S. I. Kulakovskaya

Electrochemical and ESR study of the CH bond activation. Electrocatalytical oxidation with participation of radical cation of phenazine-di-N-oxide

The mechanism of oxidation of organic substrates (cyclohexanol, ethanol, methanol, tetrahydrofurane, triethylether of orthoformic acid, dioxane, toluene and cyclohexane) in the presence of a mediator, electrochemically generated radical cation of phenazine-di-N-oxide, has been studied by the methods of ESR electrolysis and cyclic voltammetry. The study was carried out at Au, Pt and glass carbon electrodes in acetonitrile, as well as in methanol and its deuterated derivatives (CH3OD, CD3OD) used as a solvent and a substrate simultaneously. The effect of temperature, acids, water, oxygen, the nature of solvent, substrate and supporting electrolyte on the shape and intensity of ESR signal and cyclic voltammograms (CV) has been studied. ESR spectra of radical intermediates were revealed: one intermediate with g-factor 2.0023 in CH3OH and CH3OD and two intermediates with g-factors 2.0023 and 2.0036 in CD3OD. The obtained results were explained by the overall two-electron mechanism of the electrochemical oxidation of the substrate via formation of the complex of substrate with the radical cation of phenazine-di-N-oxide.

Electrochemical and ESR studies of tert-butanol oxidation mechanism in the presence of radical cations pyrazine-di-N-oxide and its substituted derivatives as mediators

The methods of cyclic voltammetry, ESR electrolysis, and quantum chemical simulation were used to study the tert-butanol (tert-BuOH) oxidation mechanism in the presence of mediator cation radicals of pyrazine-di-N-oxide, 2,5-di-Me- and 2,3,5,6-tetra-Me-pyrazine-di-N-oxdides. This study was carried out on carbon glass (CG) and Pt electrodes in 0.1 M LiClO4 solution in acetonitrile and on Au electrode in tert-butanol containing 0.05 M LiClO4. The ESR spectra of cation and anion radicals of aromatic di-N-oxides were recorded in tert-BuOH. The quantum chemical simulation of the reaction between pyrazine-di-N-oxide radical cation and C-H bond in tert-BuOH was performed. The results were explained in the terms of the general two-electron oxidation mechanism of tert-BuOH in the complex with aromatic di-N-oxide cation radical as mediator.

Electrochemical and ESR studies of the methane C-H bond activation in the presence of radical cations of pyrazine-di-N-oxide and its substituted derivatives

Activation of the methane C-H bond in the presence of electrochemically generated radical cations of pyrazine-di-N-oxide and also of 2,5-dimethyl- and 2,3,5,6-tetramethyl-pyrazine-di-N-oxides is studied by methods of cyclic voltammetry (CVA), quantum chemical simulations, and ESR electrolysis. The studies are carried out on glassy carbon (GC) and Pt electrodes in 0.1 M LiClO4 solutions in acetonitrile. ESR spectra of radical cations of aromatic di-N-oxides in the absence and in the presence of methane are recorded. The changes in the shape CVA curves and the intensity of ESR signals of di-N-oxide radical cations observed in the presence of methane point to the activation of the methane C-H bond followed by its oxidation. The reaction of pyrazinedi-N-oxide at the methane C-H bond is simulated by quantum chemical methods. The obtained results are explained within the framework of the mechanism of overall two-electron oxidation of methane within its complex with an aromatic di-N-oxide radical cation.

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.

Electrochemical and ESR-study of the mechanism of organic compound oxidation in the presence of mediators—Radical cations of substituted pyrazin-di-N-oxydes

The mechanism of methