formed between the alumina substrates and BSCCO thick films prepared from paste with composition close to Bi-2212 (and Bi-2212+10 wt.% Ag). For paste with composition close to Bi(Pb)-2223 +20 wt.% Ag, a new phase with f.c.c. structure, lattice parameter about a=24.5 A and approximate composition Al 3 Sr 2 CaBi 2 CuO x has been identified in the interface region. Understanding and control of these reactions is essential for growth of high quality BSCCO thick films on alumina. (orig.)
Large-scale synthesis of hierarchical-structured weissite (Cu2−xTe) flake arrays and their catalytic properties

International Nuclear Information System (INIS)

Cao, Xinjiang; Yan, Shancheng; Ortiz, Lazarus Santiago; Liang, Gaofeng; Sun, Bo; Huang, Ningping; Xiao, Zhongdang

2014-01-01

Graphical abstract: - Highlights: • Large-scale Cu 2−x Te flake arrays grown on copper foam were synthesized. • They possess superior catalytic efficiency on methylene blue with the assistance of H 2 O 2 . • The effects of preparing conditions on the growth of Cu 2−x Te flake arrays were investigated. - Abstract: Large-scale weissite (Cu 2−x Te) flake arrays with three-dimensional (3D) hierarchical structure have been successfully fabricated via a facile one-step solution-phase strategy through the reaction of tellurium powder and copper foam. At the end of the reaction Cu 2−x Te flakes were distributed evenly on the surface of a porous solid copper substrate. Field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) analysis showed the abundance of flakes grown on the 3D porous copper architecture, while X-ray diffraction (XRD) and energy-dispersive X-ray spectra (EDS) were used to determine the crystal structure and phase composition of these products. A series of experiments discovered that the size and morphology of the products could be affected by some reactive parameters including the reaction time, synthesis temperature and volume ratio of absolute ethanol/deionized water. Catalysis experiments using the in situ synthesized of Cu 2−x Te flakes to catalyze the degradation of methylene blue (MB) demonstrated the strong catalytic ability of these flakes
Rhodium-catalyzed [5 + 2 + 1] cycloaddition of ene-vinylcyclopropanes and CO: reaction design, development, application in natural product synthesis, and inspiration for developing new reactions for synthesis of eight-membered carbocycles.

Science.gov (United States)

Wang, Yi; Yu, Zhi-Xiang

2015-08-18

Practical syntheses of natural products and their analogues with eight-membered carbocyclic skeletons are important for medicinal and biological investigations. However, methods and strategies to construct the eight-membered carbocycles are limited. Therefore, developing new methods to synthesize the eight-membered carbocycles is highly desired. In this Account, we describe our development of three rhodium-catalyzed cycloadditions for the construction of the eight-membered carbocycles, which have great potential in addressing the challenges in the synthesis of medium-sized ring systems. The first reaction described in this Account is our computationally designed rhodium-catalyzed two-component [5 + 2 + 1] cycloaddition of ene-vinylcyclopropanes (ene-VCPs) and CO for the diastereoselective construction of bi- and tricyclic cyclooctenones. The design of this reaction is based on the hypothesis that the C(sp(3))-C(sp(3)) reductive elimination of the eight-membered rhodacycle intermediate generated from the rhodium-catalyzed cyclopropane cleavage and alkene insertion, giving Wender's [5 + 2] cycloadduct, is not easy. Under CO atmosphere, CO insertion may occur rapidly, converting the eight-membered rhodacycle into a nine-membered rhodacycle, which then undergoes an easy C(sp(2))-C(sp(3)) reductive elimination process and furnishes the [5 + 2 + 1] product. This hypothesis was supported by our preliminary DFT studies and also served as inspiration for the development of two [7 + 1] cycloadditions: the [7 + 1] cycloaddition of buta-1,3-dienylcyclopropanes (BDCPs) and CO for the construction of cyclooctadienones, and the benzo/[7 + 1] cycloaddition of cyclopropyl-benzocyclobutenes (CP-BCBs) and CO to synthesize the benzocyclooctenones. The efficiency of these rhodium-catalyzed cycloadditions can be revealed by the application in natural product synthesis. Two eight-membered ring-containing natural products, (±)-asterisca-3(15),6-diene and (+)-asteriscanolide, have been
Process limitations of a whole-cell P450 catalyzed reaction using a CYP153A-CPR fusion construct expressed in Escherichia coli

DEFF Research Database (Denmark)

Lundemo, M. T.; Notonier, S.; Striedner, G.

2016-01-01

fatty acids at the terminal position. ω-Hydroxylated fatty acids can be used in the field of high-end polymers and in the cosmetic and fragrance industry. Here, we have identified the limitations for implementation of a whole-cell P450-catalyzed reaction by characterizing the chosen biocatalyst as well......Cytochrome P450s are interesting biocatalysts due to their ability to hydroxylate non-activated hydrocarbons in a selective manner. However, to date only a few P450-catalyzed processes have been implemented in industry due to the difficulty of developing economically feasible processes...
Investigations of Pd-Cu electrocatalyst for oxygen reduction reaction in acidic media with RDE method

Energy Technology Data Exchange (ETDEWEB)

Fouda-Onana, F.; Bah, S.; Savadogo, O. [Ecole Polytechnique de Montreal, Montreal, PQ (Canada). Laboratoire de nouveaux materiaux pour l' energie et l' electrochimie

2008-07-01

The kinetics of the oxygen reduction reaction (ORR) has been studied extensively with different platinum bi-metallic alloys such as Pt-Fe, Pt-Ni, Pt-Co. However, palladium-based bi-metallic alloys are being considered as a substitute for platinum in electrocatalysts. This paper reported on a study that investigated the ORR on bi-metallic Pd-Cu electrocatalyst. Different contents in Cu were analyzed and an optimal Cu composition leading to the highest ORR activity was found. A mechanism of the ORR kinetics for this catalyst was introduced based on the value of the Tafel slope. A smooth increase in surface area up to 50 per cent Cu was observed to a constant value of 23 cm{sup 2}. Such behaviour was due to the high dispersion of Pd as Cu increased and segregated. A volcano-shape was found between the kinetic current, activation energy and the Cu composition. The maximum exchange current density and the lowest activation energy were found for Pd50Cu50, which corresponded to the highest surface area. All Pd-Cu alloys presented a higher kinetic current than Pd alone. 3 refs., 1 tab., 3 figs.
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.
Large-scale synthesis of hierarchical-structured weissite (Cu{sub 2−x}Te) flake arrays and their catalytic properties

Energy Technology Data Exchange (ETDEWEB)

Cao, Xinjiang [State Key Laboratory of Bioelectronics (Chien-Shiung Wu Lab), School of Biological Science and Medical Engineering, Southeast University, Si Pai Lou 2#, Nanjing 210096 (China); Yan, Shancheng [School of Geography and Biological Information, Nanjing University of Posts and Telecommunications, Nanjing 210046 (China); Ortiz, Lazarus Santiago; Liang, Gaofeng; Sun, Bo; Huang, Ningping [State Key Laboratory of Bioelectronics (Chien-Shiung Wu Lab), School of Biological Science and Medical Engineering, Southeast University, Si Pai Lou 2#, Nanjing 210096 (China); Xiao, Zhongdang, E-mail: zdxiao@seu.edu.cn [State Key Laboratory of Bioelectronics (Chien-Shiung Wu Lab), School of Biological Science and Medical Engineering, Southeast University, Si Pai Lou 2#, Nanjing 210096 (China)

2014-03-01

Graphical abstract: - Highlights: • Large-scale Cu{sub 2−x}Te flake arrays grown on copper foam were synthesized. • They possess superior catalytic efficiency on methylene blue with the assistance of H{sub 2}O{sub 2}. • The effects of preparing conditions on the growth of Cu{sub 2−x}Te flake arrays were investigated. - Abstract: Large-scale weissite (Cu{sub 2−x}Te) flake arrays with three-dimensional (3D) hierarchical structure have been successfully fabricated via a facile one-step solution-phase strategy through the reaction of tellurium powder and copper foam. At the end of the reaction Cu{sub 2−x}Te flakes were distributed evenly on the surface of a porous solid copper substrate. Field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) analysis showed the abundance of flakes grown on the 3D porous copper architecture, while X-ray diffraction (XRD) and energy-dispersive X-ray spectra (EDS) were used to determine the crystal structure and phase composition of these products. A series of experiments discovered that the size and morphology of the products could be affected by some reactive parameters including the reaction time, synthesis temperature and volume ratio of absolute ethanol/deionized water. Catalysis experiments using the in situ synthesized of Cu{sub 2−x}Te flakes to catalyze the degradation of methylene blue (MB) demonstrated the strong catalytic ability of these flakes.
When Ethyl Isocyanoacetate Meets Isatins: A 1,3-Dipolar/Inverse 1,3-Dipolar/Olefination Reaction for Access to 3-Ylideneoxindoles.

Science.gov (United States)

Yuan, Wen-Kui; Cui, Tao; Liu, Wei; Wen, Li-Rong; Li, Ming

2018-03-16

A new CuI/1,10-phen-catalyzed reaction for the synthesis of 3-ylideneoxindoles from readily available isatins and ethyl isocyanoacetate, in which ethyl isocyanoacetate acts as a latent two-carbon donor like the Wittig reagent, is reported. A tandem procedure including 1,3-dipolar cycloaddition/inverse 1,3-dipolar ring opening/olefination allows the preparation of 3-ylideneoxindoles with broad functional group tolerance.
Copper-Based Metal-Organic Framework Nanoparticles with Peroxidase-Like Activity for Sensitive Colorimetric Detection of Staphylococcus aureus.

Science.gov (United States)

Wang, Shuqin; Deng, Wenfang; Yang, Lu; Tan, Yueming; Xie, Qingji; Yao, Shouzhuo

2017-07-26

Cu-MOF nanoparticles with an average diameter of 550 nm were synthesized from 2-aminoterephthalic acid and Cu(NO 3 ) 2 by a mixed solvothermal method. The Cu-MOF nanoparticles can show peroxidase-like activity that can catalyze 3,3',5,5'-tetramethylbenzidine to produce a yellow chromogenic reaction in the presence of H 2 O 2 . The presence of abundant amine groups on the surfaces of Cu-MOF nanoparticles enables facile modification of Staphylococcus aureus (S. aureus) aptamer on Cu-MOF nanoparticles. By combining Cu-MOF-catalyzed chromogenic reaction with aptamer recognition and magnetic separation, a simple, sensitive, and selective colorimetric method for the detection of S. aureus was developed.
Degradation of Anthraquinone Dye Reactive Blue 4 in Pyrite Ash Catalyzed Fenton Reaction

Directory of Open Access Journals (Sweden)

Milena Becelic-Tomin

2014-01-01

Full Text Available Pyrite ash (PA is created by burning pyrite in the chemical production of sulphuric acid. The high concentration of iron oxide, mostly hematite, present in pyrite ash, gives the basis for its application as a source of catalytic iron in a modified Fenton process for anthraquinone dye reactive blue 4 (RB4 degradation. The effect of various operating variables such as catalyst and oxidant concentration, initial pH and RB4 concentration on the abatement of total organic carbon, and dye has been assessed in this study. Here we show that degradation of RB4 in the modified Fenton reaction was efficient under the following conditions: pH=2.5; [PA]0=0.2 g L−1; [H2O2]0=5 mM and initial RB4 concentration up to 100 mg L−1. The pyrite ash Fenton reaction can overcome limitations observed from the classic Fenton reaction, such as the early termination of the Fenton reaction. Metal (Pb, Zn, and Cu content of the solution after the process suggests that an additional treatment step is necessary to remove the remaining metals from the water. These results provide basic knowledge to better understand the modified, heterogeneous Fenton process and apply the PA Fenton reaction for the treatment of wastewaters which contains anthraquinone dyes.
Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers

KAUST Repository

Della Sala, Giorgio

2017-05-31

The fluoride promoted vinylogous Mukaiyama-Michael reaction (VMMR) of 2-trimethylsilyloxyfuran with diverse α,β-unsaturated ketones is described. The TBAF catalyzed VMMR afforded high anti-diastereoselectivity irrespective of the solvents used. The KF/crown ethers catalytic systems proved to be highly efficient in terms of yields and resulted in a highly diastereoselective unprecedented solvent/catalyst switchable reaction. Anti-adducts were obtained as single diastereomers or with excellent diastereoselectivities when benzo-15-crown-5 in CH2Cl2 was employed. On the other hand, high syn-diastereoselectivities (from 76:24 to 96:4) were achieved by employing dicyclohexane-18-crown-6 in toluene. Based on DFT calculations, the catalysts/solvents-dependent switchable diastereoselectivities are proposed to be the result of loose or tight cation-dienolate ion pairs.
Lipase-catalyzed glycerolysis of fats and oils in ionic liquids: a further study on the reaction system

DEFF Research Database (Denmark)

Guo, Zheng; Xu, Xuebing

2006-01-01

Candida antarctica lipase B-catalyzed glycerolysis of sunflower oil in a tetraammonium-based ionic liquid (IL) was studied to elucidate its distinct characteristics and to evaluate the contributions of important parameters. Mass transfer limitations and occurring partial phase separation were found...... and enzyme loading study. Interestingly, increasing water activity resulted in a decreasing initial reaction rate and a prolonged induction period, which possibly resulted from an elevated solvation barrier and the phase separation at higher water content. Studies on thermodynamics of glycerolysis show......) equation, and the viscosity of the mixture is strongly agitation-dependent. A comparable diffusion time constant of the oil molecule in the IL to that of the reaction shows that the glycerolysis in the IL is controlled both diffusionally and kinetically, as experimentally verified by agitation effect...
Reaction mechanism of CO oxidation on Cu2O(111): A density functional study

Science.gov (United States)

Sun, Bao-Zhen; Chen, Wen-Kai; Xu, Yi-Jun

2010-10-01

The possible reaction mechanisms for CO oxidation on the perfect Cu2O(111) surface have been investigated by performing periodic density functional theoretical calculations. We find that Cu2O(111) is able to facilitate the CO oxidation with different mechanisms. Four possible mechanisms are explored (denoted as MER1, MER2, MLH1, and MLH2, respectively): MER1 is CO(gas)+O2(ads)-->CO2(gas) MER2 is CO(gas)+O2(ads)-->CO3(ads)-->O(ads)+CO2(gas) MLH1 refers to CO(ads)+O2(ads)-->O(ads)+CO2(ads) and MLH2 refers to CO(ads)+O2(ads)-->OOCO(ads)-->O(ads)+CO2(ads). Our transition state calculations clearly reveal that MER1 and MLH2 are both viable; but MER1 mechanism preferentially operates, in which only a moderate energy barrier (60.22 kJ/mol) needs to be overcome. When CO oxidation takes place along MER2 path, it is facile for CO3 formation, but is difficult for its decomposition, thereby CO3 species can stably exist on Cu2O(111). Of course, the reaction of CO with lattice O of Cu2O(111) is also considered. However, the calculated barrier is 600.00 kJ/mol, which is too large to make the path feasible. So, we believe that on Cu2O(111), CO reacts with adsorbed O, rather than lattice O, to form CO2. This is different from the usual Mars-van Krevene mechanism. The present results enrich our understanding of the catalytic oxidation of CO by copper-based and metal-oxide catalysts.

Anchoring of Cu(II) onto surface of porous metal-organic framework through post-synthesis modification for the synthesis of benzimidazoles and benzothiazoles

Science.gov (United States)

Kardanpour, Reihaneh; Tangestaninejad, Shahram; Mirkhani, Valiollah; Moghadam, Majid; Mohammadpoor-Baltork, Iraj; Zadehahmadi, Farnaz

2016-03-01

Efficient synthesis of various benzimidazoles and benzothiazoles under mild conditions catalyzed by Cu(II) anchored onto UiO-66-NH2 metal organic framework is reported. In this manner, first, the aminated UiO-66 was modified with thiophene-2-carbaldehyde and then the prepared Schiff base was reacted with CuCl2. The prepared catalyst was characterized by FT-IR, UV-vis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). The UiO-66-NH2-TC-Cu was applied as a highly efficient catalyst for synthesis of benzimidazole and benzothiazole derivatives by the reaction of aldehydes with 1,2-diaminobenzene or 2-aminothiophenol. The Cu(II)-containing MOF was reused several times without any appreciable loss of its efficiency.
Laccase-catalyzed removal of the antimicrobials chlorophene and dichlorophen from water: Reaction kinetics, pathway and toxicity evaluation.

Science.gov (United States)

Shi, Huanhuan; Peng, Jianbiao; Li, Jianhua; Mao, Liang; Wang, Zunyao; Gao, Shixiang

2016-11-05

As active agents in cleaning and disinfecting products, antimicrobials have been widely spread in the environment and have drawn extensive attention as potential threats to the ecological system and human health. In this study, the laccase-catalyzed removal of two emerging antimicrobials, chlorophene (CP) and dichlorophen (DCP), was investigated under simulated environmental conditions. Intrinsic reaction kinetics showed that the removal of CP and DCP followed second-order reaction kinetics, first-order with respect to both the enzyme and the substrate concentration. It was also found that fulvic acid could suppress the transformation of CP and DCP by reversing the oxidation reactions through its action as a scavenger of the free radical intermediates produced from reactions between laccase and the substrates. Several reaction products were identified by a quadrupole time-of-flight mass spectrometer, and detailed reaction pathways were proposed. For both CP and DCP, direct polymerization was the principal pathway, and the coupling patterns were further corroborated based on molecular modeling. The nucleophilic substitution of chlorine by the hydroxyl group was observed, and further oxidation products capable of coupling with each other were also found. Additionally, toxicity evaluation tests using Scenedesmus obliquus confirmed that the toxicity of CP and DCP was effectively eliminated during the reaction processes. Copyright © 2016 Elsevier B.V. All rights reserved.
Ligand-Controlled Synthesis of Azoles via Ir-Catalyzed Reactions of Sulfoxonium Ylides with 2-Amino Heterocycles.

Science.gov (United States)

Phelps, Alicia M; Chan, Vincent S; Napolitano, José G; Krabbe, Scott W; Schomaker, Jennifer M; Shekhar, Shashank

2016-05-20

An iridium-catalyzed method was developed for the synthesis of imidazo-fused pyrrolopyrazines. The presence or absence of a nitrogenated ligand controlled the outcome of the reaction, leading to simple β-keto amine products in the absence of added ligand and the cyclized 7- and 8-substituted-imidazo[1,2-a]pyrrolo[2,3-e]pyrazine products in the presence of ligand. This catalyst control was conserved across a variety of ylide and amine coupling partners. The substrate was shown to act as a ligand for the iridium catalyst in the absence of other ligands via NMR spectroscopy. Kinetic studies indicated that formation of the Ir-carbene was reversible and the slow step of the reaction. These mechanistic investigations suggest that the β-keto amine products form via an intramolecular carbene N-H insertion, and the imidazopyrrolopyrazines form via an intermolecular carbene N-H insertion.
Phospholipids chiral at phosphorus. Steric course of the reactions catalyzed by phosphatidylserine synthase from Escherichia coli and yeast

International Nuclear Information System (INIS)

Raetz, C.R.H.; Carman, G.M.; Dowhan, W.; Jiang, R.T.; Waszkuc, W.; Loffredo, W.; Tsai, M.D.

1987-01-01

The steric courses of the reactions catalyzed by phosphatidylserine (PS) synthase from Escherichia coli and yeast were elucidated by the following procedure. R/sub P/ and S/sub P/ isomers of 1,2-dipalmitoyl-sn-glycero-3-[ 17 O, 18 O]phosphoethanolamine ([ 17 O, 18 O]DPPE) were synthesized and converted to (R/sub P/)- and (S/sub P/)-1,2-dipalmitoyl-sn-glycero-3-[ 16 O, 17 O, 18 O]DPPA), respectively, by incubating with phospholipase D. Condensation of [ 16 O, 17 O, 18 O]DPPA with cytidine 5'-monophosphomorpholidate in pyridine gave the desired substrate for PS synthase, [ 17 O, 18 O]cytidine 5'-diphospho-1,2-dipalmitoyl-sn-glycerol ([ 17 O, 18 O]CDP-DPG), as a mixture of several isotopic and configurational isomers. Incubation of [ 17 O, 18 O]CDP-DPG), as a mixture of several isotopic and configurational isomers. Incubation of [ 17 O, 18 O] CDP-DPG with a mixture of L-serine, PS synthase and PS decarboxylase gave [ 17 O, 18 O]DPPE. The configuration and isotopic enrichments of the starting [ 17 O, 18 O]DPPE and the product were analyzed by 31 P NMR following trimethylsilylation of the DPPE. The results indicate that the reaction of E. coli PS synthase proceeds with retention of configuration at phosphorus, which suggests a two-step mechanism involving a phosphatidyl-enzyme intermediate, while the yeast PS synthase catalyzes the reaction with inversion of configuration, which suggests a single-displacement mechanism. Such results lend strong support to the ping-pong mechanism proposed for the E. coli enzyme and the sequential Bi-Bi mechanism proposed for the yeast enzyme, both based on previous isotopic exchange experiments
Cu-Click Compatible Triazabutadienes To Expand the Scope of Aryl Diazonium Ion Chemistry.

