Preparation of fluorinated biaryls through direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates

KAUST Repository

Fang, Xin; Huang, Yuanyuan; Chen, Xiaoqing; Lin, Xiaoxi; Bai, Zhengshuai; Huang, Kuo-Wei; Yuan, Yaofeng; Weng, Zhiqiang

2013-01-01

The direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates gave the desired products of fluorinated biaryls in good to excellent yields. A diverse set of important functional groups including methoxy, aldehyde, ester

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

KAUST Repository

Morandi, Bill

2013-01-16

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

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

KAUST Repository

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

2013-01-01

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

A Palladium-Catalyzed Vinylcyclopropane (3 + 2) Cycloaddition Approach to the Melodinus Alkaloids

KAUST Repository

Goldberg, Alexander F. G.

2011-08-19

A palladium-catalyzed (3+2) cycloaddition of a vinylcyclopropane and a β-nitrostyrene is employed to rapidly assemble the cyclopentane core of the Melodinus alkaloids. The ABCD ring system of the natural product family is prepared in six steps from commercially available materials.

Synthesis of Nitriles via Palladium-Catalyzed Water Shuffling from Amides to Acetonitrile

OpenAIRE

Zhang, Wandi; Haskins, Christopher W.; Yang, Yang; Dai, Mingji

2014-01-01

Palladium-catalyzed synthesis of nitriles from amides has been described. Two similar, but complementary reaction conditions have been identified to convert various amides including α,β,γ,δ-unsaturated amides, cinnamides, aromatic amides and alkyl amides to the corresponding nitriles in good to excellent yield.

Synthesis of nitriles via palladium-catalyzed water shuffling from amides to acetonitrile.

Science.gov (United States)

Zhang, Wandi; Haskins, Christopher W; Yang, Yang; Dai, Mingji

2014-12-07

Palladium-catalyzed synthesis of nitriles from amides has been described. Two similar, but complementary reaction conditions have been identified to convert various amides including α,β,γ,δ-unsaturated amides, cinnamides, aromatic amides and alkyl amides to the corresponding nitriles in good to excellent yield.

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

Science.gov (United States)

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

2018-03-07

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

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

Science.gov (United States)

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

2016-11-29

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

Atroposelective Synthesis of Axially Chiral Biaryls by Palladium-Catalyzed Asymmetric C-H Olefination Enabled by a Transient Chiral Auxiliary.

Science.gov (United States)

Yao, Qi-Jun; Zhang, Shuo; Zhan, Bei-Bei; Shi, Bing-Feng

2017-06-01

Atroposelective synthesis of axially chiral biaryls by palladium-catalyzed C-H olefination, using tert-leucine as an inexpensive, catalytic, and transient chiral auxiliary, has been realized. This strategy provides a highly efficient and straightforward access to a broad range of enantioenriched biaryls in good yields (up to 98 %) with excellent enantioselectivities (95 to >99 % ee). Kinetic resolution of trisubstituted biaryls bearing sterically more demanding substituents is also operative, thus furnishing the optically active olefinated products with excellent selectivity (95 to >99 % ee, s-factor up to 600). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of chiral terminal-alkene-phosphine hybrid ligands for palladium-catalyzed asymmetric allylic substitutions.

Science.gov (United States)

Liu, Zhaoqun; Du, Haifeng

2010-07-02

A variety of novel chiral terminal-alkene-phosphine hybrid ligands were successfully developed from diethyl L-tartrate for palladium-catalyzed asymmetric allylic alkylations, etherifications, and amination to give the desired products in excellent yields and ee's.

Memory effects in palladium-catalyzed allylic Alkylations of 2-cyclohexen-1-yl acetate

DEFF Research Database (Denmark)

Svensen, Nina; Fristrup, Peter; Tanner, David Ackland

2007-01-01

The objective of this work was to characterize the enantiospecificity of the allylic alkylation of enantioenriched 2-cyclohexen-1-yl acetate with the enolate ion of dimethyl malonate catalyzed by unsymmetrical palladium catalysts. The precatalysts employed were (eta(3)-allyl)PdLCl, where L...

Palladium-Catalyzed Carbenylative Cross-Coupling and Carbenylative Amination Utilizing Vinylcarbenes

OpenAIRE

Agee, Christopher

2017-01-01

This work focuses on the use of N-tosylhydrazones derived from α,β-unsaturated aldehydes – precursors to vinylcarbene ligands – in palladium-catalyzed carbenylative cross-coupling and carbenylative amination reactions. These carbenylative reactions were used to form η3-allylpalladium intermediates that generate stereogenic centers at the carbene center. An initial acyclic model system was used to intercept a well-known prochiral 1,3-diphenylallyl intermediate to probe the feasibility of enant...

Preparation of fluorinated biaryls through direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates

KAUST Repository

Fang, Xin

2013-07-01

The direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates gave the desired products of fluorinated biaryls in good to excellent yields. A diverse set of important functional groups including methoxy, aldehyde, ester, nitro and halide can be well tolerated in the protocol. © 2013 Elsevier B.V. All rights reserved.

QuadraPure-Supported Palladium Nanocatalysts for Microwave-Promoted Suzuki Cross-Coupling Reaction under Aerobic Condition

Directory of Open Access Journals (Sweden)

Kin Hong Liew

2014-01-01

Full Text Available Cross-linked resin-captured palladium (XL-QPPd was readily prepared by simple physical adsorption onto the high loading QuadraPure macroporous resin and a subsequent reduction process. To enhance the mechanical stability, entrapped palladium nanocatalysts were cross-linked with succinyl chloride. Both transmission electron microscopy images and X-ray diffraction analysis revealed that the palladium nanoparticles were well dispersed with diameters ranging in 4–10 nm. The catalyst performed good catalytic activity in microwave-promoted Suzuki cross-coupling reactions in water under aerobic condition with mild condition by using various aryl halides and phenylboronic acid. In addition, the catalyst showed an excellent recyclability without significant loss of catalytic activity.

Palladium(II)-catalyzed ortho-olefination of arenes applying sulfoxides as remote directing groups.

Science.gov (United States)

Wang, Binjie; Shen, Chuang; Yao, Jinzhong; Yin, Hong; Zhang, Yuhong

2014-01-03

A novel palladium-catalyzed ortho-C(sp(2))-H olefination protocol has been developed by the use of sulfoxide as the directing group. Importantly, relatively remote coordination can be accessed to achieve the ortho olefination of benzyl, 2-arylethyl, and 3-arylpropenyl sulfoxide substrates, and the olefinated sulfoxide can be easily transformed to other functionalities.

Palladium-Catalyzed Tandem Oxidative Arylation/Olefination of Aromatic Tethered Alkenes/Alkynes.

Science.gov (United States)

Gao, Yang; Gao, Yinglan; Wu, Wanqing; Jiang, Huanfeng; Yang, Xiaobo; Liu, Wenbo; Li, Chao-Jun

2017-01-18

We describe herein a palladium-catalyzed tandem oxidative arylation/olefination reaction of aromatic tethered alkenes/alkynes for the synthesis of dihydrobenzofurans and 2 H-chromene derivatives. This reaction features a 1,2-difunctionalization of C-C π-bond with two C-H bonds using O 2 as terminal oxidant at room temperature. The products obtained are valuable synthons and important scaffolds in biological agents and natural products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

KAUST Repository

Petersen, Kimberly S.

2011-06-01

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

Palladium-catalyzed hydrodehalogenation of 1,2,4,5-tetrachlorobenzene in water-ethanol mixtures

International Nuclear Information System (INIS)

Wee, Hun-Young; Cunningham, Jeffrey A.

2008-01-01

Palladium-catalyzed hydrodehalogenation (HDH) was applied for destroying 1,2,4,5-tetrachlorobenzene (TeCB) in mixtures of water and ethanol. This investigation was performed as a critical step in the development of a new technology for clean-up of soil contaminated by halogenated hydrophobic organic contaminants. The main goals of the investigation were to demonstrate the feasibility of the technology, to determine the effect of the solvent composition (water:ethanol ratio), and to develop a model for the kinetics of the dehalogenation process. All experiments were conducted in a batch reactor at ambient temperature under mild hydrogen pressure. The experimental results are all consistent with a Langmuir-Hinshelwood model for heterogeneous catalysis. Major findings that can be interpreted within the Langmuir-Hinshelwood framework include: (1) the rate of hydrodehalogenation depends strongly on the solvent composition, increasing as the water fraction of the solvent increases; (2) the HDH rate increases as the catalyst concentration in the reactor increases; (3) when enough catalyst is present, the HDH reaction appears to follow first-order kinetics, but the kinetics appear to be zero-order at low catalyst concentrations. TeCB is converted rapidly and quantitatively to benzene, with only trace concentrations of 1,2,4-trichlorobenzene appearing as a reactive intermediate. The results obtained here have important implications for the further development of the proposed soil remediation technology, and may also be important for the treatment of other hazardous waste streams

Palladium-catalyzed hydrodehalogenation of 1,2,4,5-tetrachlorobenzene in water-ethanol mixtures

Energy Technology Data Exchange (ETDEWEB)

Wee, Hun-Young [Department of Civil Engineering, Texas A and M University, College Station, TX 77843 (United States); Cunningham, Jeffrey A. [Department of Civil and Environmental Engineering, University of South Florida, Tampa, FL 33620 (United States)], E-mail: cunning@eng.usf.edu

2008-06-30

Palladium-catalyzed hydrodehalogenation (HDH) was applied for destroying 1,2,4,5-tetrachlorobenzene (TeCB) in mixtures of water and ethanol. This investigation was performed as a critical step in the development of a new technology for clean-up of soil contaminated by halogenated hydrophobic organic contaminants. The main goals of the investigation were to demonstrate the feasibility of the technology, to determine the effect of the solvent composition (water:ethanol ratio), and to develop a model for the kinetics of the dehalogenation process. All experiments were conducted in a batch reactor at ambient temperature under mild hydrogen pressure. The experimental results are all consistent with a Langmuir-Hinshelwood model for heterogeneous catalysis. Major findings that can be interpreted within the Langmuir-Hinshelwood framework include: (1) the rate of hydrodehalogenation depends strongly on the solvent composition, increasing as the water fraction of the solvent increases; (2) the HDH rate increases as the catalyst concentration in the reactor increases; (3) when enough catalyst is present, the HDH reaction appears to follow first-order kinetics, but the kinetics appear to be zero-order at low catalyst concentrations. TeCB is converted rapidly and quantitatively to benzene, with only trace concentrations of 1,2,4-trichlorobenzene appearing as a reactive intermediate. The results obtained here have important implications for the further development of the proposed soil remediation technology, and may also be important for the treatment of other hazardous waste streams.

Synthesis of heterocyclic compounds through palladium-catalyzed C-H cyclization processes.

Science.gov (United States)

Inamoto, Kiyofumi

2013-01-01

Herein, we describe our development of synthetic methods for heterocyclic compounds based on the palladium-catalyzed carbon-hydrogen bond (C-H) functionalization/intramolecular carbon-heteroatom (nitrogen or sulfur) bond formation process. By this C-H cyclization method, we efficiently prepared various N-heterocycles, including indazoles, indoles, and 2-quinolinones, as well as S-heterocycles such as benzothiazoles and benzo[b]thiophenes. Yields are typically good to high and good functional-group tolerance is observed for each process, thereby indicating that the method provides a novel, highly applicable synthetic route to the abovementioned biologically important heterocyclic frameworks. As an application of this approach, an auto-tandem-type, one-pot process involving the oxidative Heck reaction and subsequent C-H cyclization using cinnamamides and arylboronic acids as starting materials in the presence of a palladium catalyst was also developed for the rapid construction of the 2-quinolinone nucleus.

A tandem Mannich addition–palladium catalyzed ring-closing route toward 4-substituted-3(2H-furanones

Directory of Open Access Journals (Sweden)

Jubi John

2014-06-01

Full Text Available A facile route towards highly functionalized 3(2H-furanones via a sequential Mannich addition–palladium catalyzed ring closing has been elaborated. The reaction of 4-chloroacetoacetate esters with imines derived from aliphatic and aromatic aldehydes under palladium catalysis afforded 4-substituted furanones in good to excellent yields. 4-Hydrazino-3(2H-furanones could also be synthesized from diazo esters in excellent yields by utilising the developed strategy. We could also efficiently transform the substituted furanones to aza-prostaglandin analogues.

Palladium(II-Catalyzed othro-C–H-Benzoxylation of 2-Arylpyridines by Oxidative Coupling with Aryl Acylperoxides

Directory of Open Access Journals (Sweden)

Wing-Yiu Yu

2013-04-01

Full Text Available A palladium(II-catalyzed ortho-benzoxylation of 2-arylpyridines with aryl acylperoxides was developed. With pyridyl as directing group, the benzoxylation reaction exhibits remarkable regioselectivity and excellent functional group tolerance, providing the products in up to 87% yield.

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.

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.

Mild Palladium Catalyzed ortho C-H Bond Functionalizations of Aniline Derivatives.

Science.gov (United States)

Tischler, Ms Orsolya; Tóth, Mr Balázs; Novák, Zoltán

2017-02-01

This account collects the developments and transformations which avoid the utilization of harsh reaction conditions in the field of palladium catalyzed, ortho-directed C-H activation of aniline derivatives from the first attempts to up-to-date results, including the results of our research laboratory. The discussed functionalizations performed under mild conditions include acylation, olefination, arylation, alkylation, alkoxylation reactions. Beside the optimization studies and the synthetic applications mechanistic investigations are also presented. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Directory of Open Access Journals (Sweden)

Joaquín Tamariz

2013-08-01

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

Palladium-catalyzed C-H olefination of uracils and caffeines using molecular oxygen as the sole oxidant.

Science.gov (United States)

Zhang, Xinyu; Su, Lv; Qiu, Lin; Fan, Zhenwei; Zhang, Xiaofeng; Lin, Shen; Huang, Qiufeng

2017-04-18

The palladium-catalyzed oxidative C-H olefination of uracils or caffeines with alkenes using an atmospheric pressure of molecular oxygen as the sole oxidant has been disclosed. This novel strategy offers an efficient and environmentally friendly method to biologically important C5-alkene uracil derivatives or C8-alkene caffeine derivatives.

Palladium-Catalyzed C-H Functionalization Using Guanidine as a Directing Group: Ortho Arylation and Olefination of Arylguanidines

Science.gov (United States)

Shao, Jiaan; Chen, Wenteng; Giulianotti, Marc A.; Houghten, Richard A.; Yu, Yongping

2012-01-01

Palladium-catalyzed C-H functionalization using guanidine as the directing group was achieved under mild reaction conditions. Various guanidine derivatives were produced in moderate to good yields by using simple unactivated arenes or ethyl acrylate as the source of arylation or olefination respectively. PMID:23095022

Kinetics of catalyzed tritium oxidation in air at ambient temperature

International Nuclear Information System (INIS)

Sherwood, A.E.

1980-01-01

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

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.

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 ...

Mechanistic investigation of the gold-catalyzed aerobic oxidation of alcohols

DEFF Research Database (Denmark)

Fristrup, Peter; Johansen, Louise Bahn; Christensen, Claus Hviid

2008-01-01

The mechanism for the gold-catalyzed aerobic oxidation of alcohols was studied using a series of para-substituted benzyl alcohols (Hammett methodology). The competition experiments clearly show that the rate-determining step of the reaction involves the generation of a partial positive charge in ...

Sulfonium Salts as Alkylating Agents for Palladium-Catalyzed Direct Ortho Alkylation of Anilides and Aromatic Ureas.

Science.gov (United States)

Simkó, Dániel Cs; Elekes, Péter; Pázmándi, Vivien; Novák, Zoltán

2018-02-02

A novel method for the ortho alkylation of acetanilide and aromatic urea derivatives via C-H activation was developed. Alkyl dibenzothiophenium salts are considered to be new reagents for the palladium-catalyzed C-H activation reaction, which enables the transfer of methyl and other alkyl groups from the sulfonium salt to the aniline derivatives under mild catalytic conditions.

Pyrazine-functionalized calix[4]arenes: synthesis by palladium-catalyzed cross-coupling with phosphorus pronucleophiles and metal ion extraction properties

NARCIS (Netherlands)

Nikishkin, N.; Huskens, Jurriaan; Ansari, S.A.; Mohapatra, P.K.; Verboom, Willem

2013-01-01

A series of pyrazine-based calix[4]arene extractants was prepared by a stepwise functionalization, comprising palladium-catalyzed exhaustive cross-coupling of di- and tetrasubstituted calix[4]arenes bearing chloropyrazine moieties. The extraction behavior of the synthesized ligands was studied on

Palladium mixed-metal surface-modified AB₅-type intermetallides enhance hydrogen sorption kinetics

Directory of Open Access Journals (Sweden)

Roman V. Denys

2010-09-01

Full Text Available Surface engineering approaches were adopted in the preparation of advanced hydrogen sorption materials, based on ‘low-temperature’, AB₅-type intermetallides. The approaches investigated included micro-encapsulation with palladium and mixed-metal mantles using electroless plating. The influence of micro-encapsulation on the surface morphology and kinetics of hydrogen charging were investigated. It was found that palladium-nickel (Pd-Ni co-deposition by electroless plating significantly improved the kinetics of hydrogen charging of the AB₅-type intermetallides at low hydrogen pressure and temperature, after long-term pre-exposure to air. The improvement in the kinetics of hydrogen charging was credited to a synergistic effect between the palladium and nickel atoms in the catalytic mantle and the formation of an ‘interfacial bridge’ for hydrogen diffusion by the nickel atoms in the deposited layer. The developed surface-modified materials may find application in highly selective hydrogen extraction, purification, and storage from impure hydrogen feeds.

Copolymerization of carbon monoxide and styrene catalyzed by resin-supported palladium polymer

Directory of Open Access Journals (Sweden)

2007-02-01

Full Text Available Polyketone was prepared by the copolymerization of carbon monoxide (CO and styrene (ST catalyzed by o-phenylenediamine resin-supported palladium acetate. Effects of each catalytic system component such as 2,2’-bipyridine, 1,4-quinone and p-toluene-sulphonate on the copolymerization were investigated. The resin-supported catalyst and the copolymerization product were characterized by infrared spectroscopy (IR, differential scanning calorimetry (DSC, thermogravimetry (TG, X-ray photoelectron spectroscopy (XPS, Scanning Electron Microscopy (SEM. Results indicated that the resin-supported catalyst has excellent catalytic property. Furthermore, partial catalytic activity was maintained after the catalyst was used for five times.

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.

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.

Palladium-catalyzed cyclocarbonylation of o-iodoanilines with heterocumulenes: regioselective preparation of 4(3H)-quinazolinone derivatives

Science.gov (United States)

Larksarp; Alper

2000-05-09

A catalyst system comprising palladium acetate-bidentate phosphine is effective for the cyclocarbonylation of o-iodoanilines with heterocumulenes at 70-100 degrees C for 12-24 h to give the corresponding 4(3H)-quinazolinone derivatives in good yields. Utilizing o-iodoaniline with isocyanates, carbodiimides, and ketenimines for the reaction, 2,4-(1H,3H)-quinazolinediones, 2-amino-4(3H)-quinazolinones and 2-alkyl-4(3H)-quinazolinones were obtained, respectively. The nature of the substrates including the electrophilicity of the carbon center of the carbodiimide, and the stability of the ketenimine, influence the product yields of this reaction. Urea-type intermediates are believed to be generated first in situ from the reaction of o-iodoanilines with heterocumulenes, followed by palladium-catalyzed carbonylation and cyclization to yield the products.

Palladium-Catalyzed ortho-Olefination of Phenyl Acetic and Phenyl Propylacetic Esters via C-H Bond Activation.

Science.gov (United States)

Hu, Jundie; Guan, Mingyu; Han, Jian; Huang, Zhi-Bin; Shi, Da-Qing; Zhao, Yingsheng

2015-08-21

A highly regioselective palladium-catalyzed ester-directed ortho-olefination of phenyl acetic and propionic esters with olefins via C-H bond activation has been developed. A wide variety of phenyl acetic and propionic esters were tolerated in this transformation, affording the corresponding olefinated aromatic compounds. The ortho-olefination of heterocyclic acetic and propionic esters also took place smoothly giving the products in good yields, thus proving the potential utility of this protocol in synthetic chemistry.

Palladium(II)-catalyzed desulfitative synthesis of aryl ketones from sodium arylsulfinates and nitriles: scope, limitations, and mechanistic studies.

Science.gov (United States)

Skillinghaug, Bobo; Sköld, Christian; Rydfjord, Jonas; Svensson, Fredrik; Behrends, Malte; Sävmarker, Jonas; Sjöberg, Per J R; Larhed, Mats

2014-12-19

A fast and efficient protocol for the palladium(II)-catalyzed production of aryl ketones from sodium arylsulfinates and various organic nitriles under controlled microwave irradiation has been developed. The wide scope of the reaction has been demonstrated by combining 14 sodium arylsulfinates and 21 nitriles to give 55 examples of aryl ketones. One additional example illustrated that, through the choice of the nitrile reactant, benzofurans are also accessible. The reaction mechanism was investigated by electrospray ionization mass spectrometry and DFT calculations. The desulfitative synthesis of aryl ketones from nitriles was also compared to the corresponding transformation starting from benzoic acids. Comparison of the energy profiles indicates that the free energy requirement for decarboxylation of 2,6-dimethoxybenzoic acid and especially benzoic acid is higher than the corresponding desulfitative process for generating the key aryl palladium intermediate. The palladium(II) intermediates detected by ESI-MS and the DFT calculations provide a detailed understanding of the catalytic cycle.

Palladium(II)-catalyzed ortho-C-H arylation/alkylation of N-benzoyl α-amino ester derivatives.

Science.gov (United States)

Misal Castro, Luis C; Chatani, Naoto

2014-04-14

The palladium-catalyzed arylation/alkylation of ortho-C-H bonds in N-benzoyl α-amino ester derivatives is described. In such a system both the NH-amido and the CO2R groups in the α-amino ester moieties play a role in successful C-H activation/C-C bond formation using iodoaryl coupling partners. A wide variety of functional groups and electron-rich/deficient iodoarenes are tolerated. The yields obtained range from 20 to 95%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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

2018-04-03

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

Isomerization of 2-butene-1,4-diol in aqueous solutions catalyzed by palladium(II) complexes

Energy Technology Data Exchange (ETDEWEB)

Kalabin, S.M.; Novikov, N.A.; Belov, A.P.

1989-02-01

The authors studied the isomerization of 2-butene-1,4-diol into 3-butene-1,2-diol at 18-25/degree/C. The concentrations of the diol and PdCl/sub 2/ were (1.0-5.0) /times/ 10/sup /minus/2/ mole/liter at 5-10-fold excess amounts of HCl and NaCl. These additives were used because of their inhibiting action on the oxidation of olefinic compounds. 3-Butene-1,2-diol was identified by /sup 1/H NMR method directly in the reaction solutions in which the reaction solutions in which the reactions in D/sub 2/O were carried out. It was found that palladium(II) complexes catalyze the isomerization of 2-butene-1,4-diol into 3-butene-1,2-diol. A mechanism is proposed for the reaction, which includes the intermediate formation of /eta//sup 3/-allyl complex of palladium with a coordinated hydroxyl group.

Halide-Enhanced Catalytic Activity of Palladium Nanoparticles Comes at the Expense of Catalyst Recovery

Directory of Open Access Journals (Sweden)

Azzedine Bouleghlimat

2017-09-01

Full Text Available In this communication, we present studies of the oxidative homocoupling of arylboronic acids catalyzed by immobilised palladium nanoparticles in aqueous solution. This reaction is of significant interest because it shares a key transmetallation step with the well-known Suzuki-Miyaura cross-coupling reaction. Additives can have significant effects on catalysis, both in terms of reaction mechanism and recovery of catalytic species, and our aim was to study the effect of added halides on catalytic efficiency and catalyst recovery. Using kinetic studies, we have shown that added halides (added as NaCl and NaBr can increase the catalytic activity of the palladium nanoparticles more than 10-fold, allowing reactions to be completed in less than half a day at 30 °C. However, this increased activity comes at the expense of catalyst recovery. The results are in agreement with a reaction mechanism in which, under conditions involving high concentrations of chloride or bromide, palladium leaching plays an important role. Considering the evidence for analogous reactions occurring on the surface of palladium nanoparticles under different reaction conditions, we conclude that additives can exert a significant effect on the mechanism of reactions catalyzed by nanoparticles, including switching from a surface reaction to a solution reaction. The possibility of this switch in mechanism may also be the cause for the disagreement on this topic in the literature.

Scope and Limitations of Auxiliary-Assisted, Palladium-Catalyzed Arylation and Alkylation of sp2 and sp3 C-H Bonds

Science.gov (United States)

Nadres, Enrico T.; Santos, Gerson Ivan Franco; Shabashov, Dmitry; Daugulis, Olafs

2013-01-01

The scope of palladium-catalyzed, auxiliary-assisted direct arylation and alkylation of sp2 and sp3 C-H bonds of amine and carboxylic acid derivatives has been investigated. The method employs a palladium acetate catalyst, substrate, aryl, alkyl, benzyl, or allyl halide, and inorganic base in t-amyl alcohol or water solvent at 100-140 °C. Aryl and alkyl iodides as well as benzyl and allyl bromides are competent reagents in this transformation. Picolinic acid auxiliary is used for amine γ-functionalization and 8-aminoquinoline auxiliary is used for carboxylic acid β-functionalization. Some optimization of base, additives, and solvent is required for achieving best results. PMID:24090404

Preparation of 5-acyl- and 5-aryl-substituted 1-(benzyloxy)pyrazoles via directed ortho-lithiation/transmetalation and palladium catalyzed cross- coupling

DEFF Research Database (Denmark)

Kristensen, Jesper Langgaard; Begtrup, M.; Vedsø, P.

1998-01-01

Palladium(0) catalyzed cross-coupling of 1-(benzyloxy)pyrazol-5-ylzinc halides 3a,b, prepared by transmetalation of 1-(benzyloxy)-5-lithiopyrazole (2), with acyl chlorides produced 5 acyl-1-(benzyloxy)pyrazoles 4a-d in high yields. Similar coupling of the pyrazol-5-ylzinc halide with amino-, hydr...

The Homocoupling Reaction of Aromatic Terminal Alkynes by a Highly Active Palladium(II)/AgNO₃ Cocatalyst in Aqueous Media Under Aerobic Conditions.

Science.gov (United States)

Guo, Mengping; Chen, Bo; Lv, Meiyun; Zhou, Xiuling; Wen, Yongju; Shen, Xiuli

2016-05-10

A new and efficient Pd(II)/AgNO₃-cocatalyzed homocoupling of aromatic terminal alkynes is described. Various symmetrical 1,4-disubstituted-1,3-diynes are obtained in good to excellent yields. This protocol employs a loading with relatively low palladium(II) in aqueous media under aerobic conditions.

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.

Interaction of 2-aminopyrimidine with dichloro-[1-alkyl-2-(naphthylazo imidazole]palladium(II complexes : Kinetic and mechanistic studies

Directory of Open Access Journals (Sweden)

Saha Sushanta

2007-10-01

Full Text Available Abstract Background The anticancer properties of cisplatin and palladium(II complexes stem from the ability of the cis-MCl2 fragment to bind to DNA bases. However, cisplatin also interacts with non-cancer cells, mainly through bonding molecules containing -SH groups, resulting in nephrotoxicity. This has aroused interest in the design of palladium(II complexes of improved activity and lower toxicity. The reaction of DNA bases with palladium(II complexes with chelating N,N/donors of the cis-MCl2 configuration constitutes a model system that may help explore the mechanism of cisplatin's anticancer activity. Heterocyclic compounds are found widely in nature and are essential to many biochemical processes. Amongst these naturally occurring compounds, the most thoroughly studied is that of pyrimidine. This was one of the factors that encouraged this study into the kinetics and mechanism of the interaction of 2-aminopyrimidine (2-NH2-Pym with dichloro-{1-alkyl-2-(α-naphthylazoimidazole}palladium(II [Pd(α-NaiRCl2, 1] and dichloro-{1-alkyl-2-(β-naphthylazoimidazole}palladium(II [Pd(β-NaiRCl2, 2] complexes where the alkyl R = Me (a, Et (b, or Bz (c. Results 2-NH2-Pym reacts with 1a, 1b, and 1c to yield [{1-alkyl-2-(α-naphthylazoimidazole}bis(2-aminopyrimidine]palladium(II (3a, 3b, 3c dichloride and with 2a, 2b, and 2c to yield [{1-alkyl-2-(β-naphthylazoimidazole}bis(2-aminopyrimidine]palladium(II (4a, 4b, 4c dichloride in an acetonitrile (MeCN medium. The products were characterized using spectroscopic techniques (FT-IR, UV-Vis, NMR. The ligand substitution reactions follow second order kinetics – first order dependence on the concentration of the Pd(II complex and 2-NH2-Pym. Addition of LiCl to the reaction does not influence its rate. The thermodynamic parameters (standard enthalpy of activation, Δ‡H° and standard entropy of activation, Δ‡S° were determined from variable temperature kinetic studies. The magnitude of the second order

Enhancing the performance of single-chambered microbial fuel cell using manganese/palladium and zirconium/palladium composite cathode catalysts.

Science.gov (United States)

Jadhav, Dipak A; Deshpande, Parag A; Ghangrekar, Makarand M

2017-08-01

Application of ZrO 2 , MnO 2 , palladium, palladium-substituted-zirconium oxide (Zr 0.98 Pd 0.02 O 2 ) and palladium-substituted-manganese oxide (Mn 0.98 Pd 0.02 O 2 ) cathode catalysts in a single-chambered microbial fuel cell (MFC) was explored. The highest power generation (1.28W/m 3 ) was achieved in MFC with Mn 0.98 Pd 0.02 O 2 catalyst, which was higher than that with MnO 2 (0.58W/m 3 ) alone; whereas, MFC having Zr 0.98 Pd 0.02 O 2 catalyzed cathode and non-catalyzed cathode produced powers of 1.02 and 0.23W/m 3 , respectively. Also, low-cost zirconium-palladium-composite showed better catalytic activity and capacitance over ZrO 2 with 20A/m 3 current production and demonstrated its suitability for MFC applications. Cyclic voltammetry analyses showed higher well-defined redox peaks in composite catalysts (Mn/Zr-Pd-C) over other catalyzed MFCs containing MnO 2 or ZrO 2 . Electrochemical behaviour of composite catalysts on cathode showed higher availability of adsorption sites for oxygen reduction and, hence, enhanced the rate of cathodic reactions. Thus, Mn/Zr-Pd-C-based composite catalysts exhibited superior cathodic performance and could be proposed as alternatives to costly Pd-catalyst for field applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Palladium(II-catalyzed Heck reaction of aryl halides and arylboronic acids with olefins under mild conditions

Directory of Open Access Journals (Sweden)

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.

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

Science.gov (United States)

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

2012-11-16

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

Scope and mechanism in palladium-catalyzed isomerizations of highly substituted allylic, homoallylic, and alkenyl alcohols.

Science.gov (United States)

Larionov, Evgeny; Lin, Luqing; Guénée, Laure; Mazet, Clément

2014-12-03

Herein we report the palladium-catalyzed isomerization of highly substituted allylic alcohols and alkenyl alcohols by means of a single catalytic system. The operationally simple reaction protocol is applicable to a broad range of substrates and displays a wide functional group tolerance, and the products are usually isolated in high chemical yield. Experimental and computational mechanistic investigations provide complementary and converging evidence for a chain-walking process consisting of repeated migratory insertion/β-H elimination sequences. Interestingly, the catalyst does not dissociate from the substrate in the isomerization of allylic alcohols, whereas it disengages during the isomerization of alkenyl alcohols when additional substituents are present on the alkyl chain.

Palladium(II)-Catalyzed meta-C-H Olefination: Constructing Multisubstituted Arenes through Homo-Diolefination and Sequential Hetero-Diolefination.

Science.gov (United States)

Bera, Milan; Maji, Arun; Sahoo, Santosh K; Maiti, Debabrata

2015-07-13

Divinylbenzene derivatives represent an important class of molecular building blocks in organic chemistry and materials science. Reported herein is the palladium-catalyzed synthesis of divinylbenzenes by meta-C-H olefination of sulfone-based arenes. Successful sequential olefinations in a position-selective manner provided a novel route for the synthesis of hetero-dialkenylated products, which are difficult to access using conventional methods. Additionally, 1,3,5-trialkenylated compounds can be generated upon successful removal of the directing group. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Palladium-Catalyzed Asymmetric Quaternary Stereocenter Formation

NARCIS (Netherlands)

Gottumukkala, Aditya L.; Matcha, Kiran; Lutz, Martin; de Vries, Johannes G.; Minnaard, Adriaan J.

2012-01-01

An efficient palladium catalyst is presented for the formation of benzylic quaternary stereocenters by conjugate addition of arylboronic acids to a variety of beta,beta-disubstituted carbocyclic, heterocyclic, and acyclic enones. The catalyst is readily prepared from PdCl2, PhBOX, and AgSbF6, and

Palladium-catalyzed asymmetric quaternary stereocenter formation

NARCIS (Netherlands)

Gottumukkala, A.L.; Matcha, K.; Lutz, M.; de Vries, J.G.; Minnaard, A.J.

2012-01-01

An efficient palladium catalyst is presented for the formation of benzylic quaternary stereocenters by conjugate addition of arylboronic acids to a variety of β,β-disubstituted carbocyclic, heterocyclic, and acyclic enones. The catalyst is readily prepared from PdCl2, PhBOX, and AgSbF6, and provides

Kinetics of aerobic cometabolic biodegradation of chlorinated and brominated aliphatic hydrocarbons: A review.

Science.gov (United States)

Jesus, João; Frascari, Dario; Pozdniakova, Tatiana; Danko, Anthony S

2016-05-15

This review analyses kinetic studies of aerobic cometabolism (AC) of halogenated aliphatic hydrocarbons (HAHs) from 2001-2015 in order to (i) compare the different kinetic models proposed, (ii) analyse the estimated model parameters with a focus on novel HAHs and the identification of general trends, and (iii) identify further research needs. The results of this analysis show that aerobic cometabolism can degrade a wide range of HAHs, including HAHs that were not previously tested such as chlorinated propanes, highly chlorinated ethanes and brominated methanes and ethanes. The degree of chlorine mineralization was very high for the chlorinated HAHs. Bromine mineralization was not determined for studies with brominated aliphatics. The examined research period led to the identification of novel growth substrates of potentially high interest. Decreasing performance of aerobic cometabolism were found with increasing chlorination, indicating the high potential of aerobic cometabolism in the presence of medium- and low-halogenated HAHs. Further research is needed for the AC of brominated aliphatic hydrocarbons, the potential for biofilm aerobic cometabolism processes, HAH-HAH mutual inhibition and the identification of the enzymes responsible for each aerobic cometabolism process. Lastly, some indications for a possible standardization of future kinetic studies of HAH aerobic cometabolism are provided. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Gold-catalyzed aerobic epoxidation of trans-stilbene in methylcyclohexane. Part I: Design of a reference catalyst

KAUST Repository

Guillois, Kevin

2012-02-01

The kinetics of the heterogeneous gold-catalyzed aerobic epoxidation of stilbene in the liquid phase has been shown to be hindered by diffusion limitations, due to the use of supports which are unsuitable to apolar reaction media. The choice of these supports is generally dictated by the ability of standard methods of preparation to stabilize highly dispersed gold nanoparticles on them. Hence, new methods need to be designed in order to produce catalytically active gold nanoparticles on hydrophobic supports in general and on passivated silicas in particular. By investigating Tsukuda\\'s method to produce colloidal solutions of gold nanoparticles upon reduction of the triphenylphosphine gold chloride complex in solution, we found that direct reduction of AuPPh3Cl in the presence of a commercially available silica support functionalized with dimethylsiloxane, Aerosil R972, leads, in a highly reproducible and potentially scalable way, to the best catalyst ever reported for this reaction. (C) 2011 Elsevier BM. All rights reserved.

Gold-catalyzed aerobic epoxidation of trans-stilbene in methylcyclohexane. Part I: Design of a reference catalyst

KAUST Repository

Guillois, Kevin; Burel, Laurence; Tuel, Alain; Caps, Valerie

2012-01-01

The kinetics of the heterogeneous gold-catalyzed aerobic epoxidation of stilbene in the liquid phase has been shown to be hindered by diffusion limitations, due to the use of supports which are unsuitable to apolar reaction media. The choice of these supports is generally dictated by the ability of standard methods of preparation to stabilize highly dispersed gold nanoparticles on them. Hence, new methods need to be designed in order to produce catalytically active gold nanoparticles on hydrophobic supports in general and on passivated silicas in particular. By investigating Tsukuda's method to produce colloidal solutions of gold nanoparticles upon reduction of the triphenylphosphine gold chloride complex in solution, we found that direct reduction of AuPPh3Cl in the presence of a commercially available silica support functionalized with dimethylsiloxane, Aerosil R972, leads, in a highly reproducible and potentially scalable way, to the best catalyst ever reported for this reaction. (C) 2011 Elsevier BM. All rights reserved.

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.

Acid-catalyzed kinetics of indium tin oxide etching

Energy Technology Data Exchange (ETDEWEB)

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

2014-08-28

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

Gold-catalyzed aerobic epoxidation of trans-stilbene in methylcyclohexane. Part II: Identification and quantification of a key reaction intermediate

KAUST Repository

Guillois, Kevin

2013-03-01

The gold-catalyzed aerobic oxidations of alkenes are thought to rely on the in situ synthesis of hydroperoxide species, which have however never been clearly identified. Here, we show direct experimental evidence for the presence of 1-methylcyclohexyl hydroperoxide in the aerobic co-oxidation of stilbene and methylcyclohexane catalyzed by the Au/SiO2-R972 optimized catalyst prepared in Part I. Determination of its response in gas chromatography, by triphenylphosphine titration followed by 31P NMR, allows to easily follow its concentration throughout the co-oxidation process and to clearly highlight the simultaneous existence of the methylcyclohexane autoxidation pathway and the stilbene epoxidation pathway. © 2012 Elsevier B.V. All rights reserved.

Gold-catalyzed aerobic epoxidation of trans-stilbene in methylcyclohexane. Part II: Identification and quantification of a key reaction intermediate

KAUST Repository

Guillois, Kevin; Mangematin, Sté phane; Tuel, Alain; Caps, Valerie

2013-01-01

The gold-catalyzed aerobic oxidations of alkenes are thought to rely on the in situ synthesis of hydroperoxide species, which have however never been clearly identified. Here, we show direct experimental evidence for the presence of 1-methylcyclohexyl hydroperoxide in the aerobic co-oxidation of stilbene and methylcyclohexane catalyzed by the Au/SiO2-R972 optimized catalyst prepared in Part I. Determination of its response in gas chromatography, by triphenylphosphine titration followed by 31P NMR, allows to easily follow its concentration throughout the co-oxidation process and to clearly highlight the simultaneous existence of the methylcyclohexane autoxidation pathway and the stilbene epoxidation pathway. © 2012 Elsevier B.V. All rights reserved.

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.

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.

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

NARCIS (Netherlands)

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

2007-01-01

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

Kinetics of aerobic oxidation of volatile sulfur compounds in wastewater and biofilm from sewers

DEFF Research Database (Denmark)

Rudelle, Elise Alice; Vollertsen, Jes; Hvitved-Jacobsen, Thorkild

2013-01-01

Laboratory experiments were conducted to investigate the kinetics of aerobic chemical and biological oxidation of selected odorous volatile sulfur compounds (VSCs) by wastewater and biofilm from sewers. The VSCs included methyl mercaptan (MeSH), ethyl mercaptan (EtSH), dimethyl sulfide (DMS......-spot downstream of a force main and the other was a gravity sewer transporting young aerobic wastewater. The kinetics of VSC oxidation for both wastewater and suspended biofilm samples followed a first-order rate equation. The average values of the reaction rate constants demonstrated the following order...... in the aerobic wastewater....

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

Science.gov (United States)

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

2006-12-01

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

Oxygen Activated, Palladium Nanoparticle Catalyzed, Ultrafast Cross-Coupling of Organolithium Reagents

NARCIS (Netherlands)

Heijnen, Dorus; Tosi, Filippo; Vila, Carlos; Stuart, Marc C. A.; Elsinga, Philip H.; Szymanski, Wiktor; Feringa, Ben L.

2017-01-01

The discovery of an ultrafast cross-coupling of alkyland aryllithium reagents with a range of aryl bromides is presented. The essential role of molecular oxygen to form the active palladium catalyst was established; palladium nanoparticles that are highly active in cross-coupling reactions with

Kinetic Investigations on Pd(II) Catalyzed Oxidation of Some Amino ...

African Journals Online (AJOL)

Kinetic investigations on Pd(II) catalyzed oxidation of dl-serine and dl-threonine by acidic solution of potassium bromate in the presence of mercuric acetate, as a scavenger have been made in the temperature range of 30–45°C. The rate shows zero order kinetics in bromate [BrO3‾] and order of reaction is one with respect ...

Copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines: synthesis of imidazopyridine derivatives.

Science.gov (United States)

Yu, Jipan; Jin, Yunhe; Zhang, Hao; Yang, Xiaobo; Fu, Hua

2013-12-02

A novel, efficient, and practical method for the synthesis of imidazopyridine derivatives has been developed through the copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines with N-(alkylidene)-4H-1,2,4-triazol-4-amines. The procedure occurs by cleavage of the N-N bond in the N-(alkylidene)-4H-1,2,4-triazol-4-amines and activation of an aryl C-H bond in the substituted pyridines. This is the first example of the preparation of imidazopyridine derivatives by using pyridines as the substrates by transition-metal-catalyzed C-H functionalization. This method should provide a novel and efficient strategy for the synthesis of other nitrogen heterocycles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

DEFF Research Database (Denmark)

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

2011-01-01

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

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.

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

Science.gov (United States)

Meng, Guangrong; Szostak, Michal

2016-06-15

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

Synthesis of Conjugated Small Molecules and Polymers by a Palladium Catalyzed Cyclopentannulation Strategy: Towards New Organic Semiconductors

Science.gov (United States)

Bheemireddy, Sambasiva Reddy

The utility of conjugated small molecules and polymers as organic semiconductors have seen a tremendous growth in research and development in academia as well as industry because of their processability and flexibility advantages in comparison to inorganic semiconductors. The extensive research over the years has produced a large number of p-type (hole conducting) and n-type (electron conducting) semiconductors that can be used to construct organic electronic devices. Of these materials, p-type semiconductors are more established and extensively studied because of the ease of preparation as well as their better general stability in comparison to n-type materials. Despite recent research into the development of n-type materials, fullerene (C60 and C 70) and its derivatives are still the predominant materials used as electron acceptors for OPV applications. By taking advantage of the electron accepting behavior of cyclopenta[hi]aceanthrylene fragment of C70, we have designed and synthesized new materials based on cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAHs). By using a newly developed palladium catalyzed cyclopentannulation methodology, 1,2,6,7- tetraarylcyclopenta[hi]aceanthrylenes were prepared by treating diarylethynylenes with 9,10-dibromoanthracene. Scholl cyclodehydrogenation was used to close the externally fused aryl groups to provide access to contorted 2,7,13,18- tetraalkoxytetrabenzo[f,h,r,t]rubicenes. The contortion provides access to more soluble materials than their planar counterparts but still ii allows significant pi-pi stacking between molecules. Using a modified palladium catalyzed cyclopentannulation polymerization followed by a cyclodehydrogenation reaction, a nonconventional synthesis of CP-PAH embedded ladder polymers was also achieved. These ladder polymers possess broad UV-Vis absorptions and narrow optical gaps of 1.17-1.29 eV. The synthesis of new donor-acceptor copolymers incorporating electron accepting 1,2,6,7- tetra(4

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

International Nuclear Information System (INIS)

Wang Haifeng; Lin Zhenquan; Kong Xiangmu

2006-01-01

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

Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

Energy Technology Data Exchange (ETDEWEB)

Nagaraju, D.H., E-mail: dhnagu@gmail.com [Department of Mechanical Engineering, 117 576 (Singapore); Materials Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900 (Saudi Arabia); Devaraj, S. [Department of Mechanical Engineering, 117 576 (Singapore); School of Chemical and Biotechnology, SASTRA University, Thanjavur, 613 401 (India); Balaya, P., E-mail: mpepb@nus.edu.sg [Department of Mechanical Engineering, 117 576 (Singapore); Engineering Science Program, National University of Singapore, 117 576 (Singapore)

2014-12-15

Highlights: • Palladium nanoparticles decorated graphene is synthesized in a single step. • Electro-catalytic activity of Gra/Pd toward alcohol oxidation is evaluated. • 1:1 Gra/Pd exhibits good electro-catalytic activity and efficient electron transfer. - Abstract: Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd{sup 2+} ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl{sub 2}. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells.

Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

International Nuclear Information System (INIS)

Nagaraju, D.H.; Devaraj, S.; Balaya, P.

2014-01-01

Highlights: • Palladium nanoparticles decorated graphene is synthesized in a single step. • Electro-catalytic activity of Gra/Pd toward alcohol oxidation is evaluated. • 1:1 Gra/Pd exhibits good electro-catalytic activity and efficient electron transfer. - Abstract: Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd 2+ ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl 2 . X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells

Electrochemical permeation tests on the kinetics of the hydrogen absorption of palladium and iron

International Nuclear Information System (INIS)

Dafft, E.G.

1977-01-01

Electrochemical permeation tests were performed to investigate the kinetics of the hydrogen development and hydrogen absorption. The cathode side of the samples was galvanostatically cathodically polarized in different electrolyte solutions with and without additions. THe hydrogen atoms diffusing out of the opposite side for iron and α-palladium were oxidized with potentiostatic, sufficiently anodic polarization. The thus registered stationary current is proportional to the hydrogen activity on the cathode side. Test apparatus and conditions are described. The measurements on iron are discussed. (orig./HPOE) [de

Synthesis of Formate Esters and Formamides Using an Au/TiO2-Catalyzed Aerobic Oxidative Coupling of Paraformaldehyde

Directory of Open Access Journals (Sweden)

Ioannis Metaxas

2017-12-01

Full Text Available A simple method for the synthesis of formate esters and formamides is presented based on the Au/TiO2-catalyzed aerobic oxidative coupling between alcohols or amines and formaldehyde. The suitable form of formaldehyde is paraformaldehyde, as cyclic trimeric 1,3,5-trioxane is inactive. The reaction proceeds via the formation of an intermediate hemiacetal or hemiaminal, respectively, followed by the Au nanoparticle-catalyzed aerobic oxidation of the intermediate. Typically, the oxidative coupling between formaldehyde (2 equiv and amines occurs quantitatively at room temperature within 4 h, and there is no need to add a base as in analogous coupling reactions. The oxidative coupling between formaldehyde (typically 3 equiv and alcohols is unprecedented and occurs more slowly, yet in good to excellent yields and selectivity. Minor side-products (2–12% from the acetalization of formaldehyde by the alcohol are also formed. The catalyst is recyclable and can be reused after a simple filtration in five consecutive runs with a small loss of activity.

Palladium-catalyzed aerobic regio- and stereo-selective olefination reactions of phenols and acrylates via direct dehydrogenative C(sp2)-O cross-coupling.

Science.gov (United States)

Wu, Yun-Bin; Xie, Dan; Zang, Zhong-Lin; Zhou, Cheng-He; Cai, Gui-Xin

2018-04-26

An efficient olefination protocol for the oxidative dehydrogenation of phenols and acrylates has been achieved using a palladium catalyst and O2 as the sole oxidant. This reaction exhibits high regio- and stereo-selectivity (E-isomers) with moderate to excellent isolated yields and a wide substrate scope (32 examples) including ethyl vinyl ketone and endofolliculina.

Enzyme catalyzed oxidative gelation of sugar beet pectin: Kinetics and rheology

DEFF Research Database (Denmark)

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

2012-01-01

Sugar beet pectin (SBP) is a marginally utilized co-processing product from sugar production from sugar beets. In this study, the kinetics of oxidative gelation of SBP, taking place via enzyme catalyzed cross-linking of ferulic acid moieties (FA), was studied using small angle oscillatory...

Quantitative proteomics reveals the kinetics of trypsin-catalyzed protein digestion.

Science.gov (United States)

Pan, Yanbo; Cheng, Kai; Mao, Jiawei; Liu, Fangjie; Liu, Jing; Ye, Mingliang; Zou, Hanfa

2014-10-01

Trypsin is the popular protease to digest proteins into peptides in shotgun proteomics, but few studies have attempted to systematically investigate the kinetics of trypsin-catalyzed protein digestion in proteome samples. In this study, we applied quantitative proteomics via triplex stable isotope dimethyl labeling to investigate the kinetics of trypsin-catalyzed cleavage. It was found that trypsin cleaves the C-terminal to lysine (K) and arginine (R) residues with higher rates for R. And the cleavage sites surrounded by neutral residues could be quickly cut, while those with neighboring charged residues (D/E/K/R) or proline residue (P) could be slowly cut. In a proteome sample, a huge number of proteins with different physical chemical properties coexists. If any type of protein could be preferably digested, then limited digestion could be applied to reduce the sample complexity. However, we found that protein abundance and other physicochemical properties, such as molecular weight (Mw), grand average of hydropathicity (GRAVY), aliphatic index, and isoelectric point (pI) have no notable correlation with digestion priority of proteins.

The influence of pH adjustment on kinetics parameters in tapioca wastewater treatment using aerobic sequencing batch reactor system

Science.gov (United States)

Mulyani, Happy; Budianto, Gregorius Prima Indra; Margono, Kaavessina, Mujtahid

2018-02-01

The present investigation deals with the aerobic sequencing batch reactor system of tapioca wastewater treatment with varying pH influent conditions. This project was carried out to evaluate the effect of pH on kinetics parameters of system. It was done by operating aerobic sequencing batch reactor system during 8 hours in many tapioca wastewater conditions (pH 4.91, pH 7, pH 8). The Chemical Oxygen Demand (COD) and Mixed Liquor Volatile Suspended Solids (MLVSS) of the aerobic sequencing batch reactor system effluent at steady state condition were determined at interval time of two hours to generate data for substrate inhibition kinetics parameters. Values of the kinetics constants were determined using Monod and Andrews models. There was no inhibition constant (Ki) detected in all process variation of aerobic sequencing batch reactor system for tapioca wastewater treatment in this study. Furthermore, pH 8 was selected as the preferred aerobic sequencing batch reactor system condition in those ranging pH investigated due to its achievement of values of kinetics parameters such µmax = 0.010457/hour and Ks = 255.0664 mg/L COD.

The impact of surface composition on Tafel kinetics leading to enhanced electrochemical insertion of hydrogen in palladium

Science.gov (United States)

Dmitriyeva, Olga; Hamm, Steven C.; Knies, David L.; Cantwell, Richard; McConnell, Matt

2018-05-01

Our previous work experimentally demonstrated the enhancement of electrochemical hydrogen insertion into palladium by modifying the chemical composition of the cathode surface with Pb, Pt and Bi, referred to as surface promoters. The experiment demonstrated that an optimal combination of the surface promoters led to an increase in hydrogen fugacity of more than three orders of magnitude, while maintaining the same current density. This manuscript discusses the application of Density Functional Theory (DFT) to elucidate the thermodynamics and kinetics of observed enhancement of electrochemical hydrogen insertion into palladium. We present theoretical simulations that: (1) establish the elevation of hydrogen's chemical potential on Pb and Bi surfaces to enhance hydrogen insertion, (2) confirm the increase of a Tafel activation barrier that results in a decrease of the reaction rate at the given hydrogen overpotential, and (3) explain why the surface promoter's coverage needs to be non-uniform, namely to allow hydrogen insertion into palladium bulk while simultaneously locking hydrogen below the surface (the corking effect). The discussed DFT-based method can be used for efficient scanning of different material configurations to design a highly effective hydrogen storage system.

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.

Cobalt/N-Hydroxyphthalimide(NHPI)-Catalyzed Aerobic Oxidation of Hydrocarbons with Ionic Liquid Additive

DEFF Research Database (Denmark)

Mahmood, Sajid; Xu, Bao Hua; Ren, Tian Lu

2018-01-01

A highly efficient and solvent-free system of cobalt/NHPI-catalyzed aerobic oxidation of hydrocarbons was developed using imidazolium-based ionic liquid (IL) as an additive. These amphipathic ILs were found self-assemble at the interface between the organic hydrocarbons and the aqueous phase...... the optimum reactivity. Besides, the interfacial boundary between aqueous and organic phase composed by C2-alkylated imidazolium ILs, such as [bdmim]SbF6 and [C12dmim]SbF6, not only has ternary aggregates (hydrocarbons/IL/H2O) of higher stability but renders O2 a faster diffusion rate and higher concentration......, thereby offering a high reactivity of the protocol towards hydrocarbon oxidation....

Aerobic Biodegradation Kinetics And Mineralization Of Six Petrodiesel/Soybean-Biodiesel Blends

Science.gov (United States)

The aerobic biodegradation kinetics and mineralization of six petrodiesel/soybean-biodiesel blends (B0, B20, B40, B60, B80, and B100), where B100 is 100% biodiesel, were investigated by acclimated cultures. The fatty acid methyl esters (FAMEs) of biodiesel were found to undergo ...

Highly efficient hydrogen storage system based on ammonium bicarbonate/formate redox equilibrium over palladium nanocatalysts.

Science.gov (United States)

Su, Ji; Yang, Lisha; Lu, Mi; Lin, Hongfei

2015-03-01

A highly efficient, reversible hydrogen storage-evolution process has been developed based on the ammonium bicarbonate/formate redox equilibrium over the same carbon-supported palladium nanocatalyst. This heterogeneously catalyzed hydrogen storage system is comparable to the counterpart homogeneous systems and has shown fast reaction kinetics of both the hydrogenation of ammonium bicarbonate and the dehydrogenation of ammonium formate under mild operating conditions. By adjusting temperature and pressure, the extent of hydrogen storage and evolution can be well controlled in the same catalytic system. Moreover, the hydrogen storage system based on aqueous-phase ammonium formate is advantageous owing to its high volumetric energy density. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

Energy Technology Data Exchange (ETDEWEB)

Miah, Md. Rezwan, E-mail: mrmche@yahoo.co [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Masud, Jahangir [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Ohsaka, Takeo, E-mail: ohsaka@echem.titech.ac.j [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)

2010-12-15

In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H{sub 2}O as the final product.

Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

International Nuclear Information System (INIS)

Miah, Md. Rezwan; Masud, Jahangir; Ohsaka, Takeo

2010-01-01

In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H 2 O as the final product.

Kinetics of the biodegradation of green table olive wastewaters by aerobic and anaerobic treatments

International Nuclear Information System (INIS)

Beltran, J.; Gonzalez, T.; Garcia, J.

2008-01-01

The biodegradation of the organic pollutant matter present in green table olive wastewater (GTOW) is studied in batch reactors by an aerobic biodegradation and by an anaerobic digestion. In the aerobic biodegradation, the evolution of the substrate (in terms of chemical and biochemical oxygen demand), biomass, and total polyphenolic compounds present in the wastewater are followed during the process, and a kinetic study is performed using Contois' model, which when applied to the experimental results provides the kinetic parameter of this model, resulting in a modified Contois' equation (q = 3.3S/(0.31S 0 X + X), gCOD/gVSS d -1 ). Other kinetic parameters were determined: the cellular yield coefficient (Y X/S = 5.7 x 10 -2 gVSS/gCOD) and the kinetic constant of cellular death phase (k d = 0.16 d -1 ). Similarly, in the anaerobic digestion, the evolution of the substrate digested and the methane produced are followed, and the kinetic study is conducted using a modified Monod model combined with the Levenspiel model, due to the presence of inhibition effects. This model leads to the determination of the kinetic parameters: kinetic constant when no inhibitory substance is present (k M0 = 8.4 x 10 -2 h -1 ), critical substrate concentration of inhibition (TP* = 0.34 g/L) and inhibitory parameter (n = 2.25)

Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

KAUST Repository

Nagaraju, Doddahalli H.

2014-12-01

Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd2+ ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl2. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells. © 2014 Elsevier Ltd.

The electrocatalytical reduction of m-nitrophenol on palladium nanoparticles modified glassy carbon electrodes

International Nuclear Information System (INIS)

Shi Qiaofang; Diao Guowang

2011-01-01

Highlights: ► The deposition of palladium on a GC electrode was performed by cyclic voltammetry. ► SEM images showed palladium nanoparticles deposited on a glassy carbon (GC) electrode. ► The Pd/GC electrode can effectively catalyze m-nitrophenol in aqueous media. ► The reduction of m-nitrophenol on the Pd/GC electrode depended on potential and pH. ► XPS spectra of the Pd/GC electrodes demonstrated the presence of palladium. - Abstract: Palladium nanoparticles modified glassy carbon electrodes (Pd/GC) were prepared via the electrodeposition of palladium on a glassy carbon (GC) electrode using cyclic voltammetry in different sweeping potential ranges. The scanning electron microscope images of palladium particles on the GC electrodes indicate that palladium particles with diameters of 20–50 nm were homogeneously dispersed on the GC electrode at the optimal deposition conditions, which can effectively catalyze the reduction of m-nitrophenol in aqueous solutions, but their catalytic activities are strongly related to the deposition conditions of Pd. The X-ray photoelectron spectroscopy spectra of the Pd/GC electrode confirmed that 37.1% Pd was contained in the surface composition of the Pd/GC electrode. The cyclic voltammograms of the Pd/GC electrode in the solution of m-nitrophenol show that the reduction peak of m-nitrophenol shifts towards the more positive potentials, accompanied with an increase in the peak current compared to the bare GC electrode. The electrocatalytic activity of the Pd/GC electrode is affected by pH values of the solution. In addition, the electrolysis of m-nitrophenol under a constant potential indicates that the reduction current of m-nitrophenol on the Pd/GC electrode is approximately 20 times larger than that on the bare GC electrode.

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.

Ru (III) Catalyzed Oxidation of Aliphatic Ketones by N-Bromosuccinimide in Aqueous Acetic Acid: A Kinetic Study

Science.gov (United States)

Giridhar Reddy, P.; Ramesh, K.; Shylaja, S.; Rajanna, K. C.; Kandlikar, S.

2012-01-01

Kinetics of Ru (III) catalyzed oxidation of aliphatic ketones such as acetone, ethyl methyl ketone, diethyl ketone, iso-butylmethyl ketone by N-bromosuccinimide in the presence of Hg(II) acetate have been studied in aqueous acid medium. The order of [N-bromosuccinimide] was found to be zero both in catalyzed as well as uncatalyzed reactions. However, the order of [ketone] changed from unity to a fractional one in the presence of Ru (III). On the basis of kinetic features, the probable mechanisms are discussed and individual rate parameters evaluated. PMID:22654610

A Recyclable Palladium-Catalyzed Synthesis of 2-Methylene-2,3-Dihydrobenzofuran-3-ols by Cycloisomerization of 2-(1-Hydroxyprop-2-ynylphenols in Ionic Liquids

Directory of Open Access Journals (Sweden)

Bartolo Gabriele

2013-09-01

Full Text Available A recyclable palladium-catalyzed synthesis of 2-methylene-2,3-dihydrobenzofuran-3-ols 2 by heterocyclization of 2-(1-hydroxyprop-2-ynylphenols 1 in an ionic liquid medium (BmimBF4 is presented. The process takes place under relatively mild conditions (100 °C, 5 h in the presence of catalytic amounts (2 mol % of PdI2 in conjunction with KI (5 equiv with respect to PdI2 and an organic base, such as morpholine (1 equiv with respect to 1, to give 2 in high yields (70%–86%. The PdI2-KI catalytic system could be recycled up to six times without appreciable loss of activity. Moreover, products 2 could be easily converted in a one-pot fashion into 2-hydroxymethylbenzofurans 3 (52%–71%, based on 1 and 2-methoxymethylbenzofurans 4 (52%–80%, based on 1 by acid-catalyzed allylic isomerization or allylic nucleophilic substitution.

Kinetics of transesterification of methyl acetate and n-octanol catalyzed by cation exchange resins

Energy Technology Data Exchange (ETDEWEB)

Liu, Yong; Gao, Li; Li, Xiying; Mao, Liqun [Henan University, Kaifeng (China); Wei, Min [Henan University of Technology, Zhengzhou (China)

2013-05-15

The transesterification kinetics of methyl acetate with n-octanol to octyl acetate and methanol were studied using Amberlyst 15 as catalyst in a batch stirred reactor. The influence of the agitation speed, particle size, temperature, catalyst loading, and initial reactants molar ratio was investigated in detail. A pseudo-homogeneous (PH) kinetic model was applied to correlate the experimental data in the temperature range of 313.15 K to 328.15 K. The estimated kinetic parameters made the calculated results in good agreement with the experimental data. A kinetic model describing the transesterification reaction catalyzed by cation exchange resins was developed.

Acid base catalyzed transesterification kinetics of waste cooking oil

Energy Technology Data Exchange (ETDEWEB)

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

2011-01-15

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

Mn-Catalyzed Highly Efficient Aerobic Oxidative Hydroxyazidation of Olefins: A Direct Approach to β-Azido Alcohols.

Science.gov (United States)

Sun, Xiang; Li, Xinyao; Song, Song; Zhu, Yuchao; Liang, Yu-Feng; Jiao, Ning

2015-05-13

An efficient Mn-catalyzed aerobic oxidative hydroxyazidation of olefins for synthesis of β-azido alcohols has been developed. The aerobic oxidative generation of azido radical employing air as the terminal oxidant is disclosed as the key process for this transformation. The reaction is appreciated by its broad substrate scope, inexpensive Mn-catalyst, high efficiency, easy operation under air, and mild conditions at room temperature. This chemistry provides a novel approach to high value-added β-azido alcohols, which are useful precursors of aziridines, β-amino alcohols, and other important N- and O-containing heterocyclic compounds. This chemistry also provides an unexpected approach to azido substituted cyclic peroxy alcohol esters. A DFT calculation indicates that Mn catalyst plays key dual roles as an efficient catalyst for the generation of azido radical and a stabilizer for peroxyl radical intermediate. Further calculation reasonably explains the proposed mechanism for the control of C-C bond cleavage or for the formation of β-azido alcohols.

(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.

Microrespirometric determination of the effectiveness factor and biodegradation kinetics of aerobic granules degrading 4-chlorophenol as the sole carbon source

Energy Technology Data Exchange (ETDEWEB)

Vital-Jacome, Miguel [Department of Biotechnology and Bioengineering, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional (Cinvestav-IPN), Av. IPN 2508, 07360 México DF, México (Mexico); Buitrón, Germán; Moreno-Andrade, Ivan; Garcia-Rea, Victor [Laboratory for Research on Advanced Process for Water Treatment, Unidad Académica Juriquilla, Instituto de Ingeniería, Universidad Nacional Autónoma de México, Blvd. Juriquilla 3001, Querétaro 76320, México (Mexico); Thalasso, Frederic, E-mail: thalasso@cinvestav.mx [Department of Biotechnology and Bioengineering, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional (Cinvestav-IPN), Av. IPN 2508, 07360 México DF, México (Mexico)

2016-08-05

Highlights: • Microrespirometry was used to characterize aerobic granules. • Kinetic parameters for 4-chorophenol degradation were determined. • Intrinsic and apparent kinetic parameters were quantified and contrasted. • Aerobic granules presented lower μ{sub max} and higher K{sub S} than disaggregated granules. • Microrespirometry can be useful in model development and calibration. - Abstract: In this study, a microrespirometric method was used, i.e., pulse respirometry in microreactors, to characterize mass transfer and biodegradation kinetics in aerobic granules. The experimental model was an aerobic granular sludge in a sequencing batch reactor (SBR) degrading synthetic wastewater containing 4-chlorophenol as the sole carbon source. After 15 days of acclimation, the SBR process degraded 4-chlorophenol at a removal rate of up to 0.9 kg COD m{sup −3} d{sup −1}, and the degradation kinetics were well described by the Haldane model. The microrespirometric method consisted of injecting pulses of 4-chlorophenol into the 24 wells of a microreactor system containing the SBR samples. From the respirograms obtained, the following five kinetic parameters were successfully determined during reactor operation: (i) Maximum specific oxygen uptake rate, (ii) substrate affinity constant, (iii) substrate inhibition constant, (iv) maximum specific growth rate, and (v) cell growth yield. Microrespirometry tests using granules and disaggregated granules allowed for the determination of apparent and intrinsic parameters, which in turn enabled the determination of the effectiveness factor of the granular sludge. It was concluded that this new high-throughput method has the potential to elucidate the complex biological and physicochemical processes of aerobic granular biosystems.

Microrespirometric determination of the effectiveness factor and biodegradation kinetics of aerobic granules degrading 4-chlorophenol as the sole carbon source

International Nuclear Information System (INIS)

Vital-Jacome, Miguel; Buitrón, Germán; Moreno-Andrade, Ivan; Garcia-Rea, Victor; Thalasso, Frederic

2016-01-01

Highlights: • Microrespirometry was used to characterize aerobic granules. • Kinetic parameters for 4-chorophenol degradation were determined. • Intrinsic and apparent kinetic parameters were quantified and contrasted. • Aerobic granules presented lower μ_m_a_x and higher K_S than disaggregated granules. • Microrespirometry can be useful in model development and calibration. - Abstract: In this study, a microrespirometric method was used, i.e., pulse respirometry in microreactors, to characterize mass transfer and biodegradation kinetics in aerobic granules. The experimental model was an aerobic granular sludge in a sequencing batch reactor (SBR) degrading synthetic wastewater containing 4-chlorophenol as the sole carbon source. After 15 days of acclimation, the SBR process degraded 4-chlorophenol at a removal rate of up to 0.9 kg COD m"−"3 d"−"1, and the degradation kinetics were well described by the Haldane model. The microrespirometric method consisted of injecting pulses of 4-chlorophenol into the 24 wells of a microreactor system containing the SBR samples. From the respirograms obtained, the following five kinetic parameters were successfully determined during reactor operation: (i) Maximum specific oxygen uptake rate, (ii) substrate affinity constant, (iii) substrate inhibition constant, (iv) maximum specific growth rate, and (v) cell growth yield. Microrespirometry tests using granules and disaggregated granules allowed for the determination of apparent and intrinsic parameters, which in turn enabled the determination of the effectiveness factor of the granular sludge. It was concluded that this new high-throughput method has the potential to elucidate the complex biological and physicochemical processes of aerobic granular biosystems.

Camphyl-based α-diimine palladium complexes: highly efficient precatalysts for direct arylation of thiazoles in open-air.

Science.gov (United States)

Chen, Fu-Min; Lu, Dong-Dong; Hu, Li-Qun; Huang, Ju; Liu, Feng-Shou

2017-07-21

Based on the strategy of the development of phosphine-free palladium-catalyzed direct C-H arylation, a series of camphyl-based α-diimine palladium complexes bearing sterically bulky substituents were synthesized and characterized. The palladium complexes were applied for the cross-coupling of thiazole derivatives with aryl bromides. The effect of the sterically bulky substituent on the N-aryl moiety as well as the reaction conditions was screened. Under the optimal protocols, a wide range of aryl bromides can be smoothly coupled with thiazoles in good to excellent yields in the presence of a low palladium loading of 0.2 mol% under open-air conditions.

Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

KAUST Repository

Dehury, Niranjan; Maity, Niladri; Tripathy, Suman Kumar; Basset, Jean-Marie; Patra, Srikanta

2016-01-01

Herein, we report an unprecedented example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction

Kinetics of catalyzed hydrolysis of 4-methylumbelliferyl caprylate (MUCAP) salmonella reagent

Science.gov (United States)

Al-Kady, Ahmed S.; Ahmed, El-Sadat I.; Gaber, M.; Hussein, Mohamed M.; Ebeid, El-Zeiny M.

2011-09-01

The kinetics of chemical hydrolysis including neutral, acid- and base-catalyzed hydrolysis of 4-methylumbelliferyl caprylate (MUCAP) salmonella reagent were studied at different temperatures. The rate constants and activation parameters were determined by following the build-up of fluorescence peak of the hydrolysis product 4-methylumbelliferone (4-MU). The time scale of esterase enzyme hydrolysis caused by salmonella was compared with chemical hydrolysis as a background process.

Ester versus polyketone formation in the palladium-diphosphine catalyzed carbonylation of ethene.

Science.gov (United States)

Zuidema, Erik; Bo, Carles; van Leeuwen, Piet W N M

2007-04-04

The origin of the chemoselectivity of palladium catalysts containing bidentate phosphine ligands toward either methoxycarbonylation of ethene or the copolymerization of ethene and carbon monoxide was investigated using density functional theory based calculations. For a palladium catalyst containing the electron-donating bis(dimethylphosphino)ethane (dmpe) ligand, the rate determining step for chain propagation is shown to be the insertion of ethene into the metal-acyl bond. The high barrier for chain propagation is attributed to the low stability of the ethene intermediate, (dmpe)Pd(ethene)(C(O)CH3). For the competing methanolysis process, the most likely pathway involves the formation of (dmpe)Pd(CH3OH)(C(O)CH3) via dissociative ligand exchange, followed by a solvent mediated proton-transfer/reductive- elimination process. The overall barrier for this process is higher than the barrier for ethene insertion into the palladium-acetyl bond, in line with the experimentally observed preference of this type of catalyst toward the formation of polyketone. Electronic bite angle effects on the rates of ethene insertion and ethanoyl methanolysis were evaluated using four electronically and sterically related ligands (Me)2P(CH2)nP(Me)2 (n = 1-4). Steric effects were studied for larger tert-butyl substituted ligands using a QM/MM methodology. The results show that ethene coordination to the metal center and subsequent insertion into the palladium-ethanoyl bond are disfavored by the addition of steric bulk around the metal center. Key intermediates in the methanolysis mechanism, on the other hand, are stabilized because of electronic effects caused by increasing the bite angle of the diphosphine ligand. The combined effects explain successfully which ligands give polymer and which ones give methyl propionate as the major products of the reaction.

Studies of Heterogenous Palladium and Related Catalysts for Aerobic Oxidation of Primary Alcohols

Science.gov (United States)

Ahmed, Maaz S.

alcohol solvent and the surface of the catalyst: (listed in order of strength) lone pair-surface (heterocyclic primary alcohols) > pi-surface (aryl primary alcohols) > van der Waals-surface (alkyl primary alcohols). These interactions were previously underappreciated in condensed phase heterogeneously catalyzed aerobic oxidations. Bi and Te serve as synergistic promoters that enhance both the rate and yield of the reactions relative to reactions employing Pd alone or Pd in combination with Bi or with Te as the sole promoter. We report X-ray absorption spectroscopic studies of the heterogenous catalyst. These methods show that the promoters undergo oxidation in preference to Pd, maintaining the Pd surface in the active metallic state and preventing inhibition by surface Pd-oxide formation. The data also suggest formation of a Pd-Te alloy phase that modifies the electronic properties of the Pd catalyst. Collectively, these results provide valuable insights into the synergistic benefits of multiple promoters in heterogeneous catalytic oxidation reactions.

Kinetic Characteristics of Hydrogen Transfer Through Palladium-Modified Membrane

Science.gov (United States)

Petriev, I. S.; Frolov, V. Yu.; Bolotin, S. N.; Baryshev, M. G.; Kopytov, G. F.

2018-01-01

The paper deals with hydrogen transfer through Pd-23%Ag alloy membrane, the surface of which is modified by the electrolytic deposition of highly dispersed palladium. The dependence between the density of hydrogen flow and its excess pressure on the input surface of membrane is well approximated by the first-order curve. This fact indicates that the process of hydrogen permeability is defined by its dissociation on the input surface. Activation energy of this process is 47.9 kJ/mol which considerably exceeds that of the process of hydrogen transfer through palladium (22-30 kJ/mol). This confirms the fact that the chemisorption is a rate-controlling step of the hydrogen transfer through membrane.

Catalyze and chemical inhibition of the R7T7 glass kinetics

International Nuclear Information System (INIS)

Gin, St.; Advocat, Th.

1997-01-01

This article highlights some phenomena likely to modify the glass alteration kinetics and/or the nature of the alteration products according to the chemical composition of the leaching water. It discusses experimental results showing that in neutral and basic media, the presence of inorganic anions or organic acid (simple carboxylic acid and humic acid) has relatively little effect on the long-term glass matrix alterability Actinide mobility appears to be more dependent on the concentration of complexing agents in the leaching solution. The behavior of phosphate ions, which may inhibit or catalyze the R7T7 glass alteration kinetics depending on the experimental conditions, is discussed; the gel microstructure can be related to the glass alteration kinetics by detailed examination of the alteration products. (authors)

Palladium on Carbon-Catalyzed Suzuki-Miyaura Coupling Reaction Using an Efficient and Continuous Flow System

Directory of Open Access Journals (Sweden)

Tomohiro Hattori

2015-01-01

Full Text Available The continuous flow Suzuki-Miyaura reaction between various haloarenes and arylboronic acids was successfully achieved within only ca. 20 s during the single-pass through a cartridge filled with palladium on carbon (Pd/C. No palladium leaching was observed in the collected reaction solution by atomic absorption spectrometry (detection limit: 1 ppm.

Detailed Mechanistic Studies on Palladium-Catalyzed Selective C-H Olefination with Aliphatic Alkenes: A Significant Influence of Proton Shuttling.

Science.gov (United States)

Deb, Arghya; Hazra, Avijit; Peng, Qian; Paton, Robert S; Maiti, Debabrata

2017-01-18

Directing group-assisted regioselective C-H olefination with electronically biased olefins is well studied. However, the incorporation of unactivated olefins has remained largely unsuccessful. A proper mechanistic understanding of olefination involving unactivated alkenes is therefore essential for enhancing their usage in future. In this Article, detailed experimental and computational mechanistic studies on palladium catalyzed C-H olefination with unactivated, aliphatic alkenes are described. The isolation of Pd(II) intermediates is shown to be effective for elucidating the elementary steps involved in catalytic olefination. Reaction rate and order determination, control experiments, isotopic labeling studies, and Hammett analysis have been used to understand the reaction mechanism. The results from these experimental studies implicate β-hydride elimination as the rate-determining step and that a mechanistic switch occurs between cationic and neutral pathway. Computational studies support this interpretation of the experimental evidence and are used to uncover the origins of selectivity.

Palladium-catalyzed regio- and stereoselective cross-addition of terminal alkynes to ynol ethers and synthesis of 1,4-enyn-3-ones.

Science.gov (United States)

Babu, Madala Hari; Dwivedi, Vikas; Kant, Ruchir; Reddy, Maddi Sridhar

2015-03-16

Conjugated enynes, enol ethers, and enynones are versatile building blocks that can be elaborated by a wide variety of synthetic transformations. The selective synthesis of such units is a prerequisite for their effective utilization. The synthesis of conjugated 2-phenoxyenynes through a palladium-catalyzed cross-addition of terminal alkynes to phenylethynyl ethers (hydroalkynylation) is now presented. The reaction is highly regio-, stereo-, and chemoselective, and shows excellent tolerance toward functional groups. The addition further features very mild reaction conditions (room temperature) and an inexpensive catalytic system (without a ligand and with a cheaply available Pd catalyst). The thus synthesized enynyl ethers with allylic hydroxy tethers, which survived the reaction, were shown to be ready precursors for valuable 1-en-4-yn-3-ones. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Isothermal Kinetics of Catalyzed Air Oxidation of Diesel Soot

Directory of Open Access Journals (Sweden)

R. Prasad

2011-01-01

Full Text Available To comply with the stringent emission regulations on soot, diesel vehicles manufacturers more and more commonly use diesel particulate filters (DPF. These systems need to be regenerated periodically by burning soot that has been accumulated during the loading of the DPF. Design of the DPF requires rate of soot oxidation. This paper describes the kinetics of catalytic oxidation of diesel soot with air under isothermal conditions. Kinetics data were collected in a specially designed mini-semi-batch reactor. Under the high air flow rate assuming pseudo first order reaction the activation energy of soot oxidation was found to be, Ea = 160 kJ/ mol. ©2010 BCREC UNDIP. All rights reserved(Received: 14th June 2010, Revised: 18th July 2010, Accepted: 9th August 2010[How to Cite: R. Prasad, V.R. Bella. (2010. Isothermal Kinetics of Catalyzed Air Oxidation of Diesel Soot. Bulletin of Chemical Reaction Engineering and Catalysis, 5(2: 95-101. doi:10.9767/bcrec.5.2.796.95-101][DOI:http://dx.doi.org/10.9767/bcrec.5.2.796.95-101 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/796]Cited by in: ACS 1 |

Investigation of radiation-chemical behaviour of divalent palladium in perchloric acid solutions

International Nuclear Information System (INIS)

Vladimirova, M.V.; Kalinina, S.V.

1988-01-01

Gamma-radiolysis of divalent palladium in perchloric acid solutions is studied. Absorption spectra of intermediate palladium compounds formed in the irradiated solution are taken. The analysis of literature data as well as comparative analysis of the absorption spectra obtained under irradiation of palladium (2) perchloric acid solutions with absorption spectra of palladium chlorocomplexes allows to suppose that the mentioned compounds are chlorocomplexes of palladium (2) of different composition depending on HClO 4 concentration in the initial solution and absorbed radiation dose. Radiation-chemical reduction of palladium (2) up to metal is stated to take place in the whole studied range of initial concentrations of components of the system and dose rates. Kinetic dependences of metallic palladium formation are obtained. Values of radiation-chemical yields of metallic palladium formation depending on the initial concentrations of palladium (2) and perchloric acid are given. A mechanism of radiolytic reduction of palladium (2) in the investigated system is suggested based on the experimental data, and a theoretical value of the radiation-chemical yield of palladium (2) reduction being in a good agreement with experimentally found values is calculated

Lipase-catalyzed highly enantioselective kinetic resolution of boron-containing chiral alcohols.

Science.gov (United States)

Andrade, Leandro H; Barcellos, Thiago

2009-07-16

The first application of enzymes as catalysts to obtain optically pure boron compounds is described. The kinetic resolution of boron-containing chiral alcohols via enantioselective transesterification catalyzed by lipases was studied. Aromatic, allylic, and aliphatic secondary alcohols containing a boronate ester or boronic acid group were resolved by lipase from Candida antartica (CALB), and excellent E values (E > 200) and high enantiomeric excesses (up to >99%) of both remaining substrates and acetylated product were obtained.

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.

Aerobic Pd-Catalyzed sp3 C–H Olefination: A Route to Both N-Heterocyclic Scaffolds and Alkenes

Science.gov (United States)

Stowers, Kara J.; Fortner, Kevin C.

2011-01-01

This communication describes a new method for the Pd/polyoxometalate-catalyzed aerobic olefination of unactivated sp3 C–H bonds. Nitrogen heterocycles serve as directing groups, and air is used as the terminal oxidant. The products undergo reversible intramolecular Michael addition, which protects the mono-alkenylated product from over-functionalization. Hydrogenation of the Michael adducts provides access to bicyclic nitrogen-containing scaffolds that are prevalent in alkaloid natural products. Additionally, the cationic Michael adducts undergo facile elimination to release α,β-unsaturated olefins, which can be elaborated in numerous C–C and C–heteroatom bond-forming reactions. PMID:21476513

Arsenic (III Adsorption Using Palladium Nanoparticles from Aqueous Solution

Directory of Open Access Journals (Sweden)

Farzaneh Arsiya

2017-07-01

Full Text Available The presence of Arsenic in drinking water is the greatest threat to health effects especially in water. The purpose of this study is application of green palladium nanoparticles for removal of trivalent Arsenic from aqueous solutions and also the impact of some factors such as retention time, pH, concentration of palladium nanoparticles and Arsenic concentrations was studied. The values for Arsenic removal from aqueous solutions were measured by furnace atomic adsorption spectrometry (Conter AA700. In the study, Langmuir and Freundlich isotherm models and pseudo-second order kinetic model were studied. The results of  optimization is shown that 0.5 g of nanoparticles can removed %99.8 of Arsenic with initial concentration of  0.5 g/l, in 5 minutes at pH=4. Langmuir model, Freundlich model (R2=0.94 and pseudo-second order kinetic model (R2=0.99 shown high correlation for removing of Arsenic from aqueous solutions. It was found, palladium nanoparticles can be used as an efficient method to remove Arsenic from aqueous solutions in a short time.

Substoichiometric extraction of traces of gold and palladium

International Nuclear Information System (INIS)

Colonat, J.-F.

1975-01-01

Several systems for extracting palladium at concentrations ranging from 10 -4 to 10 -6 M/l were studied. Extraction by dithizone is limited by the transformation of the primary complex into a secondary complex which takes place at concentrations around 10 -6 M. This transformation has been demonstrated kinetically. Dimethylglyoxime is an interesting reagent in substoichiometry, in spite of its comparatively low extraction constant. Various complexes which are formed in a highly chlorinated medium have been proposed. Use of copper diethyldithiocarbamate is limited principally by its stability in presence of chlorine ions. The kinetic formation of palladium diethyldithiocarbamate has been studied with greater precision. A direct determination of 100μg of palladium in a copper matrix without preliminary separation has given results comparable in every way with those of other methods. In the case of gold (III) the constants of formation with the diethyldithiocarbamate ion have been determined by an iterative method of calculation, using the influence curves of interfering metals. Finally conditions for an automatization of the substoichiometric extraction, as well as its possibilities for gold determination in the range 200-20ppm, were proposed [fr

Beckmann rearrangement of aldoximes catalyzed by transition metal salts: mechanical aspects

NARCIS (Netherlands)

Leusink, A.J.; Meerbeek, T.G.; Noltes, J.G.

1977-01-01

The Beckmann rearrangement of aldoximes catalyzed by transition metal salts like palladium and nickel acetylacetonates is shown to be a dehydration‐hydration reaction in which the anti‐oxime is converted into nitrile and the nitrile is converted into amide.

Titanium tritide radioisotope heat source development: palladium-coated titanium hydriding kinetics and tritium loading tests

International Nuclear Information System (INIS)

Van Blarigan, Peter; Shugard, Andrew D.; Walters, R. Tom

2012-01-01

We have found that a 180 nm palladium coating enables titanium to be loaded with hydrogen isotopes without the typical 400-500 C vacuum activation step. The hydriding kinetics of Pd coated Ti can be described by the Mintz-Bloch adherent film model, where the rate of hydrogen absorption is controlled by diffusion through an adherent metal-hydride layer. Hydriding rate constants of Pd coated and vacuum activated Ti were found to be very similar. In addition, deuterium/tritium loading experiments were done on stacks of Pd coated Ti foil in a representative-size radioisotope heat source vessel. The experiments demonstrated that such a vessel could be loaded completely, at temperatures below 300 C, in less than 10 hours, using existing department-of-energy tritium handling infrastructure.

Aerobic oxidation of alcohols in visible light on Pd-grafted Ti cluster

Science.gov (United States)

The titanium cluster with the reduced band gap has been synthesized having the palladium nanoparticles over the surface, which not only binds to the atmospheric oxygen but also catalyzes the oxidation of alcohols under visible light.

Aerobic composting of waste activated sludge: Kinetic analysis for microbiological reaction and oxygen consumption

International Nuclear Information System (INIS)

Yamada, Y.; Kawase, Y.

2006-01-01

In order to examine the optimal design and operating parameters, kinetics for microbiological reaction and oxygen consumption in composting of waste activated sludge were quantitatively examined. A series of experiments was conducted to discuss the optimal operating parameters for aerobic composting of waste activated sludge obtained from Kawagoe City Wastewater Treatment Plant (Saitama, Japan) using 4 and 20 L laboratory scale bioreactors. Aeration rate, compositions of compost mixture and height of compost pile were investigated as main design and operating parameters. The optimal aerobic composting of waste activated sludge was found at the aeration rate of 2.0 L/min/kg (initial composting mixture dry weight). A compost pile up to 0.5 m could be operated effectively. A simple model for composting of waste activated sludge in a composting reactor was developed by assuming that a solid phase of compost mixture is well mixed and the kinetics for microbiological reaction is represented by a Monod-type equation. The model predictions could fit the experimental data for decomposition of waste activated sludge with an average deviation of 2.14%. Oxygen consumption during composting was also examined using a simplified model in which the oxygen consumption was represented by a Monod-type equation and the axial distribution of oxygen concentration in the composting pile was described by a plug-flow model. The predictions could satisfactorily simulate the experiment results for the average maximum oxygen consumption rate during aerobic composting with an average deviation of 7.4%

Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

Energy Technology Data Exchange (ETDEWEB)

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

2018-03-06

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

Enzyme-catalyzed synthesis and kinetics of ultrasonic-assisted biodiesel production from waste tallow.

Science.gov (United States)

Adewale, Peter; Dumont, Marie-Josée; Ngadi, Michael

2015-11-01

The use of ultrasonic processing was evaluated for its ability to achieve adequate mixing while providing sufficient activation energy for the enzymatic transesterification of waste tallow. The effects of ultrasonic parameters (amplitude, cycle and pulse) and major reaction factors (molar ratio and enzyme concentration) on the reaction kinetics of biodiesel generation from waste tallow bio-catalyzed by immobilized lipase [Candida antarctica lipase B (CALB)] were investigated. Three sets of experiments namely A, B, and C were conducted. In experiment set A, two factors (ultrasonic amplitude and cycle) were investigated at three levels; in experiment set B, two factors (molar ratio and enzyme concentration) were examined at three levels; and in experiment set C, two factors (ultrasonic amplitude and reaction time) were investigated at five levels. A Ping Pong Bi Bi kinetic model approach was employed to study the effect of ultrasonic amplitude on the enzymatic transesterification. Kinetic constants of transesterification reaction were determined at different ultrasonic amplitudes (30%, 35%, 40%, 45%, and 50%) and enzyme concentrations (4, 6, and 8 wt.% of fat) at constant molar ratio (fat:methanol); 1:6, and ultrasonic cycle; 5 Hz. Optimal conditions for ultrasound-assisted biodiesel production from waste tallow were fat:methanol molar ratio, 1:4; catalyst level 6% (w/w of fat); reaction time, 20 min (30 times less than conventional batch processes); ultrasonic amplitude 40% at 5 Hz. The kinetic model results revealed interesting features of ultrasound assisted enzyme-catalyzed transesterification (as compared to conventional system): at ultrasonic amplitude 40%, the reaction activities within the system seemed to be steady after 20 min which means the reaction could proceed with or without ultrasonic mixing. Reversed phase high performance liquid chromatography indicated the biodiesel yield to be 85.6±0.08%. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Bioremediation of 2-chlorophenol containing wastewater by aerobic granules-kinetics and toxicity

Energy Technology Data Exchange (ETDEWEB)

Khan, Mohammad Zain [Environmental Research Laboratory, Department of chemistry, Aligarh Muslim University, Faculty of Science, Aligarh 202002, UP (India); Mondal, Pijush Kanti, E-mail: pijushamu@gmail.com [Environmental Research laboratory, Department of Applied Chemistry, Faculty of Engineering and Technology, Aligarh Muslim University, Aligarh 202002, UP (India); Sabir, Suhail, E-mail: sabirsuhail09@gmail.com [Environmental Research Laboratory, Department of chemistry, Aligarh Muslim University, Faculty of Science, Aligarh 202002, UP (India)

2011-06-15

Highlights: {yields} 2-Chlorophenol degrading aerobic granules were cultivated in sequencing batch reactor in presence of glucose and the organic loading rate (OLR) was increased from 6.9 to 9.7 kg COD m{sup -3} d{sup -1} during the experiment. {yields} Spectral studies confirmed that the biodegradation occurs via chlorocatechol pathway and modified ortho-cleavage. {yields} Biodegradation kinetics of 2-CP followed the Haldane model with kinetic parameters (R{sup 2} > 0.9) V{sub max} = 840 mg2-CP gMLVSS{sup -1} d{sup -1}, K{sub s} = 24.61 mg L{sup -1}, K{sub i} = 315.02 mg L{sup -1}. {yields} Genotoxic examination by plasmid nicking assay confirmed that the effluent was non-toxic. - Abstract: 2-Chlorophenol (2-CP) degrading aerobic granules were cultivated in a sequencing batch reactor (SBR) in presence of glucose. The organic loading rate (OLR) was increased from 6.9 to 9.7 kg COD m{sup -3} d{sup -1} (1150-1617 mg L{sup -1}COD per cycle) during the experiment. The alkalinity (1000 mg L{sup -1} as CaCO{sub 3}) was maintained throughout the experiment. The specific cell growth rate was found to be 0.013 d{sup -1}. A COD removal efficiency of 94% was achieved after steady state at 8 h HRT (hydraulic retention time). FTIR, UV, GC, GC/MS studies confirmed that the biodegradation of 2-CP occurs via chlorocatechol (modified ortho-cleavage) pathway. Biodegradation kinetics followed the Haldane model with kinetic parameters: V{sub max} = 840 mg2-CP gMLVSS{sup -1} d{sup -1}, K{sub s} = 24.61 mg L{sup -1}, K{sub i} = 315.02 mg L{sup -1}. Abiotic losses of 2-CP due to volatilization and photo degradation by sunlight were less than 3% and the results of genotoxicity showed that the degradation products are eco-friendly.

Using Ring Strain to Control 4π-Electrocyclization Reactions: Torquoselectivity in Ring Closing of Medium-Ring Dienes and Ring Opening of Bicyclic Cyclobutenes.

Science.gov (United States)

Boon, Byron A; Green, Aaron G; Liu, Peng; Houk, K N; Merlic, Craig A

2017-05-05

Syntheses of strained cyclic dienes were accomplished via palladium(II)-catalyzed oxidative cyclizations of terminal bis(vinylboronate esters). The reactions generate strained (E,E)-1,3-dienes that undergo spontaneous 4π-electrocyclizations to form bicyclic cyclobutenes. Formation of the cyclobutenes is driven by the strain in the medium-ring (E,E)-1,3-diene intermediate. Thermal ring openings of the cyclobutenes give (Z,Z)-1,3-diene products, again for thermodynamic reasons. DFT calculations verified the thermodynamic versus kinetic control of the reactions, and kinetic studies are in excellent agreement with the calculated energy changes. An extension of the tandem coupling/4π-electrocyclization pathway was demonstrated by a palladium(II)-catalyzed oxidative homocoupling/8π-electrocyclization cascade.

Lipase-catalyzed synthesis of palmitanilide: Kinetic model and antimicrobial activity study.

Science.gov (United States)

Liu, Kuan-Miao; Liu, Kuan-Ju

2016-01-01

Enzymatic syntheses of fatty acid anilides are important owing to their wide range of industrial applications in detergents, shampoo, cosmetics, and surfactant formulations. The amidation reaction of Mucor miehei lipase Lipozyme IM20 was investigated for direct amidation of triacylglycerol in organic solvents. The process parameters (reaction temperature, substrate molar ratio, enzyme amount) were optimized to achieve the highest yield of anilide. The maximum yield of palmitanilide (88.9%) was achieved after 24 h of reaction at 40 °C at an enzyme concentration of 1.4% (70 mg). Kinetics of lipase-catalyzed amidation of aniline with tripalmitin has been investigated. The reaction rate could be described in terms of the Michaelis-Menten equation with a Ping-Pong Bi-Bi mechanism and competitive inhibition by both the substrates. The kinetic constants were estimated by using non-linear regression method using enzyme kinetic modules. The enzyme operational stability study showed that Lipozyme IM20 retained 38.1% of the initial activity for the synthesis of palmitanilide (even after repeated use for 48 h). Palmitanilide, a fatty acid amide, exhibited potent antimicrobial activity toward Bacillus cereus. Copyright © 2015 Elsevier Inc. All rights reserved.

Palladium-Catalyzed Suzuki–Miyaura Cross-Coupling in Continuous Flow

Directory of Open Access Journals (Sweden)

Christophe Len

2017-05-01

Full Text Available Carbon–carbon cross-coupling reactions are among the most important processes in organic chemistry and Suzuki–Miyaura reactions are the most widely used protocols. For a decade, green chemistry and particularly catalysis and continuous flow, have shown immense potential in achieving the goals of “greener synthesis”. To date, it seems difficult to conceive the chemistry of the 21st century without the industrialization of continuous flow process in the area of pharmaceuticals, drugs, agrochemicals, polymers, etc. A large variety of palladium Suzuki–Miyaura cross-coupling reactions have been developed using a continuous flow sequence for preparing the desired biaryl derivatives. Our objective is to focus this review on the continuous flow Suzuki–Miyaura cross-coupling using homogeneous and heterogeneous catalysts.

Kinetics of acid base catalyzed transesterification of Jatropha curcas oil.

Science.gov (United States)

Jain, Siddharth; Sharma, M P

2010-10-01

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

NMR as a tool for kinetic studies: application to the assessment of organo tin reactivity

Energy Technology Data Exchange (ETDEWEB)

Fouquet, E.; Roulet, T. [Bordeaux-1 Univ., 33 - Talence (France); Pianet, I. [Bordeaux-1 Univ., 33 -Talence (France) CNRS, Centre d`Etudes Structurales et d`Analyse des Molecules Organiques; Willem, R. [Brussels University (VUB), Brussels (Belgium)

1998-02-01

There is a growing interest for the research of an answer to the environmental problems related to the industrial use of tetra organo tins. An interesting alternative would be to develop the chemistry of mono organo tins because of their lower toxicity and of the easy removal of ``inorganic`` tin side products. In this work, halogen exchange rates are measured for various mono organo tins with NMR techniques (EXSY spectra and 1 D {sup 119} Sn NMR), and an exchange mechanism is proposed. A correlation between kinetic data and the reactivity of the mono organo tins is then exemplified with radical allylic transfer and palladium catalyzed coupling reactions. (authors) 14 refs.

Aerobic oxidation of alcohols in visible light on Pd-grafted Ti ...

Science.gov (United States)

The titanium cluster with the reduced band gap has been synthesized having the palladium nanoparticles over the surface, which not only binds to the atmospheric oxygen but also catalyzes the oxidation of alcohols under visible light. Prepared as an invited article for submission to the Elsevier journal, Tetrahedron.

A Divergent Mechanistic Course of Pd(0)-Catalyzed Aza-Claisen Rearrangement and Aza-Rautenstrauch-Type Cyclization of N-Allyl-Ynamides

Science.gov (United States)

DeKorver, Kyle A.; Hsung, Richard P.; Lohse, Andrew G.; Zhang, Yu

2010-01-01

A fascinating mechanistic study of ynamido-palladium-π-allyl complexes is described that features isolation of a unique silyl-ketenimine via aza-Claisen rearrangement, which can be accompanied by an unusual thermal N-to-C 1,3-Ts shift in the formation of tertiary nitriles, and a novel cyclopentenimine formation via a palladium catalyzed aza-Rautenstrauch-type cyclization pathway. PMID:20337418

Kinetics of Platinum-Catalyzed Decomposition of Hydrogen Peroxide

Science.gov (United States)

Vetter, Tiffany A.; Colombo, D. Philip, Jr.

2003-07-01

CIBA Vision Corporation markets a contact lens cleaning system that consists of an AOSEPT disinfectant solution and an AOSEPT lens cup. The disinfectant is a buffered 3.0% m/v hydrogen peroxide solution and the cup includes a platinum-coated AOSEPT disc. The hydrogen peroxide disinfects by killing bacteria, fungi, and viruses found on the contact lenses. Because the concentration of hydrogen peroxide needed to disinfect is irritating to eyes, the hydrogen peroxide needs to be neutralized, or decomposed, before the contact lenses can be used again. A general chemistry experiment is described where the kinetics of the catalyzed decomposition of the hydrogen peroxide are studied by measuring the amount of oxygen generated as a function of time. The order of the reaction with respect to the hydrogen peroxide, the rate constant, and the energy of activation are determined. The integrated rate law is used to determine the time required to decompose the hydrogen peroxide to a concentration that is safe for eyes.

Large-scale ruthenium- and enzyme-catalyzed dynamic kinetic resolution of (rac-1-phenylethanol

Directory of Open Access Journals (Sweden)

Bäckvall Jan-E

2007-12-01

Full Text Available Abstract The scale-up of the ruthenium- and enzyme-catalyzed dynamic kinetic resolution (DKR of (rac-1-phenylethanol (2 is addressed. The immobilized lipase Candida antarctica lipase B (CALB was employed for the resolution, which shows high enantioselectivity in the transesterification. The ruthenium catalyst used, (η 5-C5Ph5RuCl(CO2 1, was shown to possess very high reactivity in the "in situ" redox racemization of 1-phenylethanol (2 in the presence of the immobilized enzyme, and could be used in 0.05 mol% with high efficiency. Commercially available isopropenyl acetate was employed as acylating agent in the lipase-catalyzed transesterifications, which makes the purification of the product very easy. In a successful large-scale DKR of 2, with 0.05 mol% of 1, (R-1-phenylethanol acetate (3 was obtained in 159 g (97% yield in excellent enantiomeric excess (99.8% ee.

Using Pd-salen complex as an efficient catalyst for the copper- and solvent-free coupling of acyl chlorides with terminal alkynes under aerobic conditions

Institute of Scientific and Technical Information of China (English)

Mohammad

2010-01-01

The palladium-salen complex palladium(Ⅱ) N,N'-bis{[5-(triphenylphosphonium)-methyl]salicylidene}-l,2-ethanediamine chloride was found to be a highly active catalyst for the copper- and solvent-free coupling reaction of terminal alkynes with different acyl chlorides in the presence of triethylamine as base, giving excellent ynones under aerobic conditions.

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.

ChemInform Abstract: The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications.

KAUST Repository

Ebner, David C.; Bagdanoff, Jeffrey T.; Ferreira, Eric M.; McFadden, Ryan; Caspi, Daniel D.; Trend, Raissa M.; Stoltz, Brian M.

2010-01-01

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications.

KAUST Repository

Ebner, David C.

2010-03-30

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Antibiofilm effect enhanced by modification of 1,2,3-triazole and palladium nanoparticles on polysulfone membranes

KAUST Repository

Cheng, Hong

2015-01-01

Biofouling impedes the performance of membrane bioreactors. In this study, we investigated the antifouling effects of polysulfone membranes that were modified by 1,2,3-triazole and palladium nanoparticles. The membranes to be tested were embedded within a drip flow biofilm reactor, and Pseudomonas aeruginosa PAO1 was inoculated and allowed to establish biofilm on the tested membranes. It was found that 1,2,3-triazole and palladium nanoparticles can inhibit the bacterial growth in aerobic and anaerobic conditions. The decrease in bacterial growth was observed along with a decrease in the amount of total polysaccharide and Pel polysaccharide within the biofilm matrix but not the protein content.

Antibiofilm effect enhanced by modification of 1,2,3-triazole and palladium nanoparticles on polysulfone membranes

KAUST Repository

Cheng, Hong

2015-08-01

Biofouling impedes the performance of membrane bioreactors. In this study, we investigated the antifouling effects of polysulfone membranes that were modified by 1,2,3-triazole and palladium nanoparticles. The membranes to be tested were embedded within a drip flow biofilm reactor, and Pseudomonas aeruginosa PAO1 was inoculated and allowed to establish biofilm on the tested membranes. It was found that 1,2,3-triazole and palladium nanoparticles can inhibit the bacterial growth in aerobic and anaerobic conditions. The decrease in bacterial growth was observed along with a decrease in the amount of total polysaccharide and Pel polysaccharide within the biofilm matrix but not the protein content.

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 palladium nanoparticles on alumina surface by chemical co-precipitation method and catalytic applications

Energy Technology Data Exchange (ETDEWEB)

Kumar, Avvaru Praveen; Kumar, B. Prem; Kumar, A.B.V. Kiran; Huy, Bui The [Department of Chemistry, Changwon National University, Changwon 641-773 (Korea, Republic of); Lee, Yong-Ill, E-mail: yilee@changwon.ac.kr [Department of Chemistry, Changwon National University, Changwon 641-773 (Korea, Republic of)

2013-01-15

Highlights: Black-Right-Pointing-Pointer Facile synthesis of palladium nanoparticles on alumina surface. Black-Right-Pointing-Pointer The surface morphology and properties of the nanocrystalline powders were characterized. Black-Right-Pointing-Pointer The catalytic activities of palladium nanoparticles were investigated. - Abstract: The present work reports a chemical co-precipitation process to synthesize palladium (Pd) nanoparticles using alumina as a supporting material. The optimized temperature for the formation of nanocrystalline palladium was found to be 600 Degree-Sign C. The X-ray diffraction (XRD) and Raman spectroscopy were used to study the chemical nature of the Pd in alumina matrix. The surface morphology and properties of the nanocrystalline powders were examined using thermogravimetric analysis (TG-DTA), XRD, Raman spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The calcinations in different atmospheres including in the inert medium forms the pure nano Pd{sup 0} while in the atmospheric air indicates the existence pure Pd{sup 0} along with PdO nanoparticles. The catalytic activities of the as-synthesized nanocrystalline Pd nanoparticles in the alumina matrix were investigated in Suzuki coupling, Hiyama cross-coupling, alkene and alkyne hydrogenation, and aerobic oxidation reactions.

Characterization of intracellular palladium nanoparticles synthesized by Desulfovibrio desulfuricans and Bacillus benzeovorans

Energy Technology Data Exchange (ETDEWEB)

Omajali, Jacob B., E-mail: JBO037@bham.ac.uk, E-mail: jbomajali@gmail.com; Mikheenko, Iryna P. [University of Birmingham, Unit of Functional Bionanomaterials, School of Biosciences, Institute of Microbiology and Infection (United Kingdom); Merroun, Mohamed L. [University of Granada, Department of Microbiology, Faculty of Sciences (Spain); Wood, Joseph [University of Birmingham, School of Chemical Engineering (United Kingdom); Macaskie, Lynne E. [University of Birmingham, Unit of Functional Bionanomaterials, School of Biosciences, Institute of Microbiology and Infection (United Kingdom)

2015-06-15

Early studies have focused on the synthesis of palladium nanoparticles within the periplasmic layer or on the outer membrane of Desulfovibrio desulfuricans and on the S-layer protein of Bacillus sphaericus. However, it has remained unclear whether the synthesis of palladium nanoparticles also takes place in the bacterial cell cytoplasm. This study reports the use of high-resolution scanning transmission electron microscopy with a high-angle annular dark field detector and energy dispersive X-ray spectrometry attachment to investigate the intracellular synthesis of palladium nanoparticles (Pd NPs). We show the intracellular synthesis of Pd NPs within cells of two anaerobic strains of D. desulfuricans and an aerobic strain of B. benzeovorans using hydrogen and formate as electron donors. The Pd nanoparticles were small and largely monodispersed, between 0.2 and 8 nm, occasionally from 9 to 12 nm with occasional larger nanoparticles. With D. desulfuricans NCIMB 8307 (but not D. desulfuricans NCIMB 8326) and with B. benzeovorans NCIMB 12555, the NPs were larger when made at the expense of formate, co-localizing with phosphate in the latter, and were crystalline, but were amorphous when made with H{sub 2,} with no phosphorus association. The intracellular Pd nanoparticles were mainly icosahedrons with surfaces comprising {111} facets and about 5 % distortion when compared with that of bulk palladium. The particles were more concentrated in the cell cytoplasm than the cell wall, outer membrane, or periplasm. We provide new evidence for synthesis of palladium nanoparticles within the cytoplasm of bacteria, which were confirmed to maintain cellular integrity during this synthesis.

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.

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...

Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

KAUST Repository

Dehury, Niranjan

2016-07-18

Herein, we report an unprecedented example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross coupling reaction of the resulting fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest tandem activity among its di-metallic analogues, and exceeds in terms of activity and selectivity the analogous mononuclear compound. The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate determining step in the tandem reaction. Interestingly while fluoroarylketone undergoes the multistep tandem catalysis, the chloro- and bromo-arylketones undergo only a single step C-C coupling reaction resulting in biarylketone as the final product. Unlike the pyrazole based Pd compounds, the precursor PdCl2 and the phosphine based relevant complexes (PPh3)2PdCl2 and (PPh3)4Pd are found to be unable to exhibit the tandem catalysis.

Kinetics of isotopic exchange of [1-3H]saccharides with hydrogen using palladium catalysts

International Nuclear Information System (INIS)

Akulov, G.P.; Kayumov, V.G.; Snetkova, E.V.; Kaminskij, Yu.L.

1988-01-01

The kinetics was studied of the isotopic exchange of [1- 3 H]saccharides with hydrogen on palladium catalysts. The effect was studied of different factors on the rate of isotopic exchange, e.g., of the composition and structure of saccharides, their concentration in the solution (C), the type of catalyst and of the buffer solution. It was found that by reduced rate of isotopic exchange with hydrogen, all studied saccharides may be arranged into a series independent of the type of catalyst in accordance with the sequence of declining coefficient of relative mobility of l-H atoms during the reaction. Linear dependence was found to exist between the rate constant of the isotopic exchange reaction (r) and the coefficient of relative lability. It was also found that in the range of low concentrations the observed rate constants of isotopic exchange were not dependent on concentration and in the range of higher concentrations, r decreased with increasing C. This character of dependence is justified by the side effect of the processes of sorption on the catalyst. (author). 3 figs., 1 tab., 4 refs

Synthesis of Rhodamines from Fluoresceins Using Pd-Catalyzed C–N Cross-Coupling

Science.gov (United States)

2011-01-01

A unified, convenient, and efficient strategy for the preparation of rhodamines and N,N′-diacylated rhodamines has been developed. Fluorescein ditriflates were found to undergo palladium-catalyzed C–N cross-coupling with amines, amides, carbamates, and other nitrogen nucleophiles to provide direct access to known and novel rhodamine derivatives, including fluorescent dyes, quenchers, and latent fluorophores. PMID:22091952

Palladium-catalyzed arylation of enoates with iodobenzene: stereoselective synthesis of trisubstituted olefins

International Nuclear Information System (INIS)

Fernandes, Talita de A.; Universidade Federal do Rio de Janeiro; Silva, Alcides J.M. da; Costa, Paulo R.R.; Esteves, Pierre M.; Eberlin, Marcos N.; Vaz, Boniek G.; Universidade Federal de Goias

2013-01-01

The Heck reaction between E- and Z-enoates and iodobenzene was studied in the presence of Pd(OAc) 2 . The stereochemistry in resulting adducts was dependent on the enoate geometry (stereospecific reaction). Best yields were obtained from Z-isomers in acetone using Ag 2 CO 3 as base. The main cationic palladium intermediates possibly involved in the catalytic cycle could be intercepted and characterized by electrospray ionization mass spectrometry (ESI-MS). The stereoselectivity observed was rationalized through the classic mechanism of the Heck reaction. (author)

Modeling of hydrogen/deuterium dynamics and heat generation on palladium nanoparticles for hydrogen storage and solid-state nuclear fusion.

Science.gov (United States)

Tanabe, Katsuaki

2016-01-01

We modeled the dynamics of hydrogen and deuterium adsorbed on palladium nanoparticles including the heat generation induced by the chemical adsorption and desorption, as well as palladium-catalyzed reactions. Our calculations based on the proposed model reproduce the experimental time-evolution of pressure and temperature with a single set of fitting parameters for hydrogen and deuterium injection. The model we generated with a highly generalized set of formulations can be applied for any combination of a gas species and a catalytic adsorbent/absorbent. Our model can be used as a basis for future research into hydrogen storage and solid-state nuclear fusion technologies.

Observation of Binuclear Palladium Clusters Upon ESI-MS Monitoring of the Suzuki-Miyaura Cross-Coupling Catalyzed by a Dichloro-bis(aminophosphine) Complex of Palladium

Czech Academy of Sciences Publication Activity Database

Agrawal, Divya; Schröder, Detlef; Frech, C. M.

2011-01-01

Roč. 30, č. 13 (2011), s. 3579-3587 ISSN 0276-7333 Institutional research plan: CEZ:AV0Z40550506 Keywords : catalysis * C-C coupling * electrospray ionization * palladium * Suzuki-Miyaura coupling Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.963, year: 2011

SOLVENT EFFECTS ON THE HYDRATION OF CYCLOHEXENE CATALYZED BY A STRONG ACID ION-EXCHANGE RESIN .2. EFFECT OF SULFOLANE ON THE REACTION-KINETICS

NARCIS (Netherlands)

PANNEMAN, HJ; BEENACKERS, AACM

The kinetics of the' hydration of cyclohexene, catalyzed by a strong acid ion-exchange resin, have been studied in a packed bed reactor at temperatures between 353 and 413 K and a pressure of 20 bar. The kinetic rate constants were measured as a function of temperature and solvent composition (0-90

Palladium-catalyzed arylation of enoates with iodobenzene: stereoselective synthesis of trisubstituted olefins

Energy Technology Data Exchange (ETDEWEB)

Fernandes, Talita de A. [Universidade Federal do Rio de Janeiro (UFRJ/LQB), RJ (Brazil). Nucleo de Pesquisas de Produtos Naturais. Laboratorio de Quimica Bioorganica; Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica. Interlab; Silva, Alcides J.M. da; Costa, Paulo R.R., E-mail: prrcosta2011@gmail.com [Universidade Federal do Rio de Janeiro (UFRJ/LQB), RJ (Brazil). Nucleo de Pesquisas de Produtos Naturais. Laboratorio de Quimica Bioorganica; Esteves, Pierre M. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica. Interlab; Eberlin, Marcos N., E-mail: eberlin@iqm.unicamp.br [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Instituto de Quimica. Laboratorio ThoMSon de Espectrometria de Massas; Vaz, Boniek G. [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Instituto de Quimica. Laboratorio ThoMSon de Espectrometria de Massas; Universidade Federal de Goias (UFGO), Goiania, GO (Brazil). Instituto de QuImica

2013-03-15

The Heck reaction between E- and Z-enoates and iodobenzene was studied in the presence of Pd(OAc){sub 2}. The stereochemistry in resulting adducts was dependent on the enoate geometry (stereospecific reaction). Best yields were obtained from Z-isomers in acetone using Ag{sub 2} CO{sub 3} as base. The main cationic palladium intermediates possibly involved in the catalytic cycle could be intercepted and characterized by electrospray ionization mass spectrometry (ESI-MS). The stereoselectivity observed was rationalized through the classic mechanism of the Heck reaction. (author)

Kinetics of the H 2O 2-dependent ligninase-catalyzed oxidation of veratryl alcohol in the presence of cationic surfactant studied by spectrophotometric technique

Science.gov (United States)

Liu, Airong; Huang, Xirong; Song, Shaofang; Wang, Dan; Lu, Xuemei; Qu, Yinbo; Gao, Peiji

2003-09-01

The kinetics of ligninase-catalyzed oxidation of veratryl alcohol (VA) by H 2O 2 in the aqueous medium containing cationic surfactant cetyltrimethylammonium bromide (CTAB) has been investigated using spectrophotometric technique. Steady-state kinetic studies at different concentrations of CTAB indicate that the reaction follows a ping pong mechanism and the mechanism always holds but the kinetic parameters vary with CTAB concentrations. CTAB is a weak inhibitor for ligninase; it lowers the maximum initial velocity. CTAB also causes the Michaelis constant of H 2O 2 to decrease dramatically and that of VA to increase markedly. Based on the changes in kinetic parameters of the enzyme-catalyzed reaction at different CTAB concentrations (lower than, near to and larger than its critical micelle concentration) and the effects of the CTAB monomer and the micelles on the spectra of VA and its corresponding aldehyde, a conclusion could be made that modification of the enzymatic protein by the surfactant monomer should be responsible for the above-mentioned results.

Oxygen kinetics and mechanism at electrocatalysts on the base of palladium-iron system

International Nuclear Information System (INIS)

Tarasevich, M.R.; Zhutaeva, G.V.; Bogdanovskaya, V.A.; Radina, M.V.; Ehrenburg, M.R.; Chalykh, A.E.

2007-01-01

Binary nanodispersed carbon XC72 supported PdFe catalysts with different atomic palladium-to-iron ratios are synthesized and studied in oxygen reduction reaction in acid solution at 60 o C. The Pd:Fe ratio was well controlled by the initial concentrations of Pd and Fe in the precursor solutions. The nanoparticles were characterized by transmission electron microscopy, X-ray diffractometry and X-ray photoelectron spectroscopy. The optimum Pd:Fe ratio for this reaction was determined to be 3:1. The comparison of activities of the catalysts with component ratios equaled 3:1 and 10:1 is shown that the activities are differed from each other by 10-15 times in advantage of catalyst with lesser content of palladium. This phenomenon can be related to the different particle size of both catalysts and different distribution of particles by size discovered by TEM method. The achievement of maximum activity near the ratio of Pd:Fe = 3:1 is due to as effect of alloy-forming and the influence of binary system component ratio and synthesis conditions on dispersity degree of metallic phase nanoparticles. Under optimal conditions of precursor mixture high-temperature pyrolysis, iron produces the stabilizing effect palladium. It gives rise to obtaining the uniform and finely divided (7-8 nm) metallic particles

Monodisperse gold-palladium alloy nanoparticles and their composition-controlled catalysis in formic acid dehydrogenation under mild conditions.

Science.gov (United States)

Metin, Önder; Sun, Xiaolian; Sun, Shouheng

2013-02-07

Monodisperse 4 nm AuPd alloy nanoparticles with controlled composition were synthesized by co-reduction of hydrogen tetrachloroaurate(III) hydrate and palladium(II) acetylacetonate with a borane-morpholine complex in oleylamine. These NPs showed high activity (TOF = 230 h(-1)) and stability in catalyzing formic acid dehydrogenation and hydrogen production in water at 50 °C without any additives.

Kinetics of aerobically activated sludge on terylene artificial silk printing and dyeing wastewater treatment.

Science.gov (United States)

Guan, Bao-hong; Wu, Zhong-biao; Xu, Gen-liang

2004-04-01

Aerobically activated sludge processing was carried out to treat terylene artificial silk printing and dyeing wastewater (TPD wastewater) in a lab-scale experiment, focusing on the kinetics of the COD removal. The kinetics parameters determined from experiment were applied to evaluate the biological treatability of wastewater. Experiments showed that COD removal could be divided into two stages, in which the ratio BOD/COD (B/C) was the key factor for stage division. At the rapid-removal stage with B/C>0.1, COD removal could be described by a zero order reaction. At the moderate-removal stage with B/Ckinetic parameters, the biological treatability of TPD wastewater was superior to that of traditional textile wastewater. But COD removal from TPD-wastewater was much more difficult than that from domestic and industrial wastewater, such as papermaking, beer, phenol wastewater, etc. The expected effluent quality strongly related to un-biodegradable COD and kinetics rather than total COD. The results provide useful basis for further scaling up and efficient operation of TPD wastewater treatment.

Determination of palladium content in palladium-alumina/palladium-silica/palladium-tin oxide catalyst for nuclear reactor applications

International Nuclear Information System (INIS)

Sharma, P.K.; Bassan, M.K.T.; Avhad, D.K.; Singhal, R.K.

2012-01-01

Alumina and silica act as support for finely divided palladium metal powder in synthesis of catalyst. These catalyst (Pd-Al 2 O 3 , Pd-SiO 2 and Pd-SnO 2 ) used in nuclear power reactor (moderator cover gas system) for the conversion of hydrogen. In Indian nuclear power programme these catalyst are regularly used in Kaiga 1 and 2 and Rajasthan atomic power plant 3 and 4. The performance of the catalyst, solely depends on the concentration of palladium, which is the active component in this catalyst composition. Therefore it is highly desirable to have rouged analytical methodology for the accurate estimation of palladium. Leaching of Pd from the bulk matrix is tedious due to the less reactive nature of Pd therefore complete solubilization of the matrix is carried out by fusion method

Chemoenzymatic dynamic kinetic resolution of primary amines using a recyclable palladium nanoparticle catalyst together with lipases.

Science.gov (United States)

Gustafson, Karl P J; Lihammar, Richard; Verho, Oscar; Engström, Karin; Bäckvall, Jan-E

2014-05-02

A catalyst consisting of palladium nanoparticles supported on amino-functionalized siliceous mesocellular foam (Pd-AmP-MCF) was used in chemoenzymatic dynamic kinetic resolution (DKR) to convert primary amines to amides in high yields and excellent ee's. The efficiency of the nanocatalyst at temperatures below 70 °C enables reaction conditions that are more suitable for enzymes. In the present study, this is exemplified by subjecting 1-phenylethylamine (1a) and analogous benzylic amines to DKR reactions using two commercially available lipases, Novozyme-435 (Candida antartica Lipase B) and Amano Lipase PS-C1 (lipase from Burkholderia cepacia) as biocatalysts. The latter enzyme has not previously been used in the DKR of amines because of its low stability at temperatures over 60 °C. The viability of the heterogeneous Pd-AmP-MCF was further demonstrated in a recycling study, which shows that the catalyst can be reused up to five times.

β-Secondary and solvent deuterium kinetic isotope effects and the mechanisms of base- and acid-catalyzed hydrolysis of penicillanic acid

International Nuclear Information System (INIS)

Deraniyagala, S.A.; Adediran, S.A.; Pratt, R.F.

1995-01-01

β-Secondary and solvent deuterium kinetic isotope effects have been determined at 25 degrees C for the alkaline and acid-catalyzed hydrolysis of penicillanic acid. In order to determine the former isotope effect, [6,6- 2 H 2 ]dideuteriopenicillanic acid has been synthesized. In alkaline solution, the former isotope effect was found to be 0.95 ± 0.01. These values support the B AC 2 mechanism of hydrolysis with rate-determining formation of the tetrahedral intermediate that has been proposed for other β-lactams. The measured β-secondary kinetic isotope for the acid-catalyzed reaction was 1.00 ± 0.01. The data indicates that a likely pathway of acid-catalyzed hydrolysis would be that of an A AC 1 mechanism with an intermediate acylium ion. If this were so, the calculated β-secondary isotope effect per hydrogen coplanar with the breaking C-N bond and corrected for the inductive effect of deuterium would be 1.06 ± 0.01. This suggests an early A AC 1 transition state, which would be reasonable in this case because of destabilization of the N-protonated amide with respect to the acylium ion because of ring strain. The absence of specific participation by solvent in the transition state, as would be expected of an A AC 1 but not an associative mechanism, is supported by the strongly inverse solvent deuterium kinetic isotope effect of 0.25 ± 0.00 in 1 M HCl and 0.22 ± 0.01 in 33.3 wt % H 2 SO 4 . 1 fig., 3 tabs

Rhodium-catalyzed redox-neutral coupling of phenidones with alkynes.

Science.gov (United States)

Fan, Zhoulong; Lu, Heng; Li, Wei; Geng, Kaijun; Zhang, Ao

2017-07-21

A switchable synthesis of N-substituted indole derivatives from phenidones via rhodium-catalyzed redox-neutral C-H activation has been achieved. In this protocol, we firstly disclosed that the reactivity of Rh(iii) catalysis could be enhanced through employing palladium acetate as an additive. Some representative features include external oxidant-free, applicable to terminal alkynes, short reaction time and operational simplicity. The utility of this method is further showcased by the economical synthesis of potent anticancer PARP-1 inhibitors.

Total Synthesis and Stereochemical Assignment of Delavatine A: Rh-Catalyzed Asymmetric Hydrogenation of Indene-Type Tetrasubstituted Olefins and Kinetic Resolution through Pd-Catalyzed Triflamide-Directed C-H Olefination.

Science.gov (United States)

Zhang, Zhongyin; Wang, Jinxin; Li, Jian; Yang, Fan; Liu, Guodu; Tang, Wenjun; He, Weiwei; Fu, Jian-Jun; Shen, Yun-Heng; Li, Ang; Zhang, Wei-Dong

2017-04-19

Delavatine A (1) is a structurally unusual isoquinoline alkaloid isolated from Incarvillea delavayi. The first and gram-scale total synthesis of 1 was accomplished in 13 steps (the longest linear sequence) from commercially available starting materials. We exploited an isoquinoline construction strategy and developed two reactions, namely Rh-catalyzed asymmetric hydrogenation of indene-type tetrasubstituted olefins and kinetic resolution of β-alkyl phenylethylamine derivatives through Pd-catalyzed triflamide-directed C-H olefination. The substrate scope of the first reaction covered unfunctionalized olefins and those containing polar functionalities such as sulfonamides. The kinetic resolution provided a collection of enantioenriched indane- and tetralin-based triflamides, including those bearing quaternary chiral centers. The selectivity factor (s) exceeded 100 for a number of substrates. These reactions enabled two different yet related approaches to a key intermediate 28 in excellent enantiopurity. In the synthesis, the triflamide served as not only an effective directing group for C-H bond activation but also a versatile functional group for further elaborations. The relative and absolute configurations of delavatine A were unambiguously assigned by the syntheses of the natural product and its three stereoisomers. Their cytotoxicity against a series of cancer cell lines was evaluated.

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...

Modeling of hydrogen/deuterium dynamics and heat generation on palladium nanoparticles for hydrogen storage and solid-state nuclear fusion

Directory of Open Access Journals (Sweden)

Katsuaki Tanabe

2016-01-01

Full Text Available We modeled the dynamics of hydrogen and deuterium adsorbed on palladium nanoparticles including the heat generation induced by the chemical adsorption and desorption, as well as palladium-catalyzed reactions. Our calculations based on the proposed model reproduce the experimental time-evolution of pressure and temperature with a single set of fitting parameters for hydrogen and deuterium injection. The model we generated with a highly generalized set of formulations can be applied for any combination of a gas species and a catalytic adsorbent/absorbent. Our model can be used as a basis for future research into hydrogen storage and solid-state nuclear fusion technologies.

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.

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

DEFF Research Database (Denmark)

Madec, David; Prestat, Guillaume; Martini, Elisabetta

2005-01-01

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

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.

Ruthenium-Catalyzed Aerobic Oxidation of Amines.

Science.gov (United States)

Ray, Ritwika; Hazari, Arijit Singha; Lahiri, Goutam Kumar; Maiti, Debabrata

2018-01-18

Amine oxidation is one of the fundamental reactions in organic synthesis as it leads to a variety of value-added products such as oximes, nitriles, imines, and amides among many others. These products comprise the key N-containing building blocks in the modern chemical industry, and such transformations, when achieved in the presence of molecular oxygen without using stoichiometric oxidants, are much preferred as they circumvent the production of unwanted wastes. In parallel, the versatility of ruthenium catalysts in various oxidative transformations is well-documented. Herein, this review focuses on aerobic oxidation of amines specifically by using ruthenium catalysts and highlights the major achievements in this direction and challenges that still need to be addressed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Low-cost method for fabricating palladium and palladium-alloy thin films on porous supports

Science.gov (United States)

Lee, Tae H; Park, Chan Young; Lu, Yunxiang; Dorris, Stephen E; Balachandran, Uthamalingham

2013-11-19

A process for forming a palladium or palladium alloy membrane on a ceramic surface by forming a pre-colloid mixture comprising a powder palladium source, carrier fluid, dispersant and a pore former and a binder. Ultrasonically agitating the precolloid mixture and applying to a substrate with an ultrasonic nozzle and heat curing the coating form a palladium-based membrane.

Thermo-kinetics of lipase-catalyzed synthesis of 6-O-glucosyldecanoate.

Science.gov (United States)

Gumel, A M; Annuar, M S M; Heidelberg, T; Chisti, Y

2011-10-01

Lipase-catalyzed synthesis of 6-O-glucosyldecanoate from d-glucose and decanoic acid was performed in dimethyl sulfoxide (DMSO), a mixture of DMSO and tert-butanol and tert-butanol alone with a decreasing order of polarity. The highest conversion yield (> 65%) of decanoic acid was obtained in the blended solvent of intermediate polarity mainly because it could dissolve relatively large amounts of both the reactants. The reaction obeyed Michaelis-Menten type of kinetics. The affinity of the enzyme towards the limiting substrate (decanoic acid) was not affected by the polarity of the solvent, but increased significantly with temperature. The esterification reaction was endothermic with activation energy in the range of 60-67 kJ mol⁻¹. Based on the Gibbs energy values, in the solvent blend of DMSO and tert-butanol the position of the equilibrium was shifted more towards the products compared to the position in pure solvents. Monoester of glucose was the main product of the reaction. Copyright © 2011 Elsevier Ltd. All rights reserved.

Reusable Polymer-Supported Terpyridine Palladium Complex for Suzuki-Miyaura, Mizoroki-Heck, Sonogashira, and Tsuji-Trost Reaction in Water

Directory of Open Access Journals (Sweden)

Takuya Nagamine

2011-03-01

Full Text Available A novel heterogeneous transition-metal catalyst comprising a polymer-supported terpyridine palladium(II complex was prepared and found to promote the Suzuki-Miyaura, Mizoroki-Heck, Sonogashira, and Tsuji-Trost, reactions in water under aerobic conditions with a high to excellent yield. The catalyst was recovered by simple filtration and directly reused several times without loss of catalytic activity.

Catecholase activity of dicopper(II)-bispidine complexes: stabilities and structures of intermediates, kinetics and reaction mechanism.

Science.gov (United States)

Born, Karin; Comba, Peter; Daubinet, André; Fuchs, Alexander; Wadepohl, Hubert

2007-01-01

A mechanism for the oxidation of 3,5-di-tert-butylcatechol (dtbc) with dioxygen to the corresponding quinone (dtbq), catalyzed by bispidine-dicopper complexes (bispidines are various mono- and dinucleating derivatives of 3,7-diazabicyclo[3.3.1]nonane with bis-tertiary-amine-bispyridyl or bis-tertiary-amine-trispyridyl donor sets), is proposed on the basis of (1) the stoichiometry of the reaction as well as the stabilities and structures [X-ray, density functional theory (B3LYP, TZV)] of the bispidine-dicopper(II)-3,4,5,6-tetrachlorcatechol intermediates, (2) formation kinetics and structures (molecular mechanics, MOMEC) of the end-on peroxo-dicopper(II) complexes and (3) kinetics of the stoichiometric (anaerobic) and catalytic (aerobic) copper-complex-assisted oxidation of dtbc. This involves (1) the oxidation of the dicopper(I) complexes with dioxygen to the corresponding end-on peroxo-dicopper(II) complexes, (2) coordination of dtbc as a bridging ligand upon liberation of H(2)O(2) and (3) intramolecular electron transfer to produce dtbq, which is liberated, and the dicopper(I) catalyst. Although the bispidine complexes have reactivities comparable to those of recently published catalysts with macrocyclic ligands, which seem to reproduce the enzyme-catalyzed process in various reaction sequences, a strikingly different oxidation mechanism is derived from the bispidine-dicopper-catalyzed reaction.

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...

Chemical recovery of palladium-103 from irradiated silver target

International Nuclear Information System (INIS)

Lapshina, E.V.; Kokhanyuk, V.M.; Zhuikov, B.L.; Myasoedova, G.V.; Zakhartchenko, E.A.; Phillips, D.R.; Jamriska, D.J.

2003-01-01

The goal of this work is to develop an extraction method of no-carrier-added palladium-103 from silver. Metallic silver targets may be irradiated by protons with energy of 60-200 MeV or more to generate palladium-103 simultaneously with other radioactive isotopes of rhodium, ruthenium, technetium, palladium and silver. According to the dependence experimental production yield of Pd-103 and isotopes of other elements in thick silver target vs. Proton energy the most suitable energy for maximum yield of Pd-103 and minimum yield of other elements is from about 100 to about 140 MeV. Activity of radionuclides produced in silver target depends from many factors (target thickness, irradiation time, etc.). Two methods of Pd-103 recovering from irradiated silver target are considered in this work: (1) Silver target is dissolved in nitric acid followed by silver precipitation in the form of silver chloride by addition of HCl. The solution containing Pd, Rh and other radionuclides is passed through the layer of fibrous sorbent POLYORGS-15n. Then the sorbent is washed and Pd is desorbed by hot 12 M hydrochloric acid; (2) Silver target is dissolved in nitric acid followed by passing of the obtained solution (2 M HNO 3 ) through a disk set of complex forming sorbent POLYORGS-33n. Under these conditions palladium is sorbed by the sorbent while silver, rhodium, ruthenium and technetium are passed through the sorbent. Then the sorbent is washed with 2M nitric acid, and Pd is desorbed by 12 M hydrochloric acid. Extraction of palladium is occurred during the formation of palladium complex with a chelate sorbent specific to palladium in acidic solutions. Such a sorbent makes possible separation of palladium from accompanying radionuclides such as rhodium, ruthenium and technetium. The polymeric complex-forming sorbent of fibrous structure with the groups of 3(5)-methylpyrazole (POLYORGS-15) is used. The distinctive feature of the sorbents in the form of fibrous 'filled' material is

The mechanism of the phosphine-free palladium-catalyzed hydroarylation of alkynes

DEFF Research Database (Denmark)

Ahlquist, Mårten Sten Gösta; Fabrizi, G.; Cacchi, S.

2006-01-01

The mechanism of the Pd-catalyzed hydroarylation and hydrovinylation reaction of alkynes has been studied by a combination of experimental and theoretical methods (B3LYP), with an emphasis on the phosphine-free version. The regioselectivity of the hydroarylation and hydrovinylation shows unexpected...

Synthetic strategies for controlling inter- and intramolecular interactions: Applications in single-molecule fluorescence imaging, bioluminescence imaging, and palladium catalysis

Science.gov (United States)

Conley, Nicholas R.

proximity of the Cy3 and Cy5 fluorophores, behaves as an optical photoswitch in the presence of a thiol reagent. This unique property was employed to achieve sub-diffraction-limited imaging of the stalks of Caulobacter crescentus cells with 30-nm resolution using STORM (stochastic optical reconstruction microscopy). Lastly, the synthesis of the first selenium analogue of firefly luciferin is described, and this analogue is shown to be a competent substrate for firefly luciferase (fLuc). Remarkably, it exhibits red-shifted bioluminescence emission relative to the native sulfur analogue. The in vivo performance of the selenium and sulfur analogues in imaging are compared by tail-vein injection into nude mice bearing subcutaneous tumor xenografts of a human breast cancer cell line that was stably transduced to express fLuc. Part II of this thesis begins by addressing design considerations in the development of palladium catalysts that effect oxidative transformations under mild conditions (i.e., 1 atm air, room temperature) using molecular oxygen as the terminal oxidant. A newly synthesized cationic palladium complex, [(2,9-dimethylphenanthroline)Pd(OAc)]2[OTf]2, is shown to catalyze aerobic alcohol oxidation under such conditions with an unprecedented initial turnover frequency, but the presence of partially reduced oxygen species results in competitive ligand oxidation with concomitant decrease in catalyst activity. To remedy this, oxidatively resistant ligands, which are essential for the development of next-generation, high-turnover-frequency palladium catalysts that utilize oxygen as a terminal oxidant, have been prepared and effectively employed. In addition, the first general palladium-catalyzed route to the carbonylation of diols is reported. In this system, carbon monoxide (1 atm) serves the carbonyl source, (2,9-dimethylphenanthroline)Pd(OAc) 2 acts as the catalyst, and N-chlorosuccinimide and iodosobenzene are the oxidants for 1,2- and 1,3-diols, respectively. This

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.

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

Indian Academy of Sciences (India)

Initial addition of the reaction product, hexacyanoferrate(II), does not affect the rate significantly. A plausible mechanistic scheme explaining all the observed kinetic results has been proposed. The final oxidation products are identified as indole-3-acetaldehyde, ammonium ion and carbon dioxide. The rate law associated ...

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.

Suzuki coupling reactions catalyzed by poly(N-ethyl-4-vinylpyridinium bromide stabilized palladium nanoparticles in aqueous solution

Directory of Open Access Journals (Sweden)

2008-04-01

Full Text Available InIn this work, it was investigated to use of poly(N-ethyl-4-vinylpyridinium bromide stabilized palladium nanoparticles in the Suzuki reaction between phenylboronic acid and aryl halides in aqueous solution. The nanoparticles were isolated and re-used several times with low loss of activity.

An efficient protocol for copper-free palladium-catalyzed Sonogashira cross-coupling in aqueous media at low temperatures

KAUST Repository

Marziale, Alexander N.; Schlü ter, Johannes; Eppinger, Jö rg

2011-01-01

A thorough study on copper-free Sonogashira cross-couplings in water was carried out using the palla-dacycle, [{Pd(μ-Cl){K2-P,C-P(iPr) 2(OC6H3-2-Ph)}}2] as pre-catalyst with different bases and palladium concentrations. The highly active pre

Performance of palladium nanoparticle–graphene composite as an efficient electrode material for electrochemical double layer capacitors

International Nuclear Information System (INIS)

Dar, Riyaz A.; Giri, Lily; Karna, Shashi P.; Srivastava, Ashwini K.

2016-01-01

Highlights: • Single step synthesis of palladium nanoparticles decorated-graphene nanocomposite. • Improved electron transfer kinetics and superior capacitive performance. • High specific capacitance of 637 F g −1 at a current density of 1.25 A g −1 . • Retention of 91.4% of its initial capacitance after 10000 cycles of testing. - Abstract: Palladium nanoparticle–graphene nanosheet composite (PdNP–GN) is demonstrated as an efficient electrode material in energy storage applications in supercapacitors. Palladium nanoparticle (PdNP) decorated graphene nanosheet (GN) composite was synthesized via a chemical approach in a single step by the simultaneous reduction of graphene oxide (GO) and palladium chloride from the aqueous phase using ascorbic acid as reducing agent. The materials were characterized by scanning and high resolution transmission electron microscopy, Raman, X-ray diffraction and energy dispersive X-ray spectroscopy which demonstrate that the metal nanoparticles have been uniformly deposited on the surface of graphene nanosheets. The synthesized material has been analyzed by cyclic voltammetry, electrochemical impedance spectrometry and chronopotentiometry using 1 M KCl as the supporting electrolyte for its application in electrochemical double layer supercapacitors. PdNPs-GN composite showed improved electron transfer kinetics and superior capacitive performance with large specific capacitance of 637 F g −1 , excellent cyclic performance and maximum energy and power densities of 56 Wh kg −1 and 1166 W kg −1 , respectively at a current density of 1.25 A g −1 . This highlights the importance of the synergetic effects of electrochemically efficient Pd nanoparticles and graphene for energy storage applications in supercapacitors.

Synthesis of palladium nanoparticles with leaf extract of Chrysophyllum cainito (Star apple) and their applications as efficient catalyst for C-C coupling and reduction reactions

Science.gov (United States)

Majumdar, Rakhi; Tantayanon, Supawan; Bag, Braja Gopal

2017-10-01

A simple green chemical method for the one-step synthesis of palladium nanoparticles (PdNPs) has been described by reducing palladium (II) chloride with the leaf extract of Chrysophyllum cainito in aqueous medium. The synthesis of the palladium nanoparticles completed within 2-3 h at room temperature, whereas on heat treatment (70-80 °C), the synthesis of colloidal PdNPs completed almost instantly. The stabilized PdNPs have been characterized in detail by spectroscopic, electron microscopic and light scattering measurements. The synthesized PdNPs have been utilized as a green catalyst for C-C coupling reactions under aerobic and phosphine-free conditions in aqueous medium. In addition, the synthesized PdNPs have also been utilized as a catalyst for a very efficient sodium borohydride reduction of 3- and 4-nitrophenols. The synthesized PdNPs can retain their catalytic activity for several months.

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…

Acclimation of aerobic-activated sludge degrading benzene derivatives and co-metabolic degradation activities of trichloroethylene by benzene derivative-grown aerobic sludge.

Science.gov (United States)

Wang, Shizong; Yang, Qi; Bai, Zhiyong; Wang, Shidong; Wang, Yeyao; Nowak, Karolina M

2015-01-01

The acclimation of aerobic-activated sludge for degradation of benzene derivatives was investigated in batch experiments. Phenol, benzoic acid, toluene, aniline and chlorobenzene were concurrently added to five different bioreactors which contained the aerobic-activated sludge. After the acclimation process ended, the acclimated phenol-, benzoic acid-, toluene-, aniline- and chlorobenzene-grown aerobic-activated sludge were used to explore the co-metabolic degradation activities of trichloroethylene (TCE). Monod equation was employed to simulate the kinetics of co-metabolic degradation of TCE by benzene derivative-grown sludge. At the end of experiments, the mixed microbial communities grown under different conditions were identified. The results showed that the acclimation periods of microorganisms for different benzene derivatives varied. The maximum degradation rates of TCE for phenol-, benzoic acid-, toluene-, aniline- and chlorobenzene-grown aerobic sludge were 0.020, 0.017, 0.016, 0.0089 and 0.0047 mg g SS(-1) h(-1), respectively. The kinetic of TCE degradation in the absence of benzene derivative followed Monod equation well. Also, eight phyla were observed in the acclimated benzene derivative-grown aerobic sludge. Each of benzene derivative-grown aerobic sludge had different microbial community composition. This study can hopefully add new knowledge to the area of TCE co-metabolic by mixed microbial communities, and further the understanding on the function and applicability of aerobic-activated sludge.

Aerobic Transition-Metal-Free Synthesis of 2,3-Diarylindoles and 5-Aryluracils via Oxidative Nucleophilic Substitution of Hydrogen Pathway

Energy Technology Data Exchange (ETDEWEB)

Yu, Jin; Moon, Hye Ran; Kim, Su Yeon; Kim, Jae Nyoung [Chonnam National Un iversity, Gwangju (Korea, Republic of)

2016-01-15

2,3-diarylindoles and 5-aryluracils were synthesized by ONSH pathway under transition-metal-free conditions in good to moderate yields using molecular oxygen as an oxidant. As 2,3-diarylindoles have been found in many biologically important compounds, the synthesis of this scaffold has received much attention. Most frequently, 2,3-diarylindoles have been prepared via palladium-catalyzed arylations of 2-arylindole with bromoarenes. During our recent transition metal-catalyzed arylations of indoles and uracils, we were interested in the arylation in the absence of an expensive transition metal catalyst.

Insertion of molecular oxygen into a palladium(II) methyl bond: a radical chain mechanism involving palladium(III) intermediates.

Science.gov (United States)

Boisvert, Luc; Denney, Melanie C; Hanson, Susan Kloek; Goldberg, Karen I

2009-11-04

The reaction of (bipy)PdMe(2) (1) (bipy = 2,2'-bipyridine) with molecular oxygen results in the formation of the palladium(II) methylperoxide complex (bipy)PdMe(OOMe) (2). The identity of the product 2 has been confirmed by independent synthesis. Results of kinetic studies of this unprecedented oxygen insertion reaction into a palladium alkyl bond support the involvement of a radical chain mechanism. Reproducible rates, attained in the presence of the radical initiator 2,2'-azobis(2-methylpropionitrile) (AIBN), reveal that the reaction is overall first-order (one-half-order in both [1] and [AIBN], and zero-order in [O(2)]). The unusual rate law (half-order in [1]) implies that the reaction proceeds by a mechanism that differs significantly from those for organic autoxidations and for the recently reported examples of insertion of O(2) into Pd(II) hydride bonds. The mechanism for the autoxidation of 1 is more closely related to that found for the autoxidation of main group and early transition metal alkyl complexes. Notably, the chain propagation is proposed to proceed via a stepwise associative homolytic substitution at the Pd center of 1 with formation of a pentacoordinate Pd(III) intermediate.

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

Science.gov (United States)

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

2016-02-05

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

Miswak mediated green synthesized palladium nanoparticles as effective catalysts for the Suzuki coupling reactions in aqueous media

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Mujeeb Khan

2017-05-01

Full Text Available Green and eco-friendly synthesis of palladium nanoparticles NPs is carried out under facile and eco-friendly conditions using an aqueous solution of Salvadora persica L. (SP root extract (RE as a bioreductant, which is commonly known as Miswak. The as-synthesized Pd NPs were characterized using various spectroscopic and microscopic techniques, including, UV–Vis spectroscopy, FT-IR spectroscopy, XRD, ICP-MS and TEM. Detailed investigations of the Pd NPs have confirmed that the polyphenolic phytomolecules present in the RE of Miswak not only act as a bioreductant by facilitating the reduction and growth of Pd NPs, but they also functionalize the surface of Pd NPs and stabilized them in various solvents. Furthermore, the catalytic activity of the green synthesized Pd NPs was also tested toward the Suzuki coupling reactions of various aryl halides in aqueous media. The as-prepared Pd NPs exhibited superior catalytic activity and reusability for the Suzuki coupling reaction in aqueous and aerobic conditions. The kinetics of the reaction studied by GC revealed that the conversion of various aryl halides to biphenyl takes place in a short time.

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}.

Heteroaryl ethers by oxidative palladium catalysis of pyridotriazol-1-yloxy pyrimidines with arylboronic acids.

Science.gov (United States)

Bardhan, Sujata; Wacharasindhu, Sumrit; Wan, Zhao-Kui; Mansour, Tarek S

2009-06-18

The oxidative palladium-catalyzed cross-coupling of pyrimidines containing pyridotriazol-1-yloxy (OPt) as either a urea or an amide functional group with arylboronic acids in the presence of Cs(2)CO(3) in DME containing 0.6-1.0% H(2)O is described for the preparation of heteroaryl ethers. The bromo substitution in the case of 3-(5-bromo-pyrimidin-2-yloxy)-3H-[1,2,3]triazolo[4,5-b]pyridine 1 could serve as a handle for further elaborations such as Suzuki coupling for attaching varied aryl groups.

catalyzed oxidation of some amino acids by acid bromate

African Journals Online (AJOL)

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

Lower limb loading during knee up in step aerobics: a pilot study

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Błażkiewicz Michalina

2016-11-01

Full Text Available Study aim: Step aerobics is a form of aerobic power distinguished from other types of aerobic exercise by its use of an elevated platform. The purpose of this study was to examine how the aerobic exercise “knee up” affects kinematic and kinetic parameters and, above all, the length of the muscle contractions.

Ion-exchange Resin Catalyzed Esterification of Lactic Acid with Isopropanol: a Kinetic Study

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Amrit P. Toor

2011-05-01

Full Text Available The kinetic behavior of esterification of lactic acid with isopropanol over an acidic cation exchange resin, Amberlyst 15, was studied under isothermal condition. Isopropyl lactate synthesized in this reaction is an important pharmaceutical intermediate. The experiments were carried out in a stirred batch reactor in the temperature range of 323.15 to 353.15 K. The effect of various parameters such as temperature, molar ratio and catalyst loading was studied. Variation in parameters on rate of reaction demonstrated that the reaction was intrinsically controlled. Kinetic modeling was performed using Eley-Rideal model which acceptably fits the experimental data. The activation energy was found to be 22.007 kJ/mol and frequency factor was 0.036809 l2 g-1 mol-1 min-1 for forward reaction. The value of entropy for the forward reaction was found to be 182.317 J K-1 mol-1 . © 2011 BCREC UNDIP. All rights reserved(Received: 19th January 2011, Revised: 16th March 2011; Accepted: 16th March 2011[How to Cite: A.P. Toor, M. Sharma, S. Thakur, and R. K. Wanchoo. (2011. Ion-exchange Resin Catalyzed Esterification of Lactic Acid with Isopropanol: a Kinetic Study. Bulletin of Chemical Reaction Engineering and Catalysis, 6(1: 39-45. doi:10.9767/bcrec.6.1.791.39-45][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.1.791.39-45 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/791 ] | View in  

On the Nature of the Intermediates and the Role of Chloride Ions in Pd-Catalyzed Allylic Alkylations: Added Insight from Density Functional Theory

DEFF Research Database (Denmark)

Fristrup, Peter; Ahlquist, Mårten Sten Gösta; Tanner, David Ackland

2008-01-01

The reactivity of intermediates in palladium-catalyzed allylic alkylation was investigated using DFT (B3LYP) calculations including a PB-SCRF solvation model. In the presence of both phosphine and chloride ligands, the allyl intermediate is in equilibrium between a cationic eta(3)-allylPd complex...

MODELING STYRENE HYDROGENATION KINETICS USING PALLADIUM CATALYSTS

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G. T. Justino

Full Text Available Abstract The high octane number of pyrolysis gasoline (PYGAS explains its insertion in the gasoline pool. However, its use is troublesome due to the presence of gum-forming chemicals which, in turn, can be removed via hydrogenation. The use of Langmuir-Hinshelwood kinetic models was evaluated for hydrogenation of styrene, a typical gum monomer, using Pd/9%Nb2O5-Al2O3 as catalyst. Kinetic models accounting for hydrogen dissociative and non-dissociative adsorption were considered. The availability of one or two kinds of catalytic sites was analyzed. Experiments were carried out in a semi-batch reactor at constant temperature and pressure in the absence of transport limitations. The conditions used in each experiment varied between 16 - 56 bar and 60 - 100 ºC for pressure and temperature, respectively. The kinetic models were evaluated using MATLAB and EMSO software. Models using adsorption of hydrogen and organic molecules on the same type of site fitted the data best.

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

Mechanism and activation for allosteric adenosine 5'-monophosphate nucleosidase. Kinetic alpha-deuterium isotope effects for the enzyme-catalyzed hydrolysis of adenosine 5'-monophosphate and nicotinamide mononucleotide

International Nuclear Information System (INIS)

Skoog, M.T.

1986-01-01

The kinetic alpha-deuterium isotope effect on Vmax/Km for hydrolysis of NMN catalyzed by AMP nucleosidase at saturating concentrations of the allosteric activator MgATP2- is kH/kD = 1.155 +/- 0.012. This value is close to that reported previously for the nonenzymatic hydrolysis of nucleosides of related structure, suggesting that the full intrinsic isotope effect for enzymatic NMN hydrolysis is expressed under these conditions; that is, bond-changing reactions are largely or completely rate-determining and the transition state has marked oxocarbonium ion character. The kinetic alpha-deuterium isotope effect for this reaction is unchanged when deuterium oxide replaces water as solvent, corroborating this conclusion. Furthermore, this isotope effect is independent of pH over the range 6.95-9.25, for which values of Vmax/Km change by a factor of 90, suggesting that the isotope-sensitive and pH-sensitive steps for AMP-nucleosidase-catalyzed NMN hydrolysis are the same. Values of kH/kD for AMP nucleosidase-catalyzed hydrolysis of NMN decrease with decreasing saturation of enzyme with MgATP2- and reach unity when the enzyme is less than half-saturated with this activator. This requires that the rate-determining step changes from cleavage of the covalent C-N bond to one which is isotope-independent. In contrast to the case for NMN hydrolysis, AMP nucleosidase-catalyzed hydrolysis of AMP at saturating concentrations of MgATP2- shows a kinetic alpha-deuterium isotope effect of unity. Thus, covalent bond-changing reactions are largely or completely rate-determining for hydrolysis of a poor substrate, NMN, but make little or no contribution to rate-determining step for hydrolysis of a good substrate, AMP, by maximally activated enzyme. This behavior has several precedents

Sensitization to palladium in Europe

DEFF Research Database (Denmark)

Muris, Joris; Goossens, An; Gonçalo, Margarida

2015-01-01

BACKGROUND: Recently, sodium tetrachloropalladate (Na2 PdCl4 ) was found to be a more sensitive palladium patch test allergen than palladium dichloride (PdCl2 ). OBJECTIVES: To determine the optimal test concentration of Na2 PdCl4 , to evaluate the prevalence of palladium sensitization with Na2 P...... patch test concentration. Sensitization to palladium is almost as prevalent as sensitization to nickel. The sex distribution is different between nickel-sensitized and palladium-sensitized patients, suggesting different sources of exposure.......Cl4 and PdCl2 , and to compare the results with nickel sensitization in a European multicentre study. MATERIALS AND METHODS: In addition to the European or national baseline series including NiSO4 ·6H2 0 5% pet., consecutive patients were tested with PdCl2 and Na2 PdCl4 2%, 3% and 4% pet. in eight...... European dermatology clinics. The age and sex distributions were also evaluated in patients sensitized to nickel and palladium. RESULTS: In total, 1651 patients were tested. Relative to 3% Na2 PdCl4 , 4% Na2 PdCl4 did not add any information. Two per cent Na2 PdCl4 resulted in more doubtful reactions...

Palladium-catalyzed heteroannulation approach to 7-azatryptophan with a Schöllkopf chiral auxiliary

Energy Technology Data Exchange (ETDEWEB)

Gee, Moon Bae; Kim, Tae Seung; Yun, Eul Kgun [Dept. of Chemistry, Chungnam National University, Daejeon (Korea, Republic of)

2015-05-15

Our previous results on heteroannulation with unprotected 2-amino-3-iodopyridine and internal alkynes showed very low yields of the annulated product. The synthetic limitation could be due to the low nucleophilicity of the nitrogen that exists in the three tautomeric forms of 2-amino-pyridine (Scheme 1) or to the easy formation of a palladium complex with 2-aminopyridine. First, we examined the synthesis of the azaindole precursor, followed by reaction with a Schöllkopf chiral auxiliary. The heteroannulation provided the desired annulated product 5 in 60% yield, along with an uncyclized Sonogawasihra coupling product. After purifying product 5 by column chromatography, it was converted to 7-aza-tryptophan.

Physiological and functional diversity of phenol degraders isolated from phenol-grown aerobic granules: Phenol degradation kinetics and trichloroethylene co-metabolic activities.

Science.gov (United States)

Zhang, Yi; Tay, Joo Hwa

2016-03-15

Aerobic granule is a novel form of microbial aggregate capable of degrading toxic and recalcitrant substances. Aerobic granules have been formed on phenol as the growth substrate, and used to co-metabolically degrade trichloroethylene (TCE), a synthetic solvent not supporting aerobic microbial growth. Granule formation process, rate limiting factors and the comprehensive toxic effects of phenol and TCE had been systematically studied. To further explore their potential at the level of microbial population and functions, phenol degraders were isolated and purified from mature granules in this study. Phenol and TCE degradation kinetics of 15 strains were determined, together with their TCE transformation capacities and other physiological characteristics. Isolation in the presence of phenol and TCE exerted stress on microbial populations, but the procedure was able to preserve their diversity. Wide variation was found with the isolates' kinetic behaviors, with the parameters often spanning 3 orders of magnitude. Haldane kinetics described phenol degradation well, and the isolates exhibited actual maximum phenol-dependent oxygen utilization rates of 9-449 mg DO g DW(-1) h(-1), in phenol concentration range of 4.8-406 mg L(-1). Both Michaelis-Menten and Haldane types were observed for TCE transformation, with the actual maximum rate of 1.04-21.1 mg TCE g DW(-1) h(-1) occurring between TCE concentrations of 0.42-4.90 mg L(-1). The TCE transformation capacities and growth yields on phenol ranged from 20-115 mg TCE g DW(-1) and 0.46-1.22 g DW g phenol(-1), respectively, resulting in TCE transformation yields of 10-70 mg TCE g phenol(-1). Contact angles of the isolates were between 34° and 82°, suggesting both hydrophobic and hydrophilic cell surface. The diversity in the isolates is a great advantage, as it enables granules to be versatile and adaptive under different operational conditions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reactor prospects of muon-catalyzed fusion of deuterium and tritium concentrated in transition metals

International Nuclear Information System (INIS)

Stacey, W.M. Jr.

1989-01-01

It is conjectured that the number of fusion events catalyzed by a single muon is orders of magnitude greater for deuterium and tritium concentrated in a transition metal than in gaseous form and that the recent observation of 2.5-MeV neutrons from a D 2 O electrolytic cell with palladium and titanium cathodes can thereby be interpreted in terms of cosmic muon-catalyzed deuterium-deuterium fusion. This suggests a new fusion reactor reactor consisting of deuterium and tritium concentrated in transition metal fuel elements in a fusion core that surrounds an accelerator-produced muon source. The feasibility of net energy production in such a reactor is established in terms of requirements on the number of fusion events catalyzed per muon. The technological implications for a power reactor based on this concept are examined. The potential of such a concept as a neutron source for materials testing and tritium and plutonium production is briefly discussed

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

Palladium-Catalyzed Heck Coupling Reaction of Aryl Bromides in Aqueous Media Using Tetrahydropyrimidinium Salts as Carbene Ligands

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İsmail Özdemir

2010-01-01

Full Text Available An efficient and stereoselective catalytic system for the Heck cross coupling reaction using novel 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (1, LHX and Pd(OAc2 loading has been reported. The palladium complexes derived from the salts 1a-f prepared in situ exhibit good catalytic activity in the Heck coupling reaction of aryl bromides under mild conditions.

Synthesis of Secondary Aromatic Amides via Pd-Catalyzed Aminocarbonylation of Aryl Halides Using Carbamoylsilane as an Amide Source.

Science.gov (United States)

Tong, Wenting; Cao, Pei; Liu, Yanhong; Chen, Jianxin

2017-11-03

Using N-methoxymethyl-N-organylcarbamoyl(trimethyl)silanes as secondary amides source, the direct transformation of aryl halides into the corresponding secondary aromatic amides via palladium-catalyzed aminocarbonylation is described. The reactions tolerated a broad range of functional groups on the aryl ring except big steric hindrance of substituent. The types and the relative position of substituents on the aryl ring impact the coupling efficiency.

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...

Study on the determination of palladium in biological samples by the method of neutron activation analysis

International Nuclear Information System (INIS)

Cavalcante, Cassio Queiroz

2007-01-01

Palladium is one of platinum group elements present in the nature at very low concentrations. However with the use of this element in the automobile catalyzers Pd became a new pollutant. Besides, Pd has been studied in the preparation of new antitumour drugs. Consequently, there is a need to determine Pd concentrations in biological and environmental samples. This study presents palladium results obtained in the analysis of biological samples and reference materials using instrumental thermal and epithermal neutron activation analysis (INAA and ENAA). The solvent extraction and solid phase extraction separation methods were also applied before ENAA. The samples analyzed in this study were, reference material BCR 723 - Palladium, Platinum and Rhodium in road dust, CCQM-P63 automotive catalyst material of the Proficiency Test and bovine tissue samples containing palladium prepared in the laboratory. Samples and palladium synthetic standard were irradiated at the IEA-R1 nuclear research reactor under thermal neutron flux of about 4 x 10 12 n cm-2 s-1, during a period of 4 and 16 h for INAA and ENAA, respectively. The induced gamma activity of 109 Pd to the sample and standard was measured using a hyper pure Ge detector coupled to a gamma ray spectrometer. The palladium concentration was calculated by comparative method. The gamma ray energy of 109 Pd radioisotope measured was of 88.0 keV, located in a spectrum region of low energy where occurs the interference of X rays, 'Bremsstrahlung' radiations, as well as Compton effect of 24 Na. The pre-separation of palladium from interfering elements by solvent extraction was performed using dimethylglyoxime complexant and chloroform as diluent. In the case of the pre separation procedure using solid reversed phase column, the palladium was retained using N,N-diethyl-N'-benzoyl thiourea complexant and eluted using ethanol. Aliquots of the resulting solutions from the pre-separations, free of interfering elements, were

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

Glycogen metabolism in aerobic mixed cultures

DEFF Research Database (Denmark)

Dircks, Klaus; Beun, J.J.; van Loosdrecht, M.C.M.

2001-01-01

In this study, the metabolism of glycogen storage and consumption in mixed cultures under aerobic conditions is described. The experimental results are used to calibrate a metabolic model, which as sole stoichiometric variables has the efficiency of oxidative phosphorylation (delta) and maintenance...... of glycogen and subsequent growth occur without significant loss of energy, as compared with direct growth on glucose. For kinetic modeling, Monod kinetics is used most commonly in activated sludge models to describe the rate of microbial transformation. Monod kinetics, however, does not provide a good...

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.

Confirmation of the absolute configuration of (−)-aurantioclavine

KAUST Repository

Behenna, Douglas C.

2011-04-01

We confirm our previous assignment of the absolute configuration of (-)-aurantioclavine as 7R by crystallographically characterizing an advanced 3-bromoindole intermediate reported in our previous synthesis. This analysis also provides additional support for our model of enantioinduction in the palladium(II)-catalyzed oxidative kinetic resolution of secondary alcohols. © 2010 Elsevier Ltd. All rights reserved.

Cobalt nanoparticles as recyclable catalyst for aerobic oxidation of alcohols in liquid phase

Energy Technology Data Exchange (ETDEWEB)

Mondal, Arijit; Mukherjee, Debkumar, E-mail: debkumarmukherjee@rediffmail.com [Ramsaday College, Department of Chemistry (India); Adhikary, Bibhutosh, E-mail: adhikarybibhu@yahoo.com [Indian Institute of Engineering, Sciences and Technology, Shibpur, Department of Chemistry (India); Ahmed, Md Azharuddin [University of Calcutta, Department of Physics (India)

2016-05-15

Cobalt nanoparticles prepared at room temperature from cobalt sulphate and tetrabutyl ammonium bromide as surfactant have been found to be effective oxidation catalysts. Palladium and platinum nanoparticles (average size 4–6 nm) can also be prepared from PdCl{sub 2} and K{sub 2}PtCl{sub 4}, respectively, using the same surfactant but require high temperature (~120 °C) and much longer preparation time. Agglomeration of nanoparticles prepared from metals like palladium and platinum in common solvents, however, restricts their use as catalysts. It is therefore our endeavour to find the right combination of catalyst and solvent that will be beneficial from industrial point of view. Magnetic property measurement of cobalt nanoclusters was made using SQUID to identify their reusability nature. Herein, we report the use of cobalt nanoparticles (average size 90–95 nm) in dichloromethane solvent as effective reusable catalysts for aerobic oxidation of a variety of alcohols.Graphical Abstract.

Modular in situ-Functionalization Strategy: Multicomponent Polymerization via Palladium/Norbornene Cooperative Catalysis.

Science.gov (United States)

Yoon, Ki-Young; Dong, Guangbin

2018-05-23

Herein, we report the palladium/norbornene cooperatively catalyzed polymerization, which simplifies synthesis of functional aromatic polymers, including conjugated polymers. Specifically, an A2B2C-type multicomponent polymerization is developed using ortho-amination/ipso-alkynylation reaction for preparing various amine-functionalized arylacetylene-containing polymers. Within a single catalytic cycle, the amine side-chains are site-selectively installed in situ via C-H activation during the polymerization process, which represents a major difference from conventional cross-coupling polymerizations. This in situ-functionalization strategy enables modular incorporation of functional side-chains from simple monomers, thereby conveniently affording a diverse range of functional polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics of the Factor XIa catalyzed activation of human blood coagulation Factor IX

International Nuclear Information System (INIS)

Walsh, P.N.; Bradford, H.; Sinha, D.; Piperno, J.R.; Tuszynski, G.P.

1984-01-01

The kinetics of activation of human Factor IX by human Factor XIa was studied by measuring the release of a trichloroacetic acid-soluble tritium-labeled activation peptide from Factor IX. Initial rates of trichloroacetic acid-soluble 3 H-release were linear over 10-30 min of incubation of Factor IX (88 nM) with CaCl 2 (5 mM) and with pure (greater than 98%) Factor XIa (0.06-1.3 nM), which was prepared by incubating human Factor XI with bovine Factor XIIa. Release of 3 H preceded the appearance of Factor IXa activity, and the percentage of 3 H released remained constant when the mole fraction of 3 H-labeled and unlabeled Factor IX was varied and the total Factor IX concentration remained constant. A linear correlation (r greater than 0.98, P less than 0.001) was observed between initial rates of 3 H-release and the concentration of Factor XIa, measured by chromogenic assay and by radioimmunoassay and added at a Factor IX:Factor XIa molar ratio of 70-5,600. Kinetic parameters, determined by Lineweaver-Burk analysis, include K/sub m/ (0.49 microM) of about five- to sixfold higher than the plasma Factor IX concentration, which could therefore regulate the reaction. The catalytic constant (k/sub cat/) (7.7/s) is approximately 20-50 times higher than that reported by Zur and Nemerson for Factor IX activation by Factor VIIa plus tissue factor. Therefore, depending on the relative amounts of Factor XIa and Factor VIIa generated in vivo and other factors which may influence reaction rates, these kinetic parameters provide part of the information required for assessing the relative contributions of the intrinsic and extrinsic pathways to Factor IX activation, and suggest that the Factor XIa catalyzed reaction is physiologically significant

Kinetics of Maleic Acid and Aluminum Chloride Catalyzed Dehydration and Degradation of Glucose

Energy Technology Data Exchange (ETDEWEB)

Zhang, Ximing; Hewetson, Barron B.; Mosier, Nathan S.

2015-04-16

We report the positive effect of maleic acid, a dicarboxylic acid, on the selectivity of hexose dehydration to 5-hydroxymethyfurfural (HMF) and subsequent hydrolysis to levulinic and formic acids. We also describe the kinetic analysis of a Lewis acid (AlCl3) alone and in combination with HCl or maleic acid to catalyze the isomerization of glucose to fructose, dehydration of fructose to HMF, hydration of HMF to levulinic and formic acids, and degradation of these compounds to humins. The results show that AlCl3 significantly enhances the rate of glucose conversion to HMF and levulinic acid in the presence of both maleic acid and HCl. In addition, the degradation of HMF to humins, rather than levulinic and formic acids, is reduced by 50% in the presence of maleic acid and AlCl3 compared to HCl combined with AlCl3. The results suggest different reaction mechanisms for the dehydration of glucose and rehydration of HMF between maleic acid and HCl.

Palladium-Catalyzed Anti-Markovnikov Oxidation of Allylic Amides to Protected beta-Amino Aldehydes

NARCIS (Netherlands)

Dong, Jiajia; Harvey, Emma C.; Fananas-Mastral, Martin; Browne, Wesley R.; Feringa, Bernard

2014-01-01

A general method for the preparation of N-protected beta-amino aldehydes from allylic amines or linear allylic alcohols is described. Here the Pd(II)-catalyzed oxidation of N-protected allylic amines with benzoquinone is achieved in tBuOH under ambient conditions with excellent selectivity toward

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

Palladium-cobalt particles as oxygen-reduction electrocatalysts

Science.gov (United States)

Adzic, Radoslav [East Setauket, NY; Huang, Tao [Manorville, NY

2009-12-15

The present invention relates to palladium-cobalt particles useful as oxygen-reducing electrocatalysts. The invention also relates to oxygen-reducing cathodes and fuel cells containing these palladium-cobalt particles. The invention additionally relates to methods for the production of electrical energy by using the palladium-cobalt particles of the invention.

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.

Acoustic emission during hydrogen absorption and desorption in palladium

International Nuclear Information System (INIS)

Ramesh, R.; Mukhopadhyay, C.K.; Jayakumar, T.; Baldev Raj

1996-01-01

Acoustic emission technique has been used to study charging and discharging of hydrogen in palladium. During charging, breaking of oxide film due to surface activation and saturation of hydrogen absorption have been identified by acoustic emission. In the discharging cycle, the desorption of hydrogen from the specimen leads to high AE activity immediately after initiation of discharging, followed by gradual decrease in the acoustic activity, which reaches a minimum upon completion of the desorption. The potential of the acoustic emission technique for studying the kinetics of hydrogen absorption and desorption in metals has been shown. (author)

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

Science.gov (United States)

Cybulskis, Viktor J.; Smeltz, Andrew D.; Zvinevich, Yury; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.

2016-01-01

Understanding catalytic chemistry, collecting and interpreting kinetic data, and operating chemical reactors are critical skills for chemical engineers. This laboratory experiment provides students with a hands-on supplement to a course in chemical kinetics and reaction engineering. The oxidation of methane with a palladium catalyst supported on…

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

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.

Kinetic Analysis of the Bypass of a Bulky DNA Lesion Catalyzed by Human Y-family DNA Polymerases

Science.gov (United States)

Sherrer, Shanen M.; Sanman, Laura E.; Xia, Cynthia X.; Bolin, Eric R.; Malik, Chanchal K.; Efthimiopoulos, Georgia; Basu, Ashis K.; Suo, Zucai

2012-01-01

1-Nitropyrene (1-NP), a mutagen and potential carcinogen, is the most abundant nitro polyaromatic hydrocarbon in diesel exhaust, which reacts with DNA to form predominantly N-(deoxyguanosin-8-yl)-1-aminopyrene (dGAP). If not repaired, this DNA lesion is presumably bypassed in vivo by any of human Y-family DNA polymerases kappa (hPolκ), iota (hPolτ), eta (hPolη), and Rev1 (hRev1). Our running start assays demonstrated that each of these enzymes was indeed capable of traversing a site-specifically placed dGAP on a synthetic DNA template but hRev1 was stopped after lesion bypass. The time required to bypass 50% of the dGAP sites (t50bypass ) encountered by hPolη, hPolκ and hPolτ was determined to be 2.5 s, 4.1 s, and 106.5 s, respectively. The efficiency order of catalyzing translesion synthesis of dGAP (hPolη > hPolκ > hPolτ >> hRev1) is the same as the order for these human Y-family enzymes to elongate undamaged DNA. Although hPolη bypassed dGAP efficiently, replication by both hPolκ and hPolτ was strongly stalled at the lesion site and at a site immediately downstream from dGAP. By employing pre-steady state kinetic methods, a kinetic basis was established for polymerase pausing at these DNA template sites. Besides efficiency of bypass, the fidelity of those low-fidelity polymerases at these pause sites was also significantly decreased. Thus, if the translesion DNA synthesis of dGAP in vivo is catalyzed by a human Y-family DNA polymerase, e.g. hPolη, the process is certainly mutagenic. PMID:22324639

Interaction of polybrominated diphenyl ethers and aerobic granular sludge: biosorption and microbial degradation.

Science.gov (United States)

Ni, Shou-Qing; Cui, Qingjie; Zheng, Zhen

2014-01-01

As a new category of persistent organic pollutants, polybrominated diphenyl ethers (PBDEs) have become ubiquitous global environmental contaminants. No literature is available on the aerobic biotransformation of decabromodiphenyl ether (BDE-209). Herein, we investigated the interaction of PBDEs with aerobic granular sludge. The results show that the removal of BDE-209 from wastewater is mainly via biosorption onto aerobic granular sludge. The uptake capacity increased when temperature, contact time, and sludge dosage increased or solution pH dropped. Ionic strength had a negative influence on BDE-209 adsorption. The modified pseudo first-order kinetic model was appropriate to describe the adsorption kinetics. Microbial debromination of BDE-209 did not occur during the first 30 days of operation. Further study found that aerobic microbial degradation of 4,4(')-dibromodiphenyl ether happened with the production of lower BDE congeners.

Interaction of Polybrominated Diphenyl Ethers and Aerobic Granular Sludge: Biosorption and Microbial Degradation

Directory of Open Access Journals (Sweden)

Shou-Qing Ni

2014-01-01

Full Text Available As a new category of persistent organic pollutants, polybrominated diphenyl ethers (PBDEs have become ubiquitous global environmental contaminants. No literature is available on the aerobic biotransformation of decabromodiphenyl ether (BDE-209. Herein, we investigated the interaction of PBDEs with aerobic granular sludge. The results show that the removal of BDE-209 from wastewater is mainly via biosorption onto aerobic granular sludge. The uptake capacity increased when temperature, contact time, and sludge dosage increased or solution pH dropped. Ionic strength had a negative influence on BDE-209 adsorption. The modified pseudo first-order kinetic model was appropriate to describe the adsorption kinetics. Microbial debromination of BDE-209 did not occur during the first 30 days of operation. Further study found that aerobic microbial degradation of 4,4′-dibromodiphenyl ether happened with the production of lower BDE congeners.

Synthesis and characterization of a cationic phthalimido-functionalized N-heterocyclic carbene complex of palladium(II) and its catalytic activity

KAUST Repository

Goh, Li Min Serena; Hogerl, Manuel Peter; Jokic̈, Nadežda B.; Tanase, Alexandrina D.; Bechlars, Bettina; Baratta, Walter; Mí nk, Já nos; Kü hn, Fritz

2014-01-01

A cationic phthalimido-functionalized N-heterocyclic carbene (NHC) palladium(II) complex has been synthesized from [3-methyl-1-(2′- phthalimidoethyl)imidazolium] hexafluorophosphate ([NHCMe,PhtH] PF6) by transmetalation and isolated in 67 % yield. The title complex has been applied as catalyst in the Suzuki-Miyaura cross-coupling reaction under benign aqueous conditions. The catalyst is active without any observable initiation period. High average turnover frequencies (TOFs) of up to 55000 h-1 have been reached with catalyst concentrations as low as 0.01 mol-%. A cationic phthalimido-functionalized N-heterocyclic carbene (NHC) palladium(II) complex has been prepared in high yield. The complex was activated instantly, without an initiation period, in the Suzuki-Miyaura cross-coupling reaction under benign aqueous aerobic conditions. Turnover frequencies (TOFs) up to 55000 h-1, were achieved with 0.01 mol-% of the complex. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of a cationic phthalimido-functionalized N-heterocyclic carbene complex of palladium(II) and its catalytic activity

KAUST Repository

Goh, Li Min Serena

2014-01-29

A cationic phthalimido-functionalized N-heterocyclic carbene (NHC) palladium(II) complex has been synthesized from [3-methyl-1-(2′- phthalimidoethyl)imidazolium] hexafluorophosphate ([NHCMe,PhtH] PF6) by transmetalation and isolated in 67 % yield. The title complex has been applied as catalyst in the Suzuki-Miyaura cross-coupling reaction under benign aqueous conditions. The catalyst is active without any observable initiation period. High average turnover frequencies (TOFs) of up to 55000 h-1 have been reached with catalyst concentrations as low as 0.01 mol-%. A cationic phthalimido-functionalized N-heterocyclic carbene (NHC) palladium(II) complex has been prepared in high yield. The complex was activated instantly, without an initiation period, in the Suzuki-Miyaura cross-coupling reaction under benign aqueous aerobic conditions. Turnover frequencies (TOFs) up to 55000 h-1, were achieved with 0.01 mol-% of the complex. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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 ...

Palladium transport in SiC

International Nuclear Information System (INIS)

Olivier, E.J.; Neethling, J.H.

2012-01-01

Highlights: ► We investigate the reaction of Pd with SiC at typical HTGR operating temperatures. ► The high temperature mobility of palladium silicides within polycrystalline SiC was studied. ► Corrosion of SiC by Pd was seen in all cases. ► The preferential corrosion and penetration of Pd along grain boundaries in SiC was found. ► The penetration and transport of palladium silicides in SiC along grain boundaries was found. - Abstract: This paper reports on a transmission electron microscopy (TEM) and scanning electron microscopy (SEM) study of Pd corroded SiC. The reaction of Pd with different types of SiC at typical HTGR operating temperatures was examined. In addition the high temperature mobility of palladium silicides within polycrystalline SiC was investigated. The results indicated corrosion of the SiC by Pd in all cases studied. The corrosion leads to the formation of palladium silicides within the SiC, with the predominant phase found being Pd 2 Si. Evidence for the preferential corrosion and penetration of Pd along grain boundaries in polycrystalline SiC was found. The penetration and transport, without significant corrosion, of palladium silicides into polycrystalline SiC along grain boundaries was also observed. Implications of the findings with reference to the use of Tri Isotropic particles in HTGRs will be discussed.

Chemistry in Confinement: Copper and Palladium Catalyzed Ecofriendly Organic Transformations within Porous Frameworks.

Science.gov (United States)

Kumar, Basuvaraj Suresh; Pitchumani, Kasi

2018-05-01

A concise account on the use of transition metals copper (Cu) and palladium (Pd), as their cations as well as nanoparticles exchanged/immobilized onto porous frameworks such as zeolites, metal organic frameworks (MOFs), covalent organic polymers (COPs) and hollow nanostructures, functioning as catalysts in organic synthesis is presented. This biomimetic account, "focusing on catalytic systems in confinement" within zero-dimensional microenvironments and second sphere coordination covers primarily results from our group on N-sulfonylketenimine mediated cycloaddition, hydrogenation and C-C bond forming reactions, thus providing an interesting insight into the versatility and utility of these Cu and Pd catalysts. Other significant advantages and green credentials of confinement such as stability, selectivity, reusability, promotion of multicomponent reactions, use of green solvents, atom economy, and use of ambient conditions are highlighted at appropriate places. In the final section, our views on the current achievements and the future prospects in this area are summarized. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Growth and sedimentation of fine particles produced in aqueous solutions of palladium sulfate and palladium sulfate-silver sulfate induced by gamma-ray irradiation

International Nuclear Information System (INIS)

Hatada, Motoyoshi; Jonah, C.D.

1994-10-01

It is known that palladium and palladium-silver fine particles were formed from deaerated aqueous solutions of palladium sulfate and palladium sulfate-silver sulfate induced by gamma-ray irradiation. Changes in particle size and with amount of particles in the solution with time during and after irradiation were studied using dynamic light scattering technique and UV spectrophotometer. The particles formed from palladium sulfate solution are found to be water-filled bulky particles of diameter of 200 nm, which grow by mutual coagulation even after irradiation was terminated. Average density depends on concentration of palladium ion in the solution and dose, and the lowest density was about 2 g/cm 3 for particles of 200 nm obtained from 0.06 mM solution by 2.4 kGy irradiation. The average density of the particles obtained from palladium sulfate-silver sulfate solutions was smaller than those obtained for the corresponding palladium sulfate solutions. Supersonic agitation destroyed coagulated precipitates to form fine particles, but did not form clusters of a few atoms. (author)

Synthesis of Prebiotic Caramels Catalyzed by Ion-Exchange Resin Particles: Kinetic Model for the Formation of Di-d-fructose Dianhydrides.

Science.gov (United States)

Ortiz Cerda, Imelda-Elizabeth; Thammavong, Phahath; Caqueret, Vincent; Porte, Catherine; Mabille, Isabelle; Garcia Fernandez, José Manuel; Moscosa Santillan, Mario; Havet, Jean-Louis

2018-02-21

Caramel enriched in di-d-fructose dianhydrides (DFAs, a family of prebiotic cyclic fructodisaccharides) is a functional food with beneficial properties for health. The aim of this work was to study the conversion of fructose into DFAs catalyzed by acid ion-exchange resin, in order to establish a simplified mechanism of the caramelization reaction and a kinetic model for DFA formation. Batch reactor experiments were carried out in a 250 mL spherical glass flask and afforded up to 50% DFA yields. The mechanism proposed entails order 2 reactions that describe fructose conversion on DFAs or formation of byproducts such as HMF or melanoidines. A third order 1 reaction defines DFA transformation into fructosyl-DFAs or fructo-oligosaccharides. The influence of fructose concentration, resin loading and temperature was studied to calculate the kinetic parameters necessary to scale up the process.

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.

o-Naphthoquinone-Catalyzed Aerobic Oxidation of Amines to (Ket)imines: A Modular Catalyst Approach.

Science.gov (United States)

Goriya, Yogesh; Kim, Hun Young; Oh, Kyungsoo

2016-10-07

A modular aerobic oxidation of amines to imines has been achieved using an ortho-naphthoquinone (o-NQ) catalyst. The cooperative catalyst system of o-NQ and Cu(OAc) 2 enabled the formation of homocoupled imines from benzylamines, while the presence of TFA helped the formation of cross-coupled imines in excellent yields. The current mild aerobic oxidation protocol could also be applied to the oxidation of secondary amines to imines or ketimines with the help of cocatalyst, Ag 2 CO 3 , with excellent yields.

Toward Green Acylation of (Heteroarenes: Palladium-Catalyzed Carbonylation of Olefins to Ketones

Directory of Open Access Journals (Sweden)

Jie Liu

2017-11-01

Full Text Available Green Friedel–Crafts acylation reactions belong to the most desired transformations in organic chemistry. The resulting ketones constitute important intermediates, building blocks, and functional molecules in organic synthesis as well as for the chemical industry. Over the past 60 years, advances in this topic have focused on how to make this reaction more economically and environmentally friendly by using green acylating conditions, such as stoichiometric acylations and catalytic homogeneous and heterogeneous acylations. However, currently well-established methodologies for their synthesis either produce significant amounts of waste or proceed under harsh conditions, limiting applications. Here, we present a new protocol for the straightforward and selective introduction of acyl groups into (hetero­arenes without directing groups by using available olefins with inexpensive CO. In the presence of commercial palladium catalysts, inter- and intramolecular carbonylative C–H functionalizations take place with good regio- and chemoselectivity. Compared to classical Friedel–Crafts chemistry, this novel methodology proceeds under mild reaction conditions. The general applicability of this methodology is demonstrated by the direct carbonylation of industrial feedstocks (ethylene and diisobutene as well as of natural products (eugenol and safrole. Furthermore, synthetic applications to drug molecules are showcased.

Top 10 Research Questions Related to Youth Aerobic Fitness.

Science.gov (United States)

Armstrong, Neil

2017-06-01

Peak oxygen uptake ([Formula: see text] 2 ) is internationally recognized as the criterion measure of youth aerobic fitness, but despite pediatric data being available for almost 80 years, its measurement and interpretation in relation to growth, maturation, and health remain controversial. The trainability of youth aerobic fitness continues to be hotly debated, and causal mechanisms of training-induced changes and their modulation by chronological age, biological maturation, and sex are still to be resolved. The daily physical activity of youth is characterized by intermittent bouts and rapid changes in intensity, but physical activity of the intensity and duration required to determine peak [Formula: see text] 2 is rarely (if ever) experienced by most youth. In this context, it may therefore be the transient kinetics of pulmonary [Formula: see text] 2 that best reflect youth aerobic fitness. There are remarkably few rigorous studies of youth pulmonary [Formula: see text] 2 kinetics at the onset of exercise in different intensity domains, and the influence of chronological age, biological maturation, and sex during step changes in exercise intensity are not confidently documented. Understanding the trainability of the parameters of youth pulmonary [Formula: see text] 2 kinetics is primarily based on a few comparative studies of athletes and nonathletes. The underlying mechanisms of changes due to training require further exploration. The aims of the present article are therefore to provide a brief overview of aerobic fitness during growth and maturation, increase awareness of current controversies in its assessment and interpretation, identify gaps in knowledge, raise 10 relevant research questions, and indicate potential areas for future research.

Gold-Catalyzed Aerobic Oxidation of 5-Hydroxymethylfurfural in Water at Ambient Temperature

DEFF Research Database (Denmark)

Gorbanev, Yury; Kegnæs, Søren; Woodley, John

2009-01-01

The aerobic oxidation of 5-hydroxymethylfurfural, a versatile biomass-derived chemical, is examined in water with a titania-supported gold-nanoparticle catalyst at ambient temperature (30 degrees C). The selectivity of the reaction towords 2,5-furandicarboxylic acid and the intermediate oxidation...

Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase*

Science.gov (United States)

Mishanina, Tatiana V.; Yadav, Pramod K.; Ballou, David P.; Banerjee, Ruma

2015-01-01

The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be −123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. PMID:26318450

Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase.

Science.gov (United States)

Mishanina, Tatiana V; Yadav, Pramod K; Ballou, David P; Banerjee, Ruma

2015-10-09

The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be -123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Esterification of Oleic Acid for Biodiesel Production Catalyzed by SnCl2: A Kinetic Investigation

Directory of Open Access Journals (Sweden)

Marcio J. da Silva

2008-09-01

Full Text Available The production of biodiesel from low-cost raw materials which generally contain high amounts of free fatty acids (FFAs is a valuable alternative that would make their production costs more competitive than petroleum-derived fuel. Currently, the production of biodiesel from this kind of raw materials comprises a two-stage process, which requires an initial acid-catalyzed esterification of the FFA, followed by a basecatalyzed transesterification of the triglycerides. Commonly, the acid H2SO4 is the catalyst on the first step of this process. It must be said, however, that major drawbacks such as substantial reactor corrosion and the great generation of wastes, including the salts formed due to neutralization of the mineral acid, are negative and virtually unsurmountable aspects of this protocol. In this paper, tin(II chloride dihydrate (SnCl2·2H2O, an inexpensive Lewis acid, was evaluated as catalyst on the ethanolysis of oleic acid, which is the major component of several fat and vegetable oils feedstocks. Tin chloride efficiently promoted the conversion of oleic acid into ethyl oleate in ethanol solution and in soybean oil samples, under mild reaction conditions. The SnCl2 catalyst was shown to be as active as the mineral acid H2SO4. Its use has relevant advantages in comparison to mineral acids catalysts, such as less corrosion of the reactors and as well as avoiding the unnecessary neutralization of products. Herein, the effect of the principal parameters of reaction on the yield and rate of ethyl oleate production has been investigated. Kinetic measurements revealed that the esterification of oleic acid catalyzed by SnCl2·2H2O is first-order in relation to both FFAs and catalyst concentration. Experimentally, it was verified that the energy of activation of the esterification reaction of oleic acid catalyzed by SnCl2 was very close those reported for H2SO4.

An efficient protocol for copper-free palladium-catalyzed Sonogashira cross-coupling in aqueous media at low temperatures

KAUST Repository

Marziale, Alexander N.

2011-11-01

A thorough study on copper-free Sonogashira cross-couplings in water was carried out using the palla-dacycle, [{Pd(μ-Cl){K2-P,C-P(iPr) 2(OC6H3-2-Ph)}}2] as pre-catalyst with different bases and palladium concentrations. The highly active pre-catalyst imparts good to near quantitative yields using a concentration of 0.25 mol % at 40 °C. This broadly applicable protocol exhibits high tolerance of functional groups and substitution patterns. © 2011 Elsevier Ltd. All rights reserved.

Photoredox-Catalyzed Stereoselective Conversion of Alkynes into Tetrasubstituted Trifluoromethylated Alkenes.

Science.gov (United States)

Tomita, Ren; Koike, Takashi; Akita, Munetaka

2015-10-26

A regio- and stereoselective synthesis of trifluoromethylated alkenes bearing four different substituents has been developed. Stereocontrolled sulfonyloxytrifluoromethylation of unsymmetric internal alkynes with an electrophilic CF3 reagent, namely the triflate salt of the Yagupol'skii-Umemoto reagent, in the presence of an Ir photoredox catalyst under visible-light irradiation afforded trifluoromethylalkenyl triflates with well-predictable stereochemistry resulting from anti addition of the trifluoromethyl and triflate groups. Subsequent palladium-catalyzed cross-couplings led to tetrasubstituted trifluoromethylated alkenes in a highly stereoselective manner. The present method is the first example of a facile one-pot synthesis of tetrasubstituted trifluoromethylated alkenes from simple alkynes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Palladium transport in SiC

Energy Technology Data Exchange (ETDEWEB)

Olivier, E.J., E-mail: jolivier@nmmu.ac.za [Centre for High Resolution Transmission Electron Microscopy, Nelson Mandela Metropolitan University, Port Elizabeth (South Africa); Neethling, J.H. [Centre for High Resolution Transmission Electron Microscopy, Nelson Mandela Metropolitan University, Port Elizabeth (South Africa)

2012-03-15

Highlights: Black-Right-Pointing-Pointer We investigate the reaction of Pd with SiC at typical HTGR operating temperatures. Black-Right-Pointing-Pointer The high temperature mobility of palladium silicides within polycrystalline SiC was studied. Black-Right-Pointing-Pointer Corrosion of SiC by Pd was seen in all cases. Black-Right-Pointing-Pointer The preferential corrosion and penetration of Pd along grain boundaries in SiC was found. Black-Right-Pointing-Pointer The penetration and transport of palladium silicides in SiC along grain boundaries was found. - Abstract: This paper reports on a transmission electron microscopy (TEM) and scanning electron microscopy (SEM) study of Pd corroded SiC. The reaction of Pd with different types of SiC at typical HTGR operating temperatures was examined. In addition the high temperature mobility of palladium silicides within polycrystalline SiC was investigated. The results indicated corrosion of the SiC by Pd in all cases studied. The corrosion leads to the formation of palladium silicides within the SiC, with the predominant phase found being Pd{sub 2}Si. Evidence for the preferential corrosion and penetration of Pd along grain boundaries in polycrystalline SiC was found. The penetration and transport, without significant corrosion, of palladium silicides into polycrystalline SiC along grain boundaries was also observed. Implications of the findings with reference to the use of Tri Isotropic particles in HTGRs will be discussed.

Candida Rugosa Lipase-catalyzed Kinetic Resolution of 3-(Isobutyryloxy)methyl 4-[2-(Difluoromethoxy)phenyl]-2-methyl-5,5-dioxo-1,4-dihydrobenzothieno[3,2-b]pyridine-3-carboxylate

NARCIS (Netherlands)

Sobolev, A.; Zhalubovskis, R.; Franssen, M.C.R.; Vigante, B.; Chekavichus, B.; Duburs, G.; Groot, de Æ.

2004-01-01

The lipase-catalyzed kinetic resolution of 3-(isobutyryloxy)methyl 4-[2-(difluoromethoxy)phenyl]-2-methyl-5,5-dioxo-1,4-dihydrobenzothieno[3,2-b]pyridine-3-carboxylate has been performed. The most enantioselective reaction (E = 28) was transesterification with n-butanol in water-saturated toluene at

Unexpectedly high uptake of palladium by bituminous coals

Energy Technology Data Exchange (ETDEWEB)

Lakatos, J. [Research Lab. for Mining Chemistry, Hungarian Academy of Sciences, Miskolc-Egyetemvaros (Hungary); Brown, S.D.; Snape, C.E. [Univ. of Strathclyde, Dept. of Pure and Applied Chemistry, Glasgow (United Kingdom)

1997-12-31

The uptake of palladium as a conversion catalyst onto coals of different rank was investigated. Palladium fixation occurs by a different mode to that for alkaline earth and first row transition metals. Therefore, the dispersion of relatively high concentration of palladium by an ion sorption process is even possible for bituminous coals. (orig.)

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.

Modeling aerobic biodegradation in the capillary fringe.

Science.gov (United States)

Luo, Jian; Kurt, Zohre; Hou, Deyi; Spain, Jim C

2015-02-03

Vapor intrusion from volatile subsurface contaminants can be mitigated by aerobic biodegradation. Laboratory column studies with contaminant sources of chlorobenzene and a mixture of chlorobenzene, 1,2-dichlorobenzene, and 1,4-dichlorobenzene showed that contaminants were rapidly degraded in thin reactive zones with high biomass and low substrate concentrations in the vicinity of the capillary fringe. Such behavior was well characterized by a model that includes oxygen-, substrate-, and biomass-dependent biodegradation kinetics along with diffusive transport processes. An analytical solution was derived to provide theoretical support for the simplification of reaction kinetics and the approximation of reactive zone location and mass flux relationships at steady state. Results demonstrate the potential of aerobic natural attenuation in the capillary fringe for preventing contaminant migration in the unsaturated zone. The solution indicates that increasing contaminant mass flux into the column creates a thinner reactive zone and pushes it toward the oxygen boundary, resulting in a shorter distance to the oxygen source and a larger oxygen mass flux that balances the contaminant mass flux. As a consequence, the aerobic biodegradation can reduce high contaminant concentrations to low levels within the capillary fringe and unsaturated zone. The results are consistent with the observations of thin reactive layers at the interface in unsaturated zones. The model considers biomass while including biodegradation in the capillary fringe and unsaturated zone and clearly demonstrates that microbial communities capable of using the contaminants as electron donors may lead to instantaneous degradation kinetics in the capillary fringe and unsaturated zone.

Kinetic formulae for muon-catalyzed fusion of hydrogen isotopes and their application to the description of the data for pure deuterium

International Nuclear Information System (INIS)

Gula, A.

1987-01-01

The data on the time distributions of muon-catalyzed fusion (μCF) events in pure deuterium targets published before 1987 are analysed using the kinetic formalism developed by the author and collaborators in a series of papers. The formalism enables one to describe these time distributions in an arbitrary mixture of hydrogen isotopes with strict inclusion of registration efficiency and dead time. The kinetic formulae for such distributions can be readily obtained using a prescription based on the theory of signal-flow graphs even for very complicated kinetic situations, thus, allowing one to avoid the simplifying assumptions which have been usually made in earlier analyses. Practically all important processes forming the muon-catalysis chain can be strictly taken into account in the approximation of constant transition rates. Consecutive μCF cycles can be described separately, which provides a useful tool in data analysis. The developed formalism is applied to the existing data for pure deuterium. First cycle-by-cycle time distributions reported for room temperature by the Gatchina group are analysed. 93 refs., 14 figs. (author)

Electrooxidation of aliphatic alcohols on palladium oxide catalyst prepared by pulsed electrodeposition technique

International Nuclear Information System (INIS)

Casella, Innocenzo G.

2009-01-01

Palladium film can be deposited on gold polycrystalline electrodes, from a deoxygenated alkaline solution containing 50 mM NaOH plus 0.5 mM K 2 Pd(CN) 4 . A multipulse sequence of potentials of equal amplitude and duration was used for the palladium deposition process. In particular, an optimized waveform of potentials of E 1 = 1.0 V vs. SCE and E 2 = -1.0 V vs. SCE for the relevant pulse duration of t 1 = 0.05 s and t 2 = 0.05 s, for 30 s, was used. Cyclic voltammetry and scanning electron microscopy (SEM) were employed to characterize the gold-palladium modified electrode (Au-Pd) towards the electrooxidation of aliphatic alcohols in alkaline solutions. The voltammetric study suggests that the kinetics involved in the alcohol electrooxidation at the Pd-Au electrode are sensibly higher than those observed on the bare Pd and Au electrodes. In addition, the most interesting aspect of the electrooxidation of aliphatic alcohols at the Au-Pd electrode was that as the number of methylene groups on the homologous series of aliphatic alcohols increased, the molar response also increased. Under pulsed chronoamerometric conditions (PCC), using an optimized triple pulse waveform of potentials the modified electrode exhibits interesting catalytic currents without any apparent poisoning effects during the oxidation of aliphatic alcohols.

A kinetic mechanistic study of acid-catalyzed alkylation of isobutane with C4-olefins at low temperatures

Energy Technology Data Exchange (ETDEWEB)

Doshi, B.M.

1978-01-01

A kinetic and mechanistic study of sulfuric acid-catalyzed alkylation of isobutane with C/sub 4/-Olefins at Low Temperatures(-20/sup 0/ to 0/sup 0/C) was based on a new two-step reaction sequence in which the desired first-step reactions are between acid and olefin to form sulfates and the desired second-step reactions are between sulfates and isobutane to form mostly trimethylpentanes. Linear butenes formed stable sulfates that formed alkylates of exceptionally high quality, up to 100 Research octane, whereas isobutylene and trimethylpentene mainly polymerized during the first step, and the alkylate produced had only 90 Research octane. Trimethylpentanes and dimethylhexanes, when contacted with concentrated sulfuric acid at -10/sup 0/ to +25/sup 0/C, degraded and isomerized to form C/sub 4/-C/sub 9/ and higher isoparaffins and acid-soluble hydrocarbons (conjunct polymers). For the two-step process and the degradation and isomerization reactions, kinetic models based on reaction at the interface were developed; but for isoolefins, a polymerization-cracking sequence (via C/sub 12/- and even C/sub 16/-olefins) is the preferred route. Commercial applications of the results are proposed.

: Recyclable, ligand free palladium(II) catalyst for Heck reaction

Indian Academy of Sciences (India)

well as heterogeneous palladium catalysts, generated from either palladium(0) compounds or palladium(II) acetate or chloride salts.6 Several ligands such as phosphines, phoshites, carbenes, thioethers have been successfully employed for this reaction.7 However, homogeneous catalysis results in problems of recovery.

Palladium allergy in relation to dentistry

NARCIS (Netherlands)

Muris, J.

2015-01-01

Palladium is a metal that is used as alloying metal for dental crowns and bridges. This thesis focusses on the possible impact of oral exposure to this metal on the immune system, and allergy in particular. An alternative skin test allergen for diagnosing palladium allergy is introduced: (di)sodium

The Mechanism of Redox Reaction between Palladium(II Complex Ions and Potassium Formate in Acidic Aqueous Solution

Directory of Open Access Journals (Sweden)

Wojnicki M.

2017-06-01

Full Text Available The kinetics studies of redox reaction between palladium(II chloride complex ions and potassium formate in acidic aqueous solutions was investigated. It was shown, that the reduction reaction of Pd(II is selective in respect to Pd(II complex structure. The kinetic of the process was monitored spectrophotometrically. The influence of chloride ions concentration, Pd(II initial concentration, reductant concentration, ionic strength as well as the temperature were investigated in respect to the process dynamics. Arrhenius equation parameters were determined and are equal to 65.8 kJ/mol, and A = 1.12×1011 s−1.

Spectroscopic study of low-temperature hydrogen absorption in palladium

Energy Technology Data Exchange (ETDEWEB)

Ienaga, K., E-mail: ienaga@issp.u-tokyo.ac.jp; Takata, H.; Onishi, Y.; Inagaki, Y.; Kawae, T. [Department of Applied Quantum Physics, Faculty of Engineering, Kyushu University, Motooka, Nishi-Ku, Fukuoka 819-0395 (Japan); Tsujii, H. [Department of Physics, Faculty of Education, Kanazawa University, Kakuma-machi, Kanazawa 920-1192 (Japan); Kimura, T. [Department of Physics, Kyushu University, Hakozaki, Higashi-Ku, Fukuoka 812-8581 (Japan)

2015-01-12

We report real-time detection of hydrogen (H) absorption in metallic palladium (Pd) nano-contacts immersed in liquid H{sub 2} using inelastic electron spectroscopy (IES). After introduction of liquid H{sub 2}, the spectra exhibit the time evolution from the pure Pd to the Pd hydride, indicating that H atoms are absorbed in Pd nano-contacts even at the temperature where the thermal process is not expected. The IES time and bias voltage dependences show that H absorption develops by applying bias voltage 30 ∼ 50 mV, which can be explained by quantum tunneling. The results represent that IES is a powerful method to study the kinetics of high density H on solid surface.

MONTANA PALLADIUM RESEARCH INITIATIVE

Energy Technology Data Exchange (ETDEWEB)

Peters, John; McCloskey, Jay; Douglas, Trevor; Young, Mark; Snyder, Stuart; Gurney, Brian

2012-05-09

Project Objective: The overarching objective of the Montana Palladium Research Initiative is to perform scientific research on the properties and uses of palladium in the context of the U.S. Department of Energy's Hydrogen, Fuel Cells and Infrastructure Technologies Program. The purpose of the research will be to explore possible palladium as an alternative to platinum in hydrogen-economy applications. To achieve this objective, the Initiatives activities will focus on several cutting-edge research approaches across a range of disciplines, including metallurgy, biomimetics, instrumentation development, and systems analysis. Background: Platinum-group elements (PGEs) play significant roles in processing hydrogen, an element that shows high potential to address this need in the U.S. and the world for inexpensive, reliable, clean energy. Platinum, however, is a very expensive component of current and planned systems, so less-expensive alternatives that have similar physical properties are being sought. To this end, several tasks have been defined under the rubric of the Montana Palladium Research Iniative. This broad swath of activities will allow progress on several fronts. The membrane-related activities of Task 1 employs state-of-the-art and leading-edge technologies to develop new, ceramic-substrate metallic membranes for the production of high-purity hydrogen, and develop techniques for the production of thin, defect-free platinum group element catalytic membranes for energy production and pollution control. The biomimetic work in Task 2 explores the use of substrate-attached hydrogen-producing enzymes and the encapsulation of palladium in virion-based protein coats to determine their utility for distributed hydrogen production. Task 3 work involves developing laser-induced breakdown spectroscopy (LIBS) as a real-time, in situ diagnostic technique to characterize PGEs nanoparticles for process monitoring and control. The systems engineering work in task 4

Spatially isolated palladium in porous organic polymers by direct knitting for versatile organic transformations

KAUST Repository

Wang, Xinbo; Min, Shixiong; Das, Swapan Kumar; Fan, Wei; Huang, Kuo-Wei; Lai, Zhiping

2017-01-01

We report here a direct knitting Method for preparation of highly robust, effective while air- and moisture-tolerant, and readily recyclable three-dimensional (3D) porous polymer-Pd network (PPPd) from the widely used Pd(PPh3)4. Electro-beam induced Pd atom crystallization was observed for the first time in organic polymer and revealed the ultrafine dispersion of palladium atoms. Challenging types of Suzuki-Miyaura couplings, reductive coupling of aryl halides and oxidative coupling of arylboronic acid were successively catalyzed by PPPd in aqueous media. Also catalytically selective CH functionalization reactions were achieved with orders of magnitude more efficient than conventional Pd homogeneous catalysts. The strategy developed here provides a practical method for easy-to-make yet highly efficient heterogeneous catalysis.

Spatially isolated palladium in porous organic polymers by direct knitting for versatile organic transformations

KAUST Repository

Wang, Xinbo

2017-10-03

We report here a direct knitting Method for preparation of highly robust, effective while air- and moisture-tolerant, and readily recyclable three-dimensional (3D) porous polymer-Pd network (PPPd) from the widely used Pd(PPh3)4. Electro-beam induced Pd atom crystallization was observed for the first time in organic polymer and revealed the ultrafine dispersion of palladium atoms. Challenging types of Suzuki-Miyaura couplings, reductive coupling of aryl halides and oxidative coupling of arylboronic acid were successively catalyzed by PPPd in aqueous media. Also catalytically selective CH functionalization reactions were achieved with orders of magnitude more efficient than conventional Pd homogeneous catalysts. The strategy developed here provides a practical method for easy-to-make yet highly efficient heterogeneous catalysis.

High stability of palladium/kieselguhr composites during absorption/desorption cycling for hydrogen isotope separation

Energy Technology Data Exchange (ETDEWEB)

Lei, Yang, E-mail: lei.y@outlook.com; Liu, Xiaopeng; Li, Shuo; Jiang, Lijun; Zhang, Chao; Li, Shuai; He, Di; Wang, Shumao

2016-12-15

Highlights: • Pd/K composites with as high as 57 wt.% of Pd have been successfully prepared. • Palladium particles can be effectively packed into the pores of kieselguhr substrates. • Variation of heat-treatment temperatures hardly affect hydrogen absorption capacity and hydrogen saturation time of the Pd/K. • Anti-pulverization property of Pd/K can be improved by packing palladium into the kieselguhr internal pores and heating at 1300 °C. - Abstract: Palladium/kieselguhr (Pd/K) composites with 57 wt.% of Pd were prepared by an improved dipping and thermal decomposition method and heated at elevated temperature to reduce breakdown during hydrogenation-dehydrogenation cycles. The hydrogen absorption kinetic properties of the samples heated at different temperatures were tested under the condition of 20 °C with 100 kPa hydrogen pressure. The 1300 °C heated Pd/K composites were repeated up to 4010 absorption and desorption cycles at temperature ranges between −40 °C and 200 °C. The results show that the phase structure, hydrogen absorption capacity and hydrogen saturation time of the Pd/K were not affected by the change of heat-treated temperatures. And after heat treatment at 1300 °C, the Pd/K particles were strengthened and fraction of larger than 80 mesh were as high as 93.4%.

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

DEFF Research Database (Denmark)

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

2013-01-01

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

Chemical recovery of a palladium-103 from irradiated silver target

International Nuclear Information System (INIS)

Lapshina, E.V.; Kokhanyuk, V.M.; Zhuikov, B.L.; Myasoedova, G.V.; Zakhartchenko, E.A.; Phillips, D.R.; Jamriska, D.J.

2003-01-01

The goal of this work is to develop an extraction method of no-carrier-added palladium-103 from silver. Metallic silver targets were irradiated by protons with the energy of 60-140 MeV to generate palladium-103. Other radioactive isotopes of rhodium, ruthenium, technetium, palladium and silver are also formed at the same time. Two methods of Pd-103 recovering from irradiated silver target are considered. The first one includes the dissolving of the irradiated silver target in nitric acid followed by adding of hydrochloric acid to the solution. Palladium with rhodium, ruthenium and technetium completely remained in solution while silver was precipitated in the form of silver chloride. Extraction of palladium from the obtained solution was provided by the formation of palladium complex with a chelate sorbent which is specific to palladium in acidic solutions. The sorbent makes it possible to separate palladium from admixtures of rhodium, ruthenium and technetium isotopes. The polymeric complex-forming sorbent of fibrous structure with the groups of 3 (5) - methylpyrazole (POLYORGS-15n) is used. An other possible method has been also studied. It includes again dissolving of metallic silver in nitric acid, but does not need silver chloride precipitation. Silver may be sorbed by the complex-forming sorbents, but its sorption is very sensitive to acid concentration. Chelate sorbents of fibrous structure with the groups of amidoxime and hydrazidine (POLYORGS-33n) have been successfully used in our experiments. A high efficiency of palladium extraction by POLYORGS-33n from 2-4 M nitric acid solutions was achieved. Concentrated hydrochloric acid (without heating) was used for palladium desorption with higher yield than in the first method. (authors)

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

Science.gov (United States)

Manikandan, Rajendran; Jeganmohan, Masilamani

2017-08-08

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

Decarbonylative Phosphorylation of Amides by Palladium and Nickel Catalysis: The Hirao Cross-Coupling of Amide Derivatives.

Science.gov (United States)

Liu, Chengwei; Szostak, Michal

2017-10-02

Considering the ubiquity of organophosphorus compounds in organic synthesis, pharmaceutical discovery agrochemical crop protection and materials chemistry, new methods for their construction hold particular significance. A conventional method for the synthesis of C-P bonds involves cross-coupling of aryl halides and dialkyl phosphites (the Hirao reaction). We report a catalytic deamidative phosphorylation of a wide range of amides using a palladium or nickel catalyst giving aryl phosphonates in good to excellent yields. The present method tolerates a wide range of functional groups. The reaction constitutes the first example of a transition-metal-catalyzed generation of C-P bonds from amides. This redox-neutral protocol can be combined with site-selective conventional cross-coupling for the regioselective synthesis of potential pharmacophores. Mechanistic studies suggest an oxidative addition/transmetallation pathway. In light of the importance of amides and phosphonates as synthetic intermediates, we envision that this Pd and Ni-catalyzed C-P bond forming method will find broad application. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Palladium Nanoparticle Hydrogen Sensor

Directory of Open Access Journals (Sweden)

I. Pavlovsky

2006-12-01

Full Text Available An innovative hydrogen sensor based on palladium (Pd nanoparticle networks is described in the article. Made by Applied Nanotech Inc. sensor has a fast response time, in the range of seconds, which is increased at 80 °C due to higher hydrogen diffusion rates into the palladium lattice. The low detection limit of the sensor is 10 ppm of H2, and the high limit is 40,000 ppm. This is 100% of a lowest flammability level of hydrogen. This range of sensitivities complies with the requirements that one would expect for a reliable hydrogen sensor.

[The biology of aerobic methylobacteria capable of degrading halomethanes].

Science.gov (United States)

Trotsenko, Iu A; Doronina, N V

2003-01-01

Recent data on the biology of aerobic methylotrophic bacteria capable of utilizing toxic halogenated methane derivatives as sources of carbon and energy are reviewed, with particular emphasis on the taxonomic, physiological, and biochemical diversity of mono- and dihalomethane-degrading methylobacteria and the enzymatic and genetic aspects of their primary metabolism. The initial steps of chloromethane dehalogenation to formate and HCl through a methylated corrinoid and methyletrahydrofolate are catalyzed by inducible cobalamin methyl transferase, made up of two proteins (CmuA and CmuB) encoded by the cmuA and cmuB genes. At the same time, the primary dehalogenation of dichloromethane to formaldehyde and HCl is catalyzed by cytosolic glutathione transferase with S-chloromethylglutathione as an intermediate. The latter enzyme is encoded by the structural dcmA gene and is under the negative control of the regulatory dcmR gene. In spite of considerable progress in the study of halomethane dehalogenation, some aspects concerning the structural and functional organization of this process and its regulation remain unknown, including the mechanisms of halomethane transport, the release of toxic dehalogenation products (S-chloromethylglutathione, CH2O, and HCl) from cells, and the maintenance of intracellular pH. Of particular interest is quantitative evaluation of the ecophysiological role of aerobic methylobacteria in the mineralization of halomethanes and protection of the biosphere from these toxic pollutants.

