Solid-aqueous interfaces and phenomena occurring at those interfaces are ubiquitously found in a plethora of chemical systems.When it comes to heterogeneous catalysis,however,our understanding of chemical transformati...Solid-aqueous interfaces and phenomena occurring at those interfaces are ubiquitously found in a plethora of chemical systems.When it comes to heterogeneous catalysis,however,our understanding of chemical transformations at solid-aqueous interfaces is relatively limited and primitive.This review phenomenologically describes a selection of water-engendered effects on the catalytic behavior for several prototypical acid-base-catalyzed reactions over solid catalysts,and critically assesses the general and special roles of water molecules,structural moieties derived from water,and ionic species that are dissolved in it,with an aim to extract novel concepts and principles that underpin heterogeneous acid-base catalysis in the aqueous phase.For alcohol dehydration catalyzed by solid Bronsted acids,rate inhibition by water is most typically related to the decrease in the acid strength and/or the preferential solvation of adsorbed species over the transition state as water molecules progressively solvate the acid site and form extended networks wherein protons are mobilized.Water also inhibits dehydration kinetics over most Lewis acid-base catalysts by competitive adsorption,but a few scattered reports reveal substantial rate enhancements due to the conversion of Lewis acid sites to Brønsted acid sites with higher catalytic activities upon the introduction of water.For aldol condensation on catalysts exposing Lewis acid-base pairs,the addition of water is generally observed to enhance the rate when C–C coupling is rate-limiting,but may result in rate inhibition by site-blocking when the initial unimolecular deprotonation is rate-limiting.Water can also promote aldol condensation on Brønsted acidic catalysts by facilitating inter-site communication between acid sites through hydrogen-bonding interactions.For metallozeolite-catalyzed sugar isomerization in aqueous media,the nucleation and networking of intrapore waters regulated by hydrophilic entities causes characteristic enthalpy-entropy tradeoffs as these water moieties interact with kinetically relevant hydride transfer transition states.The discussed examples collectively highlight the utmost importance of hydrogen-bonding interactions and ionization of covalently bonded surface moieties as the main factors underlying the uniqueness of water-mediated interfacial acid-base chemistries and the associated solvation effects in the aqueous phase or in the presence of water.A perspective is also provided for future research in this vibrant field.展开更多
β-Bromovinyl tellurides are new difuctional reagents which undergo palladium-catalyzed cross-coupling reaction with alkenes to give conjugated dienyl tellurides.
9-Chlorofluorene reacted with aromatic aldehydes and ketones in the presence of phase transfer catalyst, giving the Darzens condensation epoxy products.
Methyl 3-trimethylsilylpropargyl carbonate reacted with dinucleophiles under the catalysis of palladium(0) complex to give the corresponding desilylated annulation products.
The yield and stereoselectivity of the Diels-Alder reactions between furan(or 2-methylfuran)and different dienophiles are markedly enhanced by the catalysis of anhydrous YbCl_3.