Science.gov (United States)

Cornali, Brandon M; Kimani, Flora W; Jewett, John C

2016-10-07

Triazabutadienes can be used to readily generate reactive aryl diazonium ions under mild, physiologically relevant conditions. These conditions are compatible with a range of functionalities that do not tolerate traditional aryl diazonium ion generation. To increase the utility of this aryl diazonium ion releasing chemistry an alkyne-containing triazabutadiene was synthesized. The copper-catalyzed azide-alkyne cycloaddition ("Cu-click") reaction was utilized to modify the alkyne-containing triazabutadiene and shown to be compatible with the nitrogen-rich triazabutadiene. One of the triazole products was tethered to a fluorophore, thus enabling the direct fluorescent labeling of a model protein.
One-pot hydrothermal growth of raspberry-like CeO{sub 2} on CuO microsphere as copper-based catalyst for Rochow reaction

Energy Technology Data Exchange (ETDEWEB)

Jin, Zheying [School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China); State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Li, Jing [State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Shi, Laishun, E-mail: lshunsh@sdu.edu.cn [School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China); Ji, Yongjun, E-mail: yjji@ipe.ac.cn [State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Zhong, Ziyi [School of Chemical & Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore 637459 (Singapore); Su, Fabing, E-mail: fbsu@ipe.ac.cn [State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China)

2015-12-30

Graphical abstract: - Highlights: • Ce–CuO composites were prepared via a one-pot and template-free hydrothermal method. • Ce–CuO consisted of raspberry-like CeO{sub 2} particles dispersed on porous CuO microspheres. • CuO microspheres were formed by self-assembly of nanorods. • Ce–CuO exhibited superior catalytic activity for dimethyldichlorosilane synthesis. - Abstract: In this work, we prepared a novel structure comprising of raspberry-like CeO{sub 2} deposited on CuO microspheres (Ce–CuO) for Rochow reaction. The synthesis was carried out via a facile one-pot hydrothermal reaction without using any template, in which, the basic copper carbonate microspheres were first formed via self-assembly of basic copper carbonate nanorods, followed with deposition of cerium hydroxide. After calcination, they were transformed into Ce–CuO but still maintained the hierarchical structure, and meanwhile, mesoporous structure was formed (for simplicity, we will only state them as metal oxide in the following context). The samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and scanning electron microscopy (SEM) techniques. When used as a Cu-based catalyst, Ce–CuO exhibited superior catalytic property to the single CuO, CeO{sub 2} and their physically mixture in the Rochow reaction with dimethyldichlorosilane (M2) selectivity increased from ca. 65 to 83.7%. The higher M2 selectivity of Ce–CuO is mainly due to its larger surface area and the synergistic effect between CuO and CeO{sub 2}. This work demonstrates that catalytic performance of the Cu-based can be improved by adding Ce rare-earth element and by carefully controlling their structures.
Silica functionalized Cu(II) acetylacetonate Schiff base complex: An efficient catalyst for the oxidative condensation reaction of benzyl alcohol with amines

Science.gov (United States)

Anbarasu, G.; Malathy, M.; Karthikeyan, P.; Rajavel, R.

2017-09-01

Silica functionalized Cu(II) acetylacetonate Schiff base complex via the one pot reaction of silica functionalized 3-aminopropyltriethoxysilane with acetyl acetone and copper acetate has been reported. The synthesized material was well characterized by analytical techniques such as FT-IR, UV-DRS, XRD, SEM-EDX, HR-TEM, EPR, ICP-AES and BET analysis. The characterization results confirmed the grafting of Cu(II) Schiff base complex on the silica surface. The catalytic activity of synthesized silica functionalized Cu(II) acetylacetonate Schiff base complex was evaluated through the oxidative condensation reaction of benzyl alcohol to imine.
Synthesis of Mixed Cu/Ce Oxide Nanoparticles by the Oil-in-Water Microemulsion Reaction Method

Science.gov (United States)

Pemartin-Biernath, Kelly; Vela-González, Andrea V.; Moreno-Trejo, Maira B.; Leyva-Porras, César; Castañeda-Reyna, Iván E.; Juárez-Ramírez, Isaías; Solans, Conxita; Sánchez-Domínguez, Margarita

2016-01-01

Cerium oxide and mixed Cu/Ce oxide nanoparticles were prepared by the oil-in-water (O/W) microemulsion reaction method in mild conditions. The Cu/Ce molar ratio was varied between 0/100 and 50/50. According to X-ray diffraction (XRD), below 30/70 Cu/Ce molar ratio, the materials presented a single phase consistent with cubic fluorite CeO2. However, above Cu/Ce molar ratio 30/70, an excess monoclinic CuO phase in coexistence with the predominant Cu/Ce mixed oxide was detected by XRD and High-Resolution Transmission Electron Microscopy (HRTEM). Raman spectroscopy showed that oxygen vacancies increased significantly as the Cu content was increased. Band gap (Eg) was investigated as a function of the Cu/Ce molar ratio, resulting in values from 2.91 eV for CeO2 to 2.32 eV for the mixed oxide with 30/70 Cu/Ce molar ratio. These results indicate that below 30/70 Cu/Ce molar ratio, Cu2+ is at least partially incorporated into the ceria lattice and very well dispersed in general. In addition, the photodegradation of Indigo Carmine dye under visible light irradiation was explored for selected samples; it was shown that these materials can remove such contaminants, either by adsorption and/or photodegradation. The results obtained will encourage investigation into the optical and photocatalytic properties of these mixed oxides, for widening their potential applications. PMID:28773602
Synthesis of Mixed Cu/Ce Oxide Nanoparticles by the Oil-in-Water Microemulsion Reaction Method

Directory of Open Access Journals (Sweden)

Kelly Pemartin-Biernath

2016-06-01

Full Text Available Cerium oxide and mixed Cu/Ce oxide nanoparticles were prepared by the oil-in-water (O/W microemulsion reaction method in mild conditions. The Cu/Ce molar ratio was varied between 0/100 and 50/50. According to X-ray diffraction (XRD, below 30/70 Cu/Ce molar ratio, the materials presented a single phase consistent with cubic fluorite CeO2. However, above Cu/Ce molar ratio 30/70, an excess monoclinic CuO phase in coexistence with the predominant Cu/Ce mixed oxide was detected by XRD and High-Resolution Transmission Electron Microscopy (HRTEM. Raman spectroscopy showed that oxygen vacancies increased significantly as the Cu content was increased. Band gap (Eg was investigated as a function of the Cu/Ce molar ratio, resulting in values from 2.91 eV for CeO2 to 2.32 eV for the mixed oxide with 30/70 Cu/Ce molar ratio. These results indicate that below 30/70 Cu/Ce molar ratio, Cu2+ is at least partially incorporated into the ceria lattice and very well dispersed in general. In addition, the photodegradation of Indigo Carmine dye under visible light irradiation was explored for selected samples; it was shown that these materials can remove such contaminants, either by adsorption and/or photodegradation. The results obtained will encourage investigation into the optical and photocatalytic properties of these mixed oxides, for widening their potential applications.
Study of the preparation of Cu-TiC composites by reaction of soluble Ti and ball-milled carbon coating TiC

Science.gov (United States)

Xu, Xuexia; Li, Wenbin; Wang, Yong; Dong, Guozhen; Jing, Shangqian; Wang, Qing; Feng, Yanting; Fan, Xiaoliang; Ding, Haimin

2018-06-01

In this work, Cu-TiC composites have been successfully prepared by reaction of soluble Ti and carbon coating TiC. Firstly, the ball milling of graphite and TiC mixtures is used to obtain the carbon coating TiC which has fine size and improved reaction activity. After adding the ball milled carbon coating TiC into Cu-Ti melts, the soluble Ti will easily react with the carbon coating to form TiC. This process will also improve the wettability between Cu melts and TiC core. As a result, besides the TiC prepared by reaction of soluble Ti and carbon coating, the ball milled TiC will also be brought into the melts. Some of these ball-milled TiC particles will go on being coated by the formed TiC from the reaction of Ti and the coating carbon and left behind in the composites. However, most of TiC core will be further reacted with the excessive Ti and be transformed into the newly formed TiC with different stoichiometry. The results indicate that it is a feasible method to synthesize TiC in Cu melts by reaction of soluble Ti and ball-milled carbon coating TiC.
Preparation of 64Cu based on nuclear reaction of 64Ni (p,n) 64Cu: Simulations of target preparation and radionuclidic separation

International Nuclear Information System (INIS)

Sunarhadijoso Soenarjo; Wira Y Rahman; Sriyono; Triyanto

2010-01-01

As a preliminary study for production technology of 64 Cu based on nuclear reaction of 64 Ni (p,n) 64 Cu, the nickel targets were prepared by electroplating method using acidic solution of nickel chloride - boric acid and basic solution of nickel sulphate - nickel chloride mixtures on a silver-surfaced target holder. The simulated solution of Ni(II) - Cu(II) matrix was considered as the solution of post-proton-irradiated nickel containing radioactive copper. In the presented work the irradiation of nickel target was omitted, while the radioactive copper was obtained from neutron irradiation of CuO target. The separation of radioactive copper was based on anion exchange column chromatography in which the radiocopper was conditioned to form CuCl 4 2- anion complex, while the nickel was kept as Ni 2+ cation. It was found that the electroplating deposit from the acidic solution was better than that form the basic solution. By conditioning the matrix solution in 6 M HCl, the radioactive copper was indicated in the forms of Cu 2+ and CuCl 4 2- while the nickel was in the form of Ni 2+ . In the condition of 9 M HCl, the radioactive copper was in the form of CuCl 4 2- , while the nickel was found as both Ni 2+ and CuCl 4 2- . The best condition of separation was in 8 M HCl in which the radioactive copper was in the form of CuCl 4 2- , while the nickel was in the form of Ni 2+ . The retained CuCl 4 2- was then changed back into Cu 2+ cation and eluted out from the column by using 0.05 M HCl. The γ-spectrometric analysis showed a single strong peak at 511 keV in accordance to γ-annihilation peak coming from positron decay of 64 Cu, and a very weak peak at 1346 keV related to γ-ray from internal energy transition of 64 Cu. (author)
A TEMPO-free copper-catalyzed aerobic oxidation of alcohols.

Science.gov (United States)

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

2015-03-27

The copper-catalyzed aerobic oxidation of primary and secondary alcohols without an external N-oxide co-oxidant is described. The catalyst system is composed of a Cu/diamine complex inspired by the enzyme tyrosinase, along with dimethylaminopyridine (DMAP) or N-methylimidazole (NMI). The Cu catalyst system works without 2,2,6,6-tetramethyl-l-piperidinoxyl (TEMPO) at ambient pressure and temperature, and displays activity for un-activated secondary alcohols, which remain a challenging substrate for catalytic aerobic systems. Our work underscores the importance of finding alternative mechanistic pathways for alcohol oxidation, which complement Cu/TEMPO systems, and demonstrate, in this case, a preference for the oxidation of activated secondary over primary alcohols. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Isotopic Exchange Reaction Assisted with Cu (I) generated ''in situ'' For Synthesis of Ready-to-Use for on-the-spot Formulation of [131 I] Iodobenzyl Derivatives

International Nuclear Information System (INIS)

Abudaia, J.A.; Suliman, M.O.

2007-01-01

It has been examined that meta-Iodobenzylguanidine (m-IBG), para-Iodoamphetamine (p-IPA) and orth-Iodohippuric acid (o-IHA) are three commonly used Iodobenzyl derivative compounds, and can be formulated as Ready-to-Use Kits for on-the-spot labeling catalyzed with copper ion Cu+ (I) generated ''In Situ''. The labeling procedure efficiently has been established within 30 min of heating using an autoclave, 20 min. and 90 min. using dry heating block respectively. Isotopic exchange reaction with Iodine-131 radioactive of those three Ready-to-Use Kits has led to Radiochemical Purity ''RCP'' equals to 98%, > 98%, and almost 99%, and Radiochemical Yield ''RCY'' > 97%, >93% and > 98% respectively. Attention was paid to the Radiochemical Stability of those three Iodobenzyl derivatives for a period time of preservation at low temperature. As a result, this gave evidence that such Radiopharmaceuticals could be used as Ready-to-Use products at different times of preservations.
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
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.
Capped CuInS2 quantum dots for H2 evolution from water under visible light illumination

International Nuclear Information System (INIS)

Li, Tzung-Luen; Cai, Cheng-Da; Yeh, Te-Fu; Teng, Hsisheng

2013-01-01

Highlights: ► Dispersed CuInS 2 quantum dots showed remarkable photosynthetic activity using visible light. ► Photogenerated electrons in CuInS 2 were effective in H 2 production from aqueous solution. ► The bifunctional capping reagent effectively transported photogenerated electrons for reaction. ► Ru-loaded CuInS 2 quantum dots showed a quantum efficiency of 4.7% in H 2 evolution. ► Attaching CuInS 2 to TiO 2 with CdS passivation achieved a quantum efficiency of 41%. - Abstract: This study demonstrates H 2 evolution from water decomposition catalyzed by capped CuInS 2 quantum dots (QDs) that are highly dispersed in a polysulfide aqueous solution. The CuInS 2 QDs, which are obtained from solvothermal synthesis, have a size of 4.3 nm and a band gap of 1.97 eV. For photosynthetic H 2 evolution in the aqueous solution, the QDs are capped with a multidentate ligand (3-mercaptopropionic acid), which has a thiol end for attaching the QDs and a hydrophilic carboxylic end for dispersion in water. The capped QDs exhibit low activity in catalyzing H 2 evolution under visible illumination. After photodepositing 0.5 wt.% Ru, the capped QDs are active in producing H 2 with illumination. This demonstrates that the photogenerated electrons travel through the capping reagent to generate deposited Ru, which subsequently serves as an electron trap for H 2 evolution. A heterostructure formed by attaching the capped QDs on TiO 2 nanoparticles, followed by coating CdS with photodeposition, exhibits a high quantum efficiency of 41% for H 2 evolution from the polysulfide solution. These results demonstrate the potential for photosynthesis and phototherapy in biologic in vivo or microfluidic systems based on this capped QD material.
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
Syntheses of the hexahydroindene cores of indanomycin and stawamycin by combinations of iridium-catalyzed asymmetric allylic alkylations and intramolecular Diels-Alder reactions.

Science.gov (United States)

Gärtner, Martin; Satyanarayana, Gedu; Förster, Sebastian; Helmchen, Günter

2013-01-02

Short and concise syntheses of the hexahydroindene cores of the antibiotics indanomycin (X-14547 A) and stawamycin are presented. Key methods used are an asymmetric iridium-catalyzed allylic alkylation, a modified Julia olefination, a Suzuki-Miyaura coupling, and an intramolecular Diels-Alder reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Rh(I)-Catalyzed Arylation of Heterocycles via C-H Bond Activation: Expanded Scope Through Mechanistic Insight

Energy Technology Data Exchange (ETDEWEB)

Lewis, Jared; Berman, Ashley; Bergman, Robert; Ellman, Jonathan

2007-07-18

A practical, functional group tolerant method for the Rh-catalyzed direct arylation of a variety of pharmaceutically important azoles with aryl bromides is described. Many of the successful azole and aryl bromide coupling partners are not compatible with methods for the direct arylation of heterocycles using Pd(0) or Cu(I) catalysts. The readily prepared, low molecular weight ligand, Z-1-tert-butyl-2,3,6,7-tetrahydrophosphepine, which coordinates to Rh in a bidentate P-olefin fashion to provide a highly active yet thermally stable arylation catalyst, is essential to the success of this method. By using the tetrafluoroborate salt of the corresponding phosphonium, the reactions can be assembled outside of a glove box without purification of reagents or solvent. The reactions are also conducted in THF or dioxane, which greatly simplifies product isolation relative to most other methods for direct arylation of azoles employing high-boiling amide solvents. The reactions are performed with heating in a microwave reactor to obtain excellent product yields in two hours.
Thermodynamics and kinetics insight into reaction mechanism of Cu{sub 2}ZnSnSe{sub 4} nanoink based on binary metal-amine complexes in polyetheramine-synthesized process

Energy Technology Data Exchange (ETDEWEB)

Wang, Chi-Jie [Institute of Microelectronics and Department of Electrical Engineering, National Cheng Kung University, Tainan 701, Taiwan, ROC (China); Shei, Shih-Chang, E-mail: scshei@mail.nutn.edu.tw [Department of Electrical Engineering, National University of Tainan, 700, Taiwan, ROC (China); Chang, Shoou-Jinn [Institute of Microelectronics and Department of Electrical Engineering, National Cheng Kung University, Tainan 701, Taiwan, ROC (China)

2016-08-15

This paper reports on the reaction mechanism of Cu{sub 2}ZnSnSe{sub 4} (CZTSe) nanoink via a solvent-thermal reflux method using copper (Cu), zinc (Zn), tin (Sn), and selenium (Se) powders as precursors and polyetheramine as a reaction solvent. The formation of CZTSe nanoparticles in polyetheramine began with the formation of binary phase CuSe and CuSe{sub 2} due to the strong catalysis provided by polyetheramine. Finally, ternary crystals of Cu{sub 2}SnSe{sub 3} transformed into well-dispersed nanocrystals of Cu{sub 2}ZnSnSe{sub 4}. The size of the crystals was shown to decrease with reaction time due to the emulsification effect of the polyetheramine epoxy group. The PH value-reaction time curves for single Cu, Zn elements and CZTSe from all participants elements reacted together have a relationship just reversed each other and both multistage feature were observed, which indicates that the CZTSe reaction was dominated by copper and zinc elements. The PH-temperature mechanism demonstrates that the reaction was controlled by the formation of metal-amine complexes, especially, after heating the PH-time variation manner is the same for pure element and all four elements reacted together. To the best of our knowledge, this is the first study on the mechanism underlying CZTSe formation based on the reactivity and stability of reaction species. - Highlights: • Reaction mechanism of Cu{sub 2}ZnSnSe{sub 4} (CZTSe) nanoink via a solvent-thermal reflux method using polyetheramine was developed. • PH effect on thermal dynamics and characteristics of reagents and solvents in the CZTSe nanoink has been realized. • PH-temperature mechanism demonstrates that the reaction controlled by the formation of metal-amine complexes.

Kinetic study of the annealing reactions in Cu-Ni-Fe alloys; Estudio cinetico de las reacciones de recocido en aleaciones de Cu-Ni-Fe

Energy Technology Data Exchange (ETDEWEB)

Donoso, E.

2014-07-01

The thermal aging of a Cu-45Ni-4Fe, Cu-34Ni-11Fe and Cu-33Ni-22Fe alloys tempered from 1173 K have been studied from Differential Scanning Calorimetry (DSC) and microhardness measurements. The analysis of DSC curves, from room temperature to 950 K, shows the presence of one exothermic reaction associated to the formation of FeNi{sub 3} phase nucleating from a modulate structure, and one endothermic peak attributed to dissolution of this phase. Kinetic parameters were obtained using the usual Avrami-Erofeev equation, modified Kissinger method and integrated kinetic functions. Microhardness measurements confirmed the formation and dissolution of the FeNi{sub 3} phase. (Author)
The bacterial catabolism of polycyclic aromatic hydrocarbons: Characterization of three hydratase-aldolase-catalyzed reactions

Directory of Open Access Journals (Sweden)

Jake A. LeVieux

2016-12-01

Full Text Available Polycyclic aromatic hydrocarbons (PAHs are highly toxic, pervasive environmental pollutants with mutagenic, teratogenic, and carcinogenic properties. There is interest in exploiting the nutritional capabilities of microbes to remove PAHs from various environments including those impacted by improper disposal or spills. Although there is a considerable body of literature on PAH degradation, the substrates and products for many of the enzymes have never been identified and many proposed activities have never been confirmed. This is particularly true for high molecular weight PAHs (e.g., phenanthrene, fluoranthene, and pyrene. As a result, pathways for the degradation of these compounds are proposed to follow one elucidated for naphthalene with limited experimental verification. In this pathway, ring fission produces a species that can undergo a non-enzymatic cyclization reaction. An isomerase opens the ring and catalyzes a cis to trans double bond isomerization. The resulting product is the substrate for a hydratase-aldolase, which catalyzes the addition of water to the double bond of an α,β-unsaturated ketone, followed by a retro-aldol cleavage. Initial kinetic and mechanistic studies of the hydratase-aldolase in the naphthalene pathway (designated NahE and two hydratase-aldolases in the phenanthrene pathway (PhdG and PhdJ have been completed. Crystallographic work on two of the enzymes (NahE and PhdJ provides a rudimentary picture of the mechanism and a platform for future work to identify the structural basis for catalysis and the individual specificities of these hydratase-aldolases.
Synthesis of Cyclohexane-Fused Isocoumarins via Cationic Palladium(II)-Catalyzed Cascade Cyclization Reaction of Alkyne-Tethered Carbonyl Compounds Initiated by Intramolecular Oxypalladation of Ester-Substituted Aryl Alkynes.

Science.gov (United States)

Zhang, Jianbo; Han, Xiuling; Lu, Xiyan

2016-04-15

A cationic Pd(II)-catalyzed cascade cyclization reaction of alkyne-tethered carbonyl compounds was developed. This reaction is initiated by intramolecular oxypalladation of alkynes with an ester group followed by 1,2-addition of the formed C-Pd(II) bond to the carbonyl group, providing a highly efficient method for the synthesis of cyclohexane-fused isocoumarins.
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....
Graphene-oxide-supported CuAl and CoAl layered double hydroxides as enhanced catalysts for carbon-carbon coupling via Ullmann reaction

Energy Technology Data Exchange (ETDEWEB)

Ahmed, Nesreen S. [Department of Chemistry, Faculty of Science, King Abdulaziz University (Saudi Arabia); Surface Chemistry and Catalytic Studies Group, King Abdulaziz University (Saudi Arabia); Menzel, Robert [Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Bio Nano Consulting, The Gridiron Building, One Pancras Square, London N1C 4AG (United Kingdom); Wang, Yifan [Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Garcia-Gallastegui, Ainara [Bio Nano Consulting, The Gridiron Building, One Pancras Square, London N1C 4AG (United Kingdom); Bawaked, Salem M.; Obaid, Abdullah Y.; Basahel, Sulaiman N. [Department of Chemistry, Faculty of Science, King Abdulaziz University (Saudi Arabia); Surface Chemistry and Catalytic Studies Group, King Abdulaziz University (Saudi Arabia); Mokhtar, Mohamed, E-mail: mmokhtar2000@yahoo.com [Department of Chemistry, Faculty of Science, King Abdulaziz University (Saudi Arabia); Surface Chemistry and Catalytic Studies Group, King Abdulaziz University (Saudi Arabia)

2017-02-15

Two efficient catalyst based on CuAl and CoAl layered double hydroxides (LDHs) supported on graphene oxide (GO) for the carbon-carbon coupling (Classic Ullmann Homocoupling Reaction) are reported. The pure and hybrid materials were synthesised by direct precipitation of the LDH nanoparticles onto GO, followed by a chemical, structural and physical characterisation by electron microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area measurements and X-ray photoelectron spectroscopy (XPS). The GO-supported and unsupported CuAl-LDH and CoAl-LDH hybrids were tested over the Classic Ullman Homocoupling Reaction of iodobenzene. In the current study CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary and two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH. - Graphical abstract: CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary, two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. - Highlights: • CuAl LDH/GO and CoAl LDH/GO hybrid materials with different LDH compositions were prepared. • Hybrids were fully characterised and their catalytic efficiency over the Classic Ullman Reaction was studied. • CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) in 25 min reaction times. • GO provides a light-weight, charge complementary, two-dimensional material that interacts effectively with the 2D LDHs. • After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH.
Activation cross section of 63Cu(n,α)60Co reaction

International Nuclear Information System (INIS)

Lu Hanlin; Zhao Wenrong; Yu Weixiang; Yuan Xialin

1990-01-01

The mechanical properties of copper during the irradiation with intensive neutron fluence rate are significant for the safe operation of D-T fusion power reactors. The cross sections measured by activation method show a large discrepancy from 36 to 54 mb in 14 MeV region. The cross sections of 69 Cu(n, α) 60 Co reaction were measured by activation method. Two irradiations were carried out at the Cockcroft-wallon and Van de Graaff accelerators of CIAE using T(d, n) 4 He reaction to produce neutrons. The activities of 24 Na and 60 Co γ-rays for monitor and sample foils were determined absolutely by a calibrated Ge(Li) detector system with an accuracy better than 1%. The present results are compared with the others
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 ...
Kinetics and mechanism of auto- and copper-catalyzed oxidation of 1,4-naphthohydroquinone.

Science.gov (United States)

Yuan, Xiu; Miller, Christopher J; Pham, A Ninh; Waite, T David

2014-06-01

Although quinones represent a class of organic compounds that may exert toxic effects both in vitro and in vivo, the molecular mechanisms involved in quinone species toxicity are still largely unknown, especially in the presence of transition metals, which may both induce the transformation of the various quinone species and result in generation of harmful reactive oxygen species. In this study, the oxidation of 1,4-naphthohydroquinone (NH2Q) in the absence and presence of nanomolar concentrations of Cu(II) in 10 mM NaCl solution over a pH range of 6.5-7.5 has been investigated, with detailed kinetic models developed to describe the predominant mechanisms operative in these systems. In the absence of copper, the apparent oxidation rate of NH2Q increased with increasing pH and initial NH2Q concentration, with concomitant oxygen consumption and peroxide generation. The doubly dissociated species, NQ(2-), has been shown to be the reactive species with regard to the one-electron oxidation by O2 and comproportionation with the quinone species, both generating the semiquinone radical (NSQ(·-)). The oxidation of NSQ(·-) by O2 is shown to be the most important pathway for superoxide (O2(·-)) generation with a high intrinsic rate constant of 1.0×10(8)M(-1)s(-1). Both NSQ(·-) and O2(·-) served as chain-propagating species in the autoxidation of NH2Q. Cu(II) is capable of catalyzing the oxidation of NH2Q in the presence of O2 with the oxidation also accelerated by increasing the pH. Both the uncharged (NH2Q(0)) and the mono-anionic (NHQ(-)) species were found to be the kinetically active forms, reducing Cu(II) with an intrinsic rate constant of 4.0×10(4) and 1.2×10(7)M(-1)s(-1), respectively. The presence of O2 facilitated the catalytic role of Cu(II) by rapidly regenerating Cu(II) via continuous oxidation of Cu(I) and also by efficient removal of NSQ(·-) resulting in the generation of O2(·-). The half-cell reduction potentials of various redox couples at neutral p
The reaction mechanism for dehydration process catalyzed by type I dehydroquinate dehydratase from Gram-negative Salmonella enterica

Science.gov (United States)

Yao, Yuan; Li, Ze-Sheng

2012-01-01

The fundamental reaction mechanism for the dehydration process catalyzed by type I dehydroquinate dehydratase from Gram-negative Salmonella enterica has been studied by density functional theory calculations. The results indicate that the dehydration process undergoes a two-step cis-elimination mechanism, which is different from the previously proposed one. The catalytic roles of both the highly conserved residue His143 and the Schiff base formed between the substrate and Lys170 have also been elucidated. The structural and mechanistic insight presented here may direct the design of type I dehydroquinate dehydratase enzyme inhibitors as non-toxic antimicrobials, anti-fungals, and herbicides.
Determination of selenium via the fluorescence quenching effect of selenium on hemoglobin-catalyzed peroxidative reaction.

Science.gov (United States)

Chen, Ya-Hong; Zhang, Ya-Nan; Tian, Feng-Shou

2015-05-01

A new method for the determination of selenium based on its fluorescence quenching on the hemoglobin-catalyzed reaction of H2 O2 and l-tyrosine has been established. The effect of pH, foreign ions and the optimization of variables on the determination of selenium was examined. The calibration curve was found to be linear between the fluorescence quenching (F0 /F) and the concentration of selenium within the range of 0.16-4.00 µg/mL. The detection limit was 1.96 ng/mL and the relative standard deviation was 3.14%. This method can be used for the determination of selenium in Se-enriched garlic bulbs with satisfactory results. Copyright © 2014 John Wiley & Sons, Ltd.
Efficient C-O and C-N bond forming cross-coupling reactions catalyzed by core-shell structured Cu/Cu2O nanowires

KAUST Repository

Elshewy, Ahmed M.

2013-12-01

Oxygen and Nitrogen containing compounds are of utmost importance due to their interesting and diverse biological activities. The construction of the C-O and C–N bonds is of significance as it opens avenues for the introduction of ether and amine linkages in organic molecules. Despite significant advancements in this field, the construction of C-O and C–N bonds is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts or ligands in many cases. Thus, it is a challenge to develop alternative, milder, cheaper and more reproducible methodologies for the construction of these types of bonds. Herein, we introduce a new efficient ligand free catalytic system for C-O and C-N bond formation reactions.
Twisted Amides: From Obscurity to Broadly Useful Transition-Metal-Catalyzed Reactions by N-C Amide Bond Activation.

Science.gov (United States)

Liu, Chengwei; Szostak, Michal

2017-05-29

The concept of using amide bond distortion to modulate amidic resonance has been known for more than 75 years. Two classic twisted amides (bridged lactams) ingeniously designed and synthesized by Kirby and Stoltz to feature fully perpendicular amide bonds, and as a consequence emanate amino-ketone-like reactivity, are now routinely recognized in all organic chemistry textbooks. However, only recently the use of amide bond twist (distortion) has advanced to the general organic chemistry mainstream enabling a host of highly attractive N-C amide bond cross-coupling reactions of broad synthetic relevance. In this Minireview, we discuss recent progress in this area and present a detailed overview of the prominent role of amide bond destabilization as a driving force in the development of transition-metal-catalyzed cross-coupling reactions by N-C bond activation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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
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)
The reaction process of the Bi-Sr-Ca-Cu-O system and the forming mechanism of the 2212 superconducting phase

International Nuclear Information System (INIS)

Xiong Guohong; Wang Minquan; Fan Xianping; Tang Xiaoming

1993-01-01

The reaction process and the reaction behavior of each component in the Bi-Sr-Ca-Cu-O system are presented in this paper. It reveals that the reaction is carried out in three different stages: forming of an insulating interphase at 680 C-790 C, forming of the 2212 superconducting phase at 790 C-860 C and forming of semiconducting phases in the presence of the liquid phase at 860 C-970 C. It is also confirmed that the 2212 superconducting phase (T c =85 K) is formed by the reaction of a trinary interphase together with CuO, SrO and CaO. A new two-step method is presented to prepare the 2212 superconducting phase by a presynthesized interphase. (orig.)
The reaction process of the Bi-Sr-Ca-Cu-O system and the forming mechanism of the 2212 superconducting phase

Science.gov (United States)

Xiong, Guohong; Wang, Minquan; Fan, Xianping; Tang, Xiaoming

1993-02-01

The reaction process and the reaction behavior of each component in the Bi-Sr-Ca-Cu-O system are presented in this paper. It reveals that the reaction is carried out in three different stages: forming of an insulating interphase at 680°C 790°C, forming of the 2212 superconducting phase at 790°C 860°C and forming often semiconducting phases in the presence of the liquid phase at 860°C 970°C. It is also confirmed that the 2212 superconducting phase ( T c=85 K) is formed by the reaction of a trinary interphase together with CuO, SrO and CaO. A new two-step method is presented to prepare the 2212 superconducting phase by a presynthesized interphase.
The reaction process of the Bi-Sr-Ca-Cu-O system and the forming mechanism of the 2212 superconducting phase

Energy Technology Data Exchange (ETDEWEB)

Xiong Guohong (Zhejiang Univ., Hangzhou (China). Dept. of Materials Science and Engineering); Wang Minquan (Zhejiang Univ., Hangzhou (China). Dept. of Materials Science and Engineering); Fan Xianping (Zhejiang Univ., Hangzhou (China). Dept. of Materials Science and Engineering); Tang Xiaoming (Zhejiang Univ., Hangzhou (China). Center for Analysis and Measurement)

1993-02-01

The reaction process and the reaction behavior of each component in the Bi-Sr-Ca-Cu-O system are presented in this paper. It reveals that the reaction is carried out in three different stages: forming of an insulating interphase at 680 C-790 C, forming of the 2212 superconducting phase at 790 C-860 C and forming of semiconducting phases in the presence of the liquid phase at 860 C-970 C. It is also confirmed that the 2212 superconducting phase (T[sub c]=85 K) is formed by the reaction of a trinary interphase together with CuO, SrO and CaO. A new two-step method is presented to prepare the 2212 superconducting phase by a presynthesized interphase. (orig.)
Advanced foil activation techniques for the measurement of within-pin distributions of the 63Cu(n,γ)64Cu reaction rate in nuclear fuel

International Nuclear Information System (INIS)

Macku, K.; Jatuff, F.; Murphy, M.F.; Joneja, O.P.; Bischofberger, R.; Chawla, R.

2006-01-01

Different foil activation techniques have been used for measuring spatial distributions of the 63 Cu(n,γ) 64 Cu reaction within two pins of a SVEA-96 Optima2 boiling water reactor fuel assembly, at the critical facility PROTEUS. This reaction is of interest because its 1/v cross-section gives it a good representation of the 235 U fission rate. Initially, radial capture rate profiles were measured with mechanically punched copper foils. More detailed profiles were then determined by using a 0.2 mm copper wire spiral (∼200 μm resolution), as well as 5-, 10-, and 20-ring UV-lithography, electroplating, and molding (UV-LIGA) foils (up to a 100 μm resolution). For azimuthal measurements, apart from manually cut activation foils (into 8 sectors), 8- and 12-sector LIGA foils were used. The highly versatile LIGA foils have the additional advantage of being very easily separated into individual pieces after irradiation without the use of punches or other cutting tools. In order to account for the invasive character of the foil activation techniques, corrections to account for sample perturbations and for self-shielding effects were determined via simplified Monte Carlo (MCNP4C) modeling of the experimental setup. The final results from the various measurements of 63 Cu(n,γ) 64 Cu within-pin distributions have been compared with MCNP computations employing a detailed model of the full SVEA Optima2 fuel assembly
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.
Cationic Pd(II-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies

Directory of Open Access Journals (Sweden)

Takashi Nishikata

2016-05-01

Full Text Available Cationic palladium(II complexes have been found to be highly reactive towards aromatic C–H activation of arylureas at room temperature. A commercially available catalyst [Pd(MeCN4](BF42 or a nitrile-free cationic palladium(II complex generated in situ from the reaction of Pd(OAc2 and HBF4, effectively catalyzes C–H activation/cross-coupling reactions between aryl iodides, arylboronic acids and acrylates under milder conditions than those previously reported. The nature of the directing group was found to be critical for achieving room temperature conditions, with the urea moiety the most effective in promoting facile coupling reactions at an ortho C–H position. This methodology has been utilized in a streamlined and efficient synthesis of boscalid, an agent produced on the kiloton scale annually and used to control a range of plant pathogens in broadacre and horticultural crops. Mechanistic investigations led to a proposed catalytic cycle involving three steps: (1 C–H activation to generate a cationic palladacycle; (2 reaction of the cationic palladacycle with an aryl iodide, arylboronic acid or acrylate, and (3 regeneration of the active cationic palladium catalyst. The reaction between a cationic palladium(II complex and arylurea allowed the formation and isolation of the corresponding palladacycle intermediate, characterized by X-ray analysis. Roles of various additives in the stepwise process have also been studied.

Two Palladium-Catalyzed Domino Reactions from One Set of Substrates/Reagents: Efficient Synthesis of Substituted Indenes and cis-Stilbenoid Hydrocarbons from the Same Internal Alkynes and Hindered Grignard Reagents

Science.gov (United States)

Dong, Cheng-Guo; Yeung, Pik; Hu, Qiao-Sheng

2008-01-01

Two types of domino reactions from the same internal alkynes and hindered Grignard reagents based on carbopalladation, Pd-catalyzed cross-coupling reaction and C-H activation strategy are described. The realization of these domino reactions relied on the control of the use of the ligand and the reaction temperature. Our study provides an efficient access to useful polysubstituted indenes and cis-substituted stilbenes, and may offer new means to the development of tandem/domino reactions in a more efficient way. PMID:17217305
Chlorination of iodide-containing waters in the presence of CuO: Formation of periodate

KAUST Repository

Liu, Chao; Salhi, Elisabeth; Croue, Jean-Philippe; von Gunten, Urs

2014-01-01

It has been shown previously that the disproportionation of halogen-containing oxidants (e.g., HOCl, HOBr, and ClO2) is enhanced by a CuO-catalyzed process. In this study, the transformation of iodine during chlorination in the presence of CuO was investigated. There is no significant enhancement of the disproportionation of hypoiodous acid (HOI) in the presence of CuO. The formation rate of iodate (IO3 -) in the CuO-HOCl-I- system significantly increased when compared to homogeneous solutions, which was ascribed to the activation of HOCl by CuO enhancing its reactivity toward HOI. In this reaction system, iodate formation rates increase with increasing CuO (0-0.5 g L-1) and bromide (0-2 μM) doses and with decreasing pH (9.6-6.6). Iodate does not adsorb to the CuO surfaces used in this study. Nevertheless, iodate concentrations decreased after a maximum was reached in the CuO-HOCl-I-(-Br-) systems. Similarly, the iodate concentrations decrease as a function of time in the CuO-HOCl-IO3 - or CuO-HOBr-IO3 - system, and the rates increase with decreasing pH (9.6-6.6) due to the enhanced reactivity of HOCl or HOBr in the presence of CuO. It could be demonstrated that iodate is oxidized to periodate by a CuO-activated hypohalous acid, which is adsorbed on the CuO surface. No periodate could be measured in filtered solutions because it was mainly adsorbed to CuO. The adsorbed periodate was identified by scanning electron microscopy plus energy dispersive spectroscopy and X-ray photoelectron spectroscopy.
Chlorination of iodide-containing waters in the presence of CuO: Formation of periodate

KAUST Repository

Liu, Chao

2014-11-18

It has been shown previously that the disproportionation of halogen-containing oxidants (e.g., HOCl, HOBr, and ClO2) is enhanced by a CuO-catalyzed process. In this study, the transformation of iodine during chlorination in the presence of CuO was investigated. There is no significant enhancement of the disproportionation of hypoiodous acid (HOI) in the presence of CuO. The formation rate of iodate (IO3 -) in the CuO-HOCl-I- system significantly increased when compared to homogeneous solutions, which was ascribed to the activation of HOCl by CuO enhancing its reactivity toward HOI. In this reaction system, iodate formation rates increase with increasing CuO (0-0.5 g L-1) and bromide (0-2 μM) doses and with decreasing pH (9.6-6.6). Iodate does not adsorb to the CuO surfaces used in this study. Nevertheless, iodate concentrations decreased after a maximum was reached in the CuO-HOCl-I-(-Br-) systems. Similarly, the iodate concentrations decrease as a function of time in the CuO-HOCl-IO3 - or CuO-HOBr-IO3 - system, and the rates increase with decreasing pH (9.6-6.6) due to the enhanced reactivity of HOCl or HOBr in the presence of CuO. It could be demonstrated that iodate is oxidized to periodate by a CuO-activated hypohalous acid, which is adsorbed on the CuO surface. No periodate could be measured in filtered solutions because it was mainly adsorbed to CuO. The adsorbed periodate was identified by scanning electron microscopy plus energy dispersive spectroscopy and X-ray photoelectron spectroscopy.
CuO reduction induced formation of CuO/Cu2O hybrid oxides

Science.gov (United States)

Yuan, Lu; Yin, Qiyue; Wang, Yiqian; Zhou, Guangwen

2013-12-01

Reduction of CuO nanowires results in the formation of a unique hierarchical hybrid nanostructure, in which the parent oxide phase (CuO) works as the skeleton while the lower oxide (Cu2O) resulting from the reduction reaction forms as partially embedded nanoparticles that decorate the skeleton of the parent oxide. Using in situ transmission electron microscopy observations of the reduction process of CuO nanowires, we demonstrate that the formation of such a hierarchical hybrid oxide structure is induced by topotactic nucleation and growth of Cu2O islands on the parent CuO nanowires.
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...
Theoretical Study on the Aza-Diels-Alder Reaction Catalyzed by PHCl2 Lewis Acid via Pnicogen Bonding.

Science.gov (United States)

Yaghoobi, Fereshteh; Sohrabi Mahboub, Mahdi

2018-03-15

The reaction mechanism of the Aza-Diels-Alder (A-D-A) cycloaddition reaction between X 2 C═NNH 2 , where X = H, F, Cl, Br, and 1,3-butadiene catalyzed by a PHCl 2 Lewis acid was characterized using density functional theory calculations. The influences of various substituents of X on the studied reaction were analyzed using the activation strain model (ASM), which is also termed as the distortion-interaction model. Calculations showed that the smallest and largest values of the activation energies belong to the substituents of F and Br, respectively. The activation energy of the studied reactions was decreased within 8.6 kcal·mol -1 in the presence of PHCl 2 catalyst. Investigations showed that the pnicogen bonding is adequately capable of activating the A-D-A reaction. The quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis were implemented to understand the nature of C 4,Cbut ···C XIm and C 1,Cbut ···N XIm bonds at the TS structures. Additionally, the energy decomposition analysis (EDA) based on the ETS-NOCV scheme was used to characterize the nature of C 4,Cbut ···C XIm and C 1,Cbut ···N XIm bond. The results of the study mirror the fact that the PHCl 2 Lewis acid may be suggested as a simple suitable catalyst for experimental studies on the A-D-A reactions.
[(PhCH2O2P(CH32CHNCH(CH32]2PdCl2/CuI as Cocatalyst for Coupling-Cyclization of 2-Iodophenol with Terminal Alkynes in Water

Directory of Open Access Journals (Sweden)

Panli Jiang

2018-03-01

Full Text Available A new and efficient [(PhCH2O2P(CH32CHNCH(CH32]2PdCl2/CuI-co-catalyzed coupling-cyclization reactions of 2-iodophenol with terminal alkynes is described. Different 2-substitued benzo[b]furan derivatives are obtained in good to excellent yields. This protocol employs a relatively low palladium(II catalyst loading in water under air conditions.
Core-shell Si/Cu nanocomposites synthesized by self-limiting surface reaction as anodes for lithium ion batteries

Science.gov (United States)

Xu, Kaiqi; Zhang, Zhizhen; Su, Wei; Huang, Xuejie

Core-shell Si/Cu nanocomposites were synthesized via a flexible self-limiting surface reaction without extra reductant for the first time. The nano Si was uniformly coated with Cu nanoparticles with a diameter of 5-10nm, which can enhance the electronic conductivity of the nanocomposites and buffer the huge volume change during charge/discharge owing to its high ductility. Benefited from the unique structure, the Si/Cu nanocomposites exhibited a good electrochemical performance as anodes for lithium ion batteries, which exhibited a capacity retention of 656mAh/g after 50 cycles and a coulombic efficiency of more than 99%.
Microstructure and Interfacial Reactions During Vacuum Brazing of Stainless Steel to Titanium Using Ag-28 pct Cu Alloy

Science.gov (United States)

Laik, A.; Shirzadi, A. A.; Sharma, G.; Tewari, R.; Jayakumar, T.; Dey, G. K.

2015-02-01

Microstructural evolution and interfacial reactions during vacuum brazing of grade-2 Ti and 304L-type stainless steel (SS) using eutectic alloy Ag-28 wt pct Cu were investigated. A thin Ni-depleted zone of -Fe(Cr, Ni) solid solution formed on the SS-side of the braze zone (BZ). Cu from the braze alloy, in combination with the dissolved Fe and Ti from the base materials, formed a layer of ternary compound , adjacent to Ti in the BZ. In addition, four binary intermetallic compounds, CuTi, CuTi, CuTi and CuTi formed as parallel contiguous layers in the BZ. The unreacted Ag solidified as islands within the layers of CuTi and CuTi. Formation of an amorphous phase at certain locations in the BZ could be revealed. The -Ti(Cu) layer, formed due to diffusion of Cu into Ti-based material, transformed to an -Ti + CuTi eutectoid with lamellar morphology. Tensile test showed that the brazed joints had strength of 112 MPa and failed at the BZ. The possible sequence of events that led to the final microstructure and the mode of failure of these joints were delineated.
Efficient C-O and C-N bond forming cross-coupling reactions catalyzed by core-shell structured Cu/Cu2O nanowires

KAUST Repository

Elshewy, Ahmed M.

2013-01-01

linkages in organic molecules. Despite significant advancements in this field, the construction of C-O and C–N bonds is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts
The mechanism of degradation of bisphenol A using the magnetically separable CuFe_2O_4/peroxymonosulfate heterogeneous oxidation process

International Nuclear Information System (INIS)

Xu, Yin; Ai, Jia; Zhang, Hui

2016-01-01

Highlights: • Copper ferrite (CuFe_2O_4) was fabricated and utilized in heterogeneous PMS process. • The influence of reaction parameters for the mineralization of BPA were evaluated. • Possible reaction mechanism and the stability of CuFe_2O_4 were investigated. • Surface bound radicals (mainly ·OH) may be responsible for the BPA degradation. - Abstract: The removal of bisphenol A (BPA) in aqueous solution by an oxidation process involving peroxymonosulfate (PMS) activated by CuFe_2O_4 magnetic nanoparticles (MNPs) is reported herein. The effects of PMS concentration, CuFe_2O_4 dosage, initial pH, initial BPA concentration, catalyst addition mode, and anions (Cl"−, F"−, ClO_4"− and H_2PO_4"−) on BPA degradation were investigated. Results indicate that nearly complete removal of BPA (50 mg/L) within 60 min and 84.0% TOC removal in 120 min could be achieved at neutral pH by using 0.6 g/L CuFe_2O_4 MNPs and 0.3 g/L PMS. The generation of reactive radicals (mainly hydroxyl radicals) was confirmed using electron paramagnetic resonance (EPR). Possible mechanisms on the radical generation from CuFe_2O_4/PMS system are proposed based on the results of radical identification tests and XPS analysis. The lack of inhibition of the reaction by free radical scavengers such as methanol and tert-butyl alcohol suggests that these species may not be generated in the bulk solution, and methylene blue probe experiments confirm that this process does not involve free radical generation. Surface-bound, rather than free radicals generated by a surface catalyzed-redox cycle involving both Fe(III) and Cu(II), are postulated to be responsible for the mineralization of bisphenol A.
High Pressure Diels Alder Reactions of 1-Vinyl-2,2,6-trimethylcyclohexene Catalyzed by Chiral Lewis Acids; An Enantioselective Route to a Drimane Sesquiterpene Precursor.

NARCIS (Netherlands)

Knol, Joop; Meetsma, Auke; Feringa, Bernard

1995-01-01

The Diels Alder reaction of 1-vinyl-2,2,6-trimethylcyclohexene and 3-((E)-3-(methoxycarbonyl)propenoyl)-1,3-oxazolidin-2-one under high pressure, catalyzed by a chiral bis-imine copper(II) complex, yields a drimane sesquiterpene precursor in a highly regio- and diastereoselective manner with
Use of Elemental Sulfur or Selenium in a Novel One-Pot Copper-Catalyzed Tandem Cyclization of Functionalized Ynamides Leading to Benzosultams.

Science.gov (United States)

Siva Reddy, Alla; Kumara Swamy, K C

2015-06-19

A novel and efficient [Cu]-catalyzed one-pot regio- and stereospecific synthesis of benzo[1,4,2]dithiazine 1,1-dioxides and benzo[1,4,2]thiaselenazine 1,1-dioxides by cyclization of functionalized ynamides with elemental sulfur/selenium has been developed. Its generality is elegantly illustrated by extension to benzodithiazepines and benzothiaselenazepines. Involvement of water in the reaction is demonstrated by the incorporation of (2)D at the olefinic site by using D2O in place of water. Selective oxidation at sulfur in benzo[1,4,2]dithiazine 1,1-dioxide by using mCPBA as the oxidizing agent is also described.
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
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...
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.
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.
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.
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
Mechanism of C-C and C-H bond cleavage in ethanol oxidation reaction on Cu2O(111): a DFT-D and DFT+U study.

Science.gov (United States)

Xu, Han; Miao, Bei; Zhang, Minhua; Chen, Yifei; Wang, Lichang

2017-10-04

The performance of transition metal catalysts for ethanol oxidation reaction (EOR) in direct ethanol fuel cells (DEFCs) may be greatly affected by their oxidation. However, the specific effect and catalytic mechanism for EOR of transition metal oxides are still unclear and deserve in-depth exploitation. Copper as a potential anode catalyst can be easily oxidized in air. Thus, in this study, we investigated C-C and C-H bond cleavage reactions of CH x CO (x = 1, 2, 3) species in EOR on Cu 2 O(111) using PBE+U calculations, as well as the specific effect of +U correction on the process of adsorption and reaction on Cu 2 O(111). It was revealed that the catalytic performance of Cu 2 O(111) for EOR was restrained compared with that of Cu(100). Except for the C-H cleavage of CH 2 CO, all the reaction barriers for C-C and C-H cleavage were higher than those on Cu(100). The most probable pathway for CH 3 CO to CHCO on Cu 2 O(111) was the continuous dehydrogenation reaction. Besides, the barrier for C-C bond cleavage increased due to the loss of H atoms in the intermediate. Moreover, by the comparison of the traditional GGA/PBE method and the PBE+U method, it could be concluded that C-C cleavage barriers would be underestimated without +U correction, while C-H cleavage barriers would be overestimated. +U correction was proved to be necessary, and the reaction barriers and the values of the Hubbard U parameter had a proper linear relationship.

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.
Imino Diels-Alder-Based Construction of a Piperidine A-Ring Unit for Total Synthesis of the Marine Hepatotoxin Cylindrospermopsin.

Science.gov (United States)

Heintzelman, Geoffrey R.; Weinreb, Steven M.; Parvez, Masood

1996-07-12

The synthesis of a piperidine A-ring precursor to the alkaloid cylindrospermopsin (1) is described. The initial approach to the A-ring precursor focused on the imino Diels-Alder reaction of diene 8 with ethyl (N-tosylimino)acetate (9) to form the cycloadduct 10 as a single stereoisomer. However, all attempts to convert ester 10 to a requisite diene such as 5 were unsuccessful. An alternative strategy involved the Diels-Alder cycloaddition of N-tosylimine 9 with oxygenated diene 19 under either thermal or Lewis acid-catalyzed conditions to produce a mixture of cis and trans enones 20 and 21. Although the undesired cis-enone 20 was the major product under all reaction conditions, it could be converted to the desired trans enone 21 by acid-catalyzed isomerization. Copper-mediated conjugate addition of vinylmagnesium bromide to cis-enone 20 followed by stereoselective ketone reduction with L-Selectride produced alcohol 23, whose structure was confirmed by X-ray crystallography. Similarly, trans-enone 21 was converted to alcohol 25 whose structure and stereochemistry were also established by X-ray analysis. Alcohol 25 was then protected as the silyl ether 26, which was hydroborated at the terminal olefin to produce primary alcohol ester 28having the stereochemistry and functionality needed for cylindrospermopsin.
Selective and Orthogonal Post-Polymerization Modification using Sulfur(VI) Fluoride Exchange (SuFEx) and Copper-Catalyzed Azide–Alkyne Cycloaddition (CuAAC) Reactions

International Nuclear Information System (INIS)

Oakdale, James S.; Kwisnek, Luke; Fokin, Valery V.

2016-01-01

Functional polystyrenes and polyacrylamides, containing combinations of fluorosulfate, aromatic silyl ether, and azide side chains, were used as scaffolds to demonstrate the postpolymerization modification capabilities of sulfur(VI) fluoride exchange (SuFEx) and CuAAC chemistries. Fluorescent dyes bearing appropriate functional groups were sequentially attached to the backbone of the copolymers, quantitatively and selectively addressing their reactive partners. Furthermore, this combined SuFEx and CuAAC approach proved to be robust and versatile, allowing for a rare accomplishment: triple orthogonal functionalization of a copolymer under essentially ambient conditions without protecting groups.
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.
N,N'-dioxide/nickel(II)-catalyzed asymmetric inverse-electron-demand hetero-diels-alder reaction of β,γ-unsaturated α-ketoesters with enecarbamates.

Science.gov (United States)

Zhou, Yuhang; Zhu, Yin; Lin, Lili; Zhang, Yulong; Zheng, Jianfeng; Liu, Xiaohua; Feng, Xiaoming

2014-12-08

N,N'-Dioxide/nickel(II) complexes have been developed to catalyze the inverse-electron-demand hetero-Diels-Alder reaction of β,γ-unsaturated α-ketoesters with acyclic enecarbamates. After detailed screening of the reaction parameters, mild optimized reaction conditions were established, affording 3,4-dihydro-2H-pyranamines in up to 99 % yield, 99 % ee and more than 95:5 d.r. The catalytic system was also efficient for β-substituted acyclic enecarbamates, affording more challenging 2,3,4-trisubstituted 3,4-dihydro-2H-pyranamine with three contiguous stereogenic centers in excellent yields, diastereoselectivities, and enantioselectivities. The reaction could be scaled up to a gram scale with no deterioration of either enantioselectivity or yield. Based on these experiments and on previous reports, a possible transition state was proposed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

Science.gov (United States)

Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

2013-07-07

A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.
How low does iron go? Chasing the active species in fe-catalyzed cross-coupling reactions.

Science.gov (United States)

Bedford, Robin B

2015-05-19

The catalytic cross-coupling reactions of organic halides or related substrates with organometallic nucleophiles form the cornerstone of many carbon-carbon bond-forming processes. While palladium-based catalysts typically mediate such reactions, there are increasing concerns about the long-term sustainability of palladium in synthesis. This is due to the high cost of palladium, coupled with its low natural abundance, environmentally deleterious extraction (∼6 g of metal are produced per ton of ore), toxicity, and competition for its use from the automotive and consumer electronics sectors. Therefore, there is a growing interest in replacing palladium-based catalysts with those incorporating more earth-abundant elements. With its low cost, high natural abundance, and low toxicity, iron makes a particularly appealing alternative, and accordingly, the development of iron-catalyzed cross-coupling is undergoing explosive growth. However, our understanding of the mechanisms that underpin the iron-based catalytic cycles is still very much in its infancy. Mechanistic insight into catalytic reactions is not only academically important but also allows us to maximize the efficiency of processes or even to develop entirely new transformations. Key to the development of robust mechanistic models for cross-coupling is knowing the lowest oxidation state in the cycle. Once this is established, we can explore subsequent redox processes and build the catalytic manifold. Until we know with confidence what the lowest oxidation state is, any cycles proposed are largely just guesswork. To date, Fe(-II), Fe(-I), Fe(0), Fe(I), and Fe(II) have been proposed as contenders for the lowest-oxidation-state species in the cycle in iron-catalyzed cross-coupling; the aim of this Account is to pull together the various pieces of evidence in support, or otherwise, of each of these suggestions in turn. There currently exists no direct evidence that oxidation states below Fe(0) are active in the
CH{sub 4} dehydrogenation on Cu(1 1 1), Cu@Cu(1 1 1), Rh@Cu(1 1 1) and RhCu(1 1 1) surfaces: A comparison studies of catalytic activity

Energy Technology Data Exchange (ETDEWEB)

Zhang, Riguang; Duan, Tian [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Ling, Lixia [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Wang, Baojun, E-mail: wangbaojun@tyut.edu.cn [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China)

2015-06-30

Highlights: • Adsorbed Rh atom on Cu catalyst exhibits better catalytic activity for CH{sub 4} dehydrogenation. • The adsorbed Rh atom is the reaction active center for CH{sub 4} dehydrogenation. • The morphology of Cu substrate has negligible effect on CH{sub 4} dehydrogenation. - Abstract: In the CVD growth of graphene, the reaction barriers of the dehydrogenation for hydrocarbon molecules directly decide the graphene CVD growth temperature. In this study, density functional theory method has been employed to comparatively probe into CH{sub 4} dehydrogenation on four types of Cu(1 1 1) surface, including the flat Cu(1 1 1) surface (labeled as Cu(1 1 1)) and the Cu(1 1 1) surface with one surface Cu atom substituted by one Rh atom (labeled as RhCu(1 1 1)), as well as the Cu(1 1 1) surface with one Cu or Rh adatom (labeled as Cu@Cu(1 1 1) and Rh@Cu(1 1 1), respectively). Our results show that the highest barrier of the whole CH{sub 4} dehydrogenation process is remarkably reduced from 448.7 and 418.4 kJ mol{sup −1} on the flat Cu(1 1 1) and Cu@Cu(1 1 1) surfaces to 258.9 kJ mol{sup −1} on RhCu(1 1 1) surface, and to 180.0 kJ mol{sup −1} on Rh@Cu(1 1 1) surface, indicating that the adsorbed or substituted Rh atom on Cu catalyst can exhibit better catalytic activity for CH{sub 4} complete dehydrogenation; meanwhile, since the differences for the highest barrier between Cu@Cu(1 1 1) and Cu(1 1 1) surfaces are smaller, the catalytic behaviors of Cu@Cu(1 1 1) surface are very close to the flat Cu(1 1 1) surface, suggesting that the morphology of Cu substrate does not obviously affect the dehydrogenation of CH{sub 4}, which accords with the reported experimental observations. As a result, the adsorbed or substituted Rh atom on Cu catalyst exhibit a better catalytic activity for CH{sub 4} dehydrogenation compared to the pure Cu catalyst, especially on Rh-adsorbed Cu catalyst, we can conclude that the potential of synthesizing high-quality graphene with the
Fabrication of magnetically recyclable Fe3O4@Cu nanocomposites with high catalytic performance for the reduction of organic dyes and 4-nitrophenol

International Nuclear Information System (INIS)

Tang, Mingyi; Zhang, Sai; Li, Xianxian; Pang, Xiaobo; Qiu, Haixia

2014-01-01

A facile and efficient approach to synthesize Fe 3 O 4 @Cu nanocomposites using L-Lysine as a linker was developed. The morphology, composition and crystallinity of the Fe 3 O 4 @Cu nanocomposites were characterized by Fourier Transform infrared spectroscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and powder X-ray diffraction. In addition, the magnetic properties were determined with vibrating sample magnetometer. The surface of the Fe 3 O 4 contained many small Cu nanoparticles with sizes of about 3 nm. It was found that the Fe 3 O 4 @Cu nanocomposites could catalyze the degradation of organic dyes. The catalytic activities of the Fe 3 O 4 @Cu nanocomposites for the reduction of nitrophenol were also studied. The Fe 3 O 4 @Cu nanocomposites are more efficient catalysts compared with Cu nanoparticles and can easily be recovered from the reaction mixture with magnet. The cost effective and recyclable Fe 3 O 4 @Cu nanocomposites provide an exciting new material for environmental protection applications. - Highlights: • Cu nanoparticles as small as 3 nm are synthesized. • Low cost Fe 3 O 4 @Cu magnetical nanoparticles show catalytic activity for organic dyes and 4-nitrophenol. • The Fe 3 O 4 @Cu display high catalytic activity after 13 cycles
A multimodal optical and electrochemical device for monitoring surface reactions: redox active surfaces in porous silicon Rugate filters.

Science.gov (United States)

Ciampi, Simone; Guan, Bin; Darwish, Nadim A; Zhu, Ying; Reece, Peter J; Gooding, J Justin

2012-12-21

Herein, mesoporous silicon (PSi) is configured as a single sensing device that has dual readouts; as a photonic crystal sensor in a Rugate filter configuration, and as a high surface area porous electrode. The as-prepared PSi is chemically modified to provide it with stability in aqueous media and to allow for the subsequent coupling of chemical species, such as via Cu(I)-catalyzed cycloaddition reactions between 1-alkynes and azides ("click" reactions). The utility of the bimodal capabilities of the PSi sensor for monitoring surface coupling procedures is demonstrated by the covalent coupling of a ferrocene derivative, as well as by demonstrating ligand-exchange reactions (LER) at the PSi surface. Both types of reactions were monitored through optical reflectivity measurements, as well as electrochemically via the oxidation/reduction of the surface tethered redox species.
Method for predicting enzyme-catalyzed reactions

Science.gov (United States)

Hlavacek, William S.; Unkefer, Clifford J.; Mu, Fangping; Unkefer, Pat J.

2013-03-19

The reactivity of given metabolites is assessed using selected empirical atomic properties in the potential reaction center. Metabolic reactions are represented as biotransformation rules. These rules are generalized from the patterns in reactions. These patterns are not unique to reactants but are widely distributed among metabolites. Using a metabolite database, potential substructures are identified in the metabolites for a given biotransformation. These substructures are divided into reactants or non-reactants, depending on whether they participate in the biotransformation or not. Each potential substructure is then modeled using descriptors of the topological and electronic properties of atoms in the potential reaction center; molecular properties can also be used. A Support Vector Machine (SVM) or classifier is trained to classify a potential reactant as a true or false reactant using these properties.
MOF-derived Cu-Pd/nanoporous carbon composite as an efficient catalyst for hydrogen evolution reaction: A comparison between hydrothermal and electrochemical synthesis

Science.gov (United States)

Mandegarzad, Sakineh; Raoof, Jahan Bakhsh; Hosseini, Sayed Reza; Ojani, Reza

2018-04-01

In this study, a novel catalyst based on Cu-Pd bimetallic nanoparticles supported on nanoporous carbon composite (NPCC) is successfully fabricated through three-step process and used as an electrocatalyst towards hydrogen evolution reaction (HER). At the first step, MOF-199 is synthesized via two distinct strategies; (1) hydrothermal (HT) and (2) electrochemical (EC). Next, the synthesized MOF-199 is used as a template in order to prepare Cu/NPCC by direct carbonization under N2 atmosphere followed by galvanic replacement reaction of Cu metals by PdII ions. All the prepared materials are characterized by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), and nitrogen adsorption/desorption measurements. The effect of synthesis method of MOF-199 on the electrocatalytic activity of the final product towards HER is investigated. The electrochemical measurements indicate that Cu-Pd/NPCC derived from the MOF prepared by EC method (Cu-Pd/NPCC/EC) exhibits an enhanced catalytic activity towards HER in H2SO4 solution than the Cu-Pd/NPCC/HT. This improvement may be attributed to using of supporting electrolyte in the preparation of Cu-Pd/NPCC/EC.
[Sensing of Cu²⁺ Based on Fenton Reaction and Unmodified Gold Nanoparticles].

Science.gov (United States)

Xing, Yun-peng; Liu, Chun; Zhou, Xiao-hong; Zhang, Li-pei; Shi, Han-chang

2015-11-01

Heavy metal pollution has received great attentions in recent years. The traditional methods for heavy metal detection rely on the expensive laboratory instruments and need time-consuming preparation steps; therefore, it is urgent to develop quick and highly sensitive new technologies for heavy metal detection. The colorimetric method based on the gold nanoparticles (AuNPs) features with simple operation, high sensitivity and low cost, therefore, enabling it widely concerned and used in the environmental monitoring, food safety and chemical and biological sensing fields. This work developed a simple, rapid and highly sensitive strategy based on the Fenton reaction and unmodified AuNPs for the detection of Cu²⁺ in water samples. The hydroxyl radical ( · OH) generated by the Fenton reaction between the Cu²⁺ and sodium ascorbate (SA) oxidized the single stranded DNA (ssDNA) attached on the AuNPs surface into variable sequence fragments. The cleavage of ssDNA induced the aggregation of AuNPs in a certain salt solution, therefore, resulting in the changes on the absorbance of solution. The assay conditions were optimized to be pH value of 7.9, 11 mg · L⁻¹ ssDNA, 8 mmol · L⁻¹ SA and 70 mmol · L⁻¹ NaCl. Results showed that the absorbance ratio values at the wavelengths of 700 and 525 nm (A₇₀₀/A₅₂₅) were linearly correlated with the Cu²⁺ concentrations. The linear detection range was 0.1-10.0 µmol · L⁻¹ with a detection limit of 24 nmol · L⁻¹ (3σ). Spiked recoveries ranged from 87%-120% in three sorts of water, including drinking water, tap water and lake water, which confirmed that the potentials of the proposed assay for Cu²⁺ detection in reality.
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
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.
Catalytic Wittig and aza-Wittig reactions

Directory of Open Access Journals (Sweden)

Zhiqi Lao

2016-11-01

Full Text Available This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines.
Re-evaluation of microscopic and integral cross-section data for important dosimetry reactions. Re-evaluation of the excitation functions for the 24Mg(n,p)24Na, 32S(n,p)32P, 60Ni(n,p)60m+gCo, 63Cu(n,2n)62Cu, 65Cu(n,2n)64Cu, 64Zn(n,p)64Cu, 115In(n,2n)114mIn, 127I(n,2n)126I, 197Au(n,2n)196Au and 199Hg(n,n')199mHg reactions

International Nuclear Information System (INIS)

Zolotarev, K.I.

2008-08-01

Re-evaluations of cross sections and their associated covariance matrices have been carried out for ten dosimetry reactions: - excitation functions for the 63 Cu(n,2n) 62 Cu, 65 Cu(n,2n) 64 Cu, 64 Zn(n,p) 64 Cu, 115 In(n,2n) 114m In and 199 Hg(n,n') 199m Hg reactions were re-evaluated over the neutron energy range from threshold to 20 MeV; - excitation functions for the 24 Mg(n,p) 24 Na, 32 S(n,p) 32 P and 60 Ni(n,p) 60m+g Co were reevaluated in the energy range from threshold to 21 MeV; - excitation functions for the 127 I(n,2n) 126 I and 197 Au(n,2n) 196 Au reactions were reevaluated in the energy range from threshold to 32 and 40 MeV, respectively. Benchmark calculations performed for 235 U thermal fission and 252 Cf spontaneous fission neutron spectra show that the integral cross sections derived from the newly evaluated excitation functions exhibit improved agreement with related experimental data when compared with the equivalent data from the IRDF-2002 library. (author)
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.
Asymmetric Diels-Alder Reaction of α,β-Unsaturated Oxazolidin-2-one Derivatives Catalyzed by a Chiral Fe(III)-Bipyridine Diol Complex.

Science.gov (United States)

Li, Mao; Carreras, Virginie; Jalba, Angela; Ollevier, Thierry

2018-02-16

An asymmetric Fe III -bipyridine diol catalyzed Diels-Alder reaction of α,β-unsaturated oxazolidin-2-ones has been developed. Among various Fe II /Fe III salts, Fe(ClO 4 ) 3 ·6H 2 O was selected as the Lewis acid of choice. The use of a low catalyst loading (2 mol % of Fe(ClO 4 ) 3 ·6H 2 O and 2.4 mol % of Bolm's ligand) afforded high yields (up to 99%) and high enantiomeric excesses (up to 98%) of endo-cycloadducts for the Diels-Alder reaction between cyclopentadiene and substituted acryloyloxazolidin-2-ones. Other noncyclic dienes led to decreased enantioselectivities. A proposed model supports the observed stereoinduction.
Mechanism of copper(I)-catalyzed allylic alkylation of phosphorothioate esters: influence of the leaving group on α regioselectivity.