Nitrile-assisted oxidation over oxidative-annulation: Pd-catalyzed α,β-dehydrogenation of α-cinnamyl β-keto nitriles.

Science.gov (United States)

Nallagonda, Rajender; Reddy, Reddy Rajasekhar; Ghorai, Prasanta

2017-09-13

A palladium-catalyzed oxidation reaction is disclosed where the nitrile functionality on the substrate simply changes the course of the reaction. Our previous finding showed that using the Pd(ii)-catalyst in the presence of benzoquinone as an oxidant, 2-cinnamyl-1,3-dicarbonyls provides functionalized furans via oxidative cyclization. When a nitrile group is replaced with one of the carbonyl functionalities of the same substrate, the oxidative cyclization was completely suppressed; instead, the oxidation at the α,β-position occurred to provide α,β,γ,δ-diene containing β-keto nitriles.

Kinetics of Hypotension during 50 Sessions of Resistance and Aerobic Training in Hypertensive Patients: a Randomized Clinical Trial.

Science.gov (United States)

Damorim, Igor Rodrigues; Santos, Tony Meireles; Barros, Gustavo Willames Pimentel; Carvalho, Paulo Roberto Cavalcanti

2017-04-01

Resistance and aerobic training are recommended as an adjunctive treatment for hypertension. However, the number of sessions required until the hypotensive effect of the exercise has stabilized has not been clearly established. To establish the adaptive kinetics of the blood pressure (BP) responses as a function of time and type of training in hypertensive patients. We recruited 69 patients with a mean age of 63.4 ± 2.1 years, randomized into one group of resistance training (n = 32) and another of aerobic training (n = 32). Anthropometric measurements were obtained, and one repetition maximum (1RM) testing was performed. BP was measured before each training session with a digital BP arm monitor. The 50 training sessions were categorized into quintiles. To compare the effect of BP reduction with both training methods, we used two-way analysis of covariance (ANCOVA) adjusted for the BP values obtained before the interventions. The differences between the moments were established by one-way analysis of variance (ANOVA). The reductions in systolic (SBP) and diastolic BP (DBP) were 6.9 mmHg and 5.3 mmHg, respectively, with resistance training and 16.5 mmHg and 11.6 mmHg, respectively, with aerobic training. The kinetics of the hypotensive response of the SBP showed significant reductions until the 20th session in both groups. Stabilization of the DBP occurred in the 20th session of resistance training and in the 10th session of aerobic training. A total of 20 sessions of resistance or aerobic training are required to achieve the maximum benefits of BP reduction. The methods investigated yielded distinct adaptive kinetic patterns along the 50 sessions. Os treinamentos de força e aeróbio são indicados para o tratamento adjuvante da hipertensão. Entretanto, o número de sessões necessárias até estabilização do efeito hipotensor com o exercício ainda não está claramente estabelecido. Estabelecer a cinética adaptativa das respostas tensionais em função do

Kinetics and mechanism of OsOsub(4) catalyzed oxidation of chalcones by Cesub(4) in aqueous acetic sulfuric acid media

International Nuclear Information System (INIS)

Srinivasulu, P.V.; Adinarayana, M.; Sethuram, B.; Rao, T.N.

1985-01-01

Kinetics of OsOsub(4) catalyzed oxidation of chalcones by Cesup(4+) was studied in aqueous acetic-sulfuric acid medium in the temperature range 313 to 338 K. The order in oxidant is zero while the order with respect to substrate and catalyst are each fractional. The rate of the reaction decreased with increase in percentage of acetic acid while [Hsup(+)] had practically no effect on the rate. The rates of various substituted chalcones are given. A mechanism in which formation of a cyclic ester between chalcone and OsOsub(4) in a fast step followed by its decomposition in a rate-determining step is envisaged. (author)

Kinetics and mechanism of oxidation of 1-hydroxymethyl-eta/sup 3/-allypalladium chloride by p-benzoquinone in aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Belov, A.P.; Kalabin, S.M.; Statsenko, O.N.

1988-03-01

/sup 1/H NMR spectroscopy was used to show that the primary product of the oxidation of the eta/sup 3/-allyl complex of palladium, (based on 1,3-butadiene-1-hydroxymethyl-eta/sup 3/-allylpalladium chloride), by the action of p-benzoquinone in acid aqueous solutions is 4-chloro-2-buten-1-o1. The reaction kinetics were studied colorimetrically. It was found that the rate of reaction is described by a kinetic equation of the second order (first with respect to each of the reagents). It was shown that the second order rate constant increases nonlinearly with increase in the concentration of the chloride ions and hydrogen ions, and tends to a constant value in the region of high concentrations of these ions. The values of the activation parameters and the isotopic kinetic effect were determined. The kinetic equation and the mechanism of the reaction studied were compared with those of the oxidation processes of unsubstituted eta/sup 3/-allyl complexes of palladium.

Kinetic and mechanistic studies of base-catalyzed phenylselenoetherification of (Z)- and (E)-hex-4-en-1-ols.

Science.gov (United States)

Divac, Vera M; Puchta, Ralph; Bugarčić, Zorica M

2012-08-02

The mechanism of phenylselenoetherification of (Z)- and (E)-hex-4-en-1-ols using some bases (triethylamine, pyridine, quinoline, 2,2'-bipyridine) as catalysts and some solvents [tetrahydrofuran (THF) and CCl4] as reaction media was examined through studies of kinetics of the cyclization by UV-vis spectrophotometry. It was demonstrated that the intramolecular cyclization is facilitated in the presence of bases as a result of the hydrogen bond between the base and the alkenol's OH group. The rate constants in the base-catalyzed reactions are remarkably influenced by the bulkiness and basicity of the base used and the nature of the considered nitrogen donors. The obtained values for rate constants show that the reaction with triethylamine is the fastest one. THF with higher polarity and higher basic character is better as a solvent than CCl4. Quantum-chemical calculations [MP2(fc)/6-311+G**//B3LYP/6-311+G** + ZPE(B3LYP/6-311+G**] show that the cyclization of (Z)-hex-4-en-1-ol to a tetrahydrofuranoid five-membered ring is kinetically controlled, while the cyclization of (E)-hex-4-en-1-ol to the tetrahydropyranoid six-membered ring is thermodynamically controlled. This is in accordance with previous experimental findings.

Mechanistic rationalization of unusual sigmoidal kinetic profiles in the Machetti-De Sarlo cycloaddition reaction.

Science.gov (United States)

Mower, Matthew P; Blackmond, Donna G

2015-02-18

Unusual sigmoidal kinetic profiles in the Machetti-De Sarlo base-catalyzed 1,3-dipolar cycloaddition of acrylamide to N-methylnitroacetamide are rationalized by detailed in situ kinetic analysis. A dual role is uncovered in which a substrate acts as a precursor to catalyze its own reaction. Such kinetic studies provide a general protocol for distinguishing among different mechanistic origins of induction periods in complex organic reactions.

Evolution of Molybdenum Nitrogenase during the Transition from Anaerobic to Aerobic Metabolism

Science.gov (United States)

Boyd, Eric S.; Costas, Amaya M. Garcia; Hamilton, Trinity L.; Mus, Florence

2015-01-01

ABSTRACT Molybdenum nitrogenase (Nif), which catalyzes the reduction of dinitrogen to ammonium, has modulated the availability of fixed nitrogen in the biosphere since early in Earth's history. Phylogenetic evidence indicates that oxygen (O2)-sensitive Nif emerged in an anaerobic archaeon and later diversified into an aerobic bacterium. Aerobic bacteria that fix N2 have adapted a number of strategies to protect Nif from inactivation by O2, including spatial and temporal segregation of Nif from O2 and respiratory consumption of O2. Here we report the complement of Nif-encoding genes in 189 diazotrophic genomes. We show that the evolution of Nif during the transition from anaerobic to aerobic metabolism was accompanied by both gene recruitment and loss, resulting in a substantial increase in the number of nif genes. While the observed increase in the number of nif genes and their phylogenetic distribution are strongly correlated with adaptation to utilize O2 in metabolism, the increase is not correlated with any of the known O2 protection mechanisms. Rather, gene recruitment appears to have been in response to selective pressure to optimize Nif synthesis to meet fixed N demands associated with aerobic productivity and to more efficiently regulate Nif under oxic conditions that favor protein turnover. Consistent with this hypothesis, the transition of Nif from anoxic to oxic environments is associated with a shift from posttranslational regulation in anaerobes to transcriptional regulation in obligate aerobes and facultative anaerobes. Given that fixed nitrogen typically limits ecosystem productivity, our observations further underscore the dynamic interplay between the evolution of Earth's oxygen, nitrogen, and carbon biogeochemical cycles. IMPORTANCE Molybdenum nitrogenase (Nif), which catalyzes the reduction of dinitrogen to ammonium, has modulated the availability of fixed nitrogen in the biosphere since early in Earth's history. Nif emerged in an anaerobe and

Evolution of molybdenum nitrogenase during the transition from anaerobic to aerobic metabolism.

Science.gov (United States)

Boyd, Eric S; Costas, Amaya M Garcia; Hamilton, Trinity L; Mus, Florence; Peters, John W

2015-05-01

Molybdenum nitrogenase (Nif), which catalyzes the reduction of dinitrogen to ammonium, has modulated the availability of fixed nitrogen in the biosphere since early in Earth's history. Phylogenetic evidence indicates that oxygen (O2)-sensitive Nif emerged in an anaerobic archaeon and later diversified into an aerobic bacterium. Aerobic bacteria that fix N2 have adapted a number of strategies to protect Nif from inactivation by O2, including spatial and temporal segregation of Nif from O2 and respiratory consumption of O2. Here we report the complement of Nif-encoding genes in 189 diazotrophic genomes. We show that the evolution of Nif during the transition from anaerobic to aerobic metabolism was accompanied by both gene recruitment and loss, resulting in a substantial increase in the number of nif genes. While the observed increase in the number of nif genes and their phylogenetic distribution are strongly correlated with adaptation to utilize O2 in metabolism, the increase is not correlated with any of the known O2 protection mechanisms. Rather, gene recruitment appears to have been in response to selective pressure to optimize Nif synthesis to meet fixed N demands associated with aerobic productivity and to more efficiently regulate Nif under oxic conditions that favor protein turnover. Consistent with this hypothesis, the transition of Nif from anoxic to oxic environments is associated with a shift from posttranslational regulation in anaerobes to transcriptional regulation in obligate aerobes and facultative anaerobes. Given that fixed nitrogen typically limits ecosystem productivity, our observations further underscore the dynamic interplay between the evolution of Earth's oxygen, nitrogen, and carbon biogeochemical cycles. Molybdenum nitrogenase (Nif), which catalyzes the reduction of dinitrogen to ammonium, has modulated the availability of fixed nitrogen in the biosphere since early in Earth's history. Nif emerged in an anaerobe and later diversified into

Atomistic simulation of helium bubble nucleation in palladium

Energy Technology Data Exchange (ETDEWEB)

Wang Liang [Department of Applied Physics, Hunan University, Changsha 410082 (China); Hu, Wangyu [Department of Applied Physics, Hunan University, Changsha 410082 (China)], E-mail: wangyuhu2001cn@yahoo.com.cn; Xiao Shifang [Department of Applied Physics, Hunan University, Changsha 410082 (China)], E-mail: sfxiao@yahoo.com.cn; Yang Jianyu [Department of Maths and Physics, Hunan Institute of Engineering, Xiangtan 411104 (China); Deng Huiqiu [Department of Applied Physics, Hunan University, Changsha 410082 (China)

2009-09-15

A palladium crystal has been constructed with 11808 atoms. 55 helium atoms occupied the octahedral position of palladium crystal are introduced and retained in a spherical region. Molecular dynamic simulations are performed in a constant temperature and constant volume ensemble (NVT) with temperature controlled by Nose-Hoover thermostat. The interactions between palladium atoms are described with modified analytic embedded atom method (MAEAM), the interactions between palladium atom and helium atom are in the form of Morse potential, and the interactions between helium atoms are in the form of L-J potential function. With the analysis of the radial distribution function (RDF) and microstructure, it reveals that some of helium atoms form a series of clusters with different size, and the nucleation core is random at low temperature, and which is the embryo of helium bubble. Increasing temperature can accelerate the process of bubble nucleation, and the clusters will aggregate and coalesce into a bigger one in which there are no palladium atoms, and it is considered as a helium bubble.

Nanocomposite catalyst with palladium nanoparticles encapsulated in a polymeric acid: A model for tandem environmental catalysis

KAUST Repository

Isimjan, Tayirjan T.

2013-04-01

The synthesis and characterization of a novel hybrid nanocomposite catalyst comprised of palladium nanoparticles embedded in polystyrene sulfonic acid (PSSH) and supported on metal oxides is reported. The catalysts are intended for application in green catalysis, and they are shown to be effective in the hydrolysisreduction sequence of tandem catalytic reactions required for conversion of 2-phenyl-1,3-dioxolane to toluene or of phenol to cyclohexane. The two distinct components in the catalyst, Pd nanoparticles and acidic PSSH, are capable of catalyzing sequential reactions in one pot under mild conditions. This work has demonstrated a powerful approach toward designing highperformance, multifunctional, scalable, and environmentally friendly nanostructured tandem catalysts. © 2013 American Chemical Society.

Eosin Y Catalyzed Visible-Light-Promoted Aerobic Oxidative Cyclization of 2-Aminobenzothiazole

Directory of Open Access Journals (Sweden)

Vishal Srivastava

2015-12-01

Full Text Available A mild and efficient one-pot visible light irradiated synthesis of 2-aminobenzothiazole 4(a–l from arylisothiocyanate 1(a–l and secondary amines 2 have been reported in presence of eosin Y as an organophotoredox catalyst at room temperature under aerobic condition. This synthesis includes application of air and visible light as inexpensive, readily available, high atom economy, non-toxic and sustainable regents.

Synthesis of 4-substituted tetrahydropyridines by cross-coupling of enol phosphates

DEFF Research Database (Denmark)

Larsen, U.S.; Martiny, L.; Begtrup, M.

2005-01-01

Enol phosphates, synthesized from 4-piperidone, react by palladium catalyzed cross-coupling with arylboronic acids and by iron and palladium catalyzed cross-coupling with Grignard reagents to give 4-substituted tetrahydropyridines. (c) 2005 Elsevier Ltd. All rights reserved....

An intramolecular [2 + 2] cycloaddition of ketenimines via palladium-catalyzed rearrangements of N-allyl-ynamides.

Science.gov (United States)

DeKorver, Kyle A; Hsung, Richard P; Song, Wang-Ze; Wang, Xiao-Na; Walton, Mary C

2012-06-15

A cascade of Pd-catalyzed N-to-C allyl transfer-intramolecular ketenimine-[2 + 2] cycloadditions of N-allyl ynamides is described. This tandem sequence is highly stereoselective and the [2 + 2] cycloaddition could be rendered in a crossed or fused manner depending on alkene substitutions, leading to bridged and fused bicycloimines.

Californium Recovery from Palladium Wire

Energy Technology Data Exchange (ETDEWEB)

Burns, Jon D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2014-08-01

The recovery of ²⁵²Cf from palladium-²⁵²Cf cermet wires was investigated to determine the feasibility of implementing it into the cermet wire production operation at Oak Ridge National Laboratory’s Radiochemical Engineering Development Center. The dissolution of Pd wire in 8 M HNO₃ and trace amounts of HCl was studied at both ambient and elevated temperatures. These studies showed that it took days to dissolve the wire at ambient temperature and only 2 hours at 60°C. Adjusting the ratio of the volume of solvent to the mass of the wire segment showed little change in the kinetics of dissolution, which ranged from 0.176 mL/mg down to 0.019 mL/mg. A successful chromatographic separation of ¹⁵³Gd, a surrogate for ²⁵²Cf, from Pd was demonstrated using AG 50x8 cation exchange resin with a bed volume of 0.5 mL and an internal diameter of 0.8 cm.

Kinetics of an acid-base catalyzed reaction (aspartame degradation) as affected by polyol-induced changes in buffer pH and pK values.

Science.gov (United States)

Chuy, S; Bell, L N

2009-01-01

The kinetics of an acid-base catalyzed reaction, aspartame degradation, were examined as affected by the changes in pH and pK(a) values caused by adding polyols (sucrose, glycerol) to phosphate buffer. Sucrose-containing phosphate buffer solutions had a lower pH than that of phosphate buffer alone, which contributed, in part, to reduced aspartame reactivity. A kinetic model was introduced for aspartame degradation that encompassed pH and buffer salt concentrations, both of which change with a shift in the apparent pK(a) value. Aspartame degradation rate constants in sucrose-containing solutions were successfully predicted using this model when corrections (that is, lower pH, lower apparent pK(a) value, buffer dilution from the polyol) were applied. The change in buffer properties (pH, pK(a)) from adding sucrose to phosphate buffer does impact food chemical stability. These effects can be successfully incorporated into predictive kinetic models. Therefore, pH and pK(a) changes from adding polyols to buffer should be considered during food product development.

SHORT COMMUNICATION CATALYTIC KINETIC ...

African Journals Online (AJOL)

IV) catalyzes the discoloring reaction of DBS-arsenazo oxidized by potassium bromate, a new catalytic kinetic spectrophotometric method for the determination of trace titanium (IV) was developed. The linear range of the determination of ...

VSS Degradation Kinetics in High Temperature Aerobic Digestion and Microbial Community Characteristics

Directory of Open Access Journals (Sweden)

Yunfen Shi

2018-01-01

Full Text Available Piggery wastewater is a kind of high concentration organic wastewater with high concentration of pollutants, large amount of emissions, and serious environmental pollution and is difficult to deal with. Piggery wastewater was treated with autothermal hyperthermia aerobic digestion process (ATAD and its biodegradation kinetics was studied. The ATAD system was automatically heated up and the reaction temperature rose from ambient temperature of 20°C to a maximum temperature of 64°C. Based on Arrhenius formula, the empirical model is obtained through dimensional analysis. The removal of volatile suspended solids (VSS was correlated with the initial VSS concentration, water inlet temperature, aeration rate, and agitation rate in the model. In the empirical model, the apparent activation energy was 2.827 kJ·mol−1. The exponentials for the initial VSS concentration, aeration rate, and stirring rate were 1.0587, −0.0976, and −0.1618, respectively. The correlation coefficient of the exponential factor was 0.9971. The VSS removal efficiency predicted by the model was validated with an actual test, showing a maximum relative deviation of 8.82%. Sludge systems show a lower diversity of microbial populations and Bacillus occupies a very important position in the reactor. The data obtained will be useful for optimizing piggery wastewater treatment process. The new model provided good theoretical guidance with good practicality.

Hydrogen Production via Steam Reforming of Ethyl Alcohol over Palladium/Indium Oxide Catalyst

Directory of Open Access Journals (Sweden)

Tetsuo Umegaki

2009-01-01

Full Text Available We report the synergetic effect between palladium and indium oxide on hydrogen production in the steam reforming reaction of ethyl alcohol. The palladium/indium oxide catalyst shows higher hydrogen production rate than indium oxide and palladium. Palladium/indium oxide affords ketonization of ethyl alcohol with negligible by-product carbon monoxide, while indium oxide mainly affords dehydration of ethyl alcohol, and palladium affords decomposition of ethyl alcohol with large amount of by-product carbon monoxide. The catalytic feature of palladium/indium oxide can be ascribed to the formation of palladium-indium intermetallic component during the reaction as confirmed by X-ray diffraction and X-ray photoelectron spectroscopic measurements.

Fabrication of palladium-based microelectronic devices by microcontact printing

International Nuclear Information System (INIS)

Wolfe, Daniel B.; Love, J. Christopher; Paul, Kateri E.; Chabinyc, Michael L.; Whitesides, George M.

2002-01-01

This letter demonstrates the patterning of thin films of metallic palladium by microcontact printing (μCP) of octadecanethiol, and the use of the patterned films in the fabrication of a functional sensor. This technique was also used to prepare templates of palladium for the electroless deposition of copper. The resistivity of the palladium and copper microstructures was 13.8 and 2.8 μΩ cm, respectively; these values are approximately 40% larger than the values for the pure bulk metals. Palladium patterned into serpentine wires using μCP functioned as a hydrogen sensor with sensitivity of 0.03 vol % H 2 in N 2 , and a response time of ∼10 s (at room temperature)

Palladium-catalyzed Asymmetric Hydrosilylation of Styrene and Its Derivatives with Chiral Phosphoramidite Ligands Containing Chiral Ferrocenyl Amine

Energy Technology Data Exchange (ETDEWEB)

Park, Hyun-Sub; Kim, Min Young; Ahn, Hyo Jin; Han, Jin Wook [Hanyang University, Seoul (Korea, Republic of)

2016-06-15

Asymmetric hydrosilylation was one of the most effective methods, which provided optically active organosilanes as a synthetically useful intermediate in organic synthesis. One useful transformation is the Tamao-Fleming oxidation, which is an oxidation reaction of carbon[BOND]silicone bond to afford optically active alcohols with retention of configuration. It is demonstrated that a palladium catalyst coordinating with phosphoramidite ligand (S {sub a},R {sub c},R {sub c,})-L3a from (S)-BINOL and chiral bis((R)-1-ferrocenylethyl) amine shows a high catalytic activity and enantioselectivity up to 97% ee in asymmetric hydrosilylation of styrene and its derivatives. The hydrosilylation of various olefin substrates using these ligands is in progress.

Mechanistic Investigation of Palladium–Catalyzed Allylic C–H Activation

DEFF Research Database (Denmark)

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

2013-01-01

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

Rhodium-catalyzed C-H bond activation for the synthesis of quinonoid compounds: Significant Anti-Trypanosoma cruzi activities and electrochemical studies of functionalized quinones.

Science.gov (United States)

Jardim, Guilherme A M; Silva, Thaissa L; Goulart, Marilia O F; de Simone, Carlos A; Barbosa, Juliana M C; Salomão, Kelly; de Castro, Solange L; Bower, John F; da Silva Júnior, Eufrânio N

2017-08-18

Thirty four halogen and selenium-containing quinones, synthesized by rhodium-catalyzed C-H bond activation and palladium-catalyzed cross-coupling reactions, were evaluated against bloodstream trypomastigotes of T. cruzi. We have identified fifteen compounds with IC 50 /24 h values of less than 2 μM. Electrochemical studies on A-ring functionalized naphthoquinones were also performed aiming to correlate redox properties with trypanocidal activity. For instance, (E)-5-styryl-1,4-naphthoquinone 59 and 5,8-diiodo-1,4-naphthoquinone 3, which are around fifty fold more active than the standard drug benznidazole, are potential derivatives for further investigation. These compounds represent powerful new agents useful in Chagas disease therapy. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Silver-Palladium Surfaces Inhibit Biofilm Formation

DEFF Research Database (Denmark)

Chiang, Wen-Chi; Schroll, Casper; Hilbert, Lisbeth Rischel

2009-01-01

Undesired biofilm formation is a major concern in many areas. In the present study, we investigated biofilm-inhibiting properties of a silver-palladium surface that kills bacteria by generating microelectric fields and electrochemical redox processes. For evaluation of the biofilm inhibition...... efficacy and study of the biofilm inhibition mechanism, the silver-sensitive Escherichia coli J53 and the silver-resistant E. coli J53[pMG101] strains were used as model organisms, and batch and flow chamber setups were used as model systems. In the case of the silver-sensitive strain, the silver......-palladium surfaces killed the bacteria and prevented biofilm formation under conditions of low or high bacterial load. In the case of the silver-resistant strain, the silver-palladium surfaces killed surface-associated bacteria and prevented biofilm formation under conditions of low bacterial load, whereas under...

The solubility of palladium(II) bis-dimethylglyoximate

International Nuclear Information System (INIS)

Maghzian, R.

1978-01-01

The solubility of palladium(II) bis-dimethylglyoximate in different solutions has been determined. Values obtained for the solubility of the palladium complex are tabulated. The solubility is the lowest in water, ammonium acetate and a 25% acetone-water mixture. It is highest in dilute HCl and acetone but precipitation from aqueous acetone should be satisfactory for most purposes if the acetone content of the solvent is roughly less than 50% by volume. The solubility in dilute HCl reflects the concern by previous workers for losses in precipitation from mineral acid. In general, however, the losses are unlikely to be significant unless the quantity of palladium to be precipitated and weighed is small. (T.G.)

Ion flotation of rhodium(III) and palladium(II) with anionic surfactants.

Science.gov (United States)

He, X C

1991-03-01

The ion flotation of rhodium(III) and palladium(II) with some anionic surfactants has been investigated. Two flotation procedures are proposed for the separation of some platinum metals, based on differences in the kinetic properties of the chloro-complexes of rhodium(III), palladium(II) and platinum(IV). The first involves the selective flotation of Rh(H(2)O)(3+)(6) from PdCl(2-)(4) and PtCl(2-)(6) in dilute hydrochloric acid with sodium dodecylbenzenesulfonate (SDBS). After precipitation of the hydroxide and redissolution in dilute acid, the Rh(III) is converted into Rh(H(2)O)(3+)(6), Pd(II) and Pt(IV) remaining as PdCl(2-)(4) and PtCl(2-)(6) respectively, and separation is achieved by floating the Rh(H(2)O)(3+)(6) with SDBS. The second is for separation of Pd(II). Prior to flotation, the solution of PdCl(2-)(4) and PtCl(2-)(6) is heated with ammonium acetate to convert PdCl(2-)(4) into Pd(NH(3))(2+)(4). The chloro-complex of Pt(IV) is unaffected. The complex cation, Pd(NH(3))(2+)(4), is then selectively floated with SDBS. The procedures are fast, simple and do not require expensive reagents and apparatus.

Determination of palladium by flame photometry

International Nuclear Information System (INIS)

Parellada Bellod, R.

1964-01-01

A study on the determination of palladium by lame photometry, fixing the most convent experimental conditions and using solvents to increase the emission of this elements is carried out. Among the organic solvents, acetone has been found the most efficient. The interferences produced by anions and cations have also been studied and an analytical method is related, in which lines of calibration of 0 to 100 ppm palladium re used. (Author) 7 refs

Palladium-Catalyzed ortho C-H Arylation of Benzaldehydes Using ortho-Sulfinyl Aniline Transient Auxiliary.

Science.gov (United States)

Mu, Delong; He, Gang; Chen, Gong

2018-05-03

A PdII-catalyzed ortho-(Csp2)-H arylation reaction of benzaldehydes using catalytic amount of 2-methylsulfinyl-aniline as transient auxiliary was developed. This reaction is compatible with a broad range of benzaldehyde and aryl iodide substrates. Compared with other related reaction systems, an excellent regioselectivity for ortho-C(sp2)-H bonds over benzylic C(sp3)-H bonds was obtained for ortho-alkyl-benzaldehyde substrates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of palladium ions by modified carbons from rice husks

International Nuclear Information System (INIS)

Mostafa, M.R.

1994-01-01

Steam activated carbon of high surface area does not show palladium ions adsorption. Treatment of this carbon with HF acid increases to a great extent the gas adsorption capacity expressed as nitrogen surface area as well as the adsorption capacity of palladium ions from aqueous solution. HHB was loaded in different amounts on to these carbons. The acid sites represent the active fraction of the surface on which the adsorption palladium ions proceed. The uptake of palladium ions by HHB treated carbons is related to the total number of HHB molecules loaded on the carbon surface. (author)

Development of Separation Materials Containing Palladium for Hydrogen Isotopes Separation

International Nuclear Information System (INIS)

Deng Xiaojun; Luo Deli; Qian Xiaojing

2010-01-01

Displacement chromatography (DC) is a ascendant technique for hydrogen isotopes separation. The performance of separation materials is a key factor to determine the separation effect of DC. At present,kinds of materials are researched, including palladium materials and non-palladium materials. It is hardly replaceable because of its excellent separation performance, although palladium is expensive. The theory of hydrogen isotopes separation using DC was introduced at a brief manner, while several palladium separation materials were expatiated in detail(Pd/K, Pd-Al 2 O 3 , Pd-Pt alloy). Development direction of separation materials for DC was forecasted elementarily. (authors)

Pd(OAc)2/Ph3P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles.

Science.gov (United States)

Kellner, Dominik; Weger, Maximilian; Gini, Andrea; Mancheño, Olga García

2017-01-01

The palladium-catalyzed dimerization of isoprene is a practical approach of synthesizing monoterpenes. Though several highly selective methods have been reported, most of them still required pressure or costly ligands for attaining the active system and desired selectivity. Herein, we present a simple and economical procedure towards the tail-to-tail dimer using readily available Pd(OAc) 2 and inexpensive triphenylphosphine as ligand. Furthermore, simple screw cap vials are employed, allowing carrying out the reaction at low pressure. In addition, the potential of the dimer as a chemical platform for the preparation of heterocyclic terpenes by subsequent (hetero)-Diels-Alder or [4 + 1]-cycloadditions with nitrenes is also depicted.

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.

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.

General methods for analysis of sequential "n-step" kinetic mechanisms: application to single turnover kinetics of helicase-catalyzed DNA unwinding.

Science.gov (United States)

Lucius, Aaron L; Maluf, Nasib K; Fischer, Christopher J; Lohman, Timothy M

2003-10-01

Helicase-catalyzed DNA unwinding is often studied using "all or none" assays that detect only the final product of fully unwound DNA. Even using these assays, quantitative analysis of DNA unwinding time courses for DNA duplexes of different lengths, L, using "n-step" sequential mechanisms, can reveal information about the number of intermediates in the unwinding reaction and the "kinetic step size", m, defined as the average number of basepairs unwound between two successive rate limiting steps in the unwinding cycle. Simultaneous nonlinear least-squares analysis using "n-step" sequential mechanisms has previously been limited by an inability to float the number of "unwinding steps", n, and m, in the fitting algorithm. Here we discuss the behavior of single turnover DNA unwinding time courses and describe novel methods for nonlinear least-squares analysis that overcome these problems. Analytic expressions for the time courses, f(ss)(t), when obtainable, can be written using gamma and incomplete gamma functions. When analytic expressions are not obtainable, the numerical solution of the inverse Laplace transform can be used to obtain f(ss)(t). Both methods allow n and m to be continuous fitting parameters. These approaches are generally applicable to enzymes that translocate along a lattice or require repetition of a series of steps before product formation.

Activation and deactivation of neutral palladium(II) phosphinesulfonato polymerization catalysts

KAUST Repository

Rünzi, Thomas

2012-12-10

polymerization filtrates indicate the presence of (odd- and even-numbered alkyl)(anisyl)phosphine sulfonates (14) and their respective phosphine oxides (15). Furthermore, 2-(vinyl)anisole was detected in NMR tube and reactor polymerizations, which results from ethylene insertion into a palladium-anisyl bond and concomitant β-hydride elimination. In addition to these scrambling reactions, formation of alkanes or fully saturated polymer chains, bis(chelate)palladium complexes [κ2-P,O]2Pd, and palladium black was identified as an irreversible catalyst deactivation pathway. This deactivation proceeds by reaction of palladium alkyl complexes with palladium hydride complexes [κ2-P,O]Pd(H)(L) or by reaction with the free ligand H[P,O] generated by reductive elimination from [κ2-P,O]Pd(H)(L). The model hydride complex 1-H-P tBu3 has been synthesized in order to establish whether 1-H-PtBu3 or H[P,O] is responsible for the irreversible catalyst deactivation. However, upon reaction with 1-(13)CH 3-L or 1-CH2CH3-PPh3, both 1-H-PtBu3 and H[P,O] result in formation of methane or ethane, even though H[P,O] reacts faster than 1-H-PtBu3. DFT calculations show that reductive elimination to form H[P,O] and (alkyl)[P,O] from 1-H/(alkyl)-PtBu3 is kinetically accessible, as is the oxidative readdition of the P-H bond of H[P,O] and the P-anisyl bond of (alkyl)[P,O] to [Pd(PtBu3)2]. These calculations also indicate that for a reaction sequence comprising reductive elimination of H[P,O] from 1-H-PtBu3 and reaction of H[P,O] with 1-CH3-PtBu3, 1-CH3-dmso, or 1-CH2CH3-PPh3 to form methane or ethane, the rate-limiting step is reductive elimination of H[P,O] with a barrier of 124 kJ mol-1. However, a second reaction coordinate was found for the reaction of 1-H-PtBu3 with 1-CH3-P tBu3 or 1-CH3-dmso, which evolves into bimetallic transition-state geometries with a nearly linear H-(CH 3)-Pd alignment and which exhibits a barrier of 131 or 95 kJ mol -1 for the formation of methane. © 2012 American Chemical

Formal total syntheses of classic natural product target molecules via palladium-catalyzed enantioselective alkylation

Directory of Open Access Journals (Sweden)

Yiyang Liu

2014-10-01

Full Text Available Pd-catalyzed enantioselective alkylation in conjunction with further synthetic elaboration enables the formal total syntheses of a number of “classic” natural product target molecules. This publication highlights recent methods for setting quaternary and tetrasubstituted tertiary carbon stereocenters to address the synthetic hurdles encountered over many decades across multiple compound classes spanning carbohydrate derivatives, terpenes, and alkaloids. These enantioselective methods will impact both academic and industrial settings, where the synthesis of stereogenic quaternary carbons is a continuing challenge.

Constant Growth Rate Can Be Supported by Decreasing Energy Flux and Increasing Aerobic Glycolysis

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Nikolai Slavov

2014-05-01

Full Text Available Fermenting glucose in the presence of enough oxygen to support respiration, known as aerobic glycolysis, is believed to maximize growth rate. We observed increasing aerobic glycolysis during exponential growth, suggesting additional physiological roles for aerobic glycolysis. We investigated such roles in yeast batch cultures by quantifying O2 consumption, CO2 production, amino acids, mRNAs, proteins, posttranslational modifications, and stress sensitivity in the course of nine doublings at constant rate. During this course, the cells support a constant biomass-production rate with decreasing rates of respiration and ATP production but also decrease their stress resistance. As the respiration rate decreases, so do the levels of enzymes catalyzing rate-determining reactions of the tricarboxylic-acid cycle (providing NADH for respiration and of mitochondrial folate-mediated NADPH production (required for oxidative defense. The findings demonstrate that exponential growth can represent not a single metabolic/physiological state but a continuum of changing states and that aerobic glycolysis can reduce the energy demands associated with respiratory metabolism and stress survival.

Dendritic surface morphology of palladium hydride produced by electrolytic deposition

International Nuclear Information System (INIS)

Julin, Peng; Bursill, L.A.

1990-01-01

Conventional and high-resolution electron microscopic studies of electrolytically-deposited palladium hydride reveal a fascinating variety of surface profile morphologies. The observations provide direct information concerning the surface structure of palladium electrodes and the mechanism of electrolytic deposition of palladium black. Both classical electrochemical mechanisms and recent 'modified diffusion-limited-aggregation' computer simulations are discussed in comparison with the experimental results. 13 refs., 9 figs

Selective electrocatalysis of biofuel molecular oxidation using palladium nanoparticles generated on Shewanella oneidensis MR-1

DEFF Research Database (Denmark)

Wu, Ranran; Tian, Xiaochun; Xiao, Yong

2018-01-01

of formate with 200 mV less over-potential. Notably they show unique selective activity toward electrochemical oxidation of formate, whereas no electrochemical catalysis was found for oxidation of ethanol, methanol and acetate. This work demonstrates a sustainable and low-cost method for producing efficient......Production of molecular scale palladium (Pd) nanoparticles (NPs) is important due to their catalytic function in electrochemical oxidation of a number of core fuel molecules in fuel cells. Biogenic methods offer an economic and environmentally friendly synthesis route. In this work...... membrane surface. Mapping by conductive atomic force microscopy shows that the presence of these PdNPs promotes electron transfer and enhances the electric conductivity of the cells. Compared to electrodeposited PdNPs, PdNPs generated by S. oneidensis MR-1 catalyze electrochemically the oxidation...

Dual enzymatic dynamic kinetic resolution by Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase and Candida antarctica lipase B

KAUST Repository

Karume, Ibrahim

2016-10-04

The immobilization of Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase (TeSADH) using sol–gel method enables its use to racemize enantiopure alcohols in organic media. Here, we report the racemization of enantiopure phenyl-ring-containing secondary alcohols using xerogel-immobilized W110A TeSADH in hexane rather than the aqueous medium required by the enzyme. We further showed that this racemization approach in organic solvent was compatible with Candida antarctica lipase B (CALB)-catalyzed kinetic resolution. This compatibility, therefore, allowed a dual enzymatic dynamic kinetic resolution of racemic alcohols using CALB-catalyzed kinetic resolution and W110A TeSADH-catalyzed racemization of phenyl-ring-containing alcohols.

Fexofenadine Suppresses Delayed-Type Hypersensitivity in the Murine Model of Palladium Allergy

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Ryota Matsubara

2017-06-01

Full Text Available Palladium is frequently used in dental materials, and sometimes causes metal allergy. It has been suggested that the immune response by palladium-specific T cells may be responsible for the pathogenesis of delayed-type hypersensitivity in study of palladium allergic model mice. In the clinical setting, glucocorticoids and antihistamine drugs are commonly used for treatment of contact dermatitis. However, the precise mechanism of immune suppression in palladium allergy remains unknown. We investigated inhibition of the immune response in palladium allergic mice by administration of prednisolone as a glucocorticoid and fexofenadine hydrochloride as an antihistamine. Compared with glucocorticoids, fexofenadine hydrochloride significantly suppressed the number of T cells by interfering with the development of antigen-presenting cells from the sensitization phase. Our results suggest that antihistamine has a beneficial effect on the treatment of palladium allergy compared to glucocorticoids.

Dinuclear NHC-palladium complexes containing phosphine spacers: synthesis, X-ray structures and their catalytic activities towards the Hiyama coupling reaction.

Science.gov (United States)

Yang, Jin; Li, Pinhua; Zhang, Yicheng; Wang, Lei

2014-05-21

Six dinuclear N-heterocyclic carbene (NHC) palladium complexes, [PdCl2(IMes)]2(μ-dppe) (1), [PdCl2(IPr)]2(μ-dppe) (2), [PdCl2(IMes)]2(μ-dppb) (3), [PdCl2(IPr)]2(μ-dppb) (4), [PdCl2(IMes)]2(μ-dpph) (5), and [PdCl2(IPr)]2(μ-dpph) (6) [IMes = N,N'-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene; IPr = N,N'-bis-(2,6-di(iso-propyl)phenyl)imidazol-2-ylidene; dppe = 1,2-bis(diphenylphosphino)ethane, dppb = 1,4-bis(diphenylphosphino)butane; and dpph = 1,6-bis(diphenylphosphino)hexane], have been synthesized through bridge-cleavage reactions of chloro-bridged dimeric compounds, [Pd(μ-Cl)(Cl)(NHC)]2, with the corresponding diphosphine ligands. The obtained compounds were fully characterized by (1)H NMR, (13)C NMR and (31)P NMR spectroscopy, FT-IR, elemental analysis and single-crystal X-ray crystallography. Moreover, further explorations of the catalytic potential of the dinuclear carbene palladium complexes as catalysts for the Pd-catalyzed transformations have been performed under microwave irradiation conditions, and the complexes exhibited moderate to good catalytic activity in the Hiyama coupling reaction of trimethoxyphenylsilane with aryl chlorides.

Sputtering induced surface composition changes in copper-palladium alloys

International Nuclear Information System (INIS)

Sundararaman, M.; Sharma, S.K.; Kumar, L.; Krishnan, R.

1981-01-01

It has been observed that, in general, surface composition is different from bulk composition in multicomponent materials as a result of ion beam sputtering. This compositional difference arises from factors like preferential sputtering, radiation induced concentration gradients and the knock-in effect. In the present work, changes in the surface composition of copper-palladium alloys, brought about by argon ion sputtering, have been studied using Auger electron spectroscopy. Argon ion energy has been varied from 500 eV to 5 keV. Enrichment of palladium has been observed in the sputter-altered layer. The palladium enrichment at the surface has been found to be higher for 500 eV argon ion sputtering compared with argon ion sputtering at higher energies. Above 500 eV, the surface composition has been observed to remain the same irrespective of the sputter ion energy for each alloy composition. The bulk composition ratio of palladium to copper has been found to be linearly related to the sputter altered surface composition ratio of palladium to copper. These results are discussed on the basis of recent theories of alloy sputtering. (orig.)

Poly(N-vinyl-2-pyrrolidone)-stabilized palladium-platinum nanoparticles-catalyzed hydrolysis of ammonia borane for hydrogen generation

Science.gov (United States)

Rakap, Murat

2015-02-01

The catalytic use of highly efficient poly(N-vinyl-2-pyrrolidone)-stabilized palladium-platinum nanoparticles (4.2 ± 1.9 nm) in the hydrolysis of ammonia-borane is reported. The catalyst is prepared by co-reduction of two metal ions in ethanol/water mixture by an alcohol reduction method and characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and UV-Vis spectroscopy. They are recyclable and highly active for hydrogen generation from the hydrolysis of ammonia-borane even at very low concentrations and temperature, providing a record numbers of average turnover frequency value (125 mol H2/mol cat.min-1) and maximum hydrogen generation rate (3468 L H2 min-1 (mol cat)-1). They also provide activation energy of 51.7 ± 2 kJ/mol for the hydrolysis of ammonia borane.

Bedford-type palladacycle catalyzed Miyaura-borylation of aryl halides with tetrahydroxydiboron in water

KAUST Repository

Zernickel, Anna; Du, Weiyuan; Ghorpade, Seema; Sawant, Dinesh Nanaji; Makki, Arwa; Sekar, Nagaiyan; Eppinger, Jö rg

2018-01-01

A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 hours in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance.

Bedford-type palladacycle catalyzed Miyaura-borylation of aryl halides with tetrahydroxydiboron in water

KAUST Repository

Zernickel, Anna

2018-01-09

A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 hours in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance.

Enantioselective Evans-Tishchenko Reduction of b-Hydroxyketone Catalyzed by Lithium Binaphtholate

Directory of Open Access Journals (Sweden)

Makoto Nakajima

2011-06-01

Full Text Available Lithium diphenylbinaphtholate catalyzed the enantioselective Evans-Tishchenko reduction of achiral b-hydroxyketones to afford monoacyl-protected 1,3-diols with high stereoselectivities. In the reaction of racemic b-hydroxyketones, kinetic optical resolution occurred in a highly stereoselective manner.

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...

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.

Mechanistic evidence for a ring-opening pathway in the Pd-catalyzed direct arylation of benzoxazoles

DEFF Research Database (Denmark)

Sanchez, R.S.; Zhuravlev, Fedor

2007-01-01

The direct Pd-catalyzed arylation of 5-substituted benzoxazoles, used as a mechanistic model for 1,3-azoles, was investigated experimentally and computationally. The results of the primary deuterium kinetic isotope effect, Hammett studies, and H/D exchange were shown to be inconsistent with the r......The direct Pd-catalyzed arylation of 5-substituted benzoxazoles, used as a mechanistic model for 1,3-azoles, was investigated experimentally and computationally. The results of the primary deuterium kinetic isotope effect, Hammett studies, and H/D exchange were shown to be inconsistent...... with the rate-limiting electrophilic or concerted palladation. A mechanism, proposed on the basis of kinetic and computational studies, includes generation of isocyanophenolate as the key step. The DFT calculations suggest that the overall catalytic cycle is facile and is largely controlled by the C-H acidity...

Kinetics of concentration decay of specific organic matter in UASB reactors operating with and without return of aerobic sludge.

Science.gov (United States)

Pontes, P P; Chernicharo, C A L; Von Sperling, M

2014-08-01

This study aimed at assessing the influence of the return of excess aerobic sludge from a trickling filter (TF) upon the anaerobic digestion process in an upflow anaerobic sludge blanket (UASB) reactor, by evaluating its effect on the kinetics of the decay of specific organic matter (carbohydrates, proteins and lipids), as well as on the concentrations of volatile fatty acids in the UASB reactor. A pilot-scale UASB/TF system was used to perform the experiments, operating with (phase 2) and without (phase 1) excess sludge return from the TF to the UASB reactor. Sampling was carried out at different heights of the UASB reactor (0, 25, 125 and 225-cm height), and profile concentrations were determined for the following parameters: carbohydrates, proteins, lipids and volatile fatty acids. First-order kinetics showed the best fit to the decay of concentrations of carbohydrates, proteins, lipids and chemical oxygen demand (COD) in the UASB reactor. The parameters showing the best fit to the first-order kinetics were proteins and COD, during the sludge return phase. The occurrence of higher apparent reaction constants was further observed during the sludge return phase. For an influent COD concentration of 600 mg L-1 and hydraulic retention times of 2.1, 2.6 and 3.0 h in phase 1, the effluent COD concentrations were 125.3, 88.4 and 62.4 mg L-1, respectively, whereas in phase 2, the effluent COD concentrations were 75.5, 47.6 and 30.1 mg L-1, respectively.

Characterising palladium-silver and palladium-nickel alloy membranes using SEM, XRD and PIXE

International Nuclear Information System (INIS)

Keuler, J.N.; Lorenzen, L.; Sanderson, R.D.; Prozesky, V.; Przybylowicz, W.J.

1999-01-01

Palladium alloy membranes were prepared by successive electroless plating steps on an alumina-zirconia support membrane. Palladium, silver and nickel were deposited in layers and then the metal films were heat treated for 5 h in a hydrogen atmosphere at 650 deg. C. The topography of the metal coatings and cross-sections of the films (before and after heating) were characterised using scanning electron microscopy (SEM). XRD was used to determine the crystal phase of the alloy coatings. Both SEM and XRD provide only surface information and therefore micro-PIXE was used to extract depth information of the alloy coating. Concentration profiles across the thickness of the films were constructed to determine penetration of the coating into the support membrane pores during electroless plating and to investigate diffusion of coated layers during the heating step

Pd(OAc2/Ph3P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles

Directory of Open Access Journals (Sweden)

Dominik Kellner

2017-08-01

Full Text Available The palladium-catalyzed dimerization of isoprene is a practical approach of synthesizing monoterpenes. Though several highly selective methods have been reported, most of them still required pressure or costly ligands for attaining the active system and desired selectivity. Herein, we present a simple and economical procedure towards the tail-to-tail dimer using readily available Pd(OAc2 and inexpensive triphenylphosphine as ligand. Furthermore, simple screw cap vials are employed, allowing carrying out the reaction at low pressure. In addition, the potential of the dimer as a chemical platform for the preparation of heterocyclic terpenes by subsequent (hetero-Diels–Alder or [4 + 1]-cycloadditions with nitrenes is also depicted.

SUPECA kinetics for scaling redox reactions in networks of mixed substrates and consumers and an example application to aerobic soil respiration

Science.gov (United States)

Tang, Jin-Yun; Riley, William J.

2017-09-01

solution for some simple problems and found SUPECA outperformed SU kinetics. As an example application, we show that a steady-state SUPECA-based approach predicted an aerobic soil respiration moisture response function that agreed well with laboratory observations. We conclude that, as an extension to SU and ECA kinetics, SUPECA provides a robust mathematical representation of complex soil substrate-consumer interactions and can be applied to improve Earth system model (ESM) land models.

Facile Synthesis of N-Tosyl Aza-Baylis-Hillman Adducts of Acrylamide via a Pd-Catalyzed Hydration of Nitrile to Amide

International Nuclear Information System (INIS)

Kim, Eun Sun; Kim, Yu Mi; Kim, Jae Nyoung

2010-01-01

We developed an efficient palladium-catalyzed two-step protocol for the synthesis of N-tosyl aza-Baylis-Hillman adducts of acrylamide. The method involved the preparation of the corresponding Baylis-Hillman adducts of acrylonitrile and the following Pd-catalyzed hydration of nitrile with acetaldoxime. The Baylis-Hillman reaction, which involves the coupling of activated vinyl compounds with electrophiles under the catalytic influence of a tertiary amine, gives rise to adducts, so called Baylis-Hillman adducts, with a new stereocenter and has proven to be a very useful carbon-carbon bond-forming method in the synthesis of highly functionalized molecules. As the activated vinyl compounds, various compounds have been used in the Baylis-Hillman reaction including acrylates, acrylonitrile, vinyl ketones, vinyl sulfones and acrylamides. However, among the activated vinyl compounds acrylamide has not been used much for the synthesis of the corresponding Baylis-Hillman adducts due to its sluggish reactivity

Facile synthesis of bacitracin-templated palladium nanoparticles with superior electrocatalytic activity

Science.gov (United States)

Li, Yanji; Wang, Zi; Li, Xiaoling; Yin, Tian; Bian, Kexin; Gao, Faming; Gao, Dawei

2017-02-01

Palladium nanomaterials have attracted great attention on the development of electrocatalysts for fuel cells. Herein, we depicted a novel strategy in the synthesis of palladium nanoparticles with superior electrocatalytic activity. The new approach, based on the self-assembly of bacitracin biotemplate and palladium salt for the preparation of bacitracin-palladium nanoparticles (Bac-PdNPs), was simple, low-cost, and green. The complex, composed by a series of spherical Bac-PdNPs with a diameter of 70 nm, exhibited a chain-liked morphology in TEM and a face-centered cubic crystal structure in X-Ray diffraction and selected area electron diffraction. The palladium nanoparticles were mono-dispersed and stable in aqueous solution as shown in TEM and zeta potential. Most importantly, compared to the commercial palladium on carbon (Pd/C) catalyst (8.02 m2 g-1), the Bac-PdNPs showed a larger electrochemically active surface area (47.57 m2 g-1), which endowed the products an excellent electrocatalytic activity for ethanol oxidation in alkaline medium. The strategy in synthesis of Bac-PdNPs via biotemplate approach might light up new ideas in anode catalysts for direct ethanol fuel cells.