The kinetics of reaction of bromo-epoxy resin with oleic acid in the presence of dimethylbenzylamine catalyst was studied. The reaction is a zero order reaction with respect to oleic acid, first order with respect to ...The kinetics of reaction of bromo-epoxy resin with oleic acid in the presence of dimethylbenzylamine catalyst was studied. The reaction is a zero order reaction with respect to oleic acid, first order with respect to epoxy group and 0. 74 order with respect to dimethylbenzylamine. The reaction rate constants at various temperatures and activation energy were determined. The mechanism of this reaction was discussed. Keywords Tetrabromobisphenol-A, Bromo-epoxy resin, Oleic acid kinetics, Reaction mechanism展开更多
To obtain new functional aromatic polymer materiul. 3,3＇-biacenaphthene, which is used as macromolecule intermediate of,funcrion aromatic polymer material, was synthesized through the coupling reaction of acenaphthen...To obtain new functional aromatic polymer materiul. 3,3＇-biacenaphthene, which is used as macromolecule intermediate of,funcrion aromatic polymer material, was synthesized through the coupling reaction of acenaphthene catalyzing by ionic liquid （[bmim]CI/FeCl3） at mild reaction condition. Pure 3,3＇-biacenaphthene was obtained hy recrystalling and column chromatography from the reaction mixture and was determined by GC/MS, SHNMR arid FTIR analysis. The influence of various reaction conditions on the yield of 3,3＇-biacenaphthene were studied by GC analysis. The result shows that the optimun synthesis conditions of the coupling reaction are, as following： the molar ratio of FeCl3 to [BmimlCl being 3, the mole ratio of FeCl3 in [Bmim]Cl/FeCl3 to acenaphthene being 4. the reaction temperamre being 20 ℃ the reaction time being 4h and the solvent of the reaction system being PhNO2 Under those conditions, the yield of the 3.3＇-biacenaphthene will be 48.71% and selectivity, of that will be 78.56 %. Farther more, [bmim]Cl/FeCl3 has no pollution to environments and can be reused.展开更多
The thermokinetic reduced extent equations of reversible inhibitions for Michaiels-Menten enzymatic reaction were deduced, and then the criteria for distingushing inhibition type was given and the methods for calculat...The thermokinetic reduced extent equations of reversible inhibitions for Michaiels-Menten enzymatic reaction were deduced, and then the criteria for distingushing inhibition type was given and the methods for calculating kinetic parameters, KM,Ki and Urn were suggested. This theory was applied to inverstigate the inhibited thermokinetics of laccase-catalyzed oxidation of o-dihydroxybenzene by m-dihydroxybenzene. The experimental results show the inhibition belongs to reversible competitive type, KM=6.224×10-3 mol L-1, Ki=2. 363 × 10-2 mol. L-1.展开更多
The mechanism of oxygen pressure acid leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation was investigated in this study.Artificial sphalerite was fabricated with varying amounts of iron content via the ...The mechanism of oxygen pressure acid leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation was investigated in this study.Artificial sphalerite was fabricated with varying amounts of iron content via the sintering of ZnS and FeS and used for the pressure acid leaching experiment.The variations in the potential of the pressure leaching system were investigated by using a self-designed potential autoclave.The results showed that compared to the non-iron sphalerite,there was a violent redox reaction between the 25.70%Fe-artificial sphalerite and dissolved oxygen during the process of pressure leaching;and the catalytic mechanism was attributed to the redox couple Fe^3+/Fe^2+,where Fe3+oxidizes the H2S gas film and the reduced Fe2+state is subsequently oxidized by the dissolved oxygen.Furthermore,the effect of temperature,H2SO4 concentration,and oxygen partial pressure on the artificial sphalerite with different iron contents was studied.The sphalerite samples with iron content were observed to dissolve more easily in sulfuric acid compared to the non-iron samples.Moreover,the activation energy of artificial sphalerite was observed to be lower in the sample with 25.70%iron content(22.26 kJ/mol)compared to that with no iron(32.31 kJ/mol);and the apparent reaction orders were obtained with respect to H2SO4 concentration(1.10 and 1.36)and oxygen partial pressure(1.29 and 1.41),respectively.A comprehensive kinetic model was developed on the basis of the experimental data and the fitted leaching ratio plot;and the kinetic equations for the leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation were determined.展开更多