Science.gov (United States)

Sheng, Wenhao; Wang, Mian; Lein, Matthias; Jiang, Linbin; Wei, Wanxing; Wang, Jianyi

2013-10-11

The mechanism of Cu(I) -catalyzed allylic alkylation and the influence of the leaving groups (OPiv, SPiv, Cl, SPO(OiPr)2 ; Piv: pivavloyl) on the regioselectivity of the reaction have been explored by using density functional theory (DFT). A comprehensive comparison of many possible reaction pathways shows that [(iPr)2 Cu](-) prefers to bind first oxidatively to the double bond of the allylic substrate at the anti position with respect to the leaving group, and this is followed by dissociation of the leaving group. If the leaving group is not taken into account, the reaction then undergoes an isomerization and a reductive elimination process to give the α- or γ-selective product. If OPiv, SPiv, Cl, or SPO(OiPr)2 groups are present, the optimal route for the formation of both α- and γ-substituted products changes from the stepwise elimination to the direct process, in which the leaving group plays a stabilizing role for the reactant and destabilizes the transition state. The differences to the energy barrier for the α- and γ-substituted products are 2.75 kcal mol(-1) with SPO(OiPr)2 , 2.44 kcal mol(-1) with SPiv, 2.33 kcal mol(-1) with OPiv, and 1.98 kcal mol(-1) with Cl, respectively; these values show that α regioselectivity in the allylic alkylation follows a SPO(OiPr)2 >SPiv>OPiv>Cl trend, which is in satisfactory agreement with the experimental findings. This trend mainly originates in the differences between the attractive electrostatic forces and the repelling steric interactions of the SPO(OiPr)2 , SPiv, OPiv, and Cl groups on the Cu group. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding the reaction kinetics to optimize graphene growth on Cu by chemical vapor deposition

Energy Technology Data Exchange (ETDEWEB)

Kraus, Juergen; Boebel, Lena; Zwaschka, Gregor; Guenther, Sebastian [Technische Universitaet Muenchen, Zentralinstitut fuer Katalyseforschung, Chemie Department, Physikalische Chemie mit Schwerpunkt Katalyse, Garching (Germany)

2017-11-15

Understanding and controlling the growth kinetics of graphene is a prerequisite to synthesize this highly wanted material by chemical vapor deposition on Cu, e.g. for the construction of ultra-stable electron transparent membranes. It is reviewed that Cu foils contain a considerable amount of carbon in the bulk which significantly exceeds the expected amount of thermally equilibrated dissolved carbon in Cu and that this carbon must be removed before any high quality graphene may be grown. Starting with such conditioned Cu foils, systematic studies of the graphene growth kinetics in a reactive CH{sub 4}/H{sub 2} atmosphere allow to extract the following meaningful data: prediction of the equilibrium constant of the graphene formation reaction within a precision of a factor of two, the confirmation that the graphene growth proceeds from a C(ad)-phase on Cu which is in thermal equilibrium with the reactive gas phase, its apparent activation barrier and finally the prediction of the achievable growth velocity of the growing graphene flakes during chemical vapor deposition. As a result of the performed study, growth parameters are identified for the synthesis of high quality monolayer graphene with single crystalline domains of 100-1000 μm in diameter within a reasonable growth time. (copyright 2017 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)
Decomposition of NO on Cu-loaded zeolites

Energy Technology Data Exchange (ETDEWEB)

Sepulveda-Escribano, A; Marquez-Alvarez, C; Rodriquez-Ramos, I; Fierro, J L.G. [Instituto de Catalisis y Petroleoquimica, Madrid (Spain); Guerrero-Ruiz, A [Departamento de Quimica Inorganica, UNED, Madrid (Spain)

1993-05-26

Two copper ion-exchanged zeolites, Cu/NaY and Cu/NaZSM-5 have been studied by several techniques (TPR, TPD of NO, IR spectroscopy of adsorbed NO and XPS) and their catalytic activity for NO-decomposition have been determined under dynamic conditions. The results obtained here show that copper is stabilized as Cu[sup +] in Cu/NaZSM-5 after calcination in air at 673K, while in Cu/NaY the initial Cu[sup +]-ions are easier oxidized to Cu[sup 2+], this leading to a completely different catalytic behavior in the reaction of NO-decomposition. So, whereas the Cu/NaZSM-5 exhibits a high NO-conversion at the reaction temperatures (573 and 873K), the parent Cu/NaY zeolite becomes deactivated in the first stages of reaction.
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
CuI nanoparticles as a remarkable catalyst in the synthesis of benzo[b][1,5]diazepines: an eco-friendly approach.

Science.gov (United States)

Ghasemzadeh, Mohammad Ali; Safaei-Ghomi, Javad

2015-01-01

Highly efficient CuI nanoparticles catalyzed one-pot synthesis of some benzo[b][1,5]diazepine derivatives via multi-component condensation of aromatic diamines, Meldrum's acid and isocyanides. The present approach creates a variety of benzo[b][1,5]diazepines as pharmaceutical and biologically active heterocyclic compounds in excellent yields and short reaction times. The salient features of the copper iodide nanoparticles are: easy preparation, cost-effective, high stability, low loading and reusability of the catalyst. The prepared copper iodide nanoparticles were fully characterized by XRD, EDX, FT-IR, SEM and TEM analysis.
Possible pathophysiological roles of transglutaminase-catalyzed reactions in the pathogenesis of human neurodegenerative diseases

Directory of Open Access Journals (Sweden)

Enrica Serretiello

2015-09-01

Full Text Available Transglutaminases (TG, E.C. 2.3.2.13 are related and ubiquitous enzymes that catalyze the cross linking of a glutaminyl residue of a protein/peptide substrate to a lysyl residue of a protein/peptide co-substrate. These enzymes are also capable of catalyzing other post-translational reactions important for cell life. The distribution and the physiological roles of human TGs have been widely studied in numerous cell types and tissues and recently their roles in several diseases have begun to be identified. It has been hypothesized that transglutaminase activity is directly involved in the pathogenetic mechanisms responsible for several human diseases. In particular, tissue TG (tTG, TG2, a member of the TG enzyme family, has been recently shown to be involved in the molecular mechanisms responsible for a very widespread human pathology, Celiac Disease (CD, one of the most common food intolerances described in the western population. The main food agent that provokes the strong and diffuse clinical symptoms has been known for several years to be gliadin, a protein present in a very large number of human foods derived from vegetables. Recently, some biochemical and immunological aspects of this very common disease have been clarified, and “tissue” transglutaminase, a multifunctional and ubiquitous enzyme, has been identified as one of the major factors. The aim of this review is to summarize the most recent findings concerning the relationships between the biochemical properties of the transglutaminase activity and the basic molecular mechanisms responsible for some human diseases, with particular reference to neuropsychiatric disorders. Possible molecular links between CD and neuropsychiatric disorders, and the use of transglutaminase inhibitors are also discussed.
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.
Projectile-like fragments from 129Xe+natCu reactions at E/A = 40 MeV

International Nuclear Information System (INIS)

Russ, D.E.; Mignerey, A.C.; Garcia-Solis, E.J.

1996-01-01

The bombarding of heavy nuclei with energetic heavy projectiles has been one of the most important experimental tools for nuclear science. At low beam energies, (E/A) beam 100 MeV, these mean field effects are less important and nucleon-nucleon interactions dominate. Within the intermediate energy region, the situation is less clear because of both the mean field and nucleon-nucleon effects contribute. There is no consensus on the theoretical treatment of nuclear reaction in the intermediate energy regime and statistical, dynamical, and hybrid models have been used with limited success. Previous studies of 136 Xe + 209 Bi at E/A = 28 MeV carried out at Michigan State University (MSU) have been well described by a damped reaction mechanism. On the other hand, 129 Xe + nat Cu at E/A = 50 MeV also at MSU has been compared with a hybrid model with reasonable success. In order to see a transition from a damped reaction mechanism to more fragmentation-like processes, an experiment was carried out at MSU using 129 Xe beams at E/A = 30, 40, 50, and 60 MeV. The targets were Cu, Sc, and Au. The current study only looks at the projectile-like fragments (PLF) detected in the Maryland Forward Array (MFA)
Kinetics of Bio-Reactions

DEFF Research Database (Denmark)

Villadsen, John

2015-01-01

his chapter predicts the specific rates of reaction by means of a mathematical expression, the kinetics of the reaction. This expression can be derived through a mechanistic interpretation of an enzymatically catalyzed reaction, but it is essentially of empirical nature for cell reactions. The mo...
Low-temperature superacid catalysis: Reactions of n - butane and propane catalyzed by iron- and manganese-promoted sulfated zirconia

Energy Technology Data Exchange (ETDEWEB)

Tsz-Keung, Cheung; d`Itri, J.L.; Lange, F.C.; Gates, B.C. [Univ. of California, Davis, CA (United States)

1995-12-31

The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments catalytic testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure, 225-450{degrees}C, and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, these reactions were accompanied by cracking; at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part from coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup -8} mol/(g of catalyst {center_dot}s). The observation of butanes, pentanes, and methane as products is consistent with Olah superacid chemistry, whereby propane is first protonated by a very strong acid to form a carbonium ion. The carbonium ion then decomposes into methane and an ethyl cation which undergoes oligocondensation reactions with propane to form higher molecular weight alkanes. The results are consistent with the identification of iron- and manganese-promoted sulfated zirconia as a superacid.
Chemical reactions at CdS heterojunctions with CuInSe{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Aquino, Angel; Rockett, Angus [Department of Materials Science and Engineering, University of Illinois, 1304 West Green Street, Urbana, Illinois 61801 (United States)

2013-03-15

The stability of the CdS/CuInSe{sub 2} (CIS) heterojunction is critical to understanding the projected lifetime of CIS devices and the effect of processing conditions on the nanoscale chemistry of the heterojunction. This article reports the results of annealing heterojunctions between CdS deposited by chemical bath deposition and single crystal and polycrystalline CIS films between 200 and 500 Degree-Sign C for 10 to 150 min. No atomic movement was observed by secondary ion mass spectrometry at temperatures of 300 Degree-Sign C and below. At 400 Degree-Sign C even for the shortest time studied, Cu and In were found throughout the region initially consisting of CdS only and Cd was found to have moved into the CIS. In the polycrystal, annealing at 500 Degree-Sign C resulted in movement of Cd throughout the CIS layer. No time dependence was observed in the 400 and 500 Degree-Sign C anneals indicating that a reaction had occurred forming a compound that was in thermodynamic equilibrium with the remaining CIS. Diffusion turns on rapidly between 300 and 400 Degree-Sign C, indicating a high activation energy for atomic movement ({approx}2.4 eV). The onset of diffusion is consistent with the onset of Cu diffusion in CIS.
Co-{alpha}Al{sub 2}O{sub 3}-Cu as shaped catalyst in NaBH{sub 4} hydrolysis

Energy Technology Data Exchange (ETDEWEB)

Chamoun, R. [Universite Lyon 1, CNRS, UMR 5615, Laboratoire des Multimateriaux et Interfaces, 43 boulevard du 11 Novembre 1918, F-69622 Villeurbanne (France); Universite Libanaise, Faculte des Sciences II, Laboratoire de physique appliquee, 90656 Jdeidet El Metn (Lebanon); Demirci, U.B.; Miele, P. [Universite Lyon 1, CNRS, UMR 5615, Laboratoire des Multimateriaux et Interfaces, 43 boulevard du 11 Novembre 1918, F-69622 Villeurbanne (France); Zaatar, Y.; Khoury, A. [Universite Libanaise, Faculte des Sciences II, Laboratoire de physique appliquee, 90656 Jdeidet El Metn (Lebanon)

2010-07-15

A study about catalytic films of Co-supported-over-{alpha}Al{sub 2}O{sub 3} fabricated by electrophoretic deposition (EPD) is reported, the as-prepared shaped catalysts being intended to catalyze NaBH{sub 4} hydrolysis. Co-{alpha}Al{sub 2}O{sub 3} supported over Cu substrate can be prepared by a 2-step route: (i) preparation of the supported catalyst Co-{alpha}Al{sub 2}O{sub 3} (in powder form) by wet impregnation of CoCl{sub 2} over {alpha}Al{sub 2}O{sub 3}, followed by a reduction, and (ii) fabrication of Co-{alpha}Al{sub 2}O{sub 3}-Cu (thin film over Cu) by EPD. Both types of catalysts, whatever their form, are highly efficient in hydrolyzing NaBH{sub 4}, conversions of 100% and HGRs of tens of mL(H{sub 2}) min{sup -1} being achieved at 60-80 C. The Co-{alpha}Al{sub 2}O{sub 3}-Cu catalysts are even more reactive than the Co-{alpha}Al{sub 2}O{sub 3} catalysts because the surface of the former materials becomes much more acid than that of the latter ones in the course of the EPD process. The respective rate laws and reaction kinetics have been determined. Independently on the catalyst form, apparent activation energies of about 52 kJ mol{sup -1} and positive reaction orders versus the initial NaBH{sub 4} concentration (i.e. 0.3-0.7) were calculated, suggesting that the EPD does not affect the reaction mechanisms. Besides, it is showed that the hydrolysis is really catalytic as well as typical of a heterogeneous process. For example, an apparent reaction order versus the Co content of 0.9 was calculated. All of these results among others are reported and discussed in the present article. (author)
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.
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.
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
Noncanonical Reactions of Flavoenzymes

Directory of Open Access Journals (Sweden)

Pablo Sobrado

2012-11-01

Full Text Available Enzymes containing flavin cofactors are predominantly involved in redox reactions in numerous cellular processes where the protein environment modulates the chemical reactivity of the flavin to either transfer one or two electrons. Some flavoenzymes catalyze reactions with no net redox change. In these reactions, the protein environment modulates the reactivity of the flavin to perform novel chemistries. Recent mechanistic and structural data supporting novel flavin functionalities in reactions catalyzed by chorismate synthase, type II isopentenyl diphosphate isomerase, UDP-galactopyranose mutase, and alkyl-dihydroxyacetonephosphate synthase are presented in this review. In these enzymes, the flavin plays either a direct role in acid/base reactions or as a nucleophile or electrophile. In addition, the flavin cofactor is proposed to function as a “molecular scaffold” in the formation of UDP-galactofuranose and alkyl-dihydroxyacetonephosphate by forming a covalent adduct with reaction intermediates.
Synthesis of 2-monoacylglycerols and structured triacylglycerols rich in polyunsaturated fatty acids by enzyme catalyzed reactions.

Science.gov (United States)

Rodríguez, Alicia; Esteban, Luis; Martín, Lorena; Jiménez, María José; Hita, Estrella; Castillo, Beatriz; González, Pedro A; Robles, Alfonso

2012-08-10

This paper studies the synthesis of structured triacylglycerols (STAGs) by a four-step process: (i) obtaining 2-monoacylglycerols (2-MAGs) by alcoholysis of cod liver oil with several alcohols, catalyzed by lipases Novozym 435, from Candida antartica and DF, from Rhizopus oryzae, (ii) purification of 2-MAGs, (iii) formation of STAGs by esterification of 2-MAGs with caprylic acid catalyzed by lipase DF, from R. oryzae, and (iv) purification of these STAGs. For the alcoholysis of cod liver oil, absolute ethanol, ethanol 96% (v/v) and 1-butanol were compared; the conditions with ethanol 96% were then optimized and 2-MAG yields of around 54-57% were attained using Novozym 435. In these 2-MAGs, DHA accounted for 24-31% of total fatty acids. In the operational conditions this lipase maintained a stable level of activity over at least 11 uses. These results were compared with those obtained with lipase DF, which deactivated after only three uses. The alcoholysis of cod liver oil and ethanol 96% catalyzed by Novozym 435 was scaled up by multiplying the reactant amounts 100-fold and maintaining the intensity of treatment constant (IOT=3g lipase h/g oil). In these conditions, the 2-MAG yield attained was about 67%; these 2-MAGs contained 36.6% DHA. The synthesized 2-MAGs were separated and purified from the alcoholysis reaction products by solvent extraction using solvents of low toxicity (ethanol and hexane); 2-MAG recovery yield and purity of the target product were approximately 96.4% and 83.9%, respectively. These 2-MAGs were transformed to STAGs using the optimal conditions obtained in a previous work. After synthesis and purification, 93% pure STAGs were obtained, containing 38% DHA at sn-2 position and 60% caprylic acid (CA) at sn-1,3 positions (of total fatty acids at these positions), i.e. the major TAG is the STAG with the structure CA-DHA-CA. Copyright © 2012 Elsevier Inc. All rights reserved.
Enhanced Hydrogen Evolution Reactions on Nanostructured Cu{sub 2}ZnSnS{sub 4} (CZTS) Electrocatalyst

Energy Technology Data Exchange (ETDEWEB)

Digraskar, Renuka V.; Mulik, Balaji B. [Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431004, MH (India); Walke, Pravin S. [National Centre for Nanosciences and Nanotechnology, University of Mumbai, Mumbai 400098, MH (India); Ghule, Anil V. [Department of Chemistry, Shivaji University, Kolhapur, 416004, MH (India); Sathe, Bhaskar R., E-mail: bhaskarsathe@gmail.com [Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431004, MH (India)

2017-08-01

Graphical abstract: CZTS nano-electrocatalyst (2.6 ± 0.4 nm) for HER is synthesized by one step sonochemical method with uniform size distribution, which shows promisingly lower onset potential with higher current density and longer stability. - Highlights: • The nanostructured Cu{sub 2}ZnSnS{sub 4} (CZTS; ∼3 nm) based electrocatalytic systems were developed by facile sonochemical method. • The novel Cu{sub 2}ZnSnS{sub 4} based nanoclustered cathode improves the electrocatalytic performance toward hydrogen generation reaction (HER). • The electrocatalytic result exhibits lower Tafel slope, higher exchange current density, excellent current stability and lower charge transfer resistance. • The high activity due to synergetic effect of Cu, Zn, Sn and S from their internal cooperative supports. - Abstract: A novel and facile one-step sonochemical method is used to synthesize Cu{sub 2}ZnSnS{sub 4} (CZTS) nanoparticles (2.6 ± 0.4 nm) as cathode electrocatalyst for hydrogen evolution reactions. The detailed morphology, crystal and surface structure, and composition of the CZTS nanostructures were characterized by high resolution transmission electron microscopy (HR-TEM), Selected area electron diffraction (SAED), X-ray diffraction, Raman spectroscopy, FTIR analysis, Brunauer−Emmett−Teller (BET) surface area measurements, Electron dispersive analysis, X-ray photoelectron spectroscopy respectively. Electrocatalytic abilities of the nanoparticles toward Hydrogen Evolution Reactions (HER) were verified through cyclic voltammograms (CV) and Linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and Tafel polarization measurements. It reveals enhanced activity at lower onset potential 300 mV v/s RHE, achieved at exceptionally high current density −130 mA/cm{sup 2}, which is higher than the existing non-nobel metal based cathodes. Further result exhibits Tafel slope of 85 mV/dec, exchange current density of 882 mA/cm{sup 2}, excellent
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.
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...
Tunable differentiation of tertiary C-H bonds in intramolecular transition metal-catalyzed nitrene transfer reactions.

Science.gov (United States)

Corbin, Joshua R; Schomaker, Jennifer M

2017-04-13

Metal-catalyzed nitrene transfer reactions are an appealing and efficient strategy for accessing tetrasubstituted amines through the direct amination of tertiary C-H bonds. Traditional catalysts for these reactions rely on substrate control to achieve site-selectivity in the C-H amination event; thus, tunability is challenging when competing C-H bonds have similar steric or electronic features. One consequence of this fact is that the impact of catalyst identity on the selectivity in the competitive amination of tertiary C-H bonds has not been well-explored, despite the potential for progress towards predictable and catalyst-controlled C-N bond formation. In this communication, we report investigations into tunable and site-selective nitrene transfers between tertiary C(sp 3 )-H bonds using a combination of transition metal catalysts, including complexes based on Ag, Mn, Rh and Ru. Particularly striking was the ability to reverse the selectivity of nitrene transfer by a simple change in the identity of the N-donor ligand supporting the Ag(i) complex. The combination of our Ag(i) catalysts with known Rh 2 (ii) complexes expands the scope of successful catalyst-controlled intramolecular nitrene transfer and represents a promising springboard for the future development of intermolecular C-H N-group transfer methods.

Single-particle states in neutron-rich 69,71Cu by means of the (d,3He) transfer reaction

International Nuclear Information System (INIS)

Morfouace, Pierre

2014-01-01

In two (d, 3 He) transfer reactions with MUST2 at GANIL and the split-pole at Orsay, we have determined the position of the proton-hole states in the neutron-rich 71 Cu (N=42) and 69 Cu (N=40) isotopes. We have found that in 71 Cu the hole strength of the f7/2 orbital lies at higher excitation energies than expected. From beta-decay and laser spectroscopy, the f5/2 first excited particle state in these isotopes was known to come down rapidly in energy when passing N=40 and even become the ground state in 75 Cu. This sudden energy shift has been explained in a number of theoretical works. The prediction for the f7/2 spin-orbit partner was that it would change in energy too through a related effect. Experimentally, the f7/2 proton-hole state is not known for N≥40. In 71 Cu two 7/2- states around 1 MeV are candidates to be a proton-hole. The experiment at GANIL took place in March 2011. A secondary beam of 72 Zn at 38 AMeV was produced by fragmentation and purified through the LISE spectrometer. The transfer reaction in inverse kinematics was studied with the MUST2 detectors plus four 20 micrometer silicon detector to identified the 3 He of low kinetic energy. The excitation spectrum of 71 Cu was reconstruct thanks to the missing mass method and the angular distributions were extracted and compared with a reaction model using the DWUCK4 and DWUCK5 code. From this work no states have been populated around 1 MeV concluding that the centroid of the f7/2 lies at higher excitation energy. We then remeasured the single-particle strength in 69 Cu in the corresponding (d, 3 He) reaction at Orsay in March 2013 in order to extend the existing data where 60% of the f7/2 strength is missing and make sure that there is a consistent analysis of spectroscopic factors between both isotopes in order to well understood and well quantify the evolution of the f7/2 orbital when we start filling the g9/2 orbital. In this second experiment we have performed the reaction in direct
Reaction of intermetallic compounds of the ScT composition (T=Ag, Cu, Zn, Ni) with hydrogen

International Nuclear Information System (INIS)

Shilkin, S.P.; Volkova, L.S.; Tarasov, B.P.

