Progress in Reaction Kinetics and Mechanism最新文献_第9页

Fabricating Nano-Sized BiVO4/InVO4/g-C3N4 Photocatalysts for Efficient Degradation of Acid Blue 92 Azo Dye 纳米BiVO4/InVO4/g-C3N4光催化剂高效降解酸性蓝92偶氮染料的制备

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2018-06-01 DOI: 10.3184/146867818X15161889114493

M. Tasviri, Samin Bargozideh

引用次数: 5

Investigation of Reaction Mechanisms and Kinetics of the Radical Scavenging Ability of 5-Tert-Butylbenzene-1,2,3-Triol and 3,5-di-Tert-Butylbenzene-1,2-Diol Compounds Towards OOH Radical 5-叔丁基苯-1,2,3-三醇和3,5-二叔丁基苯-1,2-二醇对OOH自由基清除能力的反应机理和动力学研究

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2018-06-01 DOI: 10.3184/146867818X15161889114484

Anes El-Hadj Saïd, S. Mekelleche

{"title":"Investigation of Reaction Mechanisms and Kinetics of the Radical Scavenging Ability of 5-Tert-Butylbenzene-1,2,3-Triol and 3,5-di-Tert-Butylbenzene-1,2-Diol Compounds Towards OOH Radical","authors":"Anes El-Hadj Saïd, S. Mekelleche","doi":"10.3184/146867818X15161889114484","DOIUrl":"https://doi.org/10.3184/146867818X15161889114484","url":null,"abstract":"The antioxidant properties of the synthesised 5-tert-butylbenzene-1,2,3-triol (system A) and the designed 3,5-di-tert-butylbenzene-1,2-diol (system B) have been explored through density functional theory at the M05-2X/6-31+G(d,p) level of theory. The quantum mechanics-based test for overall free radical scavenging activity (QM- ORSA) protocol has been employed to account for their radical-scavenging capacity against the hydroperoxyl radical (HOO•) in the gas phase and in toluene solvent as a mimic lipid medium. The different mechanisms of the chemical reactions of the studied systems with HOO• have been considered, namely (i) the hydrogen atom transfer (HAT), (ii) the single electron transfer followed by proton transfer and (iii) the radical adduct formation. Our calculations provide evidence that HAT is the most favoured reaction mechanism in both the gas phase and in lipid media and the calculated thermodynamic and kinetic parameters indicate that the designed compound is more efficient than the synthesised system A and the reference system (α-tocopherol).","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"1 1","pages":"101 - 111"},"PeriodicalIF":0.7,"publicationDate":"2018-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82946246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

SiO2-Supported Co–Rh Bimetallic Catalysts for Dicyclopentadiene Hydroformylation: Relationships Between Catalytic Performance and Structure of the Catalysts 二环戊二烯氢甲酰化的二氧化硅负载Co-Rh双金属催化剂:催化剂性能与结构的关系

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2018-06-01 DOI: 10.3184/146867818X15161889114475

Libo Zhang, Chengyang Li, Yubo Ma, Tianfu Wang

{"title":"SiO2-Supported Co–Rh Bimetallic Catalysts for Dicyclopentadiene Hydroformylation: Relationships Between Catalytic Performance and Structure of the Catalysts","authors":"Libo Zhang, Chengyang Li, Yubo Ma, Tianfu Wang","doi":"10.3184/146867818X15161889114475","DOIUrl":"https://doi.org/10.3184/146867818X15161889114475","url":null,"abstract":"In this work, SiO2-supported Co–Rh bimetallic catalysts were prepared by adopting a method of impregnation and were used to catalyse the hydroformylation of dicyclopentadiene (DCPD) to diformyltricyclodecanes. Firstly, the hydroformylation of DCPD was carried out and three reaction stages were observed. In the first stage, a sharp decrease of reaction pressure was observed within 4 minutes. In the next stage, almost no reaction pressure decrease was detected over a relatively longer reaction time (70 minutes). In the final stage, the reaction pressure decreased at a relatively gentle rate, with barely any decrease of reaction pressure being observed at 460 minutes. Secondly, the hydroformylation of monoformyltricyclodecenes (MFTD) with various reaction times was carried out; the catalyst that was used at various reaction times was also recovered. Finally, the catalyst that had been used at various reaction times was characterised and analysed and the relationship between the catalytic performance and the structure of the catalysts was confirmed. In addition, combined with triphenylphosphine, the influence of pressure on the activity of Co–Rh bimetallic catalysts was investigated for the hydroformylation of MFTD.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"5 1","pages":"136 - 143"},"PeriodicalIF":0.7,"publicationDate":"2018-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87048686","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 3