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

Porous palladium coated conducting polymer nanoparticles for ultrasensitive hydrogen sensors

Science.gov (United States)

Lee, Jun Seop; Kim, Sung Gun; Cho, Sunghun; Jang, Jyongsik

2015-12-01

Hydrogen, a clean-burning fuel, is of key importance to various industrial applications, including fuel cells and in the aerospace and automotive industries. However, hydrogen gas is odorless, colorless, and highly flammable; thus appropriate safety protocol implementation and monitoring are essential. Highly sensitive hydrogen leak detection and surveillance sensor systems are needed; additionally, the ability to maintain uniformity through repetitive hydrogen sensing is becoming increasingly important. In this report, we detail the fabrication of porous palladium coated conducting polymer (3-carboxylate polypyrrole) nanoparticles (Pd@CPPys) to detect hydrogen gas. The Pd@CPPys are produced by means of facile alkyl functionalization and chemical reduction of a pristine 3-carboxylate polypyrrole nanoparticle-contained palladium precursor (PdCl2) solution. The resulting Pd@CPPy-based sensor electrode exhibits ultrahigh sensitivity (0.1 ppm) and stability toward hydrogen gas at room temperature due to the palladium sensing layer.Hydrogen, a clean-burning fuel, is of key importance to various industrial applications, including fuel cells and in the aerospace and automotive industries. However, hydrogen gas is odorless, colorless, and highly flammable; thus appropriate safety protocol implementation and monitoring are essential. Highly sensitive hydrogen leak detection and surveillance sensor systems are needed; additionally, the ability to maintain uniformity through repetitive hydrogen sensing is becoming increasingly important. In this report, we detail the fabrication of porous palladium coated conducting polymer (3-carboxylate polypyrrole) nanoparticles (Pd@CPPys) to detect hydrogen gas. The Pd@CPPys are produced by means of facile alkyl functionalization and chemical reduction of a pristine 3-carboxylate polypyrrole nanoparticle-contained palladium precursor (PdCl2) solution. The resulting Pd@CPPy-based sensor electrode exhibits ultrahigh sensitivity (0.1 ppm

Effects of small-volume soccer and vibration training on body composition, aerobic fitness, and muscular PCr kinetics for inactive women aged 20–45

DEFF Research Database (Denmark)

Connolly, Luke J.; Scott, Suzanne; Mohr, Magni

2014-01-01

Purpose: The present study investigated the effects of 16 weeks of small-volume, small-sided soccer training soccer group (SG, n = 13) and oscillating whole-body vibration training vibration group (VG, n = 17) on body composition, aerobic fitness, and muscle PCr kinetics in healthy inactive......%, p = 0.04), with no changes in VG or CO (timegroup effect: p = 0.03 and p = 0.03). Submaximal exercise HR was also reduced in SG after 16 weeks of training (6% ± 5% of HRmax, p = 0.01). Conclusion: Short duration soccer training for 16 weeks appears to be sufficient to induce favourable changes...

Thermosonic wire bonding of IC devices using palladium wire

International Nuclear Information System (INIS)

Shze, J.H.; Poh, M.T.; Tan, R.M.

1996-01-01

The feasibility of replacing gold wire by palladium wire in thermosonic wire bonding of CMOS and bipolar devices are studied in terms of the manufacturability, physical, electrical and assembly performance. The results that palladium wire is a viable option for bonding the bipolar devices but not the CMOS devices

Antibiofilm effect enhanced by modification of 1,2,3-triazole and palladium nanoparticles on polysulfone membranes

KAUST Repository

Cheng, Hong; Xie, Yihui; Villalobos, Luis Francisco; Song, Liyan; Peinemann, Klaus-Viktor; Nunes, Suzana Pereira; Hong, Pei-Ying

2016-01-01

Biofouling impedes the performance of membrane bioreactors. In this study, we investigated the antifouling effects of polysulfone membranes that were modified by 1,2,3-triazole and palladium (Pd) nanoparticles. The modified membranes were evaluated for antibacterial and antifouling efficacy in a monoculture species biofilm (i.e., drip flow biofilm reactor, DFR) and mixed species biofilm experiment (i.e., aerobic membrane reactor, AeMBR). 1,2,3-triazole and Pd nanoparticles inhibited growth of Pseudomonas aeruginosa in both aerobic and anaerobic conditions. The decrease in bacterial growth was observed along with a decrease in the amount of total polysaccharide within the monoculture species biofilm matrix. When the modified membranes were connected to AeMBR, the increase in transmembrane pressure was lower than that of the non-modified membranes. This was accompanied by a decrease in protein and polysaccharide concentrations within the mixed species biofilm matrix. Biomass amount in the biofilm layer was also lower in the presence of modified membranes, and there was no detrimental effect on the performance of the reactor as evaluated from the nutrient removal rates. 16S rRNA analysis further attributed the delay in membrane fouling to the decrease in relative abundance of selected bacterial groups. These observations collectively point to a lower fouling occurrence achieved by the modified membranes.

Antibiofilm effect enhanced by modification of 1,2,3-triazole and palladium nanoparticles on polysulfone membranes

KAUST Repository

Cheng, Hong

2016-04-12

Biofouling impedes the performance of membrane bioreactors. In this study, we investigated the antifouling effects of polysulfone membranes that were modified by 1,2,3-triazole and palladium (Pd) nanoparticles. The modified membranes were evaluated for antibacterial and antifouling efficacy in a monoculture species biofilm (i.e., drip flow biofilm reactor, DFR) and mixed species biofilm experiment (i.e., aerobic membrane reactor, AeMBR). 1,2,3-triazole and Pd nanoparticles inhibited growth of Pseudomonas aeruginosa in both aerobic and anaerobic conditions. The decrease in bacterial growth was observed along with a decrease in the amount of total polysaccharide within the monoculture species biofilm matrix. When the modified membranes were connected to AeMBR, the increase in transmembrane pressure was lower than that of the non-modified membranes. This was accompanied by a decrease in protein and polysaccharide concentrations within the mixed species biofilm matrix. Biomass amount in the biofilm layer was also lower in the presence of modified membranes, and there was no detrimental effect on the performance of the reactor as evaluated from the nutrient removal rates. 16S rRNA analysis further attributed the delay in membrane fouling to the decrease in relative abundance of selected bacterial groups. These observations collectively point to a lower fouling occurrence achieved by the modified membranes.

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

KAUST Repository

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

2016-01-01

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

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

KAUST Repository

Gómez-Herrera, Alberto

2016-08-22

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

Extremely efficient catalysis of carbon-carbon bond formation using "click" dendrimer-stabilized palladium nanoparticles.

Science.gov (United States)

Astruc, Didier; Ornelas, Cátia; Diallo, Abdou K; Ruiz, Jaime

2010-07-20

This article is an account of the work carried out in the authors' laboratory illustrating the usefulness of dendrimer design for nanoparticle palladium catalysis. The "click" synthesis of dendrimers constructed generation by generation by 1-->3 C connectivity, introduces 1,2,3-triazolyl ligands insides the dendrimers at each generation. Complexation of the ligands by Pd(II) followed by reduction to Pd(0) forms dendrimer-stabilized Pd nanoparticles (PdNPs) that are extremely reactive in the catalysis of olefin hydrogenation and C-C bond coupling reactions. The stabilization can be outer-dendritic for the small zeroth-generation dendrimer or intra-dendritic for the larger first- and second-generation dendrimers. The example of the Miyaura-Suzuki reaction that can be catalyzed by down to 1 ppm of PdNPs with a "homeopathic" mechanism (the less, the better) is illustrated here, including catalysis in aqueous solvents.

Absorption of hydrogen by vanadium-palladium alloys

International Nuclear Information System (INIS)

Artman, D.; Lynch, J.F.; Flanagan, T.B.

1976-01-01

Pressure composition isotherms (273-373 K) have been determined for the absorption of hydrogen by a series of six palladium alloys (f.c.c) in the composition range from 1 to 8 at.% vanadium. At a given hydrogen content, the equilibrium hydrogen pressure progressively increases with vanadium content. Thermodynamic parameters for the absorption of hydrogen are reported at infinite dilution of hydrogen and for the formation of the nonstoichiometric hydride from the hydrogen-saturated alloy. The relative, partial molar enthalpy of solution of hydrogen at infinite dilution increases slightly with vanadium content. The presence of vanadium, which absorbs hydrogen itself in its normal b.c.c. structure, greatly inhibits the ability of palladium to absorb hydrogen. For example, the isobaric solubility of hydrogen (1 atm, 298K) decreases from H/Pd=0.7 (palladium) to 0.024 (V(6%)-Pd). The lattice expansion due to the presence of interstitial hydrogen has been determined by X-ray diffraction. From these data it can be concluded that the formation of two non-stoichiometric hydride phases does not occur at vanadium contents greater that 5 at.% (298 K). Electrical resistance has been measured as a function of the hydrogen content of the alloys. The electrical resistance increases more markedly with hydrogen content for these alloys than for any of the palladium alloys previously examined. (Auth.)

Nano-palladium is a cellular catalyst for in vivo chemistry

Science.gov (United States)

Miller, Miles A.; Askevold, Bjorn; Mikula, Hannes; Kohler, Rainer H.; Pirovich, David; Weissleder, Ralph

2017-07-01

Palladium catalysts have been widely adopted for organic synthesis and diverse industrial applications given their efficacy and safety, yet their biological in vivo use has been limited to date. Here we show that nanoencapsulated palladium is an effective means to target and treat disease through in vivo catalysis. Palladium nanoparticles (Pd-NPs) were created by screening different Pd compounds and then encapsulating bis[tri(2-furyl)phosphine]palladium(II) dichloride in a biocompatible poly(lactic-co-glycolic acid)-b-polyethyleneglycol platform. Using mouse models of cancer, the NPs efficiently accumulated in tumours, where the Pd-NP activated different model prodrugs. Longitudinal studies confirmed that prodrug activation by Pd-NP inhibits tumour growth, extends survival in tumour-bearing mice and mitigates toxicity compared to standard doxorubicin formulations. Thus, here we demonstrate safe and efficacious in vivo catalytic activity of a Pd compound in mammals.

Palladium-Catalyzed Decarboxylative γ-Olefination of 2,5-Cyclohexadiene-1-carboxylic Acid Derivatives with Vinyl Halides.

Science.gov (United States)

Chang, Chi-Hao; Chou, Chih-Ming

2018-04-06

This study explores a Pd-catalyzed decarboxylative Heck-type Csp 3 -Csp 2 coupling reaction of 2,5-cyclohexadiene-1-carboxylic acid derivatives with vinyl halides to provide γ-olefination products. The olefinated 1,3-cyclohexadienes can be further oxidized to produce meta-alkylated stilbene derivatives. Additionally, the conjugated diene products can also undergo a Diels-Alder reaction to produce a bicyclo[2.2.2]octadiene framework.

Interaction between age and aerobic fitness in determining heart rate dynamics

International Nuclear Information System (INIS)

McNarry, M A; Lewis, M J

2012-01-01

Heart rate variability (HRV) and phase-rectified signal averaging (PRSA) estimates of heart rate dynamics are diminished in older people compared with younger people. However, it is not fully elucidated whether these differences are related to age per se or to the concomitant influence of aerobic fitness. Aerobic fitness (peak oxygen uptake, gas exchange threshold, oxygen uptake kinetics, exercise economy) was assessed in 70 healthy adults (41 male) aged 18–57 years. Participants also underwent a 24 h, ambulatory ECG for the derivation of HRV and PRSA variables. HRV was most sensitive to age and aerobic fitness when measured during the morning period (6 am–12 pm). HRV and PRSA were both diminished with age and were higher in aerobically superior participants. The decline in HRV with age was predominantly attributable to age itself (33%), with aerobic fitness representing an additional modulating factor. The present study also provides tentative evidence that assessment of the influence of aerobic fitness should not rely on .VO 2peak alone. These findings demonstrate that age per se is an important factor in determining HRV. However, given the clinical importance of diminished HRV and the immutable nature of aging, the potential significance of physical activity/training to enhance cardiac regulatory function should not be underestimated. (paper)

Preparation of Palladium/Silver-Coated Polyimide Nanotubes: Flexible, Electrically Conductive Fibers

OpenAIRE

Lushi Kong; Guanchun Rui; Guangyu Wang; Rundong Huang; Ran Li; Jiajie Yu; Shengli Qi; Dezhen Wu

2017-01-01

A simple and practical method for coating palladium/silver nanoparticles on polyimide (PI) nanotubes is developed. The key steps involved in the process are silver ion exchange/reduction and displacement reactions between silver and palladium ions. With the addition of silver, the conductivity of the PI nanotubes is greatly enhanced. Further, the polyimide nanotubes with a dense, homogeneous coating of palladium nanoparticles remain flexible after heat treatment and show the possibility for u...

Practical Stannylation of Allyl Acetates Catalyzed by Nickel with Bu3 SnOMe.

Science.gov (United States)

Komeyama, Kimihiro; Itai, Yuuhei; Takaki, Ken

2016-06-27

A practical and scalable nickel-catalyzed allylic stannylation of allyl acetates with Bu3 SnOMe is described. A variety of acyclic and cyclic allyl acetates, even with base-sensitive moieties, undergoes the stannylation by using NiBr2 /4,4'-di-tert-butylbipyridine (dtbpy)/Mn catalyst system to afford highly functionalized allyl stannanes with excellent regioselectivity and yields. Furthermore, the scope of protocol is also extended by the reaction of propargyl acetates, giving rise to propargyl or allenyl stannanes. Additionally, a unique diastereoselectivity using the nickel catalyst different from the palladium was demonstrated for the stannylation of cyclic allyl acetates. In the reaction, inexpensive and stable nickel complexes, abundant reductant (Mn), and atom-economical stannyl source were used. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Palladium configuration dependence of hydrogen detection sensitivity based on graphene FET for breath analysis

Science.gov (United States)

Sakamoto, Yuri; Uemura, Kohei; Ikuta, Takashi; Maehashi, Kenzo

2018-04-01

We have succeeded in fabricating a hydrogen gas sensor based on palladium-modified graphene field-effect transistors (FETs). The negative-voltage shift in the transfer characteristics was observed with exposure to hydrogen gas, which was explained by the change in work function. The hydrogen concentration dependence of the voltage shift was investigated using graphene FETs with palladium deposited by three different evaporation processes. The results indicate that the hydrogen detection sensitivity of the palladium-modified graphene FETs is strongly dependent on the palladium configuration. Therefore, the palladium-modified graphene FET is a candidate for breath analysis.

Coupling model of aerobic waste degradation considering temperature, initial moisture content and air injection volume.

Science.gov (United States)

Ma, Jun; Liu, Lei; Ge, Sai; Xue, Qiang; Li, Jiangshan; Wan, Yong; Hui, Xinminnan

2018-03-01

A quantitative description of aerobic waste degradation is important in evaluating landfill waste stability and economic management. This research aimed to develop a coupling model to predict the degree of aerobic waste degradation. On the basis of the first-order kinetic equation and the law of conservation of mass, we first developed the coupling model of aerobic waste degradation that considered temperature, initial moisture content and air injection volume to simulate and predict the chemical oxygen demand in the leachate. Three different laboratory experiments on aerobic waste degradation were simulated to test the model applicability. Parameter sensitivity analyses were conducted to evaluate the reliability of parameters. The coupling model can simulate aerobic waste degradation, and the obtained simulation agreed with the corresponding results of the experiment. Comparison of the experiment and simulation demonstrated that the coupling model is a new approach to predict aerobic waste degradation and can be considered as the basis for selecting the economic air injection volume and appropriate management in the future.

Lipase-catalyzed asymmetric synthesis of naphtho[2,3-c]furan-1(3H)-one derivatives by a one-pot dynamic kinetic resolution/intramolecular Diels-Alder reaction: Total synthesis of (-)-himbacine.

Science.gov (United States)

Sugiyama, Koji; Kawanishi, Shinji; Oki, Yasuhiro; Kamiya, Marin; Hanada, Ryosuke; Egi, Masahiro; Akai, Shuji

2018-04-01

One-pot sequential reactions using the acyl moieties installed by enzymatic dynamic kinetic resolution of alcohols have been little investigated. In this work, the acryloyl moiety installed via the lipase/oxovanadium combo-catalyzed dynamic kinetic resolution of a racemic dienol [4-(cyclohex-1-en-1-yl)but-3-en-2-ol or 1-(cyclohex-1-en-1-yl)but-2-en-1-ol] with a (Z)-3-(phenylsulfonyl)acrylate underwent an intramolecular Diels-Alder reaction in a one-pot procedure to produce an optically active naphtho[2,3-c]furan-1(3H)-one derivative (98% ee). This method was successfully applied to the asymmetric total synthesis of (-)-himbacine. Copyright © 2017 Elsevier Ltd. All rights reserved.

Surface topography of a palladium cathode after electrolysis in heavy water

International Nuclear Information System (INIS)

Silver, D.S.; Dash, J.; Keefe, P.S.

1993-01-01

Electrolysis was performed with a palladium cathode and an electrolyte containing both hydrogen and deuterium ions. The cathode bends toward the anode during this process. Examination of both the concave and the convex surfaces with the scanning electron microscope, scanning tunneling microscope, and atomic force microscope shows unusual surface characteristics. Rimmed craters with faceted crystals inside and multitextural surfaces were observed on an electrolyzed palladium cathode but not on palladium that has not been electrolyzed. 9 refs., 9 figs

Enzyme catalyzed oxidative cross-linking of feruloylated pectic polysaccharides from sugar beet

DEFF Research Database (Denmark)

Abang Zaidel, Dayang Norulfairuz

beet pulp as a potential starting material for production of pectin derived products which could help maintain the competitiveness of the sugar beet based industry. The overall objective of this study has been focusing on understanding the kinetics of enzyme catalyzed oxidative crosslinking......-linked by HRP catalysis in the presence of hydrogen peroxide (H2O2) to form ferulic acid dehydrodimers (diFAs). The composition of the substrate was analyzed by HPAEC, HPLC and MALDI-TOF, confirming the structural make up of the arabinan-oligosaccharide (Arabinose: 2.9- 3.4 mmol?g-1 DM; FA: 2.5-7.0 mg?g-1 DM......, identically composed, oil-in-water emulsion systems to study the effect of different methods of emulsion preparation on the emulsion stability in the presence of SBP and the kinetics of enzyme catalyzed oxidative gelation of SBP. The result shows that the different methods of emulsion preparation affect...

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

International Nuclear Information System (INIS)

Wang Haifeng; Gao Yan; Zhang Heng; Lin Zhenquan

2009-01-01

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

General Methods for Analysis of Sequential “n-step” Kinetic Mechanisms: Application to Single Turnover Kinetics of Helicase-Catalyzed DNA Unwinding

Science.gov (United States)

Lucius, Aaron L.; Maluf, Nasib K.; Fischer, Christopher J.; Lohman, Timothy M.

2003-01-01

Helicase-catalyzed DNA unwinding is often studied using “all or none” assays that detect only the final product of fully unwound DNA. Even using these assays, quantitative analysis of DNA unwinding time courses for DNA duplexes of different lengths, L, using “n-step” sequential mechanisms, can reveal information about the number of intermediates in the unwinding reaction and the “kinetic step size”, m, defined as the average number of basepairs unwound between two successive rate limiting steps in the unwinding cycle. Simultaneous nonlinear least-squares analysis using “n-step” sequential mechanisms has previously been limited by an inability to float the number of “unwinding steps”, n, and m, in the fitting algorithm. Here we discuss the behavior of single turnover DNA unwinding time courses and describe novel methods for nonlinear least-squares analysis that overcome these problems. Analytic expressions for the time courses, fss(t), when obtainable, can be written using gamma and incomplete gamma functions. When analytic expressions are not obtainable, the numerical solution of the inverse Laplace transform can be used to obtain fss(t). Both methods allow n and m to be continuous fitting parameters. These approaches are generally applicable to enzymes that translocate along a lattice or require repetition of a series of steps before product formation. PMID:14507688

Palladium-Catalysed Coupling Reactions

NARCIS (Netherlands)

de Vries, Johannes G.; Beller, M; Blaser, HU

2012-01-01

Palladium-catalysed coupling reactions have gained importance as a tool for the production of pharmaceutical intermediates and to a lesser extent also for the production of agrochemicals, flavours and fragrances, and monomers for polymers. In this review only these cases are discussed where it seems

Estudio cinético de la descomposición catalizada de peróxido de hidrógeno sobre carbón activado Kinetic study of the catalyzed decomposition of hydrogen peroxide on activated carbon

Directory of Open Access Journals (Sweden)

Elihu Paternina

2009-01-01

Full Text Available The kinetic study of decomposition of hydrogen peroxide catalyzed by activated carbon was carried out. The effect of concentrations of reactants and temperature were experimentally studied. Kinetic data were evaluated using differential method of initial rates of reaction. When a typical kinetic law for reactions in homogeneous phase is used, first order of reaction is obtained for hydrogen peroxide and activated carbon, and activation energy of 27 kJ mol-1 for the reaction was estimated. Experimentally was observed that surface of activated carbon is chemically modified during decomposition of hydrogen peroxide, based on this result a scheme of reaction was proposed and evaluated. Experimental data fits very well to a Langmuir- Hinshelwood kinetic model and activation energy of 40 kJ mol-1 was estimated for reaction in heterogeneous phase.

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.

Stoichiometry and kinetics of poly-{beta}-hydroxybutyrate metabolism in aerobic, slow growing, activated sludge cultures

Energy Technology Data Exchange (ETDEWEB)

Beun, J.J.; Paletta, F.; Loosdrecht, M.C.M. Van; Heijnen, J.J.

2000-02-20

This paper discusses the poly-{beta}-hydroxybutyrate (PHB) metabolism in aerobic, slow growing, activated sludge cultures, based on experimental data and on a metabolic model. The dynamic conditions which occur in activated sludge processes were simulated in a 2-L sequencing batch reactor (SBR) by subjecting a mixed microbial population to successive periods of external substrate availability (feast period) and no external substrate availability (famine period). Under these conditions intracellular storage and consumption of PHB was observed. It appeared that in the feast period, 66% to almost 100% of the substrate consumed is used for storage of PHB, the remainder is used for growth and maintenance processes. Furthermore, it appeared that at high sludge retention time (SRT) the growth rate in the feast and famine periods was the same. With decreasing SRT the growth rate in the feast period increased relative to the growth rate in the famine period. Acetate consumption and PHB production in the feast period both proceeded with a zero-order rate in acetate and PHB concentration respectively. PHB consumption in the famine period could best be described kinetically with a nth order degradation equation in PHB concentration. The obtained results are discussed in the context of the general activated sludge models.

Thermodynamics of the hybrid interaction of hydrogen with palladium nanoparticles

NARCIS (Netherlands)

Griessen, R.P.; Strohfeldt, N.; Giessen, H.

2015-01-01

Palladium-hydrogen is a prototypical metal-hydrogen system. It is therefore not at all surprising that a lot of attention has been devoted to the absorption and desorption of hydrogen in nanosized palladium particles. Several seminal articles on the interaction of H with Pd nanocubes and

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

Pore surface fractal analysis of palladium-alumina ceramic membrane using Frenkel-Halsey-Hill (FHH) model.

Science.gov (United States)

Ahmad, A L; Mustafa, N N N

2006-09-15

The alumina ceramic membrane has been modified by the addition of palladium in order to improve the H(2) permeability and selectivity. Palladium-alumina ceramic membrane was prepared via a sol-gel method and subjected to thermal treatment in the temperature range 500-1100 degrees C. Fractal analysis from nitrogen adsorption isotherm is used to study the pore surface roughness of palladium-alumina ceramic membrane with different chemical composition (nitric acid, PVA and palladium) and calcinations process in terms of surface fractal dimension, D. Frenkel-Halsey-Hill (FHH) model was used to determine the D value of palladium-alumina membrane. Following FHH model, the D value of palladium-alumina membrane increased as the calcinations temperature increased from 500 to 700 degrees C but decreased after calcined at 900 and 1100 degrees C. With increasing palladium concentration from 0.5 g Pd/100 ml H(2)O to 2 g Pd/100 ml H(2)O, D value of membrane decreased, indicating to the smoother surface. Addition of higher amount of PVA and palladium reduced the surface fractal of the membrane due to the heterogeneous distribution of pores. However, the D value increased when nitric acid concentration was increased from 1 to 15 M. The effect of calcinations temperature, PVA ratio, palladium and acid concentration on membrane surface area, pore size and pore distribution also studied.

Kinetic mechanism and nucleotide specificity of NADH peroxidase

International Nuclear Information System (INIS)

Stoll, V.S.; Blanchard, J.S.

1988-01-01

NADH peroxidase is a flavoprotein isolated from Streptococcus faecalis which catalyzes the pyridine nucleotide-dependent reduction of hydrogen peroxide to water. Initial velocity, product, and dead-end inhibition studies have been performed at pH 7.5 and support a ping-pong kinetic mechanism. In the absence of hydrogen peroxide, both transhydrogenation between NADH and thioNAD, and isotope exchange between [ 14 C]NADH and NAD, have been demonstrated, although in both these experiments, the maximal velocity of nucleotide exchange was less than 1.5% the maximal velocity of the peroxidatic reaction. We propose that NADH binds tightly to both oxidized and two-electron reduced enzyme. NADH oxidation proceeds stereospecifically with the transfer of the 4S hydrogen to enzyme, and then, via exchange, to water. No primary tritium kinetic isotope effect was observed, and no statistically significant primary deuterium kinetic isotope effects on V/K were determined, although primary deuterium kinetic isotope effects on V were observed in the presence and absence of sodium acetate. NADH peroxidase thus shares with other flavoprotein reductases striking kinetic, spectroscopic, and stereochemical similarities. On this basis, we propose a chemical mechanism for the peroxide cleaving reaction catalyzed by NADH peroxidase which involves the obligate formation of a flavinperoxide, and peroxo bond cleavage by nucleophilic attack by enzymatic dithiols

Facile synthesis of palladium nanoparticle doped polyaniline nanowires in soft templates for catalytic applications

Science.gov (United States)

Kshirasagar, Krushna J.; Markad, Uddhav S.; Saha, Abhijit; Sharma, Kiran Kumar K.; Sharma, Geeta K.

2017-02-01

Palladium nanoparticles doped polyaniline (Pd-PANI) nanocomposite (NCs) is synthesized in surfactant based liquid crystalline mesophase by chemical oxidation followed by radiolysis. The confinement of the liquid crystalline mesophase facilitates polymerization of aniline monomers and their 1D growth into polyaniline (PANI) nanowires by using ammonium persulfate. The PANI nanowires have an average diameter of 30-40 nm. The in situ radiolytic reduction of palladium ions ensures uniform size distribution of the palladium (Pd) nanoparticles on the surface of the PANI nanowires. The synthesized Pd-PANI nanocomposites show wire like structures of PANI (diameter ~30-40 nm) on which Pd nanoparticles of the size 10 nm are decorated. The identical average diameter of the PANI nanowires before and post gamma irradiation suggest high stability of the PANI nanowires in liquid crystalline mesophase. Surface characterization of the NCs were carried out using BET and XPS. The catalytic activity of Pd-PANI NCs are investigated in the reduction of methylene blue (MB) and 4-nitro phenol (4-NP) by sodium borohydride (NaBH4). The kinetics of the Pd-PANI NCs catalysed reactions are analysed using the Langmuir-Hinshelwood model. The apparent rate constant (k app) for the MB and 4-NP reduction reactions is 29  ×  10-3 s-1 and 20  ×  10-3 s-1 respectively with an actual Pd catalyst loading of 2.665  ×  10-4 ppm. Further, the recyclability of the Pd-PANI NCs catalyst in both the reduction reactions shows the stability of the catalyst up to four reaction cycles tested in this investigation and the multifunctional nature of the catalyst. The study provides a new approach for the directional synthesis of conducting polymer-metal nanocomposites and their possible application as a nanocatalyst in environmental remediation.

Ageing of palladium tritide: mechanical characterization, helium state and modelling

International Nuclear Information System (INIS)

Segard, M.

2010-01-01

Palladium is commonly used for the storage of tritium (the hydrogen radioactive isotope), since it forms a low-equilibrium-pressure and reversible tritide. Tritium decay into helium-3 is responsible for the ageing of the tritide, leading to the apparition of helium-3 bubbles for instance. Both experimental and theoretical aspects of this phenomenon are studied here.Previous works on ageing modelling led to two main models, dealing with:- Helium-3 bubbles nucleation (using a cellular automaton), - Bubbles growth (using continuum mechanics).These models were quite efficient, but their use was limited by the lack of input data and fitting experimental parameters.To get through these limitations, this work has consisted in studying the most relevant experimental data to improve the modelling of the palladium tritide ageing.The first part of this work was focused on the assessment of the mechanical properties of the palladium tritide (yield strength, ultimate strength, mechanical behaviour). They were deduced from the in situ tensile tests performed on palladium hydride and deuteride. In the second part, ageing characterization was undertaken, mainly focusing on: - Bubbles observations in palladium tritide using transmission electron microscopy, - Internal bubble pressure measurements using nuclear magnetic resonance, - Macroscopic swelling measurements using pycno-metry.The present work has led to significant progress in ageing understanding and has brought very valuable improvements to the modelling of such a phenomenon. (author) [fr

Palladium nanoparticle anchored polyphosphazene nanotubes ...

Indian Academy of Sciences (India)

607–610. c Indian Academy of Sciences. Palladium ... 2Department of Chemistry, APA College of Arts and Culture, Palani, Tamil Nadu 624 601, India. 3Department of .... K Dinakaran acknowledges the financial support from. Department of ...

Carbon nanotubes decorated with palladium nanoparticles : Synthesis, characterization, and catalytic activity

NARCIS (Netherlands)

Karousis, Nikolaos; Tsotsou, Georgia-Eleni; Evangelista, Fabrizio; Rudolf, Petra; Ragoussis, Nikitas; Tagmatarchis, Nikos

2008-01-01

In this article, the in situ preparation of palladium nanoparticles, as mediated by the self-regulated reduction of palladium acetate with the aid of sodium dodecyl sulfate (SDS), followed by subsequent deposition onto single-walled carbon nanotubes and multimalled carbon nanotubes (MWCNTs), is

Microwave-assisted synthesis of palladium nanocubes and nanobars

International Nuclear Information System (INIS)

Yu, Yanchun; Zhao, Yanxi; Huang, Tao; Liu, Hanfan

2010-01-01

Microwave was employed in the shape-controlled synthesis of palladium nanoparticles. Palladium nanocubes and nanobars with a mean size of about 23.8 nm were readily synthesized with H 2 PdCl 4 as a precursor, tetraethylene glycol (TEG) as both a solvent and a reducing agent in the presence of PVP and CTAB in 80 s under microwave irradiation. The structures of the as-prepared palladium nanoparticles were characterized by transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and ultraviolet-visible (UV-vis) absorption spectroscopy. The formation of PdBr 4 2- due to the coordination replacement of the ligand Cl - ions in PdCl 4 2- ions by Br - ions in the presence of bromide was responsible for the synthesis of Pd nanocubes and nanobars. In addition, a milder reducing power, a higher viscosity and a stronger affinity of TEG were beneficial to the larger sizes of Pd nanocubes and nanobars.

Mechanistic Investigation of the Ruthenium–N-Heterocyclic-Carbene-Catalyzed Amidation of Alcohols and Amines

DEFF Research Database (Denmark)

Makarov, Ilya; Fristrup, Peter; Madsen, Robert

2012-01-01

The mechanism of the ruthenium–N-heterocyclic-carbene-catalyzed formation of amides from alcohols and amines was investigated by experimental techniques (Hammett studies, kinetic isotope effects) and by a computational study by using dispersion-corrected density functional theory (DFT/ M06...

Palladium/IzQO-Catalyzed Coordination-Insertion Copolymerization of Ethylene and 1,1-Disubstituted Ethylenes Bearing a Polar Functional Group.

Science.gov (United States)

Yasuda, Hina; Nakano, Ryo; Ito, Shingo; Nozaki, Kyoko

2018-02-07

Coordination-insertion copolymerization of ethylene with 1,1-disubstituted ethylenes bearing a polar functional group, such as methyl methacrylate (MMA), is a long-standing challenge in catalytic polymerization. The major obstacle for this process is the huge difference in reactivity of ethylene versus 1,1-disubstituted ethylenes toward both coordination and insertion. Herein we report the copolymerization of ethylene and 1,1-disubstituted ethylenes by using an imidazo[1,5-a]quinolin-9-olate-1-ylidene-supported palladium catalyst. Various types of 1,1-disubstituted ethylenes were successfully incorporated into the polyethylene chain. In-depth characterization of the obtained copolymers and mechanistic inferences drawn from stoichiometric reactions of alkylpalladium complexes with methyl methacrylate and ethylene indicate that the copolymerization proceeds by the same coordination-insertion mechanism that has been postulated for ethylene.

Palladium sulphide (PdS) films as a new thermoelectric sulphide compound

Energy Technology Data Exchange (ETDEWEB)

Ares, J.R.; Diaz-Chao, P.; Clamagirand, J.; Macia, M.D.; Ferrer, I.J.; Sanchez, C. [Universidad Autonoma de Madrid (Spain). Lab. de Materiales de Interes en Energias Renovables

2010-07-01

Palladium sulphide (PdS) films have been prepared by direct sulphuration of 20 nm thick palladium films at different temperatures (200 C < T < 450 C). Sulphurated films exhibit an unique crystalline phase: PdS. Seebeck coefficient and electrical resistivity of these films are between -110 and -150 {mu}V/K and {proportional_to} 0.08 to 0.8 {omega}cm depending on the sulphuration temperature. Negative sign of Seebeck coefficient indicates an n type conduction in all films. Discussion is focused on the influence of atomic ratio between sulphur and palladium as well as impurities arising from the substrate on transport properties. (orig.)

Method for recovering palladium and technetium values from nuclear fuel reprocessing waste solutions

Science.gov (United States)

Horwitz, E. Philip; Delphin, Walter H.

1979-07-24

A method for recovering palladium and technetium values from nuclear fuel reprocessing waste solutions containing these and other values by contacting the waste solution with an extractant of tricaprylmethylammonium nitrate in an inert hydrocarbon diluent which extracts the palladium and technetium values from the waste solution. The palladium and technetium values are recovered from the extractant and from any other coextracted values with a strong nitric acid strip solution.

Development of anodic stripping voltametry for the determination of palladium in high level nuclear waste

Energy Technology Data Exchange (ETDEWEB)

Bhardwaj, T. K. [North Carolina State University, Raleigh (United States); Sharma, H. S.; Affarwal, S. K. [Bhabha Atomic Research Centre, Mumbai (India); Jain, P. C. [Meerut College, Meerut (India)

2012-12-15

Deposition potential, deposition time, square wave frequency, rotation speed of the rotating disc electrode, and palladium concentration were studied on a Glassy Carbon Electrode (GCE) in 0.01M HCl for the determination of palladium in High Level Nuclear Waste (HLNW) by anodic stripping voltammetry. Experimental conditions were optimized for the determination of palladium at two different, 10-8 and 10-7 M, levels. Error and standard deviation of this method were under 1% for all palladium standard solutions. The developed technique was successfully applied as a subsidiary method for the determination of palladium in simulated high level nuclear waste with very good precision and high accuracy (under 1 % error and standard deviation).

Thermodynamic Activity-Based Progress Curve Analysis in Enzyme Kinetics.

Science.gov (United States)

Pleiss, Jürgen

2018-03-01

Macrokinetic Michaelis-Menten models based on thermodynamic activity provide insights into enzyme kinetics because they separate substrate-enzyme from substrate-solvent interactions. Kinetic parameters are estimated from experimental progress curves of enzyme-catalyzed reactions. Three pitfalls are discussed: deviations between thermodynamic and concentration-based models, product effects on the substrate activity coefficient, and product inhibition. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetic properties and inhibition of Trypanosoma cruzi 3-hydroxy-3-methylglutaryl CoA reductase

DEFF Research Database (Denmark)

Hurtado-Guerrrero, Ramón; Pena Diaz, Javier; Montalvetti, Andrea

2002-01-01

A detailed kinetic analysis of the recombinant soluble enzyme 3-hydroxy-3-methylglutaryl CoA reductase (HMGR) from Trypanosoma cruzi has been performed. The enzyme catalyzes the normal anabolic reaction and the reductant is NADPH. It also catalyzes the oxidation of mevalonate but at a lower propo...

Eosin Y-catalyzed visible-light-mediated aerobic oxidative cyclization of N,N-dimethylanilines with maleimides.

Science.gov (United States)

Liang, Zhongwei; Xu, Song; Tian, Wenyan; Zhang, Ronghua

2015-01-01

A novel and simple strategy for the efficient synthesis of the corresponding tetrahydroquinolines from N,N-dimethylanilines and maleimides using visible light in an air atmosphere in the presence of Eosin Y as a photocatalyst has been developed. The metal-free protocol involves aerobic oxidative cyclization via sp(3) C-H bond functionalization process to afford good yields in a one-pot procedure under mild conditions.

Enhanced hydrogen reaction kinetics of nanostructured Mg-based composites with nanoparticle metal catalysts dispersed on supports

International Nuclear Information System (INIS)

Yoo, Yeong; Tuck, Mark; Kondakindi, Rajender; Seo, Chan-Yeol; Dehouche, Zahir; Belkacemi, Khaled

2007-01-01

Hydrogen reaction kinetics of nanocrystalline MgH 2 co-catalyzed with Ba 3 (Ca 1+x Nb 2-x )O 9-δ (BCN) proton conductive ceramics and nanoparticle bimetallic catalyst of Ni/Pd dispersed on single wall carbon nanotubes (SWNTs) support has been investigated. The nanoparticle bimetallic catalysts of Ni/Pd supported by SWNTs were synthesized based on a novel polyol method using NiCl 2 .6H 2 O, PdCl 2 , NaOH and ethylene glycol (EG). The nanostructured Mg composites co-catalyzed with BCN and bimetallic supported catalysts exhibited stable hydrogen desorption capacity of 6.3-6.7 wt.% H 2 and the significant enhancement of hydrogen desorption kinetics at 230-300 deg. C in comparison to either non-catalyzed MgH 2 or the nanocomposite of MgH 2 catalyzed with BCN

Palladium silicide - a new contact for semiconductor radiation detectors

International Nuclear Information System (INIS)

Totterdell, D.H.J.

1981-11-01

Silicide layers can be used as low resistance contacts in semiconductor devices. The formation of a metal rich palladium silicide Pd 2 Si is discussed. A palladium film 100A thick is deposited at 300 0 C and the resulting silicide layer used as an ohmic contact in an n + p silicon detector. This rugged contact has electrical characteristics comparable with existing evaporated gold contacts and enables the use of more reproducible bonding techniques. (author)

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

Palladium-catalyzed Reppe carbonylation.

Science.gov (United States)

Kiss, G

2001-11-01

PdX2L2/L/HA (A = weakly coordinating anion, L = phosphine) complexes are active catalysts in the hydroesterification of alkenes, alkynes, and conjugated dienes. Shell, the only major corporate player in the field, recently developed two very active catalyst systems tailored to the hydroesterification of either alkenes or alkynes. The hydroesterification of propyne with their Pd(OAc)2/PN/HA (PN = (2-pyridyl)diphenylphosphine, HA = strong acid with weakly coordinating anion, like methanesulfonic acid) catalyst has been declared commercially ready. However, despite the significant progress in the activity of Pd-hydroesterification catalysts, further improvements are warranted. Thus, for example, activity maintenance still seems to be an issue. Homogeneous Pd catalysts are prone to a number of deactivation reactions. Activity and stability promoters are often corrosive and add to the complexity of the system, making it less attractive. Nonetheless, the versatility of the process and its tolerance toward the functional groups of substrates should appeal especially to the makers of specialty products. Although hydroesterification yields esters from alkenes, alkynes, and dienes in fewer steps than hydroformylation does, the latter has some advantages at the current state of the art. (1) Hydroformylation catalysts, particularly some recently published phosphine-modified Rh systems, can achieve very high regioselectivity for the linear product that hydroesterification catalysts cannot match yet. By analogy with hydroformylation, bulkier ligands ought to be tested in hydroesterification to increase normal-ester selectivity. (2) Hydroformylation is proven, commercial. Hydroesterification can only replace it if it can provide significant economic incentives. Similar or just marginally better performance could not justify the cost of development of a new technology. (3) Hydroesterification requires pure CO while hydroformylation uses syngas, a mixture of CO and H2. The latter is typically more available and less expensive (for industrial applications CO is most often separated from syngas). (4) The acid component of the hydroesterification catalyst makes the process corrosive. It would be desirable to develop new hydroesterification catalysts that do not require acid stabilizer/activity booster. Clearly, any new hydroesterification technology will directly compete with the hydroformylation route. This is especially true for olefin feeds, since both processes add one CO to the olefin, yielding oxygenates that can be converted into identical products. For some niche applications, like the production of MMA from propyne, hydroesterification seems to have an advantage as compared to hydroformylation due to the high activity and selectivity of the Pd(OAc)2/(2-pyridyl)diphenylphosphine catalyst. Since hydroesterification is an emerging technology, it is reasonable to assume that the potential for improvement is greater than in the mature hydroformylation. It is therefore possible that hydroesterification will become competitive in the future; thus, continued effort in the field is warranted.

Palladium alloys for hydrogen diffusion

International Nuclear Information System (INIS)

1977-01-01

A palladium-base alloy with tin and/or a silicon addition and its use in the production of hydrogen from water via a cycle of chemical reactions, of which the decomposition of HI into H 2 and I 2 is the most important, is described

Succinate overproduction: A case study of computational strain design using a comprehensive Escherichia coli kinetic model

Directory of Open Access Journals (Sweden)

Ali eKhodayari

2015-01-01

Full Text Available Computational strain design prediction accuracy has been the focus for many recent efforts through the selective integration of kinetic information into metabolic models. In general, kinetic model prediction quality is determined by the range and scope of genetic and/or environmental perturbations used during parameterization. In this effort, we apply the k-OptForce procedure on a kinetic model of E. coli core metabolism constructed using the Ensemble Modeling (EM method and parameterized using multiple mutant strains data under aerobic respiration with glucose as the carbon source. Minimal interventions are identified that improve succinate yield under both aerobic and anaerobic conditions to test the fidelity of model predictions under both genetic and environmental perturbations. Under aerobic condition, k-OptForce identifies interventions that match existing experimental strategies pointing at a number of unexplored flux redirections such as routing glyoxylate flux through the glycerate metabolism to improve succinate yield. Many of the identified interventions rely on the kinetic descriptions and would not be discoverable by a purely stoichiometric description. In contrast, under fermentative (anaerobic conditions, k-OptForce fails to identify key interventions including up-regulation of anaplerotic reactions and elimination of competitive fermentative products. This is due to the fact that the pathways activated under anaerobic conditions were not properly parameterized as only aerobic flux data were used in the model construction. This study shed light on the importance of condition-specific model parameterization and provides insight onto how to augment kinetic models so as to correctly respond to multiple environmental perturbations.

Metal allergen of the 21st century--a review on exposure, epidemiology and clinical manifestations of palladium allergy

DEFF Research Database (Denmark)

Faurschou, Annesofie; Menné, Torkil; Johansen, Jeanne D

2011-01-01

Consumers are mainly exposed to palladium from jewellery and dental restorations. Palladium contact allergy is nearly always seen together with nickel allergy, as palladium and nickel tend to cross-react. We aimed to analyse the available palladium patch test data and case reports to determine...

Eosin Y-catalyzed visible-light-mediated aerobic oxidative cyclization of N,N-dimethylanilines with maleimides

Directory of Open Access Journals (Sweden)

Zhongwei Liang

2015-04-01

Full Text Available A novel and simple strategy for the efficient synthesis of the corresponding tetrahydroquinolines from N,N-dimethylanilines and maleimides using visible light in an air atmosphere in the presence of Eosin Y as a photocatalyst has been developed. The metal-free protocol involves aerobic oxidative cyclization via sp3 C–H bond functionalization process to afford good yields in a one-pot procedure under mild conditions.

Practical Synthesis of Amides via Copper/ABNO-Catalyzed Aerobic Oxidative Coupling of Alcohols and Amines.

Science.gov (United States)

Zultanski, Susan L; Zhao, Jingyi; Stahl, Shannon S

2016-05-25

A modular Cu/ABNO catalyst system has been identified that enables efficient aerobic oxidative coupling of alcohols and amines to amides. All four permutations of benzylic/aliphatic alcohols and primary/secondary amines are viable in this reaction, enabling broad access to secondary and tertiary amides. The reactions exhibit excellent functional group compatibility and are complete within 30 min-3 h at rt. All components of the catalyst system are commercially available.

Quinone-Catalyzed Selective Oxidation of Organic Molecules

Science.gov (United States)

Wendlandt, Alison E.

2016-01-01

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

Thin film platinum–palladium thermocouples for gas turbine engine applications

Energy Technology Data Exchange (ETDEWEB)

Tougas, Ian M.; Gregory, Otto J., E-mail: gregory@egr.uri.edu

2013-07-31

Thin film platinum:palladium thermocouples were fabricated on alumina and mullite surfaces using radio frequency sputtering and characterized after high temperature exposure to oxidizing environments. The thermoelectric output, hysteresis, and drift of these sensors were measured at temperatures up to 1100 °C. Auger electron spectroscopy was used to follow the extent of oxidation in each thermocouple leg and interdiffusion at the metallurgical junction. Minimal oxidation of the platinum and palladium thermoelements was observed after high temperature exposure, but considerable dewetting and faceting of the films were observed in scanning electron microscopy. An Arrhenius temperature dependence on the drift rate was observed and later attributed to microstructural changes during thermal cycling. The thin film thermocouples, however, did exhibit excellent stability at 1000 °C with drift rates comparable to commercial type-K wire thermocouples. Based on these results, platinum:palladium thin film thermocouples have considerable potential for use in the hot sections of gas turbine engines. - Highlights: • Stable thin film platinum:palladium thermocouples for gas turbine engines • Little oxidation but significant microstructural changes from thermal cycling • Minimal hysteresis during repeated thermal cycling • Drift comparable to commercial wire thermocouples.

Oxygen isotope exchange on palladium catalysts

International Nuclear Information System (INIS)

Kravchuk, L.S.; Beschetvertnaya, T.I.; Novorodskij, V.G.; Novikova, M.G.; Zaretskij, M.V.; Valieva, S.V.

1983-01-01

Oxygen heteromolecular isotope exchange on unreduced palladium catalysts, distingushing by metal content is studied. Content of 18 O in gaseous phase is eoual to 46%. Calculations of heteroexchange rates are conducted with decrease of the 18 O in the gaseous phase over solid sample. Method of oxygen thermodesorption has been used to establish that palladium, deposited on γ-Al 2 O 3 during exchange process is in oxidized state; in this case strength of Pd-O bond is determined by content dispersity) of the metal. It is shown that significant increase of exchange rate on the samples with Pd >> 0.5 mass.% content can be induced as by side decomposition reaction of its oxide and corresponding dilution of gaseous mixture by ''light'' oxygen so by possibility of exchange with oxygen of PdO phase

Morphology of one-time coated palladium-alumina composite membrane prepared by sol-gel process and electroless plating technique

Science.gov (United States)

Sari, R.; Dewi, R.; Pardi; Hakim, L.; Diana, S.

2018-03-01

Palladium coated porous alumina ceramic membrane tube was obtained using a combination of sol-gel process and electroless plating technique. The thickness, structure and composition of palladium-alumina composite membrane were analyzed by transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), and atomic force microscopy (AFM). Palladium particle size was 6.18 to 7.64 nm. Palladium membrane with thickness of approximately 301.5 to 815.1 nm was formed at the outer surface of the alumina layer. EDX data confirmed the formation of palladium-alumina membrane containing 45% of palladium. From this research it shows the combination of sol-gel process and electroless plating technique with one-time coating can produce a homogeneous and smoother palladium nano layer film on alumina substrate.

Hollow Palladium Nanoparticles Facilitated Biodegradation of an Azo Dye by Electrically Active Biofilms

KAUST Repository

Kalathil, Shafeer; Chaudhuri, Rajib Ghosh

2016-01-01

Dye wastewater severely threatens the environment due to its hazardous and toxic effects. Although many methods are available to degrade dyes, most of them are far from satisfactory. The proposed research provides a green and sustainable approach to degrade an azo dye, methyl orange, by electrically active biofilms (EABs) in the presence of solid and hollow palladium (Pd) nanoparticles. The EABs acted as the electron generator while nanoparticles functioned as the electron carrier agents to enhance degradation rate of the dye by breaking the kinetic barrier. The hollow Pd nanoparticles showed better performance than the solid Pd nanoparticles on the dye degradation, possibly due to high specific surface area and cage effect. The hollow cavities provided by the nanoparticles acted as the reaction centers for the dye degradation.

Hollow Palladium Nanoparticles Facilitated Biodegradation of an Azo Dye by Electrically Active Biofilms

KAUST Repository

Kalathil, Shafeer

2016-08-04

Dye wastewater severely threatens the environment due to its hazardous and toxic effects. Although many methods are available to degrade dyes, most of them are far from satisfactory. The proposed research provides a green and sustainable approach to degrade an azo dye, methyl orange, by electrically active biofilms (EABs) in the presence of solid and hollow palladium (Pd) nanoparticles. The EABs acted as the electron generator while nanoparticles functioned as the electron carrier agents to enhance degradation rate of the dye by breaking the kinetic barrier. The hollow Pd nanoparticles showed better performance than the solid Pd nanoparticles on the dye degradation, possibly due to high specific surface area and cage effect. The hollow cavities provided by the nanoparticles acted as the reaction centers for the dye degradation.

Hollow Palladium Nanoparticles Facilitated Biodegradation of an Azo Dye by Electrically Active Biofilms

Directory of Open Access Journals (Sweden)

Shafeer Kalathil

2016-08-01

Full Text Available Dye wastewater severely threatens the environment due to its hazardous and toxic effects. Although many methods are available to degrade dyes, most of them are far from satisfactory. The proposed research provides a green and sustainable approach to degrade an azo dye, methyl orange, by electrically active biofilms (EABs in the presence of solid and hollow palladium (Pd nanoparticles. The EABs acted as the electron generator while nanoparticles functioned as the electron carrier agents to enhance degradation rate of the dye by breaking the kinetic barrier. The hollow Pd nanoparticles showed better performance than the solid Pd nanoparticles on the dye degradation, possibly due to high specific surface area and cage effect. The hollow cavities provided by the nanoparticles acted as the reaction centers for the dye degradation.

Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

Energy Technology Data Exchange (ETDEWEB)

Paik, Seung Uk; Jung, Myoung Geun [Keimyung University, Daegu (Korea, Republic of)

2012-02-15

A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions.

Rapid Microwave-Assisted Copper-Catalyzed Nitration of Aromatic Halides with Nitrite Salts

International Nuclear Information System (INIS)

Paik, Seung Uk; Jung, Myoung Geun

2012-01-01

A rapid and efficient copper-catalyzed nitration of aryl halides has been established under microwave irradiation. The catalytic systems were found to be the most effective with 4-substituted aryl iodides leading to nearly complete conversions. Nitration of aromatic compounds is one of the important industrial processes as underlying intermediates in the manufacture of a wide range of chemicals such as dyes, pharmaceuticals, agrochemicals and explosives. General methods for the nitration of aromatic compounds utilize strongly acidic conditions employing nitric acid or a mixture of nitric and sulfuric acids, sometimes leading to problems with poor regioselectivity, overnitration, oxidized byproducts and excess acid waste in many cases of functionalized aromatic compounds. Several other nitrating agents or methods avoiding harsh reaction conditions have been explored using metal nitrates, nitrite salts, and ionic liquid-mediated or microwave-assisted nitrations. Recently, copper or palladium compounds have been successfully used as efficient catalysts for the arylation of amines with aryl halides under mild conditions

Recovery of nonradioactive palladium and rhodium from high-level radioactive wastes

International Nuclear Information System (INIS)

McDuffie, H.F.