1995-01-01

Reaction of intermetallic compounds of ScT composition (T=Ag, Cu, Zn, Ni), crystallized in CsCl structural type, with hydrogen at 0.2-10 MPa pressure and 293-673 K temperature is studied by chemical, x-ray phase and complex thermogravimetry analysis methods. It is shown that under such conditions hydrogen absorption by ScAg and ScCu is accompanied by the decay of their source matrices into scandium dihydride and metal silver and copper respectively. For ScZn a fine-dispersion mixture of scandium dihydride with zinc and hydride phase of a new zinc-containing intermetallic compound appears to be the finite reaction product. In case of ScNi a hydride phase of ScNiH 2.6 composition is produced, which is crystallized in a rhombic syngony with the lattice periods: a=0.5281±0.0007, b=0.7393±0.0009 and c=0.3327±0.0004 nm. 9 refs.; 2 tabs
Cu2Se and Cu Nanocrystals as Local Sources of Copper in Thermally Activated In Situ Cation Exchange

KAUST Repository

Casu, Alberto; Genovese, Alessandro; Manna, Liberato; Longo, Paolo; Buha, Joka; Botton, Gianluigi A.; Lazar, Sorin; Kahaly, M. Upadhyay; Schwingenschlö gl, Udo; Prato, Mirko; Li, Hongbo; Ghosh, Sandeep; Palazon, Francisco; De Donato, Francesco; Lentijo Mozo, Sergio; Zuddas, Efisio; Falqui, Andrea

2016-01-01

Among the different synthesis approaches to colloidal nanocrystals a recently developed toolkit is represented by cation exchange reactions, where the use of template nanocrystals gives access to materials that would be hardly attainable via direct synthesis. Besides, post-synthetic treatments, such as thermally activated solid state reactions, represent a further flourishing route to promote finely controlled cation exchange. Here, we report that, upon in situ heating in a transmission electron microscope, Cu2Se nanocrystals deposited on an amorphous solid substrate undergo partial loss of Cu atoms, which are then engaged in local cation exchange reactions with Cu “acceptors” phases represented by rod- and wire- shaped CdSe nanocrystals. This thermal treatment slowly transforms the initial CdSe nanocrystals into Cu2-xSe nanocrystals, through the complete sublimation of Cd and the partial sublimation of Se atoms. Both Cu “donor” and “acceptor” particles were not always in direct contact with each other, hence the gradual transfer of Cu species from Cu2Se or metallic Cu to CdSe nanocrystals was mediated by the substrate and depended on the distance between the donor and acceptor nanostructures. Differently from what happens in the comparably faster cation exchange reactions performed in liquid solution, this study shows that slow cation exchange reactions can be performed at the solid state, and helps to shed light on the intermediate steps involved in such reactions.
Cu2Se and Cu Nanocrystals as Local Sources of Copper in Thermally Activated In Situ Cation Exchange

KAUST Repository

Casu, Alberto

2016-01-27

Among the different synthesis approaches to colloidal nanocrystals a recently developed toolkit is represented by cation exchange reactions, where the use of template nanocrystals gives access to materials that would be hardly attainable via direct synthesis. Besides, post-synthetic treatments, such as thermally activated solid state reactions, represent a further flourishing route to promote finely controlled cation exchange. Here, we report that, upon in situ heating in a transmission electron microscope, Cu2Se nanocrystals deposited on an amorphous solid substrate undergo partial loss of Cu atoms, which are then engaged in local cation exchange reactions with Cu “acceptors” phases represented by rod- and wire- shaped CdSe nanocrystals. This thermal treatment slowly transforms the initial CdSe nanocrystals into Cu2-xSe nanocrystals, through the complete sublimation of Cd and the partial sublimation of Se atoms. Both Cu “donor” and “acceptor” particles were not always in direct contact with each other, hence the gradual transfer of Cu species from Cu2Se or metallic Cu to CdSe nanocrystals was mediated by the substrate and depended on the distance between the donor and acceptor nanostructures. Differently from what happens in the comparably faster cation exchange reactions performed in liquid solution, this study shows that slow cation exchange reactions can be performed at the solid state, and helps to shed light on the intermediate steps involved in such reactions.
New Production Routes for Medical Isotopes 64Cu and 67Cu Using Accelerator Neutrons

Science.gov (United States)

Kin, Tadahiro; Nagai, Yasuki; Iwamoto, Nobuyuki; Minato, Futoshi; Iwamoto, Osamu; Hatsukawa, Yuichi; Segawa, Mariko; Harada, Hideo; Konno, Chikara; Ochiai, Kentaro; Takakura, Kosuke

2013-03-01

We have measured the activation cross sections producing 64Cu and 67Cu, promising medical radioisotopes for molecular imaging and radioimmunotherapy, by bombarding a natural zinc sample with 14 MeV neutrons. We estimated the production yields of 64Cu and 67Cu by fast neutrons from \\text{natC(d,n) with 40 MeV 5 mA deuterons. We used the present result together with the evaluated cross section of Zn isotopes. The calculated 64Cu yield is 1.8 TBq (175 g 64Zn) for 12 h of irradiation; the yields of 67Cu by 67Zn(n,p)67Cu and 68Zn(n,x)67Cu were 249 GBq (184 g 67Zn) and 287 GBq (186 g 68Zn) at the end of 2 days of irradiation, respectively. From the results, we proposed a new route to produce 67Cu with very little radionuclide impurity via the 68Zn(n,x)67Cu reaction, and showed the 64Zn(n,p)64Cu reaction to be a promising route to produce 64Cu. Both 67Cu and 64Cu are noted to be produced using fast neutrons.
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.
Graphene-oxide-supported CuAl and CoAl layered double hydroxides as enhanced catalysts for carbon-carbon coupling via Ullmann reaction

Science.gov (United States)

Ahmed, Nesreen S.; Menzel, Robert; Wang, Yifan; Garcia-Gallastegui, Ainara; Bawaked, Salem M.; Obaid, Abdullah Y.; Basahel, Sulaiman N.; Mokhtar, Mohamed

2017-02-01

Two efficient catalyst based on CuAl and CoAl layered double hydroxides (LDHs) supported on graphene oxide (GO) for the carbon-carbon coupling (Classic Ullmann Homocoupling Reaction) are reported. The pure and hybrid materials were synthesised by direct precipitation of the LDH nanoparticles onto GO, followed by a chemical, structural and physical characterisation by electron microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area measurements and X-ray photoelectron spectroscopy (XPS). The GO-supported and unsupported CuAl-LDH and CoAl-LDH hybrids were tested over the Classic Ullman Homocoupling Reaction of iodobenzene. In the current study CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary and two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH.
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.
Traceless Azido Linker for the Solid-Phase Synthesis of NH-1,2,3-Triazoles via Cu-Catalyzed Azide-Alkyne Cycloaddition Reactions

DEFF Research Database (Denmark)

Cohrt, Anders Emil; Jensen, Jakob Feldthusen; Nielsen, Thomas Eiland

2010-01-01

A broadly useful acid-labile traceless azido linker for the solid-phase synthesis of NH-1,2,3-triazoles is presented. A variety of alkynes were efficiently immobilized on a range of polymeric supports by Cu(I)-mediated azide-alkyne cycloadditions. Supported triazoles showed excellent compatibility...
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.
Transesterification of used vegetable oil catalyzed by barium oxide under simultaneous microwave and ultrasound irradiations

International Nuclear Information System (INIS)

Martinez-Guerra, Edith; Gude, Veera Gnaneswar

2014-01-01

Graphical abstract: Transesterification reaction mediated by simultaneous microwave and ultrasound irradiations with barium oxide (BaO) heterogeneous catalyst. - Highlights: • Synergistic effect of simultaneous microwave/ultrasound irradiations was evaluated. • Yields were higher for the MW/US reactions compared to MW or US individually. • BaO catalyzed MW/US transesterification reaction is more environmental-friendly. • BaO catalyzed MW/US transesterification reaction provides better biodiesel yields. • Optimum power density must be identified for energy-efficient biodiesel production. - Abstract: This study presents a novel application of simultaneous microwave and ultrasound (MW/US) irradiations on transesterification of used vegetable oil catalyzed by barium oxide, heterogeneous catalyst. Experiments were conducted to study the optimum process conditions, synergistic effect of microwave and ultrasound irradiations and the effect of power density. From the process parametric optimization study, the following conditions were determined as optimum: 6:1 methanol to oil ratio, 0.75% barium oxide catalyst by wt.%, and 2 min of reaction time at a combined power output rate of 200 W (100/100 MW/US). The biodiesel yields were higher for the simultaneous MW/US mediated reactions (∼93.5%) when compared to MW (91%) and US (83.5%) irradiations individually. Additionally, the effect of power density and a discussion on the synergistic effect of the microwave and ultrasound mediated reactions were presented. A power density of 7.6 W/mL appears to be effective for MW, and MW/US irradiated reactions (94.4% and 94.7% biodiesel yields respectively), while a power density of 5.1 W/mL was appropriate for ultrasound irradiation (93.5%). This study concludes that the combined microwave and ultrasound irradiations result in a synergistic effect that reduces the heterogeneity of the transesterification reaction catalyzed by heterogeneous catalysts to enhance the biodiesel
A computational study on Lewis acid-catalyzed diastereoselective acyclic radical allylation reactions with unusual selectivity dependence on temperature and epimer precursor.

Science.gov (United States)

Georgieva, Miglena K; Santos, A Gil

2014-12-05

In stereoselective radical reactions, it is accepted that the configuration of the radical precursor has no impact on the levels of stereoinduction, as a prochiral radical intermediate is planar, with two identical faces, independently of its origin. However, Sibi and Rheault (J. Am. Chem. Soc. 2000, 122, 8873-8879) remarkably obtained different selectivities in the trapping of radicals originated from two epimeric bromides, catalyzed by chelating Lewis acids. The selectivity rationalization was made on the basis of different conformational properties of each epimer. However, in this paper we show that the two epimers have similar conformational properties, which implies that the literature proposal is unable to explain the experimental results. We propose an alternative mechanism, in which the final selectivity is dependent on different reaction rates for radical formation from each epimer. By introducing a different perspective of the reaction mechanism, our model also allows the rationalization of different chemical yields obtained from each epimer, a result not rationalized by the previous model. Adaptation to other radical systems, under different reaction conditions, is also possible.
Enhanced chemiluminescence of the luminol–KMnO4 system by CuO nanosheets and its application for determination of meropenem in water and human serum

International Nuclear Information System (INIS)

Khataee, A.R.; Fathinia, M.; Hasanzadeh, A.; Iranifam, M.; Moradkhannejhad, L.

2014-01-01

CuO nanosheets were synthesized by an easy and green sonochemical method. It was found that, CuO nanosheets could significantly catalyze the chemiluminescence (CL) reaction of luminol–KMnO 4 in an alkaline condition. Based on this finding, a new CL system (luminol–KMnO 4 –CuO nanosheets) combined with flow injection analysis has been developed for the determination of meropenem for the first time. Moreover, the CL intensity was enhanced when meropenem was presented in the reaction system. Under the optimum conditions, the enhanced CL intensity was proportional to the concentration of meropenem in the ranges of 0.005–6.00 mg L −1 , with a detection limit (3σ) of 0.0036 mg L −1 . The precision of the method was calculated by analyzing samples containing 1.0 mg L −1 meropenem (n=11) and the relative standard deviation (RSD) was 1.7%. Also, a total analysis time per sample was 30 s which confirmed the rapidity of the proposed assay. The practicality of the proposed CL system was evaluated by determining meropenem in spiked environmental water samples and human serum. A discussion on the possible CL reaction mechanism was also presented. - Highlights: • CuO nanosheets (NSs) were successfully prepared by a green sonochemical method. • CuO NSs were found to be an excellent enhancer for luminol−KMnO 4 CL system. • Meropenem was determined using a novel luminol−KMnO 4 −CuO NSs flow injection CL system. • The enhancement mechanism of meropenem on the CL emission was proposed. • Appropriate sensitivity and selectivity were notable features of the proposed method
Universal, colorimetric microRNA detection strategy based on target-catalyzed toehold-mediated strand displacement reaction

Science.gov (United States)

Park, Yeonkyung; Lee, Chang Yeol; Kang, Shinyoung; Kim, Hansol; Park, Ki Soo; Park, Hyun Gyu

2018-02-01

In this work, we developed a novel, label-free, and enzyme-free strategy for the colorimetric detection of microRNA (miRNA), which relies on a target-catalyzed toehold-mediated strand displacement (TMSD) reaction. The system employs a detection probe that specifically binds to the target miRNA and sequentially releases a catalyst strand (CS) intended to trigger the subsequent TMSD reaction. Thus, the presence of target miRNA releases the CS that mediates the formation of an active G-quadruplex DNAzyme which is initially caged and inactivated by a blocker strand. In addition, a fuel strand that is supplemented for the recycling of the CS promotes another TMSD reaction, consequently generating a large number of active G-quadruplex DNAzymes. As a result, a distinct colorimetric signal is produced by the ABTS oxidation promoted by the peroxidase mimicking activity of the released G-quadruplex DNAzymes. Based on this novel strategy, we successfully detected miR-141, a promising biomarker for human prostate cancer, with high selectivity. The diagnostic capability of this system was also demonstrated by reliably determining target miR-141 in human serum, showing its great potential towards real clinical applications. Importantly, the proposed approach is composed of separate target recognition and signal transduction modules. Thus, it could be extended to analyze different target miRNAs by simply redesigning the detection probe while keeping the same signal transduction module as a universal signal amplification unit, which was successfully demonstrated by analyzing another target miRNA, let-7d.
Measurement of cross sections for the 63Cu(α,γ)67Ga reaction from 5.9-8.7 MeV

International Nuclear Information System (INIS)

Basunia, M. Shamsuzzoha; Norman, Eric B.; Shugart, Howard A.; Smith, Alan R.; Dolinski, Michelle J.; Quiter, Brian J.

2004-01-01

We have measured cross sections for the 63Cu(alpha,gamma)67Ga reaction in the 5.9-8.7 MeV energy range using an activation technique. Natural Cu foils were bombarded with alpha beams from the 88 Cyclotron at Lawrence Berkeley National Laboratory (LBNL). Activated foils were counted using gamma spectrometry system at LBNL's Low Background Facility. The 63Cu(alpha,gamma)67Ga cross-sections were determined and compared with the latest NON-SMOKER theoretical values. Experimental cross sections were found to be in agreement with theoretical values
Diastereoselective Au-Catalyzed Allene Cycloisomerizations to Highly Substituted Cyclopentenes.

Science.gov (United States)

Reeves, Ryan D; Phelps, Alicia M; Raimbach, William A T; Schomaker, Jennifer M

2017-07-07

Site- and regiocontrolled Au-catalyzed allene carbocyclizations furnish highly substituted cyclopentenes in >1:1 dr. Significant substitution on the substrate is tolerated, with potential to install five contiguous stereocenters after alkene functionalization. Major challenges include identifying a Au/Cu catalyst that controls both the relative rates of allene epimerization/cyclization and the facial selectivity in addition of a metal enolate to the allene. Experiments to achieve stereodivergent cyclizations and transform key cyclopentenes into useful synthetic building blocks are described.
Synthesis of Cu Nanoparticles Using Copper Carbonate as Cu Source Toward Versatile Applications.

Science.gov (United States)

Yano, Kazuhisa; Ishizaki, Toshitaka; Sugiyama, Hidehiko

2018-07-01

Cu nanoparticles (NPs) coated with polyvinylpyrrolidone (PVP) were fabricated by polyol method using copper carbonate as a raw material. To increase the reaction temperature, glycol multimers such as diethylene glycol, triethylene glycol, or tetraethylene glycol were examined as a solvent. With increasing degree of multimerization, average diameter of Cu NPs decreased. The synthesis of Cu NPs was further investigated by changing reaction temperature, the amount and molecular weight of PVP in triethylene glycol as a solvent. Average diameter and standard deviation of Cu NPs were found to be highly dependent on those factors. As a result, fine Cu NPs ranging from 28 to 67 nm in average size with narrow size distribution (standard deviation: 16-28%) were obtained. The obtained Cu NPs were applied to a nanofluid, which showed higher thermal conductivity than the theoretical value. The antibacterial activity of Cu NPs was also demonstrated, and found to have strong antibacterial activity.
Facile one-pot synthesis of 1-amido alkyl-2-naphthols by RuCl2(PPh3)3-catalyzed multi-component reactions

International Nuclear Information System (INIS)

Zhu, Xiaoyan; Lee, Yong Rok; Kim, Sung Hong

2012-01-01

We have developed an efficient and general synthesis of 1-amidoalkyl-2-naphthols by RuCl 2 (PPh 3 ) 3 -catalyzed one-pot multi-component reaction of 2-naphthol with aromatic aldehydes and amides. The advantages of these methodologies are easy handling, mild reaction conditions, and use of an effective and non-toxic catalyst. Molecules bearing 1,3-amino oxygenated functional groups have been reported to exhibit a variety of biological and pharmacological activities including nucleoside antibiotics and HIV protease inhibitors such as ritonavir and lipinavir. Importantly, 1-amidoalkyl-2-naphthols can be easily converted to biologically active 1-aminomethyl-2-naphthols by amide hydrolysis. These compounds also exhibit potent antihypertensive, adrenoceptor-blocking, and Ca +2 channel-blocking activities. Because of the importance of these compounds, numerous methods for the synthesis of 1-amidoalkyl-2-naphthols have been described. The reported methods mainly include one-pot three-component reactions of 2-naphthol, aromatic aldehydes, and amides
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.
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

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.
Averaged cross sections for the reactions 68Zn(n,p)68gCu and 68Zn(n,p)68mCu for a 235U fission neutron spectrum

International Nuclear Information System (INIS)

Kestelman, A.J.; Ribeiro Guevara, S.; Arribere, M.A.; Cohen, I.M.

2007-01-01

Making use of the method developed in our laboratory for the simultaneous determination of cross sections leading to both the ground and metastable states, we have measured the 68 Zn(n,p) 68g Cu and 68 Zn(n,p) 68m Cu reactions, using Zn enriched to 99.4% in its isotope 68 Zn. The measured cross sections are (15.04±0.35) and (3.69±0.30) μb for the ground and metastable state, respectively. However, a direct determination of the cross section leading to the metastable state gives a value of (4.75±0.38) μb. A possible reason for this discrepancy-which is outside experimental uncertainties-is that some tabulated values used in our calculations for the decay parameters of 68g Cu and 68m Cu, have either larger than quoted, or unknown systematic, uncertainties
Mechanistic insight into benzenethiol catalyzed amide bond formations from thioesters and primary amines

DEFF Research Database (Denmark)

Stuhr-Hansen, Nicolai; Bork, Nicolai; Strømgaard, Kristian

2014-01-01

The influence of arylthiols on cysteine-free ligation, i.e. the reaction between an alkyl thioester and a primary amine forming an amide bond, was studied in a polar aprotic solvent. We reacted the ethylthioester of hippuric acid with cyclohexylamine in the absence or presence of various quantities...... of thiophenol (PhSH) in a slurry of disodium hydrogen phosphate in dry DMF. Quantitative conversions into the resulting amide were observed within a few hours in the presence of equimolar amounts of thiophenol. Ab initio calculations showed that the reaction mechanism in DMF is similar to the well-known aqueous...... reaction mechanism. The energy barrier of the catalyzed amidation reaction is approximately 40 kJ mol(-1) lower than the non-catalyzed amidation reaction. At least partially this can be explained by a hydrogen bond from the amine to the π-electrons of the thiophenol, stabilizing the transition state...
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.
Fabrication of magnetically recyclable Fe{sub 3}O{sub 4}@Cu nanocomposites with high catalytic performance for the reduction of organic dyes and 4-nitrophenol

Energy Technology Data Exchange (ETDEWEB)

Tang, Mingyi, E-mail: mingyitjucu@163.com [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Zhang, Sai; Li, Xianxian; Pang, Xiaobo [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Qiu, Haixia [School of Science, Tianjin University, Tianjin 300072 (China)

2014-12-15

A facile and efficient approach to synthesize Fe{sub 3}O{sub 4}@Cu nanocomposites using L-Lysine as a linker was developed. The morphology, composition and crystallinity of the Fe{sub 3}O{sub 4}@Cu nanocomposites were characterized by Fourier Transform infrared spectroscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and powder X-ray diffraction. In addition, the magnetic properties were determined with vibrating sample magnetometer. The surface of the Fe{sub 3}O{sub 4} contained many small Cu nanoparticles with sizes of about 3 nm. It was found that the Fe{sub 3}O{sub 4}@Cu nanocomposites could catalyze the degradation of organic dyes. The catalytic activities of the Fe{sub 3}O{sub 4}@Cu nanocomposites for the reduction of nitrophenol were also studied. The Fe{sub 3}O{sub 4}@Cu nanocomposites are more efficient catalysts compared with Cu nanoparticles and can easily be recovered from the reaction mixture with magnet. The cost effective and recyclable Fe{sub 3}O{sub 4}@Cu nanocomposites provide an exciting new material for environmental protection applications. - Highlights: • Cu nanoparticles as small as 3 nm are synthesized. • Low cost Fe{sub 3}O{sub 4}@Cu magnetical nanoparticles show catalytic activity for organic dyes and 4-nitrophenol. • The Fe{sub 3}O{sub 4}@Cu display high catalytic activity after 13 cycles.
Copper(I)-Catalyzed Asymmetric Desymmetrization through Inverse-Electron-Demand aza-Diels-Alder Reaction: Efficient Access to Tetrahydropyridazines Bearing a Unique α-Chiral Silane Moiety.

Science.gov (United States)

Wei, Liang; Zhou, Yu; Song, Zhi-Min; Tao, Hai-Yan; Lin, Zhenyang; Wang, Chun-Jiang

2017-04-11

An unprecedented copper(I)-catalyzed asymmetric desymmetrization of 5-silylcyclopentadienes with in situ formed azoalkene was realized through an inverse-electron-demand aza-Diels-Alder reaction (IEDDA) pathway, in which 5-silylcyclopentadienes served as efficient enophiles. This new protocol provides a facile access to the biologically important heterocyclic tetrahydropyridazines containing a unique α-chiral silane motif and three adjoining stereogenic centers in generally good yield (up to 92 %) with exclusive regioselectivity, high diastereoselectivity (>20:1 diastereomeric ratio), and excellent enantioselectivity (up to 98 % enantiomeric excess). DFT calculations and control experiments further confirmed the proposed reaction mechanism. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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.
Comparing temporal order judgments and choice reaction time tasks as indices of exogenous spatial cuing.

Science.gov (United States)

Eskes, Gail A; Klein, Raymond M; Dove, Mary Beth; Coolican, Jamesie; Shore, David I

2007-11-30

Attentional disorders are common in individuals with neurological or psychiatric conditions and impact on recovery and outcome. Thus, it is critical to develop theory-based measures of attentional function to understand potential mechanisms underlying the disorder and to evaluate the effect of intervention. The present study compared two alternative methods to measure the effects of attentional cuing that could be used in populations of individuals who may not be able to make manual responses normally or may show overall slowing in responses. Spatial attention was measured with speeded and unspeeded methods using either manual or voice responses in two standard attention paradigms: the cued target discrimination reaction time (RT) paradigm and the unspeeded temporal order judgment (TOJ) task. The comparison of speeded and unspeeded tasks specifically addresses the concern about interpreting RT differences between cued and uncued trials (taken as a proxy for attention) in the context of drastically different baseline RTs. We found significant cuing effects for both tasks (speeded RT and untimed TOJ) and both response types (vocal and manual) giving clinicians and researchers alternative methods with which to measure the effects of attention in different populations who may not be able to perform the standard speeded RT task.
A chiral Brønsted acid-catalyzed highly enantioselective Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines.

Science.gov (United States)

Unhale, Rajshekhar A; Sadhu, Milon M; Ray, Sumit K; Biswas, Rayhan G; Singh, Vinod K

2018-04-03

A chiral phosphoric acid-catalyzed asymmetric Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines, derived from 3-hydroxyisoindolinones has been demonstrated in this communication. A variety of isoindolinone-based α-amino diazo esters bearing a quaternary stereogenic center were afforded in high yields (up to 99%) with excellent enantioselectivities (up to 99% ee). Furthermore, the synthetic utility of the products has been depicted by the hydrogenation of the diazo moiety of adducts.
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
Enzymatic Synthesis and Structural Characterization of Theanderose through Transfructosylation Reaction Catalyzed by Levansucrase from Bacillus subtilis CECT 39.

