Kinetics of the electrocatalytic oxidation of glucose by Escherichia coli bacterial cells in the presence of exogenous mediators

Processes in the glucose-Escherichia coli cells-mediator-electrode bioelectrochemical system were studied using the kinetic model of processes on microbial mediator anodes. The model was constructed using the Michaelis-Menten equation. It takes into account the constants of substrate and mediator distribution between the inner medium of the cell and the working solution. The kinetic analysis of processes in the system under study showed that when Escherichia coli bacterial cells are used as a catalyst, methylene blue is a more effective mediator of electron transfer than gallocyanine.     

Electrochemical oxidation of malonic esters in acetonitrile in the presence of iodides as mediators

Electrochemical oxidation of malonic esters in acetonitrile in the presence of iodides follows two different pathways depending on the nature of the cation. In the presence of Lil, alkyl 1,1,2,2,3,3-propanetetracarboxylates were obtained in 85–98% yields. In the presence of Nal, Kl, or Bu₄NI, the formation of 1,1,2,2-ethanetetracarboxylates and their subsequent dehydrogenation to ethenetetracarboxylates was the main reaction pathway. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 620–623, March, 1997.     

Ethylene oxidation by lithium nitrate in the presence of palladium acetate in acetic acid

Data are reported on variations of the gas phase volume and product accumulation in ethylene oxidation by lithium nitrate in acetic acid solutions, catalyzed by palladium acetate. An assumption is made on the routes of nitrate ion reduction.

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CO oxidation in aqueous solutions of transition metal complexes in the presence of acetate ions

Depending on the reaction medium, acetate ions can both enhance and inhibit CO oxidation to CO₂ in the presence of Pd(II), Ag(I) and Cu(I, II) complexes.

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, - , CO CO₂ Pd(II), Ag(I) Cu(I, II).

     

醋酸铝催化合成PET

以对苯二甲酸与乙二醇原料,经过酯化缩聚反应合成聚对苯二甲酸乙二醇酯(PET),醋酸铝做催化剂,所得产品黏度为0.88。与醋酸锑催化剂相比,醋酸铝的活性较之高,且毒性小。与铝粉和氢氧化铝相比,在合成PET的反应中醋酸铝的活性较高。因此,醋酸铝是一种环保、高活性的合成聚酯的催化剂。     

Benzyl cleavage in the oxidation of cycleanine by mercuric acetate

The dehydrogenation of cycleanine with mercuric acetate in 10% AcOH (at the boil) has been studied. It has been shown that it is accompanied by oxidative cleavage similar to benzyl cleavage under the action of electron impact. The main reaction product (without complexone) is the 8-(4-hydroxymethylphenoxy)-6,7-dimethoxy-2-methylisoquinolinium salt C₁₉H₂₀NO₄Cl·1.5H₂O, mp 196°C. The oxidation of cycleanine in the presence of ethylenediaminetetraacetic acid gave the mercuride C₁₉H₁₉NO₃I₂Hg·2H₂O, mp 240°C (water).     

Benzyl cleavage in the oxidation of cycleanine by mercuric acetate

The dehydrogenation of cycleanine with mercuric acetate in 10% AcOH (at the boil) has been studied. It has been shown that it is accompanied by oxidative cleavage similar to benzyl cleavage under the action of electron impact. The main reaction product (without complexone) is the 8-(4-hydroxymethylphenoxy)-6,7-dimethoxy-2-methylisoquinolinium salt C₁₉H₂₀NO₄Cl·1.5H₂O, mp 196°C. The oxidation of cycleanine in the presence of ethylenediaminetetraacetic acid gave the mercuride C₁₉H₁₉NO₃I₂Hg·2H₂O, mp 240°C (water).All-Union Scientific-Research Institute of Medicinal Plants, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 676–680, September–October, 1979.     

Redox mediators of hydrogen sulfide oxidation in reactions with cycloalkanes

An indirect electrochemical method for thiolation of cycloalkanes C₅–C₇ has been suggested. The method is based on a new approach to activation of hydrogen sulfide by redox mediators.     

Carbonylation of methyl acetate in the presence of polymeric rhodium-containing catalysts

New catalytic systems based on RhCl₃ and polymeric nitrogen- and oxygen-containing supports were proposed for the carbonylation of methyl acetate to acetic anhydride. The catalytic systems possess a high activity typical of homogeneous catalysts. The high activity is retained upon the repeated use of the catalyst separated from the reaction products. The nitrogen-containing polymers of the chitosan type serve as cocatalysts. In their presence, the induction period disappears, and the catalytically active species are stabilized, thus enabling the replacement of expensive LiI for cheaper salts of this metal.     