1979-01-01

A possible method for recovering significant quantities of nonradioactive palladium from fission-product wastes requires essentially complete separation of the fission-product (radioactive) palladium from fission-product ruthenium. After the decay of 106 Ru via 106 Rh to 106 Pd, this nonradioactive palladium is recovered for normal commercial use. The U.S. production of palladium has never been above 1000 kg per year vs consumption of about 46,000 kg per year. Most of the supply comes from Russia and South Africa. It has been estimated that a 400-GW(e) nuclear reactor economy will make available 2000 kg per year of 106 Ru at reactor fuel discharge. A substantial increase might be achieved if plutonium were recycled as fissionable material because of the higher yields of the 106 chain from plutonium. A literature search has uncovered support for three promising approaches to the required separation of palladium from ruthenium: (1) recrystallization from solution in bismuth or in zinc; (2) selective precipitation of a titanium--ruthenium intermetallic compound from bismuth, followed by precipitation of a zinc--palladium intermetallic compound; and (3) dissolution in molten magnesium followed by partitioning between molten magnesium and a molten uranium-5 wt % chromium eutectic at a temperature above 870 0 C. Liquid-liquid extraction appears to be the most promising method from a technological point of view, although intermetallic compound formation is much more interesting chemically. Recovery of some nonradioactive 103 Rh may be possible by liquid-liquid extraction of the fuel before the decay of the 39.8-d 103 Ru has gone substantially to completion. Demonstration of the practicality of these separations will contribute a positive factor to the evaluation of resumption in the United States of nuclear fuel reprocessing and plutonium recycle in light-water-moderated reactors

In situ synthesis of carbon nanotubes decorated with palladium nanoparticles using arc-discharge in solution method

International Nuclear Information System (INIS)

Bera, Debasis; Kuiry, Suresh C.; McCutchen, Matthew; Seal, Sudipta; Heinrich, Helge; Slane, Grady C.

2004-01-01

A unique, simple, inexpensive, and one-step synthesis route to produce carbon nanotubes (CNTs) decorated with palladium nanoparticles using a simplified dc arc-discharge in solution is reported. Zero-loss energy filtered transmission electron microscopy and scanning transmission electron microscopy confirm the presence of 3 nm palladium nanoparticles. Such palladium nanoparticles form during the reduction of palladium tetra-chloro-square-planar complex. The deconvoluted x-ray photoelectron spectroscopy envelope shows the presence of palladium on the decorated CNTs. The energy dispersive spectroscopy suggests no functionalization of atomic chlorine to the sidewall of the CNTs. The presence of dislodged graphene sheets with wavy morphology supports the formation of CNTs through the 'scroll mechanism'

Bioaugmentation of aerobic sludge granules with a plasmid donor strain for enhanced degradation of 2,4-dichlorophenoxyacetic acid

International Nuclear Information System (INIS)

Quan Xiangchun; Tang Hua; Xiong Weicong; Yang Zhifeng

2010-01-01

Aerobic sludge granules pre-grown on glucose were bioaugmented with a plasmid pJP4 carrying strain Pseudomonas putida SM1443 in a fed-batch microcosm system and a lab-scale sequencing batch reactor (SBR) to enhance their degradation capacity to 2,4-dichlorophenoxyacetic acid (2,4-D). The fed-batch test results showed that the bioaugmented aerobic granule system gained 2,4-D degradation ability faster and maintained a more stable microbial community than the control in the presence of 2,4-D. 2,4-D at the initial concentration of about 160 mg/L was nearly completely removed by the bioaugmented granule system within 62 h, while the control system only removed 26% within 66 h. In the bioaugmented SBR which had been operated for 90 days, the seeded aerobic granules pre-grown on glucose successfully turned into 2,4-D degrading granules through bioaugmentation and stepwise increase of 2,4-D concentration from 8 to 385 mg/L. The granules showed a compact structure and good settling ability with the mean diameter of about 450 μm. The degradation kinetics of 2,4-D by the aerobic granules can be described with the Haldane kinetics model with V max = 31.1 mg 2,4-D/gVSS h, K i = 597.9 mg/L and K s = 257.3 mg/L, respectively. This study shows that plasmid mediated bioaugmentation is a feasible strategy to cultivate aerobic granules degrading recalcitrant pollutants.

Electrochemical behavior of fission palladium in 1-butyl-3-methylimidazolium chloride

Energy Technology Data Exchange (ETDEWEB)

Jayakumar, M.; Venkatesan, K.A.; Srinivasan, T.G. [Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)

2007-08-01

Electrochemical behavior of palladium (II) chloride in 1-butyl-3-methylimidazolium chloride has been investigated by various electrochemical transient techniques using glassy carbon working electrode at different temperatures (343-373 K). Cyclic voltammogram consisted of a prominent reduction wave at -0.61 V (vs. Pd) due to the reduction of Pd(II) to Pd, and two oxidation waves at -0.26 and 0.31 V. A nucleation loop is observed at -0.53 V. The diffusion coefficient of palladium (II) in bmimCl ({proportional_to}10{sup -7} cm{sup 2}/s) was determined and the energy of activation (63 kJ/mol) was deduced from the cyclic voltammograms at various temperatures. Nucleation and growth of palladium on glassy carbon working electrode has been investigated by chronoamperometry and chronopotentiometry. The growth and decay of chronocurrents measured for palladium deposition has been found to follow the instantaneous nucleation model with three-dimensional growth of nuclei. The surface morphology of the deposit obtained at various applied potentials revealed the formation of dendrites immediately after nucleation and spread in all the directions with time. (author)

Preparation of Palladium/Silver-Coated Polyimide Nanotubes: Flexible, Electrically Conductive Fibers.

Science.gov (United States)

Kong, Lushi; Rui, Guanchun; Wang, Guangyu; Huang, Rundong; Li, Ran; Yu, Jiajie; Qi, Shengli; Wu, Dezhen

2017-11-02

A simple and practical method for coating palladium/silver nanoparticles on polyimide (PI) nanotubes is developed. The key steps involved in the process are silver ion exchange/reduction and displacement reactions between silver and palladium ions. With the addition of silver, the conductivity of the PI nanotubes is greatly enhanced. Further, the polyimide nanotubes with a dense, homogeneous coating of palladium nanoparticles remain flexible after heat treatment and show the possibility for use as highly efficient catalysts. The approach developed here is applicable for coating various noble metals on a wide range of polymer matrices, and can be used for obtaining polyimide nanotubes with metal loaded on both the inner and outer surface.

Preparation of Palladium/Silver-Coated Polyimide Nanotubes: Flexible, Electrically Conductive Fibers

Directory of Open Access Journals (Sweden)

Lushi Kong

2017-11-01

Full Text Available A simple and practical method for coating palladium/silver nanoparticles on polyimide (PI nanotubes is developed. The key steps involved in the process are silver ion exchange/reduction and displacement reactions between silver and palladium ions. With the addition of silver, the conductivity of the PI nanotubes is greatly enhanced. Further, the polyimide nanotubes with a dense, homogeneous coating of palladium nanoparticles remain flexible after heat treatment and show the possibility for use as highly efficient catalysts. The approach developed here is applicable for coating various noble metals on a wide range of polymer matrices, and can be used for obtaining polyimide nanotubes with metal loaded on both the inner and outer surface.

Radiochemical neutron activation analysis of high pure palladium and platinum by ion exchange chromatography

International Nuclear Information System (INIS)

Sadikov, I.I.; Zinov'ev, V.G.; Sadikova, Z.O.; Salimov, M.I.

2006-01-01

Full text: The palladium and platinum are widely used for jewel manufacture because of their beautiful white color. However the most part of these metals are widely adopted in the world as catalysts. Many works on analytical chemistry of platinum group elements published during last years are devoted to determination of platinum and palladium in other materials. There are no articles on analysis technique of the palladium and platinum purity published during last 20 years. Available publications are very old and are published till 70th of the last century, and implement chemical and spectral methods. At the same time, the palladium and platinum are very suitable for NAA. Therefore the purpose of our research was development of high-sensitivity and multielement techniques of radiochemical neutron activation analysis of a high pure palladium and platinum. Research of nuclear characteristics of palladium and platinum has shown that radioactive nuclides with different yields are formed under the reactor neutrons. 109 , 111 , 111m Pd, 109m , 111 Ag, 191 , 197 , 199 Pt, 199 Au are the most important among them. 109Pd separation factor is equal to 1*10 5 at palladium analysis, whereas 197 Pt and 199 Au separation factor is equal to 1*10 4 at the platinum analysis every other day after irradiation. Palladium and platinum can be separated by precipitation, extraction and ion exchange methods. For separation of radioactive nuclide of the matrix elements from the impurity elements we used ion exchange chromatography system Dowex-1x8 - 1 M HNO 3 for palladium and Dowex-1x8 - 0.1 M HNO 3 for platinum. At the HNO 3 acid concentrations variation from 0,1 M to 1 M more then 25 elements have distribution factors less than 1 and 10 elements have distribution factors 5 while matrix elements have distribution factors higher than 100. It allows an effective separation of these elements from palladium and platinum. Optimum sizes of the chromatographic column and the column effluent

Deduction of kinetic mechanism in multisubstrate enzyme reactions from tritium isotope effects. Application to dopamine beta-hydroxylase

International Nuclear Information System (INIS)

Klinman, J.P.; Humphries, H.; Voet, J.G.

1980-01-01

Primary tritium isotope effects have been measured for the hydroxylation of [2-3H] dopamine catalyzed by dopamine beta-hydroxylase. Experimental values vary from 8.8 +/- 1.4 at 0.02 mM oxygen to 4.1 +/- 0.6 at 1.0 mM oxygen. It is shown that the observed dependence of the isotope effect on oxygen concentration provides unequivocal evidence for a kinetically significant dissociation of both dopamine and oxygen from enzyme, ternary complex. This approach, which is applicable to any multisubstrate enzyme characterized by detectable kinetic isotope effects, provides an alternate to classical methods for the elucidation of kinetic order in enzyme-catalyzed reactions

Factors affecting the corrosion of SiC layer by fission product palladium

International Nuclear Information System (INIS)

Dewita, E.

2000-01-01

HTR is one of the advanced nuclear reactors which has inherent safety system, graphite moderated and helium gas cooled. In general, these reactors are designed with the TRISO coated particle consist of four coating layers that are porous pyrolytic carbon (PyC). inner dense PyC (IPyC), silicon carbide (SiC), and outer dense PyC (OPyC). Among the four coating layers, the SiC plays an important role beside in retaining metallic fission products, it also provides mechanical strength to fuel particle. However, results of post irradiation examination indicate that fission product palladium can react with and corrode SiC layer, This assessment is conducted to get the comprehension about resistance of SiC layer on irradiation effects, especially in order to increase the fuel bum-up. The result of this shows that the corrosion of SiC layer by fission product palladium is beside depend on the material characteristics of SiC, and also there are other factors that affect on the SiC layer corrosion. Fuel enrichment, bum-up, and irradiation time effect on the palladium flux in fuel kernel. While, the fuel density, vapour pressure of palladium (the degree depend on the irradiation temperature and kernel composition) effect on palladium migration in fuel particle. (author)

Glutathione reductase: solvent equilibrium and kinetic isotope effects

International Nuclear Information System (INIS)

Wong, K.K.; Vanoni, M.A.; Blanchard, J.S.

1988-01-01

Glutathione reductase catalyzes the NADPH-dependent reduction of oxidized glutathione (GSSG). The kinetic mechanism is ping-pong, and we have investigated the rate-limiting nature of proton-transfer steps in the reactions catalyzed by the spinach, yeast, and human erythrocyte glutathione reductases using a combination of alternate substrate and solvent kinetic isotope effects. With NADPH or GSSG as the variable substrate, at a fixed, saturating concentration of the other substrate, solvent kinetic isotope effects were observed on V but not V/K. Plots of Vm vs mole fraction of D 2 O (proton inventories) were linear in both cases for the yeast, spinach, and human erythrocyte enzymes. When solvent kinetic isotope effect studies were performed with DTNB instead of GSSG as an alternate substrate, a solvent kinetic isotope effect of 1.0 was observed. Solvent kinetic isotope effect measurements were also performed on the asymmetric disulfides GSSNB and GSSNP by using human erythrocyte glutathione reductase. The Km values for GSSNB and GSSNP were 70 microM and 13 microM, respectively, and V values were 62 and 57% of the one calculated for GSSG, respectively. Both of these substrates yield solvent kinetic isotope effects greater than 1.0 on both V and V/K and linear proton inventories, indicating that a single proton-transfer step is still rate limiting. These data are discussed in relationship to the chemical mechanism of GSSG reduction and the identity of the proton-transfer step whose rate is sensitive to solvent isotopic composition. Finally, the solvent equilibrium isotope effect measured with yeast glutathione reductase is 4.98, which allows us to calculate a fractionation factor for the thiol moiety of GSH of 0.456

Crystal size effect on the electrochemical oxidation of formate on carbon-supported palladium nanoparticles

International Nuclear Information System (INIS)

Santos, Rayana Marcela Izidoro da Silva; Nakazato, Roberto Zenhei; Ciapina, Eduardo Goncalves

2016-01-01

Full text: The electrochemical oxidation of formate in alkaline electrolytes has emerged an a promising anodic reaction in the Direct Formate Fuel Cells[1]. Although palladium is considered to be one of the best electro catalyst for the oxidation of formate, important structure-activity relationships are still not understood. In the present work, we investigated the effect of the size of the palladium crystals in the electrochemical oxidation of formate in 0.1 mol L -1 KOH. Carbon-supported palladium nanoparticles (Pd/C) were prepared by chemical reduction of palladium (II) chloride in aqueous media by sodium borohydride in the presence of varying quantities of sodium citrate in the reaction media to obtain metallic crystals with distinct sizes. Analysis of the X-ray diffraction profile revealed the presence of palladium crystals in the range of 6 to 19 nm. Potentiostatic oxidation of formate on the distinct Pd/C samples revealed a volcano-like dependence of the specific activity with the size of the palladium crystals, presenting the highest activity for crystals around 7.5 nm. Reference: [1] A.M. Bartrom, J.L. Haan, The direct formate fuel cell with an alkaline anion exchange membrane, J. Power Sources. 214 (2012) 68-74. (author)

Silver-palladium catalysts for the direct synthesis of hydrogen peroxide

Science.gov (United States)

Khan, Zainab; Dummer, Nicholas F.; Edwards, Jennifer K.

2017-11-01

A series of bimetallic silver-palladium catalysts supported on titania were prepared by wet impregnation and assessed for the direct synthesis of hydrogen peroxide, and its subsequent side reactions. The addition of silver to a palladium catalyst was found to significantly decrease hydrogen peroxide productivity and hydrogenation, but crucially increase the rate of decomposition. The decomposition product, which is predominantly hydroxyl radicals, can be used to decrease bacterial colonies. The interaction between silver and palladium was characterized using scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR). The results of the TPR and XPS indicated the formation of a silver-palladium alloy. The optimal 1% Ag-4% Pd/TiO2 bimetallic catalyst was able to produce approximately 200 ppm of H2O2 in 30 min. The findings demonstrate that AgPd/TiO2 catalysts are active for the synthesis of hydrogen peroxide and its subsequent decomposition to reactive oxygen species. The catalysts are promising for use in wastewater treatment as they combine the disinfectant properties of silver, hydrogen peroxide production and subsequent decomposition. This article is part of a discussion meeting issue 'Providing sustainable catalytic solutions for a rapidly changing world'.

Recovery of Elemental Palladium by Shewanella putrefaciens

Science.gov (United States)

Akasaka, S.; Xia, X.; Sawada, K.; Enokida, Y.; Yamamoto, I.; Ohnuki, T.

2006-12-01

Microbial reduction of metals plays an important role in environmental behavior and provides a technique for the recovery of metals from industrial wastewater. Recently, demand for platinum group metals (PGMs) increases by their catalytic properties. The extreme rarity of PGMs have led to a growing interest in their recovery. Palladium, one of PGMs, has different oxidation states of Pd(II) and Pd(0). The oxidized form of Pd(II) is soluble, while the reduced form of Pd(0) is insoluble. In this study, microbial reduction of palladium by Fe(III)- reducing bacterium, Shewanella putrefaceins was conducted. This bacterium is known to be capable of reducing metals, such as Mn(IV), U(VI), or Tc(VII) with organic C or H2 as an electron donor. In order to investigate the potential of S. putrefaciens to reduce Pd(II) in solution, resting cells or heat-killed cells were suspended under anaerobic conditions with lactate or H2 as an electron donor. The cells of S. putrefaciens (NBRC3908) were grown in aerobic medium, harvested by centrifugation, and then washed with 25 mmol/dm3 HEPES and 100 mmol/dm3 NaCl (HEPES-NaCl) solution (pH 7.0). The heat-killed cells were autoclaved for 20 min at 121 degrees C. The cell suspension (21.5 mg in dry weight) was resuspended in the HEPES-NaCl solution which contained 1.0 mmol/dm3 Na2PdCl4 (Wako Pure chemical Industries, Ltd). The suspensions were bubbled with N2 for 15 min before 10 mmol/dm3 lactate or 4.8 v/v% H2 was added. The suspensions were then incubated at 30 degrees C. Redox potential (Eh) and pH of the solutions were measured in an inert glove box with Ar gas. Concentration of Pd(II) was measured by Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES). Deposited Pd and cells were analyzed by X-ray powder diffraction (XRD) and Scanning Electron Microscope (SEM) with Energy-Dispersive Spectroscopy (EDS). Approximately 86% of Pd(II) of the initial concentration was removed from solution by the resting cells within 24 h when

Graphite-supported gold nanoparticles as efficient catalyst for aerobic oxidation of benzylic amines to imines and N-substituted 1,2,3,4-tetrahydroisoquinolines to amides: synthetic applications and mechanistic study.

Science.gov (United States)

So, Man-Ho; Liu, Yungen; Ho, Chi-Ming; Che, Chi-Ming

2009-10-05

Selective oxidation of amines using oxygen as terminal oxidant is an important area in green chemistry. In this work, we describe the use of graphite-supported gold nanoparticles (AuNPs/C) to catalyze aerobic oxidation of cyclic and acyclic benzylic amines to the corresponding imines with moderate-to-excellent substrate conversions (43-100%) and product yields (66-99%) (19 examples). Oxidation of N-substituted 1,2,3,4-tetrahydroisoquinolines in the presence of aqueous NaHCO3 solution gave the corresponding amides in good yields (83-93%) with high selectivity (up to amide/enamide=93:4) (6 examples). The same protocol can be applied to the synthesis of benzimidazoles from the reaction of o-phenylenediamines with benzaldehydes under aerobic conditions (8 examples). By simple centrifugation, AuNPs/C can be recovered and reused for ten consecutive runs for the oxidation of dibenzylamine to N-benzylidene(phenyl)methanamine without significant loss of catalytic activity and selectivity. This protocol "AuNPs/C+O2" can be scaled to the gram scale, and 8.9 g (84 % isolated yield) of 3,4-dihydroisoquinoline can be obtained from the oxidation of 10 g 1,2,3,4-tetrahydroisoquinoline in a one-pot reaction. Based on the results of kinetic studies, radical traps experiment, and Hammett plot, a mechanism involving the hydrogen-transfer reaction from amine to metal and oxidation of M-H is proposed.

Palladium(II)-Stabilized Pyridine-2-Diazotates: Synthesis, Structural Characterization, and Cytotoxicity Studies.

Science.gov (United States)

Tskhovrebov, Alexander G; Vasileva, Anna A; Goddard, Richard; Riedel, Tina; Dyson, Paul J; Mikhaylov, Vladimir N; Serebryanskaya, Tatiyana V; Sorokoumov, Viktor N; Haukka, Matti

2018-02-05

Well-defined diazotates are scarce. Here we report the synthesis of unprecedented homoleptic palladium(II) diazotate complexes. The palladium(II)-mediated nitrosylation of 2-aminopyridines with NaNO 2 results in the formation of metal-stabilized diazotates, which were found to be cytotoxic to human ovarian cancer cells.

Removal of oxytetracycline and determining its biosorption properties on aerobic granular sludge.

Science.gov (United States)

Mihciokur, Hamdi; Oguz, Merve

2016-09-01

This study investigates biosorption of Oxytetracycline, a broad-spectrum antibiotic, using aerobic granular sludge as an adsorbent in aqueous solutions. A sequencing batch reactor fed by a synthetic wastewater was operated to create aerobic granular sludge. Primarily, the pore structure and surface area of granular sludge, the chemical structure and the molecular sizes of the pharmaceutical, operating conditions, such as pH, stirring rate, initial concentration of Oxytetracycline, during adsorption process was verified. Subsequently, thermodynamic and kinetic aspects of the adsorption were examined and adsorption isotherm studies were carried out. It was shown that the aerobic granular sludge was a good alternative for biosorption of this pharmaceutical. The pharmaceutical was adsorbed better at pH values of 6-8. The adsorption efficiency increased with rising ionic strength. Also, it was seen that the adsorption process was an exothermic process in terms of thermodynamics. The adsorption can be well explained by Langmuir isotherm model. Copyright © 2016 Elsevier B.V. All rights reserved.

Interaction between Palladium Nanoparticles and Surface-Modified Carbon Nanotubes: Role of Surface Functionalities

DEFF Research Database (Denmark)

Zhang, Bingsen; Shao, Lidong; Zhang, Wei

2014-01-01

degrees C. We focus on probing the effects of oxygen and nitrogen-containing functional groups on supported palladium nanoparticles (NPs) in the model catalytic system. The stability of palladium NPs supported on CNTs depends strongly on the surface properties of CNTs. Moreover, the oxygen...... feature, instability, and subtle response of the components upon application of an external field. Herein, we use insitu TEM, electron energy loss spectroscopy, and X-ray photoelectron spectroscopy techniques to record the interaction in palladium on carbon nanotubes (CNTs) from room temperature to 600...

Carbonylation of 1-hexene in the presence of palladium-anion-exchange resin catalysts

Energy Technology Data Exchange (ETDEWEB)

Lapidus, A.L.; Pirozhkov, S.D.; Buiya, M.A.; Lunin, A.F.; Karapetyan, L.P.; Saldadze, K.M.

1986-06-20

Activated charcoal, silica gel, and zeolites containing palladium are active in the carbonylation of lower olefins by carbon monoxide. In the present work, they studied the carbonylation of 1-hexene in the presence of a series of palladium catalysts containing An-221, An-251, and AN-511 anion-exchange catalysts produced in the USSR as the supports. A catalyst obtained by the deposition of palladium(II) on weakly basic anion-exchange resins displays high efficiency in the carbonylation of 1-hexene with the formation of a nixture of enanthoic and 2-methylcaproic acids.

Nanostructured palladium tailored via carbonyl chemical route towards oxygen reduction reaction

International Nuclear Information System (INIS)

Luo, Y.; Mora-Hernández, J.M.; Estudillo-Wong, L.A.; Arce-Estrada, E.M.; Alonso-Vante, N.

2015-01-01

Graphical Abstract: Mass-depending morphologies of nanostructured Palladium obtained via the carbonyl chemical route. Display Omitted -- Highlights: •Mass-depending morphology was observed in nanostructured palladium supported on carbon prepared by the carbonyl chemical route. •The Morphological effect of carbon supported Pd was investigated towards ORR. -- Abstract: Carbon supported palladium nanostructures were synthesized via the carbonyl chemical route. Compared with nanostructured platinum, prepared via carbonyl chemical route, Pd nanomaterials showed mass-loading morphology, whereas particle size and morphology of Pt nanostructures was constant. The oxygen reduction reaction (ORR) on nanostructured Pd, with different morphology in both acid and alkaline medium was investigated. A relationship, based on X-ray diffraction structural analysis pattern, transmission electron microscope, with the Pd morphological effect on ORR activity was identified

Shaping surface of palladium nanospheres through the control of reaction parameters

International Nuclear Information System (INIS)

Wang Lianmeng; Tan Enzhong; Guo Lin; Wang Lihua; Han Xiaodong

2011-01-01

Solid, cracked, and flower-shaped surfaces of palladium nanospheres with high yields and good uniformity were successfully prepared by a wet chemical method. On the basis of the experimental data, the same size of palladium nanosphere with different surface morphologies can be regulated only by changing the amount of ammonium hydroxide and reductant in one experimental system. The as-prepared products were studied by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and x-ray diffraction (XRD). In addition, surface-enhanced Raman scattering (SERS) spectra on the as-prepared different surface of palladium nanospheres exhibit high activity towards p-aminothiophenol (PATP) detection, and the result further reveals that the predominance of the a1 vibration mode in the SERS spectra via an electromagnetic (EM) mechanism is significant.

Sample Handling and Chemical Kinetics in an Acoustically Levitated Drop Microreactor

Science.gov (United States)

2009-01-01

Accurate measurement of enzyme kinetics is an essential part of understanding the mechanisms of biochemical reactions. The typical means of studying such systems use stirred cuvettes, stopped-flow apparatus, microfluidic systems, or other small sample containers. These methods may prove to be problematic if reactants or products adsorb to or react with the container’s surface. As an alternative approach, we have developed an acoustically-levitated drop reactor eventually intended to study enzyme-catalyzed reaction kinetics related to free radical and oxidative stress chemistry. Microliter-scale droplet generation, reactant introduction, maintenance, and fluid removal are all important aspects in conducting reactions in a levitated drop. A three capillary bundle system has been developed to address these needs. We report kinetic measurements for both luminol chemiluminescence and the reaction of pyruvate with nicotinamide adenine dinucleotide, catalyzed by lactate dehydrogenase, to demonstrate the feasibility of using a levitated drop in conjunction with the developed capillary sample handling system as a microreactor. PMID:19769373

Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols.

Science.gov (United States)

Li, Junjun; Liu, Yuxuan; Tang, Weijun; Xue, Dong; Li, Chaoqun; Xiao, Jianliang; Wang, Chao

2017-10-17

The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of palladium in various samples by atomic absorption spectrometry after preconcentration with dimethylglyoxime on silica gel

International Nuclear Information System (INIS)

Tokalioglu, Serife; Oymak, Tuelay; Kartal, Senol

2004-01-01

A preconcentration method based on the adsorption of palladium-dimethylglyoxime (DMG) complex on silica gel for the determination of palladium at trace levels by atomic absorption spectrometry (AAS) has been developed. The retained palladium as Pd(DMG) 2 complex was eluted with 1 mol l -1 HCl in acetone. The effect of some analytical parameters such as pH, amount of reagent and the sample volume on the recovery of palladium was examined in synthetic solutions containing street dust matrix. The influence of some matrix ions on the recovery of palladium was investigated by using the developed method when the elements were present both individually and together. The results showed that 2500 μg ml -1 Na + , K + , Mg 2+ , Al 3+ and Fe 3+ ; 5000 μg ml -1 Ca 2+ ; 500 μg ml -1 Pb 2+ ; 125 μg ml -1 Zn 2+ ; 50 μg ml -1 Cu 2+ and 25 μg ml -1 Ni 2+ did not interfere with the palladium signal. At the optimum conditions determined experimentally, the recovery for palladium was found to be 95.3±1.2% at the 95% confidence level. The relative standard deviation and limit of detection (3s/b) of the method were found to be 1.7% and 1.2 μg l -1 , respectively. In order to determine the adsorption behaviour of silica gel, the adsorption isotherm of palladium was studied and the binding equilibrium constant and adsorption capacity were calculated to be 0.38 l mg -1 and 4.06 mg g -1 , respectively. The determination of palladium in various samples was performed by using both flame AAS and graphite furnace AAS. The proposed method was successfully applied for the determination of palladium in the street dust, anode slime, rock and catalytic converter samples

Evaluation of (+)-sparteine-like diamines for asymmetric synthesis.

Science.gov (United States)

Dearden, Michael J; McGrath, Matthew J; O'Brien, Peter

2004-08-20

Three new (+)-sparteine-like diamines were prepared from (-)-cytisine and evaluated as sparteine surrogates in the alpha-lithiation rearrangement of cyclooctene oxide and the palladium(II)/diamine catalyzed oxidative kinetic resolution of 1-indanol. The new diamines exhibited opposite enantioselectivity to that observed with (-)-sparteine but increasing the steric hindrance of the N-alkyl group beyond N-Et had a detrimental effect on enantioselectivity. The optimal N-Me diamine was evaluated with much success in five other (-)-sparteine-mediated processes involving different metals (lithium, magnesium, and copper) and different types of reaction mechanisms. Copyright 2004 American Chemical Society

Aerobic methylcyclohexane-promoted epoxidation of stilbene over gold nanoparticles supported on Gd-doped titania

KAUST Repository

Mendez, Violaine; Guillois, Kevin; Daniè le, Sté phane; Tuel, Alain; Caps, Valerie

2010-01-01

Aerobic partial oxidations of alkanes and alkenes are important processes of the petrochemical industry. The radical mechanisms involved can be catalyzed by soluble salts of transition metals (Co, Cu, Mn...). We show here that the model methylcyclohexane/stilbene co-oxidation reaction can be efficiently catalyzed at lower temperature by supported gold nanoparticles. The support has little influence on gold intrinsic activity but more on the apparent reaction rates which are a combination of catalytic activity and diffusion limitations. These are here minimized by using gadolinium-doped titania nanocrystallites as support for gold nanoparticles. This material is obtained by mild hydrolysis of a new Gd4TiO(OiPr)14 bimetallic oxoalkoxide. It leads to enhanced wettability of the < 3 nm gold particles in the tert-butyl hydroperoxide (TBHP)-initiated epoxidation of stilbene in methylcyclohexane; Au/TiO2:Gd3+ is in turn as active as the state-of-the-art hydrophobic Au/SiO2 catalyst. The rate-determining step of this reaction is identified as the gold-catalyzed homolytic decomposition of TBHP generating radicals and initiating the methylcyclohexane-mediated epoxidation of stilbene, yielding a methylcyclohexan-1-ol/trans-stilbene oxide mixture. Methylcyclohexan-1-ol can also be obtained in the absence of the alkene in the gold-catalyzed solvent-free autoxidation of methylcyclohexane, evidencing the catalytic potential of gold nanoparticles for low temperature C-H activation. © 2010 The Royal Society of Chemistry.

Calcite Dissolution Kinetics

Science.gov (United States)

Berelson, W.; Subhas, A.; Dong, S.; Naviaux, J.; Adkins, J. F.

2016-12-01

A geological buffer for high atmospheric CO2 concentrations is neutralization via reaction with CaCO3. We have been studying the dissolution kinetics of carbonate minerals using labeled 13C calcite and Picarro-based measurements of 13C enrichments in solution DIC. This methodology has greatly facilitated our investigation of dissolution kinetics as a function of water carbonate chemistry, temperature and pressure. One can adjust the saturation state Omega by changing the ion activity product (e.g. adjusting carbonate ion concentration), or by changing the solubility product (e.g. adjusting temperature or pressure). The canonical formulation of dissolution rate vs. omega has been refined (Subhas et al. 2015) and shows distinct non-linear behavior near equilibrium and rates in sea water of 1-3 e-6 g/cm2day at omega = 0.8. Carbonic anhydrase (CA), an enzyme that catalyzes the hydration of dissolved CO2 to carbonic acid, was shown (in concentrations 500x. This result points to the importance of carbonic acid in enhancing dissolution at low degrees of undersaturation. CA activity and abundance in nature must be considered regarding the role it plays in catalyzing dissolution. We also have been investigating the role of temperature on dissolution kinetics. An increase of 16C yields an order of magnitude increase in dissolution rate. Temperature (and P) also change Omega critical, the saturation state where dissolution rates change substantially. Increasing pressure (achieved in a pressure reaction chamber we built) also shifts Omega critical closer to equilibrium and small pressure increases have large impact on dissolution kinetics. Dissolution rates are enhanced by an order of magnitude for a change in pressure of 1500 psi relative to the dissolution rate achieved by water chemistry effects alone for an omega of 0.8. We've shown that the thermodynamic determination of saturation state does not adequately describe the kinetics of dissolution. The interplay of mineral

Preparation of Palladium-Impregnated Ceria by Metal Complex Decomposition for Methane Steam Reforming Catalysis

Directory of Open Access Journals (Sweden)

Worawat Wattanathana

2017-01-01

Full Text Available Palladium-impregnated ceria materials were successfully prepared via an integrated procedure between a metal complex decomposition method and a microwave-assisted wetness impregnation. Firstly, ceria (CeO2 powders were synthesized by thermal decomposition of cerium(III complexes prepared by using cerium(III nitrate or cerium(III chloride as a metal source to form a metal complex precursor with triethanolamine or benzoxazine dimer as an organic ligand. Palladium(II nitrate was consequently introduced to the preformed ceria materials using wetness impregnation while applying microwave irradiation to assist dispersion of the dopant. The palladium-impregnated ceria materials were obtained by calcination under reduced atmosphere of 10% H2 in He stream at 700°C for 2 h. Characterization of the palladium-impregnated ceria materials reveals the influences of the metal complex precursors on the properties of the obtained materials. Interestingly, the palladium-impregnated ceria prepared from the cerium(III-benzoxazine dimer complex revealed significantly higher BET specific surface area and higher content of the more active Pdδ+ (δ > 2 species than the materials prepared from cerium(III-triethanolamine complexes. Consequently, it exhibited the most efficient catalytic activity in the methane steam reforming reaction. By optimization of the metal complex precursors, characteristics of the obtained palladium-impregnated ceria catalysts can be modified and hence influence the catalytic activity.

Palladium emissions in the environment: analytical methods, environmental assessment and health effects

National Research Council Canada - National Science Library

Alt, Friedrich; Zereini, Fathi

2006-01-01

... (Eds)). But there is a clear lack of information concerning palladium. It is very important to condense the present state of research findings from emission to potential health risks for the environment and humans. Very important is the chapter about analytical determination of palladium, which shows clearly the problems of several analytic...

The study of hydrogen electrosorption in layered nickel foam/palladium/carbon nanofibers composite electrodes

International Nuclear Information System (INIS)

Skowronski, J.M.; Czerwinski, A.; Rozmanowski, T.; Rogulski, Z.; Krawczyk, P.

2007-01-01

In the present work, the process of hydrogen electrosorption occurring in alkaline KOH solution on the nickel foam/palladium/carbon nanofibers (Ni/Pd/CNF) composite electrodes is examined. The layered Ni/Pd/CNF electrodes were prepared by a two-step method consisting of chemical deposition of a thin layer of palladium on the nickel foam support to form Ni/Pd electrode followed by coating the palladium layer with carbon nanofibers layer by means of the CVD method. The scanning electron microscope was used for studying the morphology of both the palladium and carbon layer. The process of hydrogen sorption/desorption into/from Ni/Pd as well as Ni/Pd/CNF electrode was examined using the cyclic voltammetry method. The amount of hydrogen stored in both types of composite electrodes was shown to increase on lowering the potential of hydrogen sorption. The mechanism of the anodic desorption of hydrogen changes depending on whether or not CNF layer is present on the Pd surface. The anodic peak corresponding to the removal of hydrogen from palladium is lower for Ni/Pd/CNF electrode as compared to that measured for Ni/Pd one due to a partial screening of the Pd surface area by CNF layer. The important feature of Ni/Pd/CNF electrode is anodic peak appearing on voltammetric curves at potential ca. 0.4 V more positive than the peak corresponding to hydrogen desorption from palladium. The obtained results showed that upon storing the hydrogen saturated Ni/Pd/CNF electrode at open circuit potential, diffusion of hydrogen from carbon to palladium phase occurs due to interaction between carbon fibers and Pd sites on the nickel foam support

Evidence for hydrogen-assisted recovery of cold-worked palladium: hydrogen solubility and mechanical properties studies

Directory of Open Access Journals (Sweden)

Maria Ferrer

2017-07-01

Full Text Available The influence of hydrogen as an agent to accelerate the thermal recovery of cold-worked palladium has been investigated. The techniques used to characterize the effects of hydrogen on the thermal recovery of palladium were hydrogen solubility and mechanical property measurements. Results show that the presence of modest amounts of hydrogen during annealing of cold-worked palladium does enhance the degree of thermal recovery, with a direct correlation between the amount of hydrogen during annealing and the degree of recovery. The results indicate that the damage resulting from cold-working palladium can be more effectively and efficiently reversed by suitable heat treatments in the presence of appropriate amounts of hydrogen, as compared to heat treatment in vacuum. The somewhat novel technique of using changes in the hydrogen solubility of palladium as an indicator of thermal recovery has been validated and complements the more traditional technique of mechanical property measurements.

VO2 kinetics and performance in soccer players after intense training and inactivity

DEFF Research Database (Denmark)

Christensen, Peter Møller; Krustrup, Peter; Gunnarsson, Thomas P.

2011-01-01

18 elite soccer players were, for a two-week period, assigned to a high intensity training group (HI, n=7) performing 10 training sessions mainly consisting of aerobic high intensity training (8×2 min) and speed endurance training (10-12×30-s sprints) or a training cessation group (TC, n=11......PURPOSE:: To examine the effects of a short-term period with intensified training or training cessation of trained soccer players on VO2 kinetics at 75% maximal aerobic speed (MAS), oxidative enzymes and performance in repeated high intensity exercise. METHODS:: After the last match of the season......) that refrained from training. RESULTS:: For TC, VO2 kinetics became slower (P...

γ-Diimine palladium(II based complexes mediated polymerization of methyl methacrylate

Directory of Open Access Journals (Sweden)

Mahmoud Sunjuk

2017-02-01

Full Text Available The synthesis of new palladium(II complexes of the type [Pd(A–NC–ph–CN–ACl2] (4a–e (A = cyclohexyl (a, 2-isoprpropyl (b, pyrenyl (c, naphthyl (d, and 2,6-diisopropyl (e is described. The isolated γ-diimine ligands and their corresponding palladium(II complexes were characterized by their physical properties, elemental analysis, 1H NMR-, 13C NMR, and infrared spectroscopy. The palladium(II complexes (4a–e were employed successfully as catalysts for atom transfer radical polymerization (ATRP of methyl methacrylate (MMA in the presence of ethyl-2-bromoisobutyrate (EBIB as initiator at 90 °C. Polymerization with these catalyst systems afforded polymers with low molecular weight distribution (Mw/Mn and syndio-rich atactic poly (MMA with relatively higher [rr] diads.

Investigation of mechanical and structural characteristics of platinum and palladium at high temperatures

Energy Technology Data Exchange (ETDEWEB)

Trumie, B. T.; Gomidzelovie, L.; Marjanovic, S. R.; Krstic, V. R.

2015-03-30

In order to broaden future application of products based on platinum and palladium a comparative analysis of their high-temperature mechanical properties was performed. Platinum and palladium are of great importance and are widely used in chemical industry, electronics, for making laboratory dishes, to name a few. Mechanical properties of pure metals, such as: tensile strength, creep rate and rupture time were investigated using universal testing machine for tensile testing of materials. Microstructure of samples was investigated by optical microscopy. Based on obtained results it can be concluded that the platinum, compared to palladium, is superior for high-temperature applications. (Author)

Investigation of mechanical and structural characteristics of platinum and palladium at high temperatures

International Nuclear Information System (INIS)

Trumie, B. T.; Gomidzelovie, L.; Marjanovic, S. R.; Krstic, V. R.

2015-01-01

In order to broaden future application of products based on platinum and palladium a comparative analysis of their high-temperature mechanical properties was performed. Platinum and palladium are of great importance and are widely used in chemical industry, electronics, for making laboratory dishes, to name a few. Mechanical properties of pure metals, such as: tensile strength, creep rate and rupture time were investigated using universal testing machine for tensile testing of materials. Microstructure of samples was investigated by optical microscopy. Based on obtained results it can be concluded that the platinum, compared to palladium, is superior for high-temperature applications. (Author)

Some remarks on the neutron elastic- and enelastic-scattering cross sections of palladium

International Nuclear Information System (INIS)

Chiba, S.; Guenther, P.T.; Smith, A.B.

1989-05-01

The cross sections for the elastic-scattering of 5.9, 7.1 and 8.0 MeV neutrons from elemental palladium were measured at forty scattering angles distributed between ∼15/degree/ and 160/degree/. The inelastic-scattering cross sections for the excitation of palladium levels at energies of 260 keV to 560 keV were measured with high resolution at the same energies, and at a scattering angle of 80/degree/. The experimental results were combined with lower-energy values previously obtained by this group to provide a comprehensive data base extending from near the inelastic-scattering threshold to 8 MeV. That data base was interpreted in terms of a coupled-channel model, including the inelastic excitation of one- and two-phonon vibrational levels of the even isotopes of palladium. It was concluded that the palladium inelastic-scattering cross section, at the low energies of interest in assessment of fast-fission-reactor performance, are large (∼50% greater than given in widely used evaluated fission-product data files). They primarily involve compound-nucleus processes, with only a small direct-reaction component attributable to the excitation of the one-phonon, 2 + , vibrational levels of the even isotopes of palladium. 24 refs., 6 figs

Competition Between Self-birth and Catalyzed Death in Aggregation Growth with Catalysis Injection

International Nuclear Information System (INIS)

Chen Dan; Lin Zhenquan; Sun Yunfei; Ke Jianhong

2009-01-01

We propose two irreversible aggregation growth models of aggregates of two distinct species (A and B) to study the interactions between virus aggregates and medicine efficacy aggregates in the virus-medicine cooperative evolution system. The A-species aggregates evolve driven by self monomer birth and B-species aggregate-catalyzed monomer death in model I and by self birth, catalyzed death, and self monomer exchange reactions in model II, while the catalyst B-species aggregates are assumed to be injected into the system sustainedly or at a periodic time-dependent rate. The kinetic behaviors of the A-species aggregates are investigated by the rate equation approach based on the mean-field theory with the self birth rate kernel I A (k) = Ik, catalyzed death rate kernel J AB (k) = Jk and self exchange rate kernel K A (k, l) = Kkl. The kinetic behaviors of the A-species aggregates are mainly dominated by the competition between the two effects of the self birth (with the effective rate I) and the catalyzed death (with the effective rate JB 0 ), while the effects of the self exchanges of the A-species aggregates which appear in an effective rate KA 0 play important roles in the cases of I > JB 0 and I = JB 0 . The evolution behaviors of the total mass M A 1 (t) and the total aggregate number M A 0 (t) are obtained, and the aggregate size distribution α k (t) of species A is found to approach a generalized scaling form in the case of I ≥ JB 0 and a special modified scaling form in the case of I 0 . The periodical evolution of the B-monomers concentration plays an exponential form of the periodic modulation. (interdisciplinary physics and related areas of science and technology)

Kinetics of Ethyl Acetate Synthesis Catalyzed by Acidic Resins

Science.gov (United States)

Antunes, Bruno M.; Cardoso, Simao P.; Silva, Carlos M.; Portugal, Ines

2011-01-01

A low-cost experiment to carry out the second-order reversible reaction of acetic acid esterification with ethanol to produce ethyl acetate is presented to illustrate concepts of kinetics and reactor modeling. The reaction is performed in a batch reactor, and the acetic acid concentration is measured by acid-base titration versus time. The…

Functionalized Palladium Nanoparticles for Hydrogen Peroxide Biosensor

Directory of Open Access Journals (Sweden)

H. Baccar

2011-01-01

Full Text Available We present a comparison between two biosensors for hydrogen peroxide (H2O2 detection. The first biosensor was developed by the immobilization of Horseradish Peroxidase (HRP enzyme on thiol-modified gold electrode. The second biosensor was developed by the immobilization of cysteamine functionalizing palladium nanoparticles on modified gold surface. The amino groups can be activated with glutaraldehyde for horseradish peroxidase immobilization. The detection of hydrogen peroxide was successfully observed in PBS for both biosensors using the cyclic voltammetry and the chronoamperometry techniques. The results show that the limit detection depends on the large surface-to-volume ratio attained with palladium nanoparticles. The second biosensor presents a better detection limit of 7.5 μM in comparison with the first one which is equal to 75 μM.

Kinetics of the gas-solid hydroxyethylation of potato starch

NARCIS (Netherlands)

Kuipers, N.J M; Beenackers, A.A C M

The kinetics of the reaction between gaseous ethylene oxide and semidry granular potato starch was studied in a pressure-controlled semibatch reactor with and without impregnation of the starch with the catalyst sodium hydroxide. Four parallel reactions are involved: the catalyzed (with reaction

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

Palladium-catalysed arylation of sulfonamide stabilised enolates

CSIR Research Space (South Africa)

Zeevaart, JG

2005-03-07

Full Text Available Alpha-Arylation of inethanesulfonamides using palladium catalysis is described. For example, treatment of N-benzyl-Nmethylmethanesulfonamide with catalytic Pd (OAc) (2) in the presence of sodium tert-butoxide, triphenylphosphine and toluene afforded...

HE3 outgassing from four working palladium and uranium beds

International Nuclear Information System (INIS)

Souers, P. C.; Coronado, P. R.; Fearon, F. M.; Garza, R. G.; Shaw , J. F.; Stump, R. K.; Tsugawa, R. T.

1988-01-01

The He 3 output from two palladium and two uranium beds storing T 2 and D-T was studied as a function of time. Three of the beds were started new and watched for a year; the fourth bed was twelve years old. All four were beds used in routine tritium handling. Initial stoichiometries were PdT/sub 0.3/ and UT/sub 0.7/ so that both operated at similar 1 to 130 kPa pressures. The He 3 from palladium ranged from the 0.002 mo1% lower level of sensitivity to 0.01% for PdT 2 at one year of age. The UT system showed 0.1% He 3 at 4 to 62 days and 0.1 to 10% at longer times, with the first cuts being high in He 3 . The palladium bed with 95 to 97% pure T 2 enriches the output to as high as 97 to 99%. 9 refs., 1 fig., 2 tabs

Development of polymeric palladium-nanoparticle membrane-installed microflow devices and their application in hydrodehalogenation.

Science.gov (United States)

Yamada, Yoichi M A; Watanabe, Toshihiro; Ohno, Aya; Uozumi, Yasuhiro

2012-02-13

We have developed a variety of polymeric palladium-nanoparticle membrane-installed microflow devices. Three types of polymers were convoluted with palladium salts under laminar flow conditions in a microflow reactor to form polymeric palladium membranes at the laminar flow interface. These membranes were reduced with aqueous sodium formate or heat to create microflow devices that contain polymeric palladium-nanoparticle membranes. These microflow devices achieved instantaneous hydrodehalogenation of aryl chlorides, bromides, iodides, and triflates by 10-1000 ppm within a residence time of 2-8 s at 50-90 °C by using safe, nonexplosive, aqueous sodium formate to quantitatively afford the corresponding hydrodehalogenated products. Polychlorinated biphenyl (10-1000 ppm) and polybrominated biphenyl (1000 ppm) were completely decomposed under similar conditions, yielding biphenyl as a fungicidal compound. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural and kinetic basis for substrate selectivity in Populus tremuloides sinapyl alcohol dehydrogenase.

Science.gov (United States)

Bomati, Erin K; Noel, Joseph P

2005-05-01

We describe the three-dimensional structure of sinapyl alcohol dehydrogenase (SAD) from Populus tremuloides (aspen), a member of the NADP(H)-dependent dehydrogenase family that catalyzes the last reductive step in the formation of monolignols. The active site topology revealed by the crystal structure substantiates kinetic results indicating that SAD maintains highest specificity for the substrate sinapaldehyde. We also report substantial substrate inhibition kinetics for the SAD-catalyzed reduction of hydroxycinnamaldehydes. Although SAD and classical cinnamyl alcohol dehydrogenases (CADs) catalyze the same reaction and share some sequence identity, the active site topology of SAD is strikingly different from that predicted for classical CADs. Kinetic analyses of wild-type SAD and several active site mutants demonstrate the complexity of defining determinants of substrate specificity in these enzymes. These results, along with a phylogenetic analysis, support the inclusion of SAD in a plant alcohol dehydrogenase subfamily that includes cinnamaldehyde and benzaldehyde dehydrogenases. We used the SAD three-dimensional structure to model several of these SAD-like enzymes, and although their active site topologies largely mirror that of SAD, we describe a correlation between substrate specificity and amino acid substitution patterns in their active sites. The SAD structure thus provides a framework for understanding substrate specificity in this family of enzymes and for engineering new enzyme specificities.

Noise temperature measurements for the determination of the thermodynamic temperature of the melting point of palladium

Energy Technology Data Exchange (ETDEWEB)

Edler, F.; Kuhne, M.; Tegeler, E. [Bundesanstalt Physikalisch-Technische, Berlin (Germany)

2004-02-01

The thermodynamic temperature of the melting point of palladium in air was measured by noise thermometric methods. The temperature measurement was based on noise comparison using a two-channel arrangement to eliminate parasitic noises of electronic components by cross correlation. Three miniature fixed points filled with pure palladium (purity: {approx}99.99%, mass: {approx}90 g) were used to realize the melts of the fixed point metal. The measured melting temperature of palladium in air amounted to 1552.95 deg C {+-} 0.21 K (k = 2). This temperature is 0.45 K lower than the temperature of the melting point of palladium measured by radiation thermometry. (authors)

COMPOSITIONS BASED ON PALLADIUM(II AND COPPER(II COMPOUNDS, HALIDE IONS, AND BENTONITE FOR OZONE DECOMPOSITION

Directory of Open Access Journals (Sweden)

T. L. Rakitskaya

2017-05-01

bromide ion. For Cu(II-KBr/N-Bent composition, kinetic and calculation data show that, in the presence of bromide ions, copper(II inhibits the ozone decomposition. For Pd(II-KBr/NBent composition, it has been found that the maximum activity is attained at СPd(II = 1.02·10-5 mol/g. For bimetallic Pd(II- Cu(II-KBr/N-Bent composition, changes in τ0, τ1/2, k1/2, and Q1/2 parameters depending on a Pd(II content are similar to those for monometallic Pd(II-KBr/NBent composition; however, values of the parameters are higher for the monometallic system. Thus, the inhibiting effect of Cu(II is observed even in the presence of palladium(II.

Effects of trace element concentration on enzyme controlled stable isotope fractionation during aerobic biodegradation of toluene.