Science.gov (United States)

Ruiz-Aceituno, Laura; Sanz, Maria Luz; de Las Rivas, Blanca; Muñoz, Rosario; Kolida, Sofia; Jimeno, Maria Luisa; Moreno, F Javier

2017-12-06

This work addresses the high-yield and fast enzymatic production of theanderose, a naturally occurring carbohydrate, also known as isomaltosucrose, whose chemical structure determined by NMR is α-d-glucopyranosyl-(1 → 6)-α-d-glucopyranosyl-(1 → 2)-β-d-fructofuranose. The ability of isomaltose to act as an acceptor in the Bacillus subtilis CECT 39 levansucrase-catalyzed transfructosylation reaction to efficiently produce theanderose in the presence of sucrose as a donor is described by using four different sucrose:isomaltose concentration ratios. The maximum theanderose concentration ranged from 122.4 to 130.4 g L -1 , was obtained after only 1 h and at a moderate temperature (37 °C), leading to high productivity (109.7-130.4 g L -1 h -1 ) and yield (up to 37.3%) values. The enzymatic synthesis was highly regiospecific, since no other detectable acceptor reaction products were formed. The development of efficient and cost-effective procedures for the biosynthesis of unexplored but appealing oligosaccharides as potential sweeteners, such as theanderose, could help to expand its potential applications which are currently limited by their low availability.
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.
An overview of R and D activities for the Cu-Cl, cycle with emphasis on the hydrolysis reaction

International Nuclear Information System (INIS)

Lewis, M.A.; Ferrandon, M.S.; Tatterson, D.F.

2010-01-01

This paper describes the status of the development effort for the Cu-Cl thermochemical cycle. Most of the recent work has been focused on the hydrolysis reaction, which is challenging because of the need for excess steam to achieve high yields. Two types of spray reactors were tested and the ultrasonic nozzle gave excellent results. The conceptual process design for the overall process now includes a spray reactor. Engineering methods to increase efficiency are proposed. Preliminary values for the efficiency and capital costs for producing hydrogen using the Cu-Cl cycle have been calculated. (authors)
Structural analysis of CuO / CeO{sub 2}-based catalytic materials intended for PROX reaction: Part I; Analise estrutural de materiais cataliticos a base de CuO/CeO{sub 2} destinados a reacao de PROX: parte I

Energy Technology Data Exchange (ETDEWEB)

Neiva, L.S.; Simoes, A.N.; Bispo, A.; Ribeiro, M.A.; Gama, L., E-mail: lsoutoneiva@yahoo.com.br [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Aademica de Engenharia de Materiais

2011-07-01

This work relates the synthesis process of CuO/CeO{sub 2} catalytic materials by a combustion reaction method as well as it introduces a structural analysis of the developed material, this structural analysis had as main focus to evaluate the influence of the doping substance (CuO) when being incorporated in the hostess matrix structure that is CeO{sub 2}. The CuO/CeO catalytic materials developed in this work are destined to preferential oxidation of CO reaction (PROX). The developed materials were characterized by XRD, SEM and textural complete analysis by the BET method. According to the results, the CuO incorporation changed crystallinity of the structure of the catalytic materials. On the other hand, the morphologic and textural characteristics did not showed significant differences regarding the presence of the doping substance (CuO) in the structure of the developed materials. The porosity of the structures of the developed catalytic materials belongs to the type macroporous. (author)
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.
The mechanism of degradation of bisphenol A using the magnetically separable CuFe{sub 2}O{sub 4}/peroxymonosulfate heterogeneous oxidation process

Energy Technology Data Exchange (ETDEWEB)

Xu, Yin; Ai, Jia [Department of Environmental Engineering, Wuhan University, Wuhan 430079 (China); Shenzhen Research Institute of Wuhan University, Shenzhen 518057 (China); Zhang, Hui, E-mail: eeng@whu.edu.cn [Department of Environmental Engineering, Wuhan University, Wuhan 430079 (China); Shenzhen Research Institute of Wuhan University, Shenzhen 518057 (China)

2016-05-15

Highlights: • Copper ferrite (CuFe{sub 2}O{sub 4}) was fabricated and utilized in heterogeneous PMS process. • The influence of reaction parameters for the mineralization of BPA were evaluated. • Possible reaction mechanism and the stability of CuFe{sub 2}O{sub 4} were investigated. • Surface bound radicals (mainly ·OH) may be responsible for the BPA degradation. - Abstract: The removal of bisphenol A (BPA) in aqueous solution by an oxidation process involving peroxymonosulfate (PMS) activated by CuFe{sub 2}O{sub 4} magnetic nanoparticles (MNPs) is reported herein. The effects of PMS concentration, CuFe{sub 2}O{sub 4} dosage, initial pH, initial BPA concentration, catalyst addition mode, and anions (Cl{sup −}, F{sup −}, ClO{sub 4}{sup −} and H{sub 2}PO{sub 4}{sup −}) on BPA degradation were investigated. Results indicate that nearly complete removal of BPA (50 mg/L) within 60 min and 84.0% TOC removal in 120 min could be achieved at neutral pH by using 0.6 g/L CuFe{sub 2}O{sub 4} MNPs and 0.3 g/L PMS. The generation of reactive radicals (mainly hydroxyl radicals) was confirmed using electron paramagnetic resonance (EPR). Possible mechanisms on the radical generation from CuFe{sub 2}O{sub 4}/PMS system are proposed based on the results of radical identification tests and XPS analysis. The lack of inhibition of the reaction by free radical scavengers such as methanol and tert-butyl alcohol suggests that these species may not be generated in the bulk solution, and methylene blue probe experiments confirm that this process does not involve free radical generation. Surface-bound, rather than free radicals generated by a surface catalyzed-redox cycle involving both Fe(III) and Cu(II), are postulated to be responsible for the mineralization of bisphenol A.
Massive spalling of Cu-Zn and Cu-Al intermetallic compounds at the interface between solders and Cu substrate during liquid state reaction

Science.gov (United States)

Kotadia, H. R.; Panneerselvam, A.; Mokhtari, O.; Green, M. A.; Mannan, S. H.

2012-04-01

The interfacial intermetallic compound (IMC) formation between Cu substrate and Sn-3.8Ag-0.7Cu-X (wt.%) solder alloys has been studied, where X consists of 0-5% Zn or 0-2% Al. The study has focused on the effect of solder volume as well as the Zn or Al concentration. With low solder volume, when the Zn and Al concentrations in the solder are also low, the initial Cu-Zn and Al-Cu IMC layers, which form at the solder/substrate interface, are not stable and spall off, displaced by a Cu6Sn5 IMC layer. As the total Zn or Al content in the system increases by increasing solder volume, stable CuZn or Al2Cu IMCs form on the substrate and are not displaced. Increasing concentration of Zn has a similar effect of stabilizing the Cu-Zn IMC layer and also of forming a stable Cu5Zn8 layer, but increasing Al concentration alone does not prevent spalling of Al2Cu. These results are explained using a combination of thermodynamic- and kinetics-based arguments.
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.
Formation of a hydrogen-bonded barbiturate [2]-rotaxane.

Science.gov (United States)

Tron, Arnaud; Thornton, Peter J; Rocher, Mathias; Jacquot de Rouville, Henri-Pierre; Desvergne, Jean-Pierre; Kauffmann, Brice; Buffeteau, Thierry; Cavagnat, Dominique; Tucker, James H R; McClenaghan, Nathan D

2014-03-07

Interlocked structures containing the classic Hamilton barbiturate binding motif comprising two 2,6-diamidopyridine units are reported for the first time. Stable [2]-rotaxanes can be accessed either through hydrogen-bonded preorganization by a barbiturate thread followed by a Cu(+)-catalyzed "click" stoppering reaction or by a Cu(2+)-mediated Glaser homocoupling reaction.
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.

Alkanes from Bioderived Furans by using Metal Triflates and Palladium-Catalyzed Hydrodeoxygenation of Cyclic Ethers.

Science.gov (United States)

Song, Hai-Jie; Deng, Jin; Cui, Min-Shu; Li, Xing-Long; Liu, Xin-Xin; Zhu, Rui; Wu, Wei-Peng; Fu, Yao

2015-12-21

Using a metal triflate and Pd/C as catalysts, alkanes were prepared from bioderived furans in a one-pot hydrodeoxygenation (HDO) process. During the reaction, the metal triflate plays a crucial role in the ring-opening HDO of furan compounds. The entire reaction process has goes through two major phases: at low temperatures, saturation of the exocyclic double bond and furan ring are catalyzed by Pd/C; at high temperatures, the HDO of saturated furan compounds is catalyzed by the metal triflate. The reaction mechanism was verified by analyzing the changes of the intermediates during the reaction. In addition, different metal triflates, solvents, and catalyst recycling were also investigated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Enhanced bromate formation during chlorination of bromide-containing waters in the presence of CuO: Catalytic disproportionation of hypobromous acid

KAUST Repository

Liu, Chao; von Gunten, Urs; Croue, Jean-Philippe

2012-01-01

of bromide-containing waters in the presence of cupric oxide (CuO). CuO was effective to catalyze hypochlorous acid (HOCl) or hypobromous acid (HOBr) decay (e.g., at least 104 times enhancement for HOBr at pH 8.6 by 0.2 g L-1 CuO). Significant halate
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.
A versatile method for the preparation of conjugates of peptides with DNA/PNA/analog by employing chemo-selective click reaction in water

Science.gov (United States)

Gogoi, Khirud; Mane, Meenakshi V.; Kunte, Sunita S.; Kumar, Vaijayanti A.

2007-01-01

The specific 1,3 dipolar Hüisgen cycloaddition reaction known as ‘click-reaction’ between azide and alkyne groups is employed for the synthesis of peptide–oligonucleotide conjugates. The peptide nucleic acids (PNA)/DNA and peptides may be appended either by azide or alkyne groups. The cycloaddition reaction between the azide and alkyne appended substrates allows the synthesis of the desired conjugates in high purity and yields irrespective of the sequence and functional groups on either of the two substrates. The versatile approach could also be employed to generate the conjugates of peptides with thioacetamido nucleic acid (TANA) analog. The click reaction is catalyzed by Cu (I) in either water or in organic medium. In water, ∼3-fold excess of the peptide-alkyne/azide drives the reaction to completion in 2 h with no side products. PMID:17981837
Dissociation pathways of a single dimethyl disulfide on Cu(111): Reaction induced by simultaneous excitation of two vibrational modes

Energy Technology Data Exchange (ETDEWEB)

Motobayashi, Kenta, E-mail: kmotobayashi@cat.hokudai.ac.jp [Catalysis Research Center, Hokkaido University, Sapporo 001-0021 (Japan); Department of Advanced Materials Science, The University of Tokyo, Kashiwa 277-8561 (Japan); Surface and Interface Science Laboratory, RIKEN, Wako 351-0198 (Japan); Kim, Yousoo [Surface and Interface Science Laboratory, RIKEN, Wako 351-0198 (Japan); Arafune, Ryuichi [International Center for Materials Nanoarchitectonics, National Institute for Materials Science, Tsukuba 305-0044 (Japan); Ohara, Michiaki; Ueba, Hiromu; Kawai, Maki, E-mail: maki@k.u-tokyo.ac.jp [Department of Advanced Materials Science, The University of Tokyo, Kashiwa 277-8561 (Japan)

2014-05-21

We present a novel reaction mechanism for a single adsorbed molecule that proceeds via simultaneous excitation of two different vibrational modes excited by inelastic tunneling electrons from a scanning tunneling microscope. Specifically, we analyze the dissociation of a single dimethyl disulfide (DMDS, (CH{sub 3}S){sub 2}) molecule on Cu(111) by using a versatile theoretical method, which permits us to simulate reaction rates as a function of sample bias voltage. The reaction is induced by the excitation of C-H stretch and S-S stretch modes by a two-electron process at low positive bias voltages. However, at increased voltages, the dissociation becomes a single-electron process that excites a combination mode of these stretches, where excitation of the C-H stretch is the energy source and excitation of the S-S stretch mode enhances the anharmonic coupling rate. A much smaller dissociation yield (few orders of magnitude) at negative bias voltages is understood in terms of the projected density of states of a single DMDS on Cu(111), which reflects resonant excitation through the molecular orbitals.
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
Infrared laser induced organic reactions. 2. Laser vs. thermal inducment of unimolecular and hydrogen bromide catalyzed bimolecular dehydration of alcohols

International Nuclear Information System (INIS)

Danen, W.C.

1979-01-01

It has been demonstrated that a mixture of reactant molecules can be induced by pulsed infrared laser radiation to react via a route which is totally different from the pathway resulting from heating the mixture at 300 0 C. The high-energy unimolecular elimination of H 2 O from ethanol in the presence of 2-propanol and HBr can be selectively induced with a pulsed CO 2 laser in preference to either a lower energy bimolecular HBr-catalyzed dehydration or the more facile dehydration of 2-propanol. Heating the mixture resulted in the almost exclusive reaction of 2-propanol to produce propylene. It was demonstrated that the bimolecular ethanol + HBr reaction cannot be effectively induced by the infrared laser radiation as evidenced by the detrimental effect on the yield of ethylene as the HBr pressure was increased. The selective, nonthermal inducement of H 2 O elimination from vibrationally excited ethanol in the presence of 2-propanol required relatively low reactant pressures. At higher pressures intermolecular V--V energy transfer allowed the thermally more facile dehydration from 2-propanol to become the predominant reaction channel
Excitation function of (p,α) nuclear reaction on enriched {sup 67}Zn. Possibility of production of {sup 64}Cu at low energy cyclotron

Energy Technology Data Exchange (ETDEWEB)

Szelecsenyi, Ferenc; Kovacs, Zoltan [Hungarian Academy of Sciences, Debrecen (Hungary). Cyclotron Application Dept.; Nagatsu, Kotaro; Zhang, Ming-Rong; Suzuki, Kazutosi [National Institute of Radiological Sciences, Chiba (Japan). Molecular Imaging Center

2014-09-01

The potential for production of the medically relevant {sup 64}Cu has been investigated by proton irradiation of highly enriched {sup 67}Zn targets. The excitation function of the {sup 67}Zn(p,α){sup 64}Cu a nuclear reaction was measured by the stacked-foil technique up to 30 MeV. The prediction of the TALYS code was also compared to the measured cross section results. Based on the improved database of the {sup 67}Zn(p,α){sup 64}Cu reaction, thick target yield as a function of energy was also deduced. Production possibility of {sup 64}Cu is discussed in detail, employing different energy proton beams and with regards to the {sup 61}Cu and {sup 67}Cu contamination levels as a function of the target enrichment level. By using 1 μA beam intensity, 6.3505 h irradiation time and enriched {sup 67}Zn target ({sup 64}Zn ≤ 0.5%, {sup 66}Zn ≤ 9%, {sup 67}Zn ≥ 80%, {sup 68}Zn ≤ 10% and {sup 70}Zn ≤ 0.5%), the expected EOB (End Of bombardment) yields are 43.66, 88.80 and 156.14MBq/μA at 12, 15 and 18 MeV proton energies, respectively. Application time-frames were also deduced where the total radio-copper contamination level remains below 1%. (orig.)
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).
Reaction mechanisms and rate constants of waste degradation in landfill bioreactor systems with enzymatic-enhancement.

Science.gov (United States)

Jayasinghe, P A; Hettiaratchi, J P A; Mehrotra, A K; Kumar, S

2014-06-01

Augmenting leachate before recirculation with peroxidase enzymes is a novel method to increase the available carbon, and therefore the food supply to microorganisms at the declining phase of the anaerobic landfill bioreactor operation. In order to optimize the enzyme-catalyzed leachate recirculation process, it is necessary to identify the reaction mechanisms and determine rate constants. This paper presents a kinetic model developed to ascertain the reaction mechanisms and determine the rate constants for enzyme catalyzed anaerobic waste degradation. The maximum rate of reaction (Vmax) for MnP enzyme-catalyzed reactors was 0.076 g(TOC)/g(DS).day. The catalytic turnover number (k(cat)) of the MnP enzyme-catalyzed was 506.7 per day while the rate constant (k) of the un-catalyzed reaction was 0.012 per day. Copyright © 2014 Elsevier Ltd. All rights reserved.
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.
Treatment of reverse osmosis (RO) concentrate by the combined Fe/Cu/air and Fenton process (1stFe/Cu/air-Fenton-2ndFe/Cu/air).

Science.gov (United States)

Ren, Yi; Yuan, Yue; Lai, Bo; Zhou, Yuexi; Wang, Juling

2016-01-25

To decompose or transform the toxic and refractory reverse osmosis (RO) concentrate and improve the biodegradability, 1stFe/Cu/air-Fenton-2ndFe/Cu/air were developed to treat RO concentrate obtained from an amino acid production plant in northern China. First, their operating conditions were optimized thoroughly. Furthermore, 5 control experiments were setup to confirm the superiority of 1stFe/Cu/air-Fenton-2ndFe/Cu/air and synergistic reaction between Fe/Cu/air and Fenton. The results suggest that the developed method could obtain high COD removal (65.1%) and BOD5/COD ratio (0.26) due to the synergistic reaction between Fe/Cu/air and Fenton. Under the optimal conditions, the influent and effluent of 1stFe/Cu/air-Fenton-2ndFe/Cu/air and 5 control experiments were analyzed by using UV, FTIR, EEM and LC, which confirm the superiority of 1stFe/Cu/air-Fenton-2ndFe/Cu/air. Therefore, the developed method in this study is a promising process for treatment of RO concentrate. Copyright © 2015 Elsevier B.V. All rights reserved.
Partial Cross Sections of Neutron-Induced Reactions on nCu at En = 6, 8, 10, 12, 14, and 16 MeV for 0νββ Background Studies

Science.gov (United States)

Gooden, M. E.; Fallin, B. A.; Finch, S. W.; Kelley, J. H.; Howell, C. R.; Rusev, G.; Tonchev, A. P.; Tornow, W.; Stanislav, V.

2014-05-01

Partial cross-section measurements of (n,n'γ) reactions on natCu were carried out at TUNL using monoenergetic neutrons at six energies of En = 6, 8, 10, 12, 14, 16 MeV. These studies were performed to provide accurate cross-section data on materials abundant in experimental setups involving HPGe detectors used to search for rare events, like the neutrino-less double-beta decay of 76Ge. Spallation and (α,n) neutrons are expected to cause the largest source of external background in the energy region of interest. At TUNL pulsed neutron beams were produced via the 2H(d,n)3He reaction and the deexcitation γ rays from the reaction natCu(n,xγ) were detected with clover HPGe detectors. Cross-section results for the strongest transtions in 63Cu and 65Cu will be reported, and will compared to model calculations and to data recently obtained at LANL with a white neutron beam.
Cu catalyzed oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran and 2,5-furandicarboxylic acid under benign reaction conditions

DEFF Research Database (Denmark)

Hansen, Thomas S.; Sádaba, Irantzu; Garcia, Eduardo

2013-01-01

containing promoters (NCPs) to obtain excellent yields. In acetonitrile a 95% DFF yield was obtained after 24h with ambient pressure of dioxygen at room temperature in the presence of different NCPs, which – to our knowledge – is the best result reported thus far for this reaction. The use of NCPs made...... it further possible to apply various traditional solvents, e.g. acetone, methanol and methyl isobutyl ketone for the reaction. The latter can be used as extraction solvent for HMF synthesis in aqueous media and thus integrate the two processes. Additionally, HMF was oxidized to 2,5-furandicarboxylic acid...
Reactive scattering of H2 from Cu(100): comparison of dynamics calculations based on the specific reaction parameter approach to density functional theory with experiment.

Science.gov (United States)

Sementa, L; Wijzenbroek, M; van Kolck, B J; Somers, M F; Al-Halabi, A; Busnengo, H F; Olsen, R A; Kroes, G J; Rutkowski, M; Thewes, C; Kleimeier, N F; Zacharias, H

2013-01-28

We present new experimental and theoretical results for reactive scattering of dihydrogen from Cu(100). In the new experiments, the associative desorption of H(2) is studied in a velocity resolved and final rovibrational state selected manner, using time-of-flight techniques in combination with resonance-enhanced multi-photon ionization laser detection. Average desorption energies and rotational quadrupole alignment parameters were obtained in this way for a number of (v = 0, 1) rotational states, v being the vibrational quantum number. Results of quantum dynamics calculations based on a potential energy surface computed with a specific reaction parameter (SRP) density functional, which was derived earlier for dihydrogen interacting with Cu(111), are compared with the results of the new experiments and with the results of previous molecular beam experiments on sticking of H(2) and on rovibrationally elastic and inelastic scattering of H(2) and D(2) from Cu(100). The calculations use the Born-Oppenheimer and static surface approximations. With the functional derived semi-empirically for dihydrogen + Cu(111), a chemically accurate description is obtained of the molecular beam experiments on sticking of H(2) on Cu(100), and a highly accurate description is obtained of rovibrationally elastic and inelastic scattering of D(2) from Cu(100) and of the orientational dependence of the reaction of (v = 1, j = 2 - 4) H(2) on Cu(100). This suggests that a SRP density functional derived for H(2) interacting with a specific low index face of a metal will yield accurate results for H(2) reactively scattering from another low index face of the same metal, and that it may also yield accurate results for H(2) interacting with a defected (e.g., stepped) surface of that same metal, in a system of catalytic interest. However, the description that was obtained of the average desorption energies, of rovibrationally elastic and inelastic scattering of H(2) from Cu(100), and of the
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.
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.
Tuning Catalytic Performance through a Single or Sequential Post-Synthesis Reaction(s) in a Gas Phase

Energy Technology Data Exchange (ETDEWEB)

Shan, Junjun [Department; Department; Zhang, Shiran [Department; Department; Choksi, Tej [Department; Nguyen, Luan [Department; Department; Bonifacio, Cecile S. [Department; Li, Yuanyuan [Department; Zhu, Wei [Department; Department; College; Tang, Yu [Department; Department; Zhang, Yawen [College; Yang, Judith C. [Department; Greeley, Jeffrey [Department; Frenkel, Anatoly I. [Department; Tao, Franklin [Department; Department

2016-12-05

Catalytic performance of a bimetallic catalyst is determined by geometric structure and electronic state of the surface or even the near-surface region of the catalyst. Here we report that single and sequential postsynthesis reactions of an as-synthesized bimetallic nanoparticle catalyst in one or more gas phases can tailor surface chemistry and structure of the catalyst in a gas phase, by which catalytic performance of this bimetallic catalyst can be tuned. Pt–Cu regular nanocube (Pt–Cu RNC) and concave nanocube (Pt–Cu CNC) are chosen as models of bimetallic catalysts. Surface chemistry and catalyst structure under different reaction conditions and during catalysis were explored in gas phase of one or two reactants with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The newly formed surface structures of Pt–Cu RNC and Pt–Cu CNC catalysts strongly depend on the reactive gas(es) used in the postsynthesis reaction(s). A reaction of Pt–Cu RNC-as synthesized with H2 at 200 °C generates a near-surface alloy consisting of a Pt skin layer, a Cu-rich subsurface, and a Pt-rich deep layer. This near-surface alloy of Pt–Cu RNC-as synthesized-H2 exhibits a much higher catalytic activity in CO oxidation in terms of a low activation barrier of 39 ± 4 kJ/mol in contrast to 128 ± 7 kJ/mol of Pt–Cu RNC-as synthesized. Here the significant decrease of activation barrier demonstrates a method to tune catalytic performances of as-synthesized bimetallic catalysts. A further reaction of Pt–Cu RNC-as synthesized-H2 with CO forms a Pt–Cu alloy surface, which exhibits quite different catalytic performance in CO oxidation. It suggests the capability of generating a different surface by using another gas. The capability of tuning surface chemistry and structure of bimetallic catalysts was also demonstrated in restructuring of Pt–Cu CNC-as synthesized.
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.
An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

Energy Technology Data Exchange (ETDEWEB)

Svelle, Stian

2004-07-01

The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

High spin states in 62Cu

International Nuclear Information System (INIS)

Tsan Ung Chan; Agard, M.; Bruandet, J.F.; Giorni, A.; Glasser, F.; Longequeue, J.P.; Morand, C.