Substituted pyrazine-di-N-oxides as the mediators of catalytic oxidation of organic compounds

The mechanism of oxidation of 2,5-dimethyl-, 2,3,5,6-tetramethyl-, 2,3-dimethyl-5,6-cyclohexa, and 3-phenyl-5,6-cyclohexapyrazine-di-N-oxides is studied by cyclic voltammetry, quantum chemical simulations, and ESR electrolysis. The studies are carried out on electrodes of glassy carbon and Pt in 0.1 M LiClO₄ solutions in acetonitrile. ESR spectra of radical cations of substituted pyrazine-di-N-oxides are recorded. The effects of the temperature, oxygen, and the additions of water, pyridine, and acid on the shape of cyclic voltamograms and the intensity of ESR signals of pyrazine-di-N-oxides are studied. A quantum-chemical simulation of the reaction of pyrazine-di-N-oxide radical cations with acetonitrile is carried out. The oxidation of substituted pyrazine-di-N-oxides is described by the E₁C₁E₂C₂ mechanism, which includes the stage of the formation of a complex between the di-N-oxide radical cation and acetonitrile.     

Initiated oxidation of dibutyl ether in the presence of inhibitors

It was found that unlike ionol, amines effectively inhibit the oxidation of dibutyl ether. The stoichiometric inhibition coefficient for amines is close to two. During the initiated oxidation of dibutyl ether in the presence of inhibitors, an exchange takes place of cyanoisopropyl peroxy radicals for the peroxy radicals of dibutyl ether. The mechanism of the reaction with p-phenylenediamine (p-PDA) probably consists in the formation of a fairly stable complex consisting of an amine molecule and two peroxy radicals. This reaction does not result in the formation of a hydroperoxide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1268–1273, June, 1990.     

Anodic oxidation of gadolinium metal in the presence of thenoyltrifluoroacetone

The possibility of preparing gadolinium chelates of various compositions by electrolysis of a nonaqueous solution containing thenoyltrifluoroacetone was examined.     

Electrochemical oxidation of tertiary phosphines in the presence of camphene

Anodic oxidation of tertiary phosphines (tripropyl-, tributyl-, and triphenylphosphine) in the presence of a bicyclic alkene (camphene) on a platinum and a glassy carbon electrodes was studied. For the first time the voltammetric characteristics of the process of camphene anodic oxidation were obtained. The electrochemical reactions with alkyl and aromatic phosphine were found to be dissimilar. The results of preparative electrooxidation of trialkylphosphines showed that in the course of electrolysis the tertiary phosphine cation-radicals generated on the anode enter into two concurrent reactions: (1) with the parent phosphine to form eventually trialkylphosphonium salts and trialkylphosphine oxides presumably as complex compounds and (2) with camphene to form trialkylcamphenylphosphonium salts and probably phosphonium salts with a monocyclic substituent. Preparative electrochemical oxidation of triphenylphosphine in the presence of camphene affords almost exclusively either triphenylphosphine oxide (in the experiment with platinum anode) or the triphenylphosphine oxide complex with perchloric acid (at the electrolysis on a glassy carbon anode).     

The oxidation of isopropylbenzene in the presence of copper nanopowders

The oxidation of isopropylbenzene with oxygen in the presence of copper nanopowders prepared under various wireelectrical explosion conditions was studied. The oxidative conversion of isopropylbenzene was observed only for nanopowders with a linear function of oxygen absorption. Holding copper nanopowders in a vacuum stimulated their initiating activity. A lower initial temperature of the oxidation of nanopowders in air corresponded to a higher rate of oxygen absorption by isopropylbenzene. The amount of absorbed oxygen was not equivalent to the conversion of isopropylbenzene.     

Amination of 5-hydroxy-1,4-naphthoquinone in the presence of copper acetate

The reaction of 5-hydroxy-1,4-naphthoquinone with butylamine in the presence of copper(II) acetate monohydrate on heating resulted in the formation of a mixture of regioisomeric 2,6- and 2,8-bis(butylamino)-5-hydroxy-1,4-naphthoquinones.     

离子液体催化合成乙二醇丁醚醋酸酯

以乙二醇单丁醚和冰醋酸为原料,在离子液体N-甲基吡咯烷酮硫酸氢盐([Hnmp] HSO4)催化下,合成了乙二醇丁醚醋酸酯.考察了催化剂用量、物料配比、反应时间、带水剂等因素对反应收率的影响.利用气相色谱仪分析了产物的纯度;利用核磁共振谱仪和质谱仪表征了产物的结构.结果表明,合成产物的纯度大于99.0％.[Hnmp]H ...