Science.gov (United States)

Mancini, Silvia A; Hirschorn, Sarah K; Elsner, Martin; Lacrampe-Couloume, Georges; Sleep, Brent E; Edwards, Elizabeth A; Lollar, Barbara Sherwood

2006-12-15

The effects of iron concentration on carbon and hydrogen isotopic fractionation during aerobic biodegradation of toluene by Pseudomonas putida mt-2 were investigated using a low iron medium and two different high iron media. Mean carbon enrichment factors (epsilonc) determined using a Rayleigh isotopic model were smaller in culture grown under high iron conditions (epsilonc = -1.7+/-0.1%) compared to low iron conditions (epsilonc = -2.5+/-0.3%). Mean hydrogen enrichment factors (epsilonH) were also significantly smaller for culture grown under high iron conditions (epsilonH = -77 +/-4%) versus low iron conditions (EpsilonH = -159+/-11%). A mechanistic model for enzyme kinetics was used to relate differences in the magnitude of isotopic fractionation for low iron versus high iron cultures to the efficiency of the enzymatic transformation. The increase of carbon and hydrogen enrichment factors at low iron concentrations suggests a slower enzyme-catalyzed substrate conversion step (k2) relative to the enzyme-substrate binding step (k-l) at low iron concentration. While the observed differences were subtle and, hence, do not significantly impact the ability to use stable isotope analysis in the field, these results demonstrated that resolvable differences in carbon and hydrogen isotopic fractionation were related to low and high iron conditions. This novel result highlights the need to further investigate the effects of other trace elements known to be key components of biodegradative enzymes.

Preparation of palladium impregnated alumina adsorbents: Thermal and neutron activation analysis

Energy Technology Data Exchange (ETDEWEB)

Mukherjee, Sumanta; Gupta, N.K.; Roy, S.P.; Dash, S.; Kumar, A.; Bamankar, Y.R.; Rao, T.V. Vittal [Product Development Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Kumar, N. [Fuel Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Naik, Y., E-mail: ynaik@barc.gov.in [Product Development Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

2016-02-10

Highlights: • Pd/Al{sub 2}O{sub 3} composite microspheres particles with high surface area were prepared sol–gel process. • Scanning electron microscopy (SEM) studies on silver coated particle. • Content of the palladium was determined using Neutron Activation Analysis (NAA). • Decomposition study has been done by quadrupole mass analyser. - Abstract: Pd/Al{sub 2}O{sub 3} composite microspheres particles with high surface area were prepared sol–gel process. The decomposition of dried gel-particles was studied by TGA/DTA and FT-IR technique. TGA studies indicated that formation of palladium is marked by a broad exothermic peak with a loss of water and oxidation of trapped HMTA/Urea nitrate mixture. The main decomposition reaction took place in the temperature range of 660–1250 K in helium and relatively lower temperature of 400 K to 1250 K in oxygen. Optical microscopy indicated that the distribution of palladium is uniform. SEM studies on silver coated particle indicated that there was surface erosion of some gel spheres while in few of them micro cracks were seen at high resolution. Content of the palladium was determined using Neutron Activation Analysis (NAA). Decomposition at various temperatures was studied using Residual gas analyser and decomposition species were identified using quadrupole mass analyser.

Self-assembly of palladium nanoparticles on functional TiO{sub 2} nanotubes for a nonenzymatic glucose sensor

Energy Technology Data Exchange (ETDEWEB)

Chen, Xianlan [School of Science, Honghe University, Mengzi, Yunnan 661100 (China); College of Chemistry, Qishan Campus, Fuzhou University, Fuzhou, Fujian 350108 (China); Fujian Key Lab of Medical Instrument & Pharmaceutical Technology, Yishan Campus, Fuzhou University, Fuzhou, Fujian 350002 (China); Li, Gang; Zhang, Guowei [School of Science, Honghe University, Mengzi, Yunnan 661100 (China); Hou, Keyu [College of Chemistry, Qishan Campus, Fuzhou University, Fuzhou, Fujian 350108 (China); Fujian Key Lab of Medical Instrument & Pharmaceutical Technology, Yishan Campus, Fuzhou University, Fuzhou, Fujian 350002 (China); Pan, Haibo, E-mail: hbpan@fzu.edu.cn [College of Chemistry, Qishan Campus, Fuzhou University, Fuzhou, Fujian 350108 (China); Fujian Key Lab of Medical Instrument & Pharmaceutical Technology, Yishan Campus, Fuzhou University, Fuzhou, Fujian 350002 (China); Du, Min [Fujian Key Lab of Medical Instrument & Pharmaceutical Technology, Yishan Campus, Fuzhou University, Fuzhou, Fujian 350002 (China)

2016-05-01

Polydiallyldimethylammonium chloride, PDDA, was used as a stabilizer and linker for functionalized TiO{sub 2} nanotubes (TiO{sub 2} NTs). Self-assembled process with palladium nanoparticles (NPs) was successfully synthesized and used for the oxidation of glucose on glassy carbon electrodes. Based on the voltammetric and amperometric results, Pd NPs efficiently catalyzed the oxidation of glucose at − 0.05 V in the presence of 0.1 M NaCl and showed excellent resistance toward interference poisoning from such interfering species as ascorbic acid, uric acid and urea. To further increase sensitivity, the Pd NPs-PDDA-TiO{sub 2} NTs/GCE was electrochemically treated with H{sub 2}SO{sub 4} and NaOH, the glucose oxidation current was magnified 2.5 times than that before pretreatments due to greatly enhancing the electron transport property of the sensor based on the increased defect sites and surface oxide species. In view of the physiological level of glucose, the wide linear concentration range of glucose (4 × 10{sup −7}–8 × 10{sup −4} M) with a detection limit of 8 × 10{sup −8} M (S/N = 3) was obviously good enough for clinical application. - Highlights: • PDDA was used as a stabilizer and linker for functionalized TiO{sub 2} nanotubes. • Self-assembled process with palladium nanoparticles was synthesized. • After treated both H{sub 2}SO{sub 4} and NaOH, the glucose response was magnified to 2.5 times. • The wide linear concentration range of glucose was obtained with a limit of 8 × 10{sup −8} M.

Mechanistic basis for high stereoselectivity and broad substrate scope in the (salen)Co(III)-catalyzed hydrolytic kinetic resolution.

Science.gov (United States)

Ford, David D; Nielsen, Lars P C; Zuend, Stephan J; Musgrave, Charles B; Jacobsen, Eric N

2013-10-16

In the (salen)Co(III)-catalyzed hydrolytic kinetic resolution (HKR) of terminal epoxides, the rate- and stereoselectivity-determining epoxide ring-opening step occurs by a cooperative bimetallic mechanism with one Co(III) complex acting as a Lewis acid and another serving to deliver the hydroxide nucleophile. In this paper, we analyze the basis for the extraordinarily high stereoselectivity and broad substrate scope observed in the HKR. We demonstrate that the stereochemistry of each of the two (salen)Co(III) complexes in the rate-determining transition structure is important for productive catalysis: a measurable rate of hydrolysis occurs only if the absolute stereochemistry of each of these (salen)Co(III) complexes is the same. Experimental and computational studies provide strong evidence that stereochemical communication in the HKR is mediated by the stepped conformation of the salen ligand, and not the shape of the chiral diamine backbone of the ligand. A detailed computational analysis reveals that the epoxide binds the Lewis acidic Co(III) complex in a well-defined geometry imposed by stereoelectronic rather than steric effects. This insight serves as the basis of a complete stereochemical and transition structure model that sheds light on the reasons for the broad substrate generality of the HKR.

Preliminary design of fusion reactor fuel cleanup system by palladium alloy membrane method

International Nuclear Information System (INIS)

Yoshida, Hiroshi; Konishi, Satoshi; Naruse, Yuji

1981-10-01

A design of palladium diffuser and Fuel Cleanup System (FCU) for D-T fusion reactor is proposed. Feasibility of palladium alloy membrane method is discussed based on the early studies by the authors. Operating conditions of the palladium diffuser are determined experimentally. Dimensions of the diffuser are estimated from computer simulation. FCU system is designed under the feed conditions of Tritium Systems Test Assembly (TSTA) at Los Alamos Scientific Laboratory. The system is composed of Pd-diffusers, catalytic oxidizer, freezer and zink beds, and has some advantages in system layout and operation. This design can readily be extended to other conditions of plasma exhaust gases. (author)

Uptake and elimination kinetics of heavy metals by earthworm ...

African Journals Online (AJOL)

Earthworm inoculation of petroleum hydrocarbon contaminated soil is thought to catalyze the bioremediation. Most bioremediation studies focus on the petroleum hydrocarbon content and not on the heavy metals. Here, the uptake kinetics of heavy metals by earthworm in used engine oil contaminated soil was investigated.

Extracellular Palladium Nanoparticle Production using Geobacter sulfurreducens

KAUST Repository

Yates, Matthew D.

2013-09-03

Sustainable methods are needed to recycle precious metals and synthesize catalytic nanoparticles. Palladium nanoparticles can be produced via microbial reduction of soluble Pd(II) to Pd(0), but in previous tests using dissimilatory metal reducing bacteria (DMRB), the nanoparticles were closely associated with the cells, occupying potential reductive sites and eliminating the potential for cell reuse. The DMRB Geobacter sulfurreducens was shown here to reduce soluble Pd(II) to Pd(0) nanoparticles primarily outside the cell, reducing the toxicity of metal ions, and allowing nanoparticle recovery without cell destruction that has previously been observed using other microorganisms. Cultures reduced 50 ± 3 mg/L Pd(II) with 1% hydrogen gas (v/v headspace) in 6 h incubation tests [100 mg/L Pd(II) initially], compared to 8 ± 3 mg/L (10 mM acetate) without H2. Acetate was ineffective as an electron donor for palladium removal in the presence or absence of fumarate as an electron acceptor. TEM imaging verified that Pd(0) nanoparticles were predominantly in the EPS surrounding cells in H2-fed cultures, with only a small number of particles visible inside the cell. Separation of the cells and EPS by centrifugation allowed reuse of the cell suspensions and effective nanoparticle recovery. These results demonstrate effective palladium recovery and nanoparticle production using G. sulfurreducens cell suspensions and renewable substrates such as H2 gas. © 2013 American Chemical Society.

CATALYTIC KINETIC RESOLUTION OF 5-ALKOXY-2(5H)-FURANONES

OpenAIRE

FABER, WS; Kok, Johan C; DELANGE, B; FERINGA, BL; Faber, Wijnand S.; Lange, Ben de; Feringa, Bernard

1994-01-01

The kinetic resolution of racemic 5-alkoxy-2(5H)-furanones, using a chiral aminoalcohol catalyzed 1-4-addition of arylthiols, was examined. Using various butenolides it was shown that a gamma-alkoxy substituent appears to be essential to reach high enantioselectivities whereas electron-donating substituents in the arylthiols also increase the selectivity. Cinchona alkaloids are the preferred catalysts for the kinetic resolution, with quinine and quinidine leading to the most efficient and sel...

Fate and persistence of a pathogenic NDM-1-positive Escherichia coli strain in anaerobic and aerobic sludge microcosms

KAUST Repository

Mantilla-Calderon, David

2017-04-15

The presence of emerging biological pollutants in treated wastewater effluents has gained attention due to increased interest in water reuse. To evaluate the effectiveness of the removal of such contaminants by the conventional wastewater treatment process, the fate and decay kinetics of NDM-1-positive Escherichia coli strain PI7 and its plasmid-encoded antibiotic resistance genes (ARGs) were assessed in microcosms of anaerobic and aerobic sludge. Results showed that E. coli PI7 decayed at a significantly slower rate under anaerobic conditions. Approximate half-lives were 32.4 ± 1.4 h and 5.9 ± 0.9 h in the anaerobic and aerobic microcosms, respectively. In the aerobic microcosms, after 72 h of operation, E. coli PI7 remained detectable but no further decay was observed. Instead, 1 in every 10000 E. coli cells was identified to be recalcitrant to decay and persist indefinitely in the sludge. ARGs associated with the E. coli PI7 were detected to have transferred to other native microorganisms in the sludge, or are released to the liquid fraction upon host decay. Extracellular DNA quickly degraded in the liquid fraction of the aerobic sludge. In contrast, no DNA decay was detected in the anaerobic sludge water matrix throughout the 24 h sampling period. This study suggests an increased likelihood of environmental dispersion of ARGs associated with anaerobically treated wastewater effluents and highlights the potential importance of persister cells in the dissemination of E. coli in the environment during reuse events of treated wastewater.IMPORTANCE This study examines the decay kinetics of a pathogenic and antibiotic resistant strain of Escherichia coli in microcosms simulating biological treatment units of aerobic and anaerobic sludge. The results of this study points at a significantly prolonged persistence of the E. coli and the associated antibiotic resistance gene in the anaerobic sludge. However, horizontal transfer of the plasmid encoding the antibiotic

Fate and Persistence of a Pathogenic NDM-1-Positive Escherichia coli Strain in Anaerobic and Aerobic Sludge Microcosms.

Science.gov (United States)

Mantilla-Calderon, David; Hong, Pei-Ying

2017-07-01

The presence of emerging biological pollutants in treated wastewater effluents has gained attention due to increased interest in water reuse. To evaluate the effectiveness of the removal of such contaminants by the conventional wastewater treatment process, the fate and decay kinetics of NDM-1-positive Escherichia coli strain PI7 and its plasmid-encoded antibiotic resistance genes (ARGs) were assessed in microcosms of anaerobic and aerobic sludge. Results showed that E. coli PI7 decayed at a significantly lower rate under anaerobic conditions. Approximate half-lives were 32.4 ± 1.4 h and 5.9 ± 0.9 h in the anaerobic and aerobic microcosms, respectively. In the aerobic microcosms, after 72 h of operation, E. coli PI7 remained detectable, but no further decay was observed. Instead, 1 in every 10,000 E. coli cells was identified to be recalcitrant to decay and persist indefinitely in the sludge. ARGs associated with the E. coli PI7 strain were detected to have transferred to other native microorganisms in the sludge or were released to the liquid fraction upon host decay. Extracellular DNA quickly degraded in the liquid fraction of the aerobic sludge. In contrast, no DNA decay was detected in the anaerobic sludge water matrix throughout the 24-h sampling period. This study suggests an increased likelihood of environmental dispersion of ARGs associated with anaerobically treated wastewater effluents and highlights the potential importance of persister cells in the dissemination of E. coli in the environment during reuse events of treated wastewater. IMPORTANCE This study examines the decay kinetics of a pathogenic and antibiotic resistant strain of Escherichia coli in microcosms simulating biological treatment units of aerobic and anaerobic sludge. The results of this study point at a significantly prolonged persistence of the E. coli and the associated antibiotic resistance gene in the anaerobic sludge. However, horizontal transfer of the plasmid encoding the

Bioorthogonal Diversification of Peptides through Selective Ruthenium(II)-Catalyzed C-H Activation.

Science.gov (United States)

Schischko, Alexandra; Ren, Hongjun; Kaplaneris, Nikolaos; Ackermann, Lutz

2017-02-01

Methods for the chemoselective modification of amino acids and peptides are powerful techniques in biomolecular chemistry. Among other applications, they enable the total synthesis of artificial peptides. In recent years, significant momentum has been gained by exploiting palladium-catalyzed cross-coupling for peptide modification. Despite major advances, the prefunctionalization elements on the coupling partners translate into undesired byproduct formation and lengthy synthetic operations. In sharp contrast, we herein illustrate the unprecedented use of versatile ruthenium(II)carboxylate catalysis for the step-economical late-stage diversification of α- and β-amino acids, as well as peptides, through chemo-selective C-H arylation under racemization-free reaction conditions. The ligand-accelerated C-H activation strategy proved water-tolerant and set the stage for direct fluorescence labelling as well as various modes of peptide ligation with excellent levels of positional selectivity in a bioorthogonal fashion. The synthetic utility of our approach is further demonstrated by twofold C-H arylations for the complexity-increasing assembly of artificial peptides within a multicatalytic C-H activation manifold. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anionic Palladium(0) and Palladium(II) Ate Complexes.

Science.gov (United States)

Kolter, Marlene; Böck, Katharina; Karaghiosoff, Konstantin; Koszinowski, Konrad

2017-10-16

Palladium ate complexes are frequently invoked as important intermediates in Heck and cross-coupling reactions, but so far have largely eluded characterization at the molecular level. Here, we use electrospray-ionization mass spectrometry, electrical conductivity measurements, and NMR spectroscopy to show that the electron-poor catalyst [L 3 Pd] (L=tris[3,5-bis(trifluoromethyl)phenyl]phosphine) readily reacts with Br - ions to afford the anionic, zero-valent ate complex [L 3 PdBr] - . In contrast, more-electron-rich Pd catalysts display lower tendencies toward the formation of ate complexes. Combining [L 3 Pd] with LiI and an aryl iodide substrate (ArI) results in the observation of the Pd II ate complex [L 2 Pd(Ar)I 2 ] - . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Double role of the hydroxy group of phosphoryl in palladium(II)-catalyzed ortho-olefination: a combined experimental and theoretical investigation.

Science.gov (United States)

Liu, Liu; Yuan, Hang; Fu, Tingting; Wang, Tao; Gao, Xiang; Zeng, Zhiping; Zhu, Jun; Zhao, Yufen

2014-01-03

Density functional theory calculations have been carried out on Pd-catalyzed phosphoryl-directed ortho-olefination to probe the origin of the significant reactivity difference between methyl hydrogen benzylphosphonates and dimethyl benzylphosphonates. The overall catalytic cycle is found to include four basic steps: C-H bond activation, transmetalation, reductive elimination, and recycling of catalyst, each of which is constituted from different steps. Our calculations reveal that the hydroxy group of phosphoryl plays a crucial role almost in all steps, which can not only stabilize the intermediates and transition states by intramolecular hydrogen bonds but also act as a proton donor so that the η(1)-CH3COO(-) ligand could be protonated to form a neutral acetic acid for easy removal. These findings explain why only the methyl hydrogen benzylphosphonates and methyl hydrogen phenylphosphates were found to be suitable reaction partners. Our mechanistic findings are further supported by theoretical prediction of Pd-catalyzed ortho-olefination using methyl hydrogen phenylphosphonate, which is verified by experimental observations that the desired product was formed in a moderate yield.

Morphological Study Of Palladium Thin Films Deposited By Sputtering

Energy Technology Data Exchange (ETDEWEB)

Salcedo, K L; Rodriguez, C A [Grupo Plasma Laser y Aplicaciones, Ingenieria Fisica, Universidad Tecnologica de Pereira (Colombia); Perez, F A [WNANO, West Virginia University (United States); Riascos, H [Grupo Plasma Laser y Aplicaciones, Departamento de Fisica, Universidad Tecnologica de Pereira (Colombia)

2011-01-01

This paper presents a morphological analysis of thin films of palladium (Pd) deposited on a substrate of sapphire (Al{sub 2}O{sub 3}) at a constant pressure of 3.5 mbar at different substrate temperatures (473 K, 523 K and 573 K). The films were morphologically characterized by means of an Atomic Force Microscopy (AFM); finding a relation between the roughness and the temperature. A morphological analysis of the samples through AFM was carried out and the roughness was measured by simulating the X-ray reflectivity curve using GenX software. A direct relation between the experimental and simulation data of the Palladium thin films was found.

Morphological Study Of Palladium Thin Films Deposited By Sputtering

International Nuclear Information System (INIS)

Salcedo, K L; Rodriguez, C A; Perez, F A; Riascos, H

2011-01-01

This paper presents a morphological analysis of thin films of palladium (Pd) deposited on a substrate of sapphire (Al 2 O 3 ) at a constant pressure of 3.5 mbar at different substrate temperatures (473 K, 523 K and 573 K). The films were morphologically characterized by means of an Atomic Force Microscopy (AFM); finding a relation between the roughness and the temperature. A morphological analysis of the samples through AFM was carried out and the roughness was measured by simulating the X-ray reflectivity curve using GenX software. A direct relation between the experimental and simulation data of the Palladium thin films was found.

Supported palladium nanoparticles synthesized by living plants as a catalyst for Suzuki-Miyaura reactions.

Directory of Open Access Journals (Sweden)

Helen L Parker

Full Text Available The metal accumulating ability of plants has previously been used to capture metal contaminants from the environment; however, the full potential of this process is yet to be realized. Herein, the first use of living plants to recover palladium and produce catalytically active palladium nanoparticles is reported. This process eliminates the necessity for nanoparticle extraction from the plant and reduces the number of production steps compared to traditional catalyst palladium on carbon. These heterogeneous plant catalysts have demonstrated high catalytic activity in Suzuki coupling reactions between phenylboronic acid and a range of aryl halides containing iodo-, bromo- and chloro- moieties.

Copper(I)/TEMPO Catalyzed Aerobic Oxidation of Primary Alcohols to Aldehydes with Ambient Air

Science.gov (United States)

Hoover, Jessica M.; Steves, Janelle E.; Stahl, Shannon S.

2012-01-01

This protocol describes a practical laboratory-scale method for aerobic oxidation of primary alcohols to aldehydes, using a chemoselective CuI/TEMPO catalyst system. The catalyst is prepared in situ from commercially available reagents, and the reactions are performed in a common organic solvent (acetonitrile) with ambient air as the oxidant. Three different reaction conditions and three procedures for the isolation and purification of the aldehyde product are presented. The oxidations of eight different alcohols, described here, include representative examples of each reaction condition and purification method. Reaction times vary from 20 min to 24 h, depending on the alcohol, while the purification methods each take about 2 h. The total time necessary for the complete protocol ranges from 3 – 26 h. PMID:22635108

Oxidative kinetic resolution of racemic alcohols catalyzed by chiral ferrocenyloxazolinylphosphine-ruthenium complexes.

Science.gov (United States)

Nishibayashi, Yoshiaki; Yamauchi, Akiyoshi; Onodera, Gen; Uemura, Sakae

2003-07-25

Oxidative kinetic resolution of racemic secondary alcohols by using acetone as a hydrogen acceptor in the presence of a catalytic amount of [RuCl(2)(PPh(3))(ferrocenyloxazolinylphosphine)] (2) proceeds effectively to recover the corresponding alcohols in high yields with an excellent enantioselectivity. When 1-indanol is employed as a racemic alcohol, the oxidation proceeds quite smoothly even in the presence of 0.0025 mol % of the catalyst 2 to give an optically active 1-indanol in good yield with high enantioselectivity (up to 94% ee), where turnover frequency (TOF) exceeds 80,000 h(-1). From a practical viewpoint, the kinetic resolution is investigated in a large scale, optically pure (S)-1-indanol (75 g, 56% yield, >99% ee) being obtained from racemic 1-indanol (134 g) by employing this kinetic resolution method twice.

Settling properties of aerobic granular sludge (AGS) and aerobic granular sludge molasses (AGSM)

Science.gov (United States)

Mat Saad, Azlina; Aini Dahalan, Farrah; Ibrahim, Naimah; Yasina Yusuf, Sara; Aqlima Ahmad, Siti; Khalil, Khalilah Abdul

2018-03-01

Aerobic granulation technology is applied to treat domestic and industrial wastewater. The Aerobic granular sludge (AGS) cultivated has strong properties that appears to be denser and compact in physiological structure compared to the conventional activated sludge. It offers rapid settling for solid:liquid separation in wastewater treatment. Aerobic granules were developed using sequencing batch reactor (SBR) with intermittent aerobic - anaerobic mode with 8 cycles in 24 hr. This study examined the settling velocity performance of cultivated aerobic granular sludge (AGS) and aerobic granular sludge molasses (AGSM). The elemental composition in both AGS and AGSM were determined using X-ray fluorescence (XRF). The results showed that AGSM has higher settling velocity 30.5 m/h compared to AGS.

Superconductivity and the structural phase transitions in palladium hydride and palladium deuteride

International Nuclear Information System (INIS)

Standley, R.W.

1980-01-01

The results of two experimental studies of the superconducting transition temperature, T/sub c/, of palladium hydride, PdH/sub x/, and palladium deuteride, PdD/sub x/, are presented. In the first study, the superconducting transition temperature of PdH/sub x/(D/sub x/) is studied as a function of H(D) concentration, x, in the temperature range from 0.2 K to 4K. The data join smoothly with those reported previously by Miller and Satterthwaite at higher temperatures, and the composite data are described by the empirical relation T/sub c/ = 150.8 (x-x/sub o/) 2 244 , where x/sub o/ = 0.715 for hydride samples and 0.668 for deuteride samples. The results, when compared with the theoretical predictions of Klein and Papaconstantopoulos, et al., raise questions about the validity of their explanation of the reverse isotope effect, which is based solely on a difference in force constants. In the second study, the effect of the order-disorder structural transition associated with the 50 K anomaly on the superconductivity of PdH/sub x/(D/sub x/) is investigated. Samples were quenched to low temperatures in the disordered state, and their transition temperatures measured. The samples were then annealed just below the anomaly temperature, and the ordering process followed by monitoring the change in sample resistance. The transition temperatures in the ordered state were then measured

A dataset for preparing pristine graphene-palladium nanocomposites using swollen liquid crystal templates

Science.gov (United States)

Vats, Tripti; Siril, Prem Felix

2017-12-01

Pristine graphene (G) has not received much attention as a catalyst support, presumably due to its relative inertness as compared to reduced graphene oxide (RGO). In the present work, we used swollen liquid crystals (SLCs) as nano-reactors for graphene-palladium nanocomposites synthesis. The 'soft' confinement of SLCs directs the growth of palladium (Pd) nanoparticles over the G sheets. In this dataset we include all the parameters and details of different techniques used for the characterization of G, SLCs and synthesized G-Pd nanocomposites. The synthesized G-palladium nanocomposites (Pd-G) exhibited improved catalytic activity compared with Pd-RGO and Pd nanoparticles, in the hydrogenation of nitrophenols and C-C coupling reactions.

Rubber muscle actuation with pressurized CO2 from enzyme-catalyzed urea hydrolysis

Science.gov (United States)

Sutter, Thomas M.; Dickerson, Matthew B.; Creasy, Terry S.; Justice, Ryan S.

2013-09-01

A biologically inspired pneumatic pressure source was designed and sized to supply high pressure CO2(g) to power a rubber muscle actuator. The enzyme urease served to catalyze the hydrolysis of urea, producing CO2(g) that flowed into the actuator. The actuator’s power envelope was quantified by testing actuator response on a custom-built linear-motion rig. Reaction kinetics and available work density were determined by replacing the actuator with a double-action piston and measuring volumetric gas generation against a fixed pressure on the opposing piston. Under the conditions investigated, urease catalyzed the generation of up to 0.81 MPa (117 psi) of CO2(g) in the reactor headspace within 18 min, and the evolved gas produced a maximum work density of 0.65 J ml-1.

Rubber muscle actuation with pressurized CO2 from enzyme-catalyzed urea hydrolysis

International Nuclear Information System (INIS)

Sutter, Thomas M; Dickerson, Matthew B; Creasy, Terry S; Justice, Ryan S

2013-01-01

A biologically inspired pneumatic pressure source was designed and sized to supply high pressure CO 2(g) to power a rubber muscle actuator. The enzyme urease served to catalyze the hydrolysis of urea, producing CO 2(g) that flowed into the actuator. The actuator’s power envelope was quantified by testing actuator response on a custom-built linear-motion rig. Reaction kinetics and available work density were determined by replacing the actuator with a double-action piston and measuring volumetric gas generation against a fixed pressure on the opposing piston. Under the conditions investigated, urease catalyzed the generation of up to 0.81 MPa (117 psi) of CO 2(g) in the reactor headspace within 18 min, and the evolved gas produced a maximum work density of 0.65 J ml −1 . (paper)

Development and Comparison of the Substrate Scope of Pd-Catalysts for the Aerobic Oxidation of Alcohols

Science.gov (United States)

Schultz, Mitchell J.; Hamilton, Steven S.; Jensen, David R.; Sigman, Matthew S.

2009-01-01

Three catalysts for aerobic oxidation of alcohols are discussed and the effectiveness of each is evaluated for allylic, benzylic, aliphatic, and functionalized alcohols. Additionally, chiral nonracemic substrates as well as chemoselective and diastereoselective oxidations are investigated. In this study, the most convenient system for the Pd-catalyzed aerobic oxidation of alcohols is Pd(OAc)2 in combination with triethylamine. This system functions effectively for the majority of alcohols tested and uses mild conditions (3 to 5 mol % of catalyst, room temperature). Pd(IiPr)(OAc)2(H2O) (1) also successfully oxidizes the majority of alcohols evaluated. This system has the advantage of significantly lowering catalyst loadings but requires higher temperatures (0.1 to 1 mol % of catalyst, 60 °C). A new catalyst is also disclosed, Pd(IiPr)(OPiv)2 (2). This catalyst operates under very mild conditions (1 mol %, room temperature, and air as the O2 source) but with a more limited substrate scope. PMID:15844968

Recovery of hydrogen from impurities using a palladium membrane reactor

International Nuclear Information System (INIS)

Willms, R.S.; Okuno, K.

1993-01-01

One of the important steps in processing the exhaust from a fusion reactor is recovering tritium which is incorporated into molecules such as water and methane. One device which may prove to be very effective for this purpose is a palladium membrane reactor. This is a reactor which incorporates a Pd/Ag membrane in the reactor geometry. Reactions such as water gas shift, steam reforming and methane cracking can be carried out over the reactor catalyst, and the product hydrogen can be simultaneously removed from the reacting mixture. Because product is removed, greater than usual conversions can be obtained. In addition ultrapure hydrogen is produced, eliminating the need for an additional processing step. A palladium membrane reactor has been built and tested with three different catalysts. Initial results with a Ni-based catalyst show that it is very effective at promoting all three reactions listed above. Under the proper conditions, hydrogen recoveries approaching 100% have been observed. This study serves to experimentally validate the palladium membrane reactor as potentially important tool for fusion fuel processing

Electrocatalytic aerobic epoxidation of alkenes: Experimental and DFT investigation

International Nuclear Information System (INIS)

Magdesieva, Tatiana V.; Borisova, Nataliya E.; Dolganov, Alexander V.; Ustynyuk, Yuri A.

2012-01-01

A new method for electrocatalytic aerobic epoxidation of alkenes catalyzed by binuclear Cu(II) complexes with azomethine ligands based on 2,6-diformyl-4-tert-butylphenol is described. In acetonitrile–water (5%), at the potential of Cu II /Cu I redox couple (–0.8 V vs. Ag/AgCl/KCl) at room temperature the epoxide is obtained in an average yield of around 50%. Contrary to the majority of known epoxidations, no strong oxidants are involved and no free hydrogen peroxide is formed in the reaction, thus making it ecologically friendly. The DFT quantum-chemical modeling of the reaction mechanism revealed that a copper hydroperoxo-complex rather than hydrogen peroxide or a copper oxo-complex oxidizes alkene. The process is very selective since neither products of hydroxylation of benzene ring in styrene nor of allylic oxidation of cyclohexene were detected.

Oxygen and carbon dioxide mass transfer and the aerobic, autotrophic cultivation of moderate and extreme thermophiles : a case study related to the microbial desulfurization of coal

NARCIS (Netherlands)

Boogerd, F C; Bos, P; Kuenen, J.G.; Heijnen, J.; van der Lans, R G

Mass transfers of O(2), CO(2), and water vapor are among the key processes in the aerobic, autotrophic cultivation of moderate and extreme thermophiles. The dynamics and kinetics of these processes are, in addition to the obvious microbial kinetics, of crucial importance for the industrial

Examining physiotherapist use of structured aerobic exercise testing to decrease barriers to aerobic exercise.

Science.gov (United States)

Foster B Sc, Evan; Fraser, Julia E; Inness PhD, Elizabeth L; Munce, Sarah; Biasin, Louis; Poon, Vivien; Bayley, Mark

2018-04-03

To determine the frequency of physiotherapist-administered aerobic exercise testing/training, the proportion of physiotherapists who administer this testing/training, and the barriers that currently exist across different practice environments. A secondary objective is to identify the learning needs of physiotherapists for the development of an education curriculum in aerobic exercise testing and training with electrocardiograph (ECG) administration and interpretation. National, cross-sectional survey. Registered physiotherapists practicing in Canada. Out of 137 participants, most (75%) physiotherapists prescribed aerobic exercise on a regular basis (weekly); however, 65% had never conducted an aerobic exercise test. There were no significant differences in frequency of aerobic exercise testing across different practice environments or across years of physiotherapy experience. Physiotherapists perceived the main barriers to aerobic exercise testing as being a lack of equipment/space (78%), time (65%), and knowledge (56%). Although most (82%) were uncomfortable administering 12-lead ECG-monitored aerobic exercise tests, 60% stated they would be interested in learning more about ECG interpretation. This study found that physiotherapists are regularly implementing aerobic exercise. This exercise was infrequently guided by formal aerobic exercise testing, which could increase access to safe and effective exercise within the optimal aerobic training zone. As well, this could facilitate training in patients with cardiovascular diagnoses that require additional testing for medical clearance. Increased ECG training and access to equipment for physiotherapists may augment pre-screening aerobic exercise testing. This training should include learning the key arrhythmias for aerobic exercise test termination as defined by the American College of Sports Medicine.

In-situ observation of deuteride formation in palladium electrochemical cathode by X-ray diffraction method

International Nuclear Information System (INIS)

Yamamoto, Takao; Oka, Takashi; Taniguchi, Ryoichi

1990-01-01

In-situ X-ray diffraction observation of palladium foil cathode (10 μm) was carried out during electrolysis of 0.1N-LiOD heavy water solution in order to estimate the deuterium content in palladium during the detection of charged particles in our previous work. A complete transformation into β-palladium deuteride phase was observed, and its maximum lattice constant 4.06 A was evaluated as corresponding to D/Pd = 0.73. The deuterium concentration in the previous work was estimated as higher than this considering the difference in cell conditions. (author)

Palladium complexes with 3-phenylpropylamine ligands: synthesis, structures, theoretical studies and application in the aerobic oxidation of alcohols as heterogeneous catalysts

Czech Academy of Sciences Publication Activity Database

Karami, K.; Naeini, N.H.; Eigner, Václav; Dušek, Michal; Lipkowski, J.; Hervés, P.; Tavakol, H.

2015-01-01

Roč. 5, č. 124 (2015), s. 102424-102435 ISSN 2046-2069 R&D Projects: GA ČR GA15-12653S Institutional support: RVO:68378271 Keywords : single-crystal structure analysis * paladium complex * aerobic oxidation Subject RIV: CC - Organic Chemistry Impact factor: 3.289, year: 2015

Sol-gel synthesized of nanocomposite palladium-alumina ceramic membrane for H{sub 2} permeability: Preparation and characterization

Energy Technology Data Exchange (ETDEWEB)

Ahmad, A.L.; Mustafa, N.N.N. [School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, Penang (Malaysia)

2007-08-15

Palladium-alumina membrane with mesopore and narrow pore size distribution was prepared by the sol-gel method. Effect of the finely dispersed metal on the microstructure and the characteristic properties of the palladium-alumina membrane were investigated. Observations were made on membrane weight loss, morphology, pore structure, pore size, surface area, pore surface fractal and membrane's crystal structure. Autosorb analysis, X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) analysis were employed in the membrane characterization. Autosorb analysis found that, BET surface area decreased and pore size of the membrane increased with the increasing of calcinations temperature (500-1100{sup o}C) and with the increasing of palladium amount in the membrane. FTIR and TG/DTA analysis show that the suitable temperature for calcinations of palladium-alumina membrane is at 700{sup o}C. Palladium metals are highly dispersed at calcinations temperature of 700{sup o}C as observed by TEM analysis. The fine crystallinity of the palladium and {gamma}-alumina phase was obtained after calcined at 700{sup o}C. The SEM morphology shows a smooth and free crack layer of palladium-alumina membrane after repeating the process of dipping, drying and calcinations at temperature of 700{sup o}C. The membrane also successfully coated with a good adhesion on support. The thickness of the final membrane layer was estimated as 9{mu} m. (author)

Kinetic Behaviors of a Competitive Population and Fitness System in Exchange-Driven Growth

International Nuclear Information System (INIS)

Lu Ke; Lin Zhenquan; Sun Yunfei

2008-01-01

We proposed an aggregation model of two species aggregates of fitness and population to study the interaction between the two species in their exchange-driven processes of the same species by introducing the monomer birth of fitness catalyzed by the population, where the fitness aggregates perform self-death process and the population aggregates perform self-birth process. The kinetic behaviors of the aggregate size distributions of the fitness and population were analyzed by the rate equation approach with their exchange rate kernel K 1 (k,j) = K 1 kj and K 2 (k,j) = K 2 kj, the fitness aggregate's self-death rate kernel J 1 (k) = J 1 k, population aggregate's self-birth rate kernel J 2 (k) = J 2 k and population-catalyzed fitness birth rate kernel I(k,j) = Ikj v . The kinetic behavior of the fitness was found depending crucially on the parameter v, which reflects the dependence of the population-catalyzed fitness birth rate on the size of the catalyst (population) aggregate. (i) In the v ≤ 0 case, the effect of catalyzed-birth of fitness is rather weak and the exchange-driven aggregation and self-death of the fitness dominate the process, and the fitness aggregate size distribution a k (t) does not have scale form. (ii) When v > 0, the effect of the population-catalyzed birth of fitness gets strong enough, and the catalyzed-birth and self-death of the fitness aggregates, together with the self-birth of the population aggregates dominate the evolution process of the fitness aggregates. The aggregate size distribution a k (t) approaches a generalized scaling form

Palladium coated fibre Bragg grating based hydrogen sensor

International Nuclear Information System (INIS)

Kasinathan, M.; Sosamma, S.; Kishore, S.; Elumalai, V.; Krishnan, R.; Babu Rao, C.; Dash, Sitaram; Murali, N.; Jayakumar, T.

2011-01-01

Detection of steam generator leaks in fast nuclear reactors is carried out by monitoring hydrogen in argon cover-gas. Hydrogen released during sodium cleaning of fast reactor components is required to be monitored. Hydrogen sensors with good sensitivity, stability and response time are required for all the above applications. We report a new type of hydrogen sensor with a Fibre Bragg Grating (FBG) coated with palladium thin film which is used to detect the leak of hydrogen gas in the Steam Generator (SG) module of the Fast Breeder Reactor (FBR). If water leaks into sodium, it results in sodium-water reaction. In this reaction hydrogen and sodium hydroxide are formed. Due to the explosive risk of hydrogen system, hydrogen sensors are of great interest in this case. It is known that hydrogen forms an explosive mixture with air once its concentration exceeds beyond the explosion limit of four percent. The advantages of FBG based hydrogen sensor over the other hydrogen sensors are its inherent property of safety from sparking, immunity to ambient electromagnetic interference. The sensing mechanism in this device is based on mechanical strain that is induced in the palladium coating when it absorbs hydrogen. This process physically stretches the grating and causes the grating period and grating's refractive index, to change. The Bragg wavelength shift is directly proportional to the strain induced and can be directly related to the percentage of hydrogen exposure. The online monitoring of palladium thin film coating on FBG is carried out and recorded the wavelength change and strain induced on the FBG. A hydrogen sensor set up have been fabricated which consists of SS vessel of capacity 10 litres, provided with pressure gauge, Argon filling line with a valve, Hydrogen injection line with flange, a vent line with valve and Hydrogen sensor fixing point. The Palladium coated FBG based Hydrogen sensor is tested in this experimental facility in the exposure of hydrogen in

CATALYTIC KINETIC RESOLUTION OF 5-ALKOXY-2(5H)-FURANONES

NARCIS (Netherlands)

FABER, WS; Kok, Johan C; DELANGE, B; FERINGA, BL; Faber, Wijnand S.; Lange, Ben de; Feringa, Bernard

1994-01-01

The kinetic resolution of racemic 5-alkoxy-2(5H)-furanones, using a chiral aminoalcohol catalyzed 1-4-addition of arylthiols, was examined. Using various butenolides it was shown that a gamma-alkoxy substituent appears to be essential to reach high enantioselectivities whereas electron-donating

Controlled immobilization of palladium nanoparticles in two different fluorinated polymeric aggregate cores and their application in catalysis

DEFF Research Database (Denmark)

Kijima, Tetsushi; Javakhishvili, Irakli; Jankova Atanasova, Katja

2012-01-01

Fluoroalkyl end-capped betaine-type cooligomeric nanocomposites-immobilized palladium nanoparticles were prepared by the reactions of palladium chloride with sodium acetate in the presence of sodium chloride and the corresponding fluorinated cooligomers. Outer blocks of poly(2,3,4,5,6-pentafluoro....... These fluorinated nanocomposites-immobilized palladium nanoparticles were also applied to the catalysts for Suzuki-Miyaura cross-coupling reaction, and the different reactivity between these nanocomposites was observed....

Analysis of the anomalous hydrogen solubilities in deformed palladiums

Energy Technology Data Exchange (ETDEWEB)

Park, Choong Nyeon; Lee, Ho Jong

1987-02-01

The anomalous hydrogen solubilities in the deformed palladiums were analyzed by empolying modified Kirchheim's model with considering the partially coherent strain energy which would induced during hydride precipitation around edge dislocations. The dislocation densities, obtained by this model, of the various cold worked and/or reversible US transformed palladium samples were the order of 10/sup 11/cm/sup -2/. The partially coherent strain energies were about 3 kJ/molH and nearly same in the various samples. This value could be compared with the incoherent strain energy, 0.4kJ/molH, which was obtained from the hysteresis on P-C isotherm, and the coherent strain energy calulated, 9.6kJ/molH.

Highly efficient aerobic oxidation of alcohols by using less-hindered nitroxyl-radical/copper catalysis: optimum catalyst combinations and their substrate scope.

Science.gov (United States)

Sasano, Yusuke; Kogure, Naoki; Nishiyama, Tomohiro; Nagasawa, Shota; Iwabuchi, Yoshiharu

2015-04-01

The oxidation of alcohols into their corresponding carbonyl compounds is one of the most fundamental transformations in organic chemistry. In our recent report, 2-azaadamantane N-oxyl (AZADO)/copper catalysis promoted the highly chemoselective aerobic oxidation of unprotected amino alcohols into amino carbonyl compounds. Herein, we investigated the extension of the promising AZADO/copper-catalyzed aerobic oxidation of alcohols to other types of alcohol. During close optimization of the reaction conditions by using various alcohols, we found that the optimum combination of nitroxyl radical, copper salt, and solution concentration was dependent on the type of substrate. Various alcohols, including highly hindered and heteroatom-rich ones, were efficiently oxidized into their corresponding carbonyl compounds under mild conditions with lower amounts of the catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic Study of Esterification of Acetic Acid with n-butanol and isobutanol Catalyzed by Ion Exchange Resin

Directory of Open Access Journals (Sweden)

Amrit Pal Toor

2011-05-01

Full Text Available Esters are an important pharmaceutical intermediates and very useful perfumery agents. In this study the esterification of acetic acid with n-butanol and iso-butanol over an acidic cation exchange resin, Amberlyst 15 were carried out. The effects of certain parameters such as temperature, catalyst loading, initial molar ratio between reactants on the rate of reaction were studied. The experiments were conducted in a stirred batch reactor in the temperature range of 351.15 K to 366.15K.Variation of parameters on rate of reaction demonstrated that the reaction was intrinsically controlled.The activation energy for the esterification of acetic acid with n-butanol and iso butanol is found to be 28.45 k J/mol and 23.29 kJ/mol respectively. ©2011 BCREC UNDIP. All rights reserved.(Received: 16th December 2010, Revised: 19th March 2011; Accepted: 7th April 2011[How to Cite: A.P. Toor, M. Sharma, G. Kumar, and R. K. Wanchoo. (2011. Kinetic Study of Esterification of Acetic Acid with n-butanol and isobutanol Catalyzed by Ion Exchange Resin. Bulletin of Chemical Reaction Engineering and Catalysis, 6(1: 23-30. doi:10.9767/bcrec.6.1.665.23-30][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.1.665.23-30 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/665 ] | View in 

Tetradentate N2O2 Chelated Palladium(II Complexes: Synthesis, Characterization, and Catalytic Activity towards Mizoroki-Heck Reaction of Aryl Bromides

Directory of Open Access Journals (Sweden)

Siti Kamilah Che Soh

2013-01-01

Full Text Available Four air and moisture-stable palladium(II-Schiff base complexes, N,N′-bis(α-methylsalicylidenepropane-1,3-diamine palladium(II (2a, N,N′-bis(4-methyl-α-methylsalicylidenepropane-1,3-diamine palladium(II (2b, N,N′-bis(3,5-di-tert-butylsalicylidenepropane-1,3-diamine palladium(II (2c, and N,N′-bis(4-methoxy-salicylidenepropane-1,3-diamine palladium(II (2d, have been successfully synthesised and characterised by CHN elemental analyses and conventional spectroscopic methods. These complexes were investigated as catalysts in the phosphine-free Mizoroki-Heck cross-coupling reactions of aryl bromides with methyl acrylate.

Copper-based electrochemical sensor with palladium electrode for cathodic stripping voltammetry of manganese.

Science.gov (United States)

Kang, Wenjing; Pei, Xing; Bange, Adam; Haynes, Erin N; Heineman, William R; Papautsky, Ian

2014-12-16

In this work, we report on the development of a palladium-based, microfabricated point-of-care electrochemical sensor for the determination of manganese using square wave cathodic stripping voltammetry. Heavy metals require careful monitoring, yet current methods are too complex for a point-of-care system. Voltammetry offers an attractive approach to metal detection on the microscale, but traditional carbon, gold, or platinum electrodes are difficult or expensive to microfabricate, preventing widespread use. Our sensor uses palladium working and auxiliary electrodes and integrates them with a copper-based reference electrode for simple fabrication and compatibility with microfabrication and printed circuit board processing, while maintaining competitive performance in electrochemical detection. Copper electrodes were prepared on glass substrate using a combination of microfabrication procedures followed by electrodeposition of palladium. The disposable sensor system was formed by bonding a poly(dimethylsiloxane) (PDMS) well to the glass substrate. Cathodic stripping voltammetry of manganese using our new disposable palladium-based sensors exhibited 334 nM (18.3 ppb) limit of detection in borate buffer. The sensor was used to demonstrate manganese determination in natural water samples from a pond in Burnet Woods, located in Cincinnati, OH, and the Ohio River.

Green synthesis of palladium nanoparticles with carboxymethyl cellulose for degradation of azo-dyes

Energy Technology Data Exchange (ETDEWEB)

Li, Gang; Li, Yun; Wang, Zhengdong; Liu, Huihong, E-mail: huihongliu@126.com

2017-02-01

Palladium nanoparticles (PdNPs) were synthesized through friendly environmental method using PdCl{sub 2} and carboxymethyl cellulose (CMC) in an aqueous solution (pH 6) at controlled water bath (80 °C) for 30 min. CMC functioned as both reducing and stabilizing agent. The characterization through high resolution-transmission electron microscopic (HRTEM) and X-ray Fluorescence Spectrometry (XRF) inferred that the as-synthesized PdNPs were spherical in shape with a face cubic crystal (FCC) structure. The results from dynamic light scattering (DLS) suggested the PdNPs had the narrow size distribution with an average size of 2.5 nm. The negative zeta potential (−52.6 mV) kept the as-synthesized PdNPs stable more than one year. The PdNPs showed the excellent catalytic activity by reducing degradation of azo-dyes, such as p-Aminoazobenzene, acid red 66, acid orange 7, scarlet 3G and reactive yellow 179, in the present of sodium borohydride. - Highlights: • Green synthesis of palladium nanoparticles using carboxymethyl cellulose. • The synthesis of palladium nanoparticles were performed easily. • Carboxymethyl cellulose acts as both reducing and stabilization agents. • The as-synthesized palladium nanoparticles show excellent catalytic activity.

Catalytic activity of bimetallic AuPd alloys supported MgO and MnO2 nanostructures and their role in selective aerobic oxidation of alcohols

Directory of Open Access Journals (Sweden)

Hamed Alshammari

2017-10-01

Full Text Available The use of metal oxides as supports for gold and palladium (Au-Pd nano alloys constitutes new horizons to improve catalysts materials for very important reactions. From the literatures, Pd-based bimetallic nanostructures have great properties and active catalytic performance. In this study, nanostructures of magnesium oxide (MgO and manganese dioxide (MnO₂ were synthesised and utilized as supports for Au-Pd nanoparticle catalysts. Gold and palladium were deposited on these supports using sol-immobilisation method. The MgO and MnO2 supported Au-Pd catalysts were evaluated for the oxidation of benzyl alcohol and 1-octanol, respectively. These catalysts were found to be more selective, active and reusable than the corresponding monometallic Au and Pd catalysts. The effect of base supports on the disproportionation reaction during the oxidation process was investigated. The results show that MgO stopped the disproportionation reaction for both aromatic and aliphatic alcohols while MnO₂ stopped it in the case of benzyl alcohol only. The outcomes of this work shed light on the selective aerobic oxidation of alcohols using bimetallic Au-Pd nanoalloys and pave the way to a complete investigation of more basic metal oxides for various aliphatic alcohols.

Recent Insight into the Kinetic Mechanisms and Conformational Dynamics of Y-Family DNA Polymerases

OpenAIRE

Maxwell, Brian A.; Suo, Zucai

2014-01-01

The kinetic mechanisms by which DNA polymerases catalyze DNA replication and repair have long been areas of active research. Recently discovered Y-family DNA polymerases catalyze the bypass of damaged DNA bases that would otherwise block replicative DNA polymerases and stall replication forks. Unlike DNA polymerases from the five other families, the Y-family DNA polymerases have flexible, solvent-accessible active sites that are able to tolerate various types of damaged template bases and all...

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

Science.gov (United States)

Li, Changkun; Kähny, Matthias; Breit, Bernhard

2014-12-08

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

Palladium alloy membrane process for the treatment of hydrogen isotopes

Energy Technology Data Exchange (ETDEWEB)

Chung, Hongsuk; Paek, Seungwoo; Lee, Minsoo; Kim, Kwangrag; Yim, Sungpaal; Ahn, Dohee [KAERI, Daejeon (Korea, Republic of); Shim, Myunghwa [Univ. of Science and Technology, Daejeon (Korea, Republic of)

2005-11-15

Tritium is a radioactive isotope of hydrogen and it has a half-life of 12.3 years; it decays to He-3 by emitting a low energy beta radiation with an average energy of 5.7 keV and a maximum energy of 18.6 keV. Transfer of environmentally tritiated water to humans takes place via an inhalation, diffusion through the skin and ingestion. Radioactive waste containing tritium is continuously generated by the nuclear industry in, for example, nuclear reactor operations and a radioisotope production, as well as in medical research. Methods for removing tritium from liquid waste provide an alternative to the control of tritium emissions and a personnel exposure. A combined electrolysis and catalytic exchange process is a very effective method to remove small quantities of tritium from light or heavy waste water streams. The process consists of three main steps: (a) A front end step that exchanges the tritium to a less toxic hydrogen phase. This can be performed either through a chemical exchange in the presence of a platinum supported catalyst or through the decomposition of water. (b) A back end process that purifies the tritiated hydrogen gas which evolved from the electrolysis. This can be performed through a palladium alloy membrane separator. (c) A means of storing the concentrated gas safely. Uranium is used if the storage is temporary; titanium is usually employed for long term storage. To gain a better understanding of the tritiated hydrogen gas purification process, a mathematical model of the palladium alloy membrane has been used. This model is described herein, and the representative results of the model calculations are presented. The authors selected the palladium alloy membrane for the hydrogen purification process by considering the membrane properties, such as a chemical resistance, mechanical stability, thermal stability, high permeability, and a stable operation. The solution-diffusion model can be a useful tool for designing a membrane permeator. The