1977-06-01

The 62 Cu nucleus has been studied via the reactions 60 Ni(α,pnγ), 63 Cu(p,pnγ), 52 Cr( 14 N,2p2nγ) using different in beam γ-spectroscopy techniques. The intensity of the principal γ-lines observed in different reactions leading to the 62 Cu has been compared. A brief discussion is made in terms of the independent particle model. A level scheme including levels with spin up to 9 + is proposed [fr
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.
Radiolabeling and biodistribution of 62Cu-dithiocarbamate

International Nuclear Information System (INIS)

Matsumoto, Kazuya; Fujibayashi, Yasuhisa; Yokoyama, Akira; Konishi, Junji.

1990-01-01

The newly developed 62 Zn/ 62 Cu generator system has made available the production of the short-lived 62 Cu (T 1/2 = 9.8 min) positron radionuclide, eluted as 62 Cu-glycine. In the search for 62 Cu labeled radiopharmaceuticals for positron CT (PET) brain diagnostic studies, two ligands N,N-diethyl- and N,N-dimethyl-dithiocarbamic acid (DDC and DmDC) were selected, based on their Cu chelating abilities and the neutral lipophilic character of their copper chelates. In the present work, an in vitro study with non-radioactive Cu-glycine showed that both ligands easily formed the stable, neutral Cu-DDC and Cu-DmDC chelates (1:2 metal-ligand complexes) based on the ligand exchange reaction. Then the 62 Zn/ 62 Cu generator eluate, the 62 Cu-glycine was used for the radiolabeling of DDC and DmDC. The following HPLC analysis revealed that the ligand exchange reaction proceeded rapidly; the radiochemical purities of 62 Cu-DDC and 62 Cu-DmDC were extremely high (non-detectable 62 Cu-glycine) and both chelates were more lipophilic than 62 Cu-glycine. The mouse biodistribution of both radiolabeled compounds, 62 Cu-DDC and 62 Cu-DmDC indicated a brain accumlation of 2.8 and 5.3 times higher than 62 Cu-glycine, 15 min post injection, respectively. The brain accumulation observed with both 62 Cu-DDC and 62 Cu-DmDC might be due to their stable, neutral and lipophilic character; the latter enhanced by the presence of the methylated side chains. The gathered results indicated the applicability of dithiocarbamic acid derivatives in the production of new 62 Cu-labeled compounds using the 62 Zn/ 62 Cu generator system based on the ligand exchange reaction with 62 Cu-glycine eluate. Further studies with Cu-dithiocarbamic acid derivatives for development of new generator-produced 62 Cu positron radiopharmaceuticals can be recalled. (author)
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.
Expanding P450 catalytic reaction space through evolution and engineering

Science.gov (United States)

McIntosh, John A.; Farwell, Christopher C.; Arnold, Frances H.

2014-01-01

Advances in protein and metabolic engineering have led to wider use of enzymes to synthesize important molecules. However, many desirable transformations are not catalyzed by any known enzyme, driving interest in understanding how new enzymes can be created. The cytochrome P450 enzyme family, whose members participate in xenobiotic metabolism and natural products biosynthesis, catalyzes an impressive range of difficult chemical reactions that continues to grow as new enzymes are characterized. Recent work has revealed that P450-derived enzymes can also catalyze useful reactions previously accessible only to synthetic chemistry. The evolution and engineering of these enzymes provides an excellent case study for how to genetically encode new chemistry and expand biology’s reaction space. PMID:24658056
Computational study for the circular redox reaction of N2O with CO catalyzed by fullerometallic cations C60Fe+ and C70Fe.

Science.gov (United States)

Anafcheh, Maryam; Naderi, Fereshteh; Khodadadi, Zahra; Ektefa, Fatemeh; Ghafouri, Reza; Zahedi, Mansour

2017-03-01

We applied density functional calculations to study the circular redox reaction mechanism of N 2 O with CO catalyzed by fullerometallic cations C 60 Fe + and C 70 Fe + . The on-top sites of six-membered rings (η 6 ) of fullerene cages are the most preferred binding sites for Fe + cation, and the hexagon to pentagon migration of Fe + is unlikely under ambient thermodynamic conditions. The initial ion/molecule reaction, N 2 O rearrangement and N 2 abstraction on the considered fullerometallic cations are easier than those on the bare Fe + cation in the gas phase. Generally, our results indicate that fullerometallic ions, C 60 Fe + and C 70 Fe + , are more favorable substrates for redox reaction of N 2 O with CO in comparison to the other previously studied carbon nanostructures such as graphene and nanotubes. Copyright © 2016 Elsevier Inc. All rights reserved.
DNA and Protein Requirements for Substrate Conformational Changes Necessary for Human Flap Endonuclease-1-catalyzed Reaction*

Science.gov (United States)

Algasaier, Sana I.; Exell, Jack C.; Bennet, Ian A.; Thompson, Mark J.; Gotham, Victoria J. B.; Shaw, Steven J.; Craggs, Timothy D.; Finger, L. David; Grasby, Jane A.

2016-01-01

Human flap endonuclease-1 (hFEN1) catalyzes the essential removal of single-stranded flaps arising at DNA junctions during replication and repair processes. hFEN1 biological function must be precisely controlled, and consequently, the protein relies on a combination of protein and substrate conformational changes as a prerequisite for reaction. These include substrate bending at the duplex-duplex junction and transfer of unpaired reacting duplex end into the active site. When present, 5′-flaps are thought to thread under the helical cap, limiting reaction to flaps with free 5′-termini in vivo. Here we monitored DNA bending by FRET and DNA unpairing using 2-aminopurine exciton pair CD to determine the DNA and protein requirements for these substrate conformational changes. Binding of DNA to hFEN1 in a bent conformation occurred independently of 5′-flap accommodation and did not require active site metal ions or the presence of conserved active site residues. More stringent requirements exist for transfer of the substrate to the active site. Placement of the scissile phosphate diester in the active site required the presence of divalent metal ions, a free 5′-flap (if present), a Watson-Crick base pair at the terminus of the reacting duplex, and the intact secondary structure of the enzyme helical cap. Optimal positioning of the scissile phosphate additionally required active site conserved residues Tyr40, Asp181, and Arg100 and a reacting duplex 5′-phosphate. These studies suggest a FEN1 reaction mechanism where junctions are bound and 5′-flaps are threaded (when present), and finally the substrate is transferred onto active site metals initiating cleavage. PMID:26884332
Aza Cope Rearrangement of Propargyl Enammonium Cations Catalyzed By a Self-Assembled `Nanozyme

Energy Technology Data Exchange (ETDEWEB)

Hastings, Courntey J.; Fiedler, Dorothea; Bergman, Robert G.; Raymond, Kenneth N.

2008-02-27

The tetrahedral [Ga{sub 4}L{sub 6}]{sup 12-} assembly (L = N,N-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene) encapsulates a variety of cations, including propargyl enammonium cations capable of undergoing the aza Cope rearrangement. For propargyl enammonium substrates that are encapsulated in the [Ga{sub 4}L{sub 6}]{sup 12-} assembly, rate accelerations of up to 184 are observed when compared to the background reaction. After rearrangement, the product iminium ion is released into solution and hydrolyzed allowing for catalytic turnover. The activation parameters for the catalyzed and uncatalyzed reaction were determined, revealing that a lowered entropy of activation is responsible for the observed rate enhancements. The catalyzed reaction exhibits saturation kinetics; the rate data obey the Michaelis-Menten model of enzyme kinetics, and competitive inhibition using a non-reactive guest has been demonstrated.
Novel Platinum-Catalyzed Ring-Opening of 1,2-Cyclopropanated Sugars with Alcohols

DEFF Research Database (Denmark)

Beyer, Jürgen; Madsen, Robert

1998-01-01

Reaction of 1,2-cyclopropanated sugars with a catalytic amount ofZeise's dimer [Pt(C2H4)Cl2]2 and an alcohol gives 2-C-branched glycosides by a novel platinum catalyzed ring-opening. A wide variety of alcohols can participate in this ring-opening reaction giving 2-C-branched glycosides ranging from...
Evaluation of copper slag to catalyze advanced oxidation processes for the removal of phenol in water

International Nuclear Information System (INIS)

Huanosta-Gutiérrez, T.; Dantas, Renato F.; Ramírez-Zamora, R.M.; Esplugas, S.

2012-01-01

Highlights: ► We evaluate the use of an industrial residue (copper slag) as catalyst in water treatment. ► The copper slag was effective to remove organic pollutants (phenol) from water. ► During experimentation, Cu and Fe leaching were not higher than the acceptable levels. ► Slag/H 2 O 2 /UV and slag/H 2 O 2 treatments promoted biodegradability increment of the contaminated water. ► The control of the reaction time would minimize the environmental impact of the produced effluents in terms of acute toxicity. - Abstract: The aim of this work was to evaluate the use of copper slag to catalyze phenol degradation in water by advanced oxidation processes (AOPs). Copper slag was tested in combination with H 2 O 2 (slag/H 2 O 2 ) and H 2 O 2 /UV (slag/H 2 O 2 /UV). The studied methods promoted the complete photocatalytic degradation of phenol. Besides, they were able to reduce about 50% the TOC content in the samples. Slag/H 2 O 2 /UV and slag/H 2 O 2 treatments have favored biodegradability increment along the reaction time. Nevertheless, the irradiated method achieved higher values of the biodegradability indicator (BOD 5 /TOC). The toxicity assessment indicated the formation of more toxic compounds in both treatments. However, the control of the reaction time would minimize the environmental impact of the effluents.
A density functional theory study of partial oxidation of propylene on Cu2O(0 0 1) and CuO(0 0 1) surfaces

Science.gov (United States)

Düzenli, Derya; Atmaca, Deniz Onay; Gezer, Miray Gülbiter; Onal, Isik

2015-11-01

This work theoretically investigates propylene epoxidation reaction on Cu2O(0 0 1) and CuO(0 0 1) surfaces using periodical DFT method to determine the active copper species within the reaction mechanism. The transition states and energy profiles are calculated for the formation of surface intermediates such as oxametallopropylene (OMP) over Cu2O(0 0 1) and oxygen bridging (OB) over CuO(0 0 1) and allylic H-stripping reaction (AHS) over both surfaces as well as for formation of products. Propylene oxide (PO) and acetone are obtained through OMP and OB surface intermediates and acrolein generation is observed through allylic H-stripping reaction (AHS). The calculations revealed that the corresponding surface intermediates for epoxidation reaction need to overcome an activation barrier of 13 kcal/mol over CuO surface whereas they occur without an energy barrier over Cu2O surface indicating the higher activity of Cu+ species. Acrolein is also found to be a thermodynamically more favorable product for both surfaces especially over CuO surface due to the presence of more surface oxygen atoms on which the basicity has been evaluated by the adsorption of sulfur dioxide. This indicates that the lattice oxygen inherent in both surface types does not participate in PO production.
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.
Surface structure and reaction property of CuCl2-PdCl2 bimetallic catalyst in methanol oxycarbonylation: A DFT approach

International Nuclear Information System (INIS)

Meng, Qingsen; Wang, Shengping; Shen, Yongli; Yan, Bing; Wu, Yuanxin; Ma, Xinbin

2014-01-01

Surface structure of CuCl 2 -PdCl 2 bimetallic catalyst (Wacker-type catalyst) was built employing density functional theory (DFT) calculations, and the reaction mechanism of methanol oxycarbonylation over the CuCl 2 -PdCl 2 surfaces was also investigated. On the CuCl 2 -PdCl 2 surface, the active site for methanol oxidation was confirmed as Cu-Cl-Cu (Pd). Comparing with pure CuCl 2 surface, the introduction of Pd atom causes the electron repopulation on the surface and lowers the energy barrier for methanol oxidation, but the number of the active site decreases with the increasing of Pd doping volume. Agreed with previous experimental results, the Pd site is most favorable for the CO insertion, indicated by the lowest activation barrier for the formation of COOCH 3 on Pd atom. The lowest energy barrier for the formation of DMC appears when COOCH 3 species adsorbed on Pd atom and methoxyl adsorbed on Cu atoms, which is 0.42 eV. Finally, the reconstruction of the unsaturated surface is a spontaneous and exothermic process. Comparing with other surfaces, the rate-limiting step, methanol oxidation, on CuCl 2 -PdCl 2 surface with Pd/Cu = 1:17 has the lowest energy barrier, which is agreed with the experimental observation that PdCl 2 -CuCl 2 catalyst with Pd/Cu = 1:20 has the favorable activity. The adsorbed methoxyl will further lower the activation barrier of methanol oxidation, which is agreed with experimental observation that the Wacker-type catalysts have an induction period in the methanol oxidative carbonylation system.
Parameters affecting incorporation and by-product formation during the production of structured phospholipids by lipase-catalyzed acidolysis in solvent free system

DEFF Research Database (Denmark)

Vikbjerg, Anders Falk; Mu, Huiling; Xu, Xuebing

2005-01-01

By-product formation is a serious problem in the lipase-catalyzed acyl exchange of phospholipids (PL). By-products are formed due to parallel hydrolysis reactions and acyl migration in the reaction system. A clear elucidation of these side reactions is important for practical operation in order...... to minimize by-products during reaction. In the present study we examined the Lipozyme RM IM-catalyzed acidolysis for the production of structured phospholipids between phosphatidylcholine (PC) and caprylic acid in the solvent free system. A five-factor response surface design was used to evaluate...
Combined experimental and theoretical approach to understand the reactivity of a mononuclear Cu(II)-hydroperoxo complex in oxygenation reactions.

Science.gov (United States)

Kamachi, Takashi; Lee, Yong-Min; Nishimi, Tomonori; Cho, Jaeheung; Yoshizawa, Kazunari; Nam, Wonwoo

2008-12-18

A copper(II) complex bearing a pentadentate ligand, [Cu(II)(N4Py)(CF(3)SO(3))(2)] (1) (N4Py = N,N-bis(2-pyridylmethyl)bis(2-pyridyl)methylamine), was synthesized and characterized with various spectroscopic techniques and X-ray crystallography. A mononuclear Cu(II)-hydroperoxo complex, [Cu(II)(N4Py)(OOH)](+) (2), was then generated in the reaction of 1 and H(2)O(2) in the presence of base, and the reactivity of the intermediate was investigated in the oxidation of various substrates at -40 degrees C. In the reactivity studies, 2 showed a low oxidizing power such that 2 reacted only with triethylphosphine but not with other substrates such as thioanisole, benzyl alcohol, 1,4-cyclohexadiene, cyclohexene, and cyclohexane. In theoretical work, we have conducted density functional theory (DFT) calculations on the epoxidation of ethylene by 2 and a [Cu(III)(N4Py)(O)](+) intermediate (3) at the B3LYP level. The activation barrier is calculated to be 39.7 and 26.3 kcal/mol for distal and proximal oxygen attacks by 2, respectively. This result indicates that the direct ethylene epoxidation by 2 is not a plausible pathway, as we have observed in the experimental work. In contrast, the ethylene epoxidation by 3 is a downhill and low-barrier process. We also found that 2 cannot be a precursor to 3, since the homolytic cleavage of the O-O bond of 2 is very endothermic (i.e., 42 kcal/mol). On the basis of the experimental and theoretical results, we conclude that a mononuclear Cu(II)-hydroperoxo species bearing a pentadentate N5 ligand is a sluggish oxidant in oxygenation reactions.
Facile synthesis of Cu2O/CuO/RGO nanocomposite and its superior cyclability in supercapacitor

International Nuclear Information System (INIS)

Wang, Kun; Dong, Xiangmao; Zhao, Chongjun; Qian, Xiuzhen; Xu, Yunlong

2015-01-01

A reduced graphene oxide (RGO)-based nanocomposite of redox counterpart of the oxides of Cu(I)-Cu(II) pair for Faradaic reaction, Cu 2 O/CuO/RGO, was controllably synthesized through a facile, eco-friendly one-step hydrothermal-assisted redox reaction of elemental Cu and graphene oxide (GO) without the addition of any other reagents. The resultant Cu 2 O/CuO/RGO nanocomposites were characterized by X-ray diffraction (XRD), Raman spectroscopy, Thermogravimetric analysis (TG), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM). It is found that, when dealloyed nanoporous Cu was used as a Cu source, the uniform spherical Cu 2 O/CuO nanoparticles with double size scales (∼25 nm and ∼5 nm) were anchored on RGO sheets. This Cu 2 O/CuO/RGO nanocomposite redox counterpart exhibits improved rate capability and excellent cycling stability, i.e., only ca. 21.4% of the capacity was lost when the discharge current density increases from 1 A g −1 (173.4 F g −1 ) to 10 A g −1 (136.3 F g −1 ). Especially, the capacity remains almost unchanged (98.2%) after 100,000 cycles at 10 A g −1 . The good electrochemical performance and simple accessibility prove that this Cu 2 O/CuO/RGO composite consisting of a pair of redox counterparts is a promising material for supercapacitor applications
Eosin Y photoredox catalyzed net redox neutral reaction for regiospecific annulation to 3-sulfonylindoles via anion oxidation of sodium sulfinate salts.

Science.gov (United States)

Rohokale, Rajendra S; Tambe, Shrikant D; Kshirsagar, Umesh A

2018-01-24

An eosin Y photoredox catalyzed net redox neutral process for 3-sulfonylindoles via the anionic oxidation of sodium sulfinate salts and its radical cascade cyclization with 2-alkynyl-azidoarenes was developed with visible light as a mediator. The reaction offers metal and oxidant/reductant free, visible light mediated vicinal sulfonamination of alkynes to 2-aryl/alkyl-3-sulfonylindoles and proceeds via the generation of a sulfur-centered radical through direct oxidation of the sulfinate anion by an excited photocatalyst with a reductive quenching cycle. The mild conditions, use of an organic dye as photo-catalyst, bench stability and easily accessible starting materials make the present approach green and attractive.
A copper-catalyzed bioleaching process for enhancement of cobalt dissolution from spent lithium-ion batteries

International Nuclear Information System (INIS)

Zeng, Guisheng; Deng, Xiaorong; Luo, Shenglian; Luo, Xubiao; Zou, Jianping

2012-01-01

Highlights: ► Catalytic ion was first applied to the bioleaching process of spent lithium-ion batteries. ► The bioleaching efficiency was great improved from 43.1% to 99.9% in the presence of copper ion. ► A new reaction model was proposed to explain the catalytic mechanism. - Abstract: A copper-catalyzed bioleaching process was developed to recycle cobalt from spent lithium-ion batteries (mainly LiCoO 2 ) in this paper. The influence of copper ions on bioleaching of LiCoO 2 by Acidithiobacillus ferrooxidans (A.f) was investigated. It was shown that almost all cobalt (99.9%) went into solution after being bioleached for 6 days in the presence of 0.75 g/L copper ions, while only 43.1% of cobalt dissolution was obtained after 10 days without copper ions. EDX, XRD and SEM analyses additionally confirmed that the cobalt dissolution from spent lithium-ion batteries could be improved in the presence of copper ions. The catalytic mechanism was investigated to explain the enhancement of cobalt dissolution by copper ions, in which LiCoO 2 underwent a cationic interchange reaction with copper ions to form CuCo 2 O 4 on the surface of the sample, which could be easily dissolved by Fe 3+ .
Diffusion characteristics in the Cu-Ti system

Energy Technology Data Exchange (ETDEWEB)

Laik, Arijit; Kale, Gajanan Balaji [Bhabha Atomic Reseach Centre, Mumbai (India). Materials Science Div.; Bhanumurthy, Karanam [Bhabha Atomic Reseach Centre, Mumbai (India). Scientific Information Resource Div.; Kashyap, Bhagwati Prasad [Indian Institute of Technology Bombay, Mumbai (India). Dept. of Metallurgical Engineering

2012-06-15

The formation and growth of intermetallic compounds by diffusion reaction of Cu and Ti were investigated in the temperature range 720 - 860 C using bulk diffusion couples. Only four, out of the seven stable intermediate compounds of the Cu-Ti system, were formed in the diffusion reaction zone in the sequence CuTi, Cu{sub 4}Ti, Cu{sub 4}Ti{sub 3} and CuTi{sub 2}. The activation energies required for the growth of these compounds were determined. The diffusion characteristics of Cu{sub 4}Ti, CuTi and Cu{sub 4}Ti{sub 3} and Cu(Ti) solid solution were evaluated. The activation energies for diffusion in these compounds were 192.2, 187.7 and 209.2 kJ mol{sup -1} respectively, while in Cu(Ti), the activation energy increased linearly from 201.0 kJ mol{sup -1} to 247.5 kJ mol{sup -1} with increasing concentration of Ti, in the range 0.5 - 4.0 at.%. The impurity diffusion coefficient of Ti in Cu and its temperature dependence were also estimated. A correlation between the impurity diffusion parameters for several elements in Cu matrix has been established. (orig.)
The natural catalytic function of CuGE glucuronoyl esterase in hydrolysis of genuine lignin-carbohydrate complexes from birch

DEFF Research Database (Denmark)

Mosbech, Caroline; Holck, Jesper; Meyer, Anne S.

2018-01-01

Glucuronoyl esterases belong to carbohydrate esterase family 15 and catalyze de-esterification. Their natural function is presumed to be cleavage of ester linkages in lignin-carbohydrate complexes particularly those linking lignin and glucuronoyl residues in xylans in hardwood. Here, we show...... for the first time a detailed product profile of aldouronic acids released from birchwood lignin by a glucuronoyl esterase from the white-rot fungus Cerrena unicolor (CuGE). CuGE releases substrate for GH10 endo-xylanase which results in significantly increased product release compared to the action of endo......-xylanase alone. CuGE also releases neutral xylo-oligosaccharides that can be ascribed to the enzymes feruloyl esterase side activity as demonstrated by release of ferulic acid from insoluble wheat arabinoxylan. The data verify the enzyme's unique ability to catalyze removal of all glucuronoxylan associated...

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