A bifunctional heterogeneous catalyst containing two mutually incompatible acidic and basic sites, which exhibits cooperative catalytic behavior in the aldol condensation of acetone and various aldehydes, was synthesi...A bifunctional heterogeneous catalyst containing two mutually incompatible acidic and basic sites, which exhibits cooperative catalytic behavior in the aldol condensation of acetone and various aldehydes, was synthesized by postgrafting of 1,5,7- triazabicyclo[4.4.0] dec-5-ene （TBD, a sterically hindered organic base） onto AI-MCM-41 molecular sieve. 2009 Xiao Bing Lu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
Through the method of initial heat release rate, the kinetic property of tyrosine oxidation catalyzed by tyrosinase from Pseudomonas maltophilia was investigated using a LKB-2107 batch microcalorimeter. Tyrosine was c...Through the method of initial heat release rate, the kinetic property of tyrosine oxidation catalyzed by tyrosinase from Pseudomonas maltophilia was investigated using a LKB-2107 batch microcalorimeter. Tyrosine was catalyzed and oxidized into L-dopa, then into melanin catalyzed by tyrosinase. We found that the tyrosinase reaction obeyed the Michaelis-Menten kinetics, and at 298.15K and pH 7.0, the initial exothermic rate (W0 ) are in the range of 0.1567~0.5704 mJ·s-1, the maximum exothermic rate (Wmax) are in 0.4152 ~ 0.8143mol·L-1, and mean value of the Michaelis constant (Km) is 2.199±0.105104 mol·L-1.展开更多
A new analytical method is proposed for the determination of heroin based on a sequential perturbation caused by trace amounts of heroin in the Cu(Ⅱ)-catalyzed oscillating reaction between hydrogen peroxide and sodiu...A new analytical method is proposed for the determination of heroin based on a sequential perturbation caused by trace amounts of heroin in the Cu(Ⅱ)-catalyzed oscillating reaction between hydrogen peroxide and sodium thiocyanate in an alkaline medium with the aid of a continuous-flow stirred tank reactor(CSTR). The method relies on the linear relationship between the change in oscillation period of the system and the concentration of heroin, with a detecting limit of 4.0×10^(-7) mol/L. The calibration curve fits a linear equation very well when the concentration of heroin is in the range of 2.0×10^(-6)_1.2×10^(-5) mol/L(r=0.9971). This method features good precision(RSD=0.98%). The influences of temperature, injection point, flow rate and reaction variables on the oscillation period were investigated in detail and a possible mechanism of the performance of heroin in the Cu(Ⅱ)-catalyzed oscillating reaction system is also discussed. The proposed method opens a new avenue for the determination of heroin.展开更多
文摘Solid-aqueous interfaces and phenomena occurring at those interfaces are ubiquitously found in a plethora of chemical systems.When it comes to heterogeneous catalysis,however,our understanding of chemical transformations at solid-aqueous interfaces is relatively limited and primitive.This review phenomenologically describes a selection of water-engendered effects on the catalytic behavior for several prototypical acid-base-catalyzed reactions over solid catalysts,and critically assesses the general and special roles of water molecules,structural moieties derived from water,and ionic species that are dissolved in it,with an aim to extract novel concepts and principles that underpin heterogeneous acid-base catalysis in the aqueous phase.For alcohol dehydration catalyzed by solid Bronsted acids,rate inhibition by water is most typically related to the decrease in the acid strength and/or the preferential solvation of adsorbed species over the transition state as water molecules progressively solvate the acid site and form extended networks wherein protons are mobilized.Water also inhibits dehydration kinetics over most Lewis acid-base catalysts by competitive adsorption,but a few scattered reports reveal substantial rate enhancements due to the conversion of Lewis acid sites to Brønsted acid sites with higher catalytic activities upon the introduction of water.For aldol condensation on catalysts exposing Lewis acid-base pairs,the addition of water is generally observed to enhance the rate when C–C coupling is rate-limiting,but may result in rate inhibition by site-blocking when the initial unimolecular deprotonation is rate-limiting.Water can also promote aldol condensation on Brønsted acidic catalysts by facilitating inter-site communication between acid sites through hydrogen-bonding interactions.For metallozeolite-catalyzed sugar isomerization in aqueous media,the nucleation and networking of intrapore waters regulated by hydrophilic entities causes characteristic enthalpy-entropy tradeoffs as these water moieties interact with kinetically relevant hydride transfer transition states.The discussed examples collectively highlight the utmost importance of hydrogen-bonding interactions and ionization of covalently bonded surface moieties as the main factors underlying the uniqueness of water-mediated interfacial acid-base chemistries and the associated solvation effects in the aqueous phase or in the presence of water.A perspective is also provided for future research in this vibrant field.
基金This work was supported by Natural Science Foundation of Zhejiang Province.
文摘β-Bromovinyl tellurides are new difuctional reagents which undergo palladium-catalyzed cross-coupling reaction with alkenes to give conjugated dienyl tellurides.
文摘9-Chlorofluorene reacted with aromatic aldehydes and ketones in the presence of phase transfer catalyst, giving the Darzens condensation epoxy products.
文摘Methyl 3-trimethylsilylpropargyl carbonate reacted with dinucleophiles under the catalysis of palladium(0) complex to give the corresponding desilylated annulation products.
文摘The yield and stereoselectivity of the Diels-Alder reactions between furan(or 2-methylfuran)and different dienophiles are markedly enhanced by the catalysis of anhydrous YbCl_3.
文摘The kinetics of reaction of bromo-epoxy resin with oleic acid in the presence of dimethylbenzylamine catalyst was studied. The reaction is a zero order reaction with respect to oleic acid, first order with respect to epoxy group and 0. 74 order with respect to dimethylbenzylamine. The reaction rate constants at various temperatures and activation energy were determined. The mechanism of this reaction was discussed. Keywords Tetrabromobisphenol-A, Bromo-epoxy resin, Oleic acid kinetics, Reaction mechanism
基金National Natural Science Foundation of China (No. 20207003)
文摘To obtain new functional aromatic polymer materiul. 3,3＇-biacenaphthene, which is used as macromolecule intermediate of,funcrion aromatic polymer material, was synthesized through the coupling reaction of acenaphthene catalyzing by ionic liquid （[bmim]CI/FeCl3） at mild reaction condition. Pure 3,3＇-biacenaphthene was obtained hy recrystalling and column chromatography from the reaction mixture and was determined by GC/MS, SHNMR arid FTIR analysis. The influence of various reaction conditions on the yield of 3,3＇-biacenaphthene were studied by GC analysis. The result shows that the optimun synthesis conditions of the coupling reaction are, as following： the molar ratio of FeCl3 to [BmimlCl being 3, the mole ratio of FeCl3 in [Bmim]Cl/FeCl3 to acenaphthene being 4. the reaction temperamre being 20 ℃ the reaction time being 4h and the solvent of the reaction system being PhNO2 Under those conditions, the yield of the 3.3＇-biacenaphthene will be 48.71% and selectivity, of that will be 78.56 %. Farther more, [bmim]Cl/FeCl3 has no pollution to environments and can be reused.
文摘The thermokinetic reduced extent equations of reversible inhibitions for Michaiels-Menten enzymatic reaction were deduced, and then the criteria for distingushing inhibition type was given and the methods for calculating kinetic parameters, KM,Ki and Urn were suggested. This theory was applied to inverstigate the inhibited thermokinetics of laccase-catalyzed oxidation of o-dihydroxybenzene by m-dihydroxybenzene. The experimental results show the inhibition belongs to reversible competitive type, KM=6.224×10-3 mol L-1, Ki=2. 363 × 10-2 mol. L-1.
基金Projects(51804136,51764016)supported by the National Natural Science Foundation of ChinaProject(U1402271)supported by the Joint Funds of the National Natural Science Foundation of China+2 种基金Project(20181BAB216017)supported by the Jiangxi Provincial Natural Science Foundation,ChinaProject(GK-201803)supported by the Research Fund Program of State Key Laboratory of Rare Metals Separation and Comprehensive Utilization,ChinaProjects(yy2016001,yy2016012)supported by the Research Fund Program of the State Key Laboratory of Pressure Hydrometallurgical Technology of Associated Nonferrous Metal Resources,China。
文摘The mechanism of oxygen pressure acid leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation was investigated in this study.Artificial sphalerite was fabricated with varying amounts of iron content via the sintering of ZnS and FeS and used for the pressure acid leaching experiment.The variations in the potential of the pressure leaching system were investigated by using a self-designed potential autoclave.The results showed that compared to the non-iron sphalerite,there was a violent redox reaction between the 25.70%Fe-artificial sphalerite and dissolved oxygen during the process of pressure leaching;and the catalytic mechanism was attributed to the redox couple Fe^3+/Fe^2+,where Fe3+oxidizes the H2S gas film and the reduced Fe2+state is subsequently oxidized by the dissolved oxygen.Furthermore,the effect of temperature,H2SO4 concentration,and oxygen partial pressure on the artificial sphalerite with different iron contents was studied.The sphalerite samples with iron content were observed to dissolve more easily in sulfuric acid compared to the non-iron samples.Moreover,the activation energy of artificial sphalerite was observed to be lower in the sample with 25.70%iron content(22.26 kJ/mol)compared to that with no iron(32.31 kJ/mol);and the apparent reaction orders were obtained with respect to H2SO4 concentration(1.10 and 1.36)and oxygen partial pressure(1.29 and 1.41),respectively.A comprehensive kinetic model was developed on the basis of the experimental data and the fitted leaching ratio plot;and the kinetic equations for the leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation were determined.
基金support by a Foundation for the Author of National Excellent Doctoral Dissertation of China(No.FANEDD,200759)the Outstanding Young Scientist Foundation of NSFC(No.20625414)
文摘A bifunctional heterogeneous catalyst containing two mutually incompatible acidic and basic sites, which exhibits cooperative catalytic behavior in the aldol condensation of acetone and various aldehydes, was synthesized by postgrafting of 1,5,7- triazabicyclo[4.4.0] dec-5-ene （TBD, a sterically hindered organic base） onto AI-MCM-41 molecular sieve. 2009 Xiao Bing Lu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
基金This work were supported by the National Natural Science Foundation of China(No.30170010,29973030)The Teaching and Research Award Program for Outstanding Young Professors in High Education Institute,MOE,China(2001).
文摘Through the method of initial heat release rate, the kinetic property of tyrosine oxidation catalyzed by tyrosinase from Pseudomonas maltophilia was investigated using a LKB-2107 batch microcalorimeter. Tyrosine was catalyzed and oxidized into L-dopa, then into melanin catalyzed by tyrosinase. We found that the tyrosinase reaction obeyed the Michaelis-Menten kinetics, and at 298.15K and pH 7.0, the initial exothermic rate (W0 ) are in the range of 0.1567~0.5704 mJ·s-1, the maximum exothermic rate (Wmax) are in 0.4152 ~ 0.8143mol·L-1, and mean value of the Michaelis constant (Km) is 2.199±0.105104 mol·L-1.
基金Supported by the Project of International Cooperation between China and U kraine(No.0 4 3- 0 5 ) and the Project ofKJCXGC- 0 1Northwest Norm al U niversityChina
文摘A new analytical method is proposed for the determination of heroin based on a sequential perturbation caused by trace amounts of heroin in the Cu(Ⅱ)-catalyzed oscillating reaction between hydrogen peroxide and sodium thiocyanate in an alkaline medium with the aid of a continuous-flow stirred tank reactor(CSTR). The method relies on the linear relationship between the change in oscillation period of the system and the concentration of heroin, with a detecting limit of 4.0×10^(-7) mol/L. The calibration curve fits a linear equation very well when the concentration of heroin is in the range of 2.0×10^(-6)_1.2×10^(-5) mol/L(r=0.9971). This method features good precision(RSD=0.98%). The influences of temperature, injection point, flow rate and reaction variables on the oscillation period were investigated in detail and a possible mechanism of the performance of heroin in the Cu(Ⅱ)-catalyzed oscillating reaction system is also discussed. The proposed method opens a new avenue for the determination of heroin.