Behaviour Modelling of Organic Bases in the Oxyalkylation Reaction of Proton-Containing Nucleophiles 含质子亲核试剂氧烷基化反应中有机碱的行为模拟

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2018-06-01 DOI: 10.3184/146867818X15161889114501

S. Bakhtin, E. Shved, Yuliia Bespal’ko, Yu. Z. Stepanova

{"title":"Behaviour Modelling of Organic Bases in the Oxyalkylation Reaction of Proton-Containing Nucleophiles","authors":"S. Bakhtin, E. Shved, Yuliia Bespal’ko, Yu. Z. Stepanova","doi":"10.3184/146867818X15161889114501","DOIUrl":"https://doi.org/10.3184/146867818X15161889114501","url":null,"abstract":"The mechanism of action of nucleophilic and non-nucleophilic bases in the system “acetic acid (HOAc) – epichlorohydrin (ECH) – R3X (R = alkyl, X = N, P)” has been studied. The observed orders of the reaction with respect to the components were found. It has been proved that the catalytic activity of the starting bases is determined by their nucleophilicity, rather than basicity. It is shown that the crucial stage of the reaction is the quaternisation of the starting base with the formation of a reactive intermediate, the acetate anion. Monitoring of possible paths of oxirane ring-opening by the initial base and the acetate anion was carried out. The behaviour of the model base, triphenylphosphine, in the quaternisation reaction was studied by UV spectroscopy. The rate constants of quaternisation in the reaction of tribenzylamine and triphenylphosphine with ECH have been estimated. The activation parameters of the stages of oxirane ring-opening by trimethylamine and the acetate anion were calculated using a quantum chemical method. It has been shown that the starting base attacks only the activated oxirane, while the acetate anion is capable of nucleophilic opening of both activated and non-activated ECH rings. A scheme for the catalytic opening of the oxirane ring by the bases in the system “ECH – HOAc – R3X” is proposed, which includes a series of both consecutive and parallel stages leading to the formation of the reaction product.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"42 1","pages":"121 - 135"},"PeriodicalIF":0.7,"publicationDate":"2018-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89155813","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 6

Hydroformylation of Dicyclopentadiene to Monoformyltricyclodecenes over Supported Ultra-Low Content Rh Catalysts 负载型超低含量Rh催化剂上双环戊二烯氢甲酰化制单酰基三环癸烯

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2018-06-01 DOI: 10.3184/146867818X15233705894356

Chengyang Li, Hongyi Li, Libo Zhang, Yubo Ma, Tianfu Wang

引用次数: 1

Kinetics and Mechanism of Alkaline Hydrolysis of N-(o-Aminophenyl)Phthalimide in the Presence and Absence of Cationic Micelles and Sodium Salts of Aliphatic Acids N-(邻氨基苯基)邻苯二胺在阳离子胶束和脂肪酸钠盐存在和不存在情况下的碱性水解动力学和机理

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2018-06-01 DOI: 10.3184/146867818X15161889114510

W. Ahmad, I. I. Fagge, Yoke-Leng Sim, Mohammad Niyaz Khan

引用次数: 0

Effects of Some Operating Parameters on Sorption and Desorption Kinetics Related to Spotted Golden Thistle Stalks and Methylene Blue; Isotherm Study at Optimal pH and Sorbent Regeneration 一些操作参数对斑点金蓟茎和亚甲基蓝吸附解吸动力学的影响最佳pH和吸附剂再生的等温研究

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2018-06-01 DOI: 10.3184/146867818X15233705894365

Z. S. Bereksi, H. Benaïssa

{"title":"Effects of Some Operating Parameters on Sorption and Desorption Kinetics Related to Spotted Golden Thistle Stalks and Methylene Blue; Isotherm Study at Optimal pH and Sorbent Regeneration","authors":"Z. S. Bereksi, H. Benaïssa","doi":"10.3184/146867818X15233705894365","DOIUrl":"https://doi.org/10.3184/146867818X15233705894365","url":null,"abstract":"In this work, the sorptive removal assessment of methylene blue by spotted golden thistle stalks was enhanced. Sorption was positively impacted by increasing temperature, initial pH or ionic strength. The sorbent isoelectrical point is 2.6 according to zeta potential measurements. The Elovich and Avrami models best fitted the sorption kinetic data; and an original prediction of equilibrium time is proposed. At 25 °C and for optimal initial pH = 7, the experimental maximal sorption capacity is 75 mg g−1. The Langmuir, Redlich–Peterson, Sips and Tóth models led to good correlations of isothermal data. Desorption percentages are important in both mineral and organic acidic media; the highest levels up to 91% were recorded for 1 × 10−2 M HCl solutions. The pseudo second-order model fitted satisfactorily the desorption kinetics. An innovative concept of regeneration is proposed, which promises significant savings of eluent and operating time. The sorbent regeneration assessment showed constant uptake abilities after five cycles of use.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"16 1","pages":"173 - 188"},"PeriodicalIF":0.7,"publicationDate":"2018-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87006304","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 2

Effect of Reactivity on Kinetics and a Mechanistic Investigation of the Reaction between Dimethyl Acetylenedicarboxylate and 1,3-Dicarbonyl Compounds in the Presence of a Catalyst: A Spectrophotometric Approach 反应活性对催化剂存在下二甲基乙酰二羧酸酯与1,3-二羰基化合物反应动力学的影响及机理研究:分光光度法

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2018-03-01 DOI: 10.3184/146867818X15161889114439

Mahdieh Darijani, S. Habibi‐Khorassani, M. Shahraki

{"title":"Effect of Reactivity on Kinetics and a Mechanistic Investigation of the Reaction between Dimethyl Acetylenedicarboxylate and 1,3-Dicarbonyl Compounds in the Presence of a Catalyst: A Spectrophotometric Approach","authors":"Mahdieh Darijani, S. Habibi‐Khorassani, M. Shahraki","doi":"10.3184/146867818X15161889114439","DOIUrl":"https://doi.org/10.3184/146867818X15161889114439","url":null,"abstract":"A kinetic and mechanistic investigation, using conventional UV-Vis spectrophotometry, of the reaction between dimethyl acetylenedicarboxylate (DMAD) and 1,3-dicarbonyl compounds including acetylacetone (ACAC) and dibenzoylmethane (DBM), has been conducted in a methanol environment with triphenylarsine (TPA) acting as a catalyst. Previously, in a similar reaction, triphenylphosphine (TPP) (instead of TPA) had been employed as a reactant (not a catalyst) for the generation of an ylide (final product). In the present work, of significance is the differential behaviour of TPA which, as a catalyst in the reaction environment, leads to a cyclopropane compound. Of other significance is the different behaviours of the two reactants in the kinetics and mechanism of the reaction. In previous work, TPP acted as a weak nucleophile (a reactant), so the first step of the reaction was recognised as the rate-determining step (RDS). Here, TPA reacts as a stronger nucleophile and a catalyst, resulting in the fourth step of the reaction (step4, k4, a proton transfer process) being recognised as the RDS. The reaction followed second-order kinetics. The proposed mechanism was adapted in accord with the experimental results and the steady-state assumption. The results showed that the reaction rate decreases in the presence of DBM, which participates in the second step (step2), compared to ACAC when it is present as another 1,3-dicarbonyl compound (structural effect). In addition, in previous work, the partial order of the reaction with respect to the 1,3-dicarbonyl compound was zero, while it is one in the present work. As a significant result, not only did a change in the structure of one of the reactants (TPA instead of TPP) create a different product, but also the kinetics and reaction mechanism changed. In addition, the reaction is enthalpy-controlled.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"20 1","pages":"79 - 90"},"PeriodicalIF":0.7,"publicationDate":"2018-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86848735","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 9

Kinetic Studies of the Reactions between Dichlorido(1,2-Diaminoethane)Zinc(II) and Biologically Relevant Nucleophiles in the Presence of Chloride 氯离子存在下二氯(1,2-二氨基乙烷)锌(II)与亲核试剂反应动力学研究

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2018-03-01 DOI: 10.3184/146867818X15066862094897

T. Soldatović, Enisa Selimović

{"title":"Kinetic Studies of the Reactions between Dichlorido(1,2-Diaminoethane)Zinc(II) and Biologically Relevant Nucleophiles in the Presence of Chloride","authors":"T. Soldatović, Enisa Selimović","doi":"10.3184/146867818X15066862094897","DOIUrl":"https://doi.org/10.3184/146867818X15066862094897","url":null,"abstract":"The mole-ratio method was used for determining metal–ligand stoichiometry for the reaction between [ZnCl2(en)] (where en = 1,2-diaminoethane or ethylenediamine) and chloride ion at pH 7.2. The results have shown step-wise formation of 1:1 and 1:2 complexes and indicate additional coordination of chloride ions in the first coordination sphere. The kinetics of ligand substitution reactions of the zinc(II) complex and biologically relevant nucleophiles such as inosine-5′-monophosphate (5′-IMP), guanosine-5′-monophosphate (5′-GMP), L-methionine (L-Met), glutathione (GSH) and DL-aspartic acid (DL-Asp) were investigated at pH 7.2 as a function of nucleophile concentration in the presence of 0.010 M NaCl. The reactions were followed under pseudo first-order conditions by UV-Vis spectrophotometry. The substitution reactions include two steps of consecutive displacement of chlorido ligands and changes in coordination geometry. In the presence of an excess of chloride, the octahedral complex anion [ZnCl4(en)]2- formed. The first step of the substitution reactions could be interpreted as substitution of the axial chlorido ligands in the cis position to bidentate ethylenediamine by the biologically relevant nucleophiles, while the second step could be interpreted as substitution of the equatorial chlorido ligand. The order of reactivity of the investigated nucleophiles for the first reaction step is 5′-IMP > GSH > L-Met > DL-Asp > 5′-GMP, while for the second reaction step the order of reactivity is GSH > L-Met > 5′-IMP > DL-Asp > 5′-GMP.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"1 1","pages":"53 - 61"},"PeriodicalIF":0.7,"publicationDate":"2018-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90115301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 3

Nuclease Activity of Diaza-Crown Ether Complexes of Cerium(III) with Different Functional Groups as Side Arms 以不同官能团为侧臂的铈(III)二氮冠醚配合物的核酸酶活性

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2018-03-01 DOI: 10.3184/146867818X15161889114448

Bingying Jiang, Shulan Cai, Jia‐qing Xie, Fa-mei Feng

{"title":"Nuclease Activity of Diaza-Crown Ether Complexes of Cerium(III) with Different Functional Groups as Side Arms","authors":"Bingying Jiang, Shulan Cai, Jia‐qing Xie, Fa-mei Feng","doi":"10.3184/146867818X15161889114448","DOIUrl":"https://doi.org/10.3184/146867818X15161889114448","url":null,"abstract":"Cerium(III) complexes of two ligands of a diaza-crown ether with different functional groups as side arms were synthesised and characterised. The catalytic ability of the cerium(III) complexes for pUC19 DNA cleavage was investigated and compared using agarose gel electrophoresis. The results indicate that the catalytic activity of the complex CeL2 [L2 = 2,2′- (1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-7,16-diyl) diacetamide] with two carbamoylmethyl groups is significantly higher than the complex CeL1 [L1 = 2,2′- (1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-7,16-diyl) diethanol] with two hydroxyethyl groups under the same conditions. The optimum catalytic concentrations of CeL1 and CeL2 were 7.69 × 10−5 and 3.08 × 10−5 mol L−1 respectively and excessively high concentrations of the complexes can reduce their catalytic efficiency due to the formation of inactive μ-hydroxo dimers. The optimum catalytic acidities of CeL1 and CeL2 were pH 7.0 and 7.5 respectively and excessively high pH of the reaction system can reduce the catalytic efficiency of the complexes due to the formation of cerium(III) hydroxide. DNA cleavage promoted by the two complexes takes place via the same hydrolytic pathway and so the activity difference of the two complexes is attributed to the stability of the complexes, rather than the catalytic mechanism.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"5 1","pages":"91 - 99"},"PeriodicalIF":0.7,"publicationDate":"2018-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73928970","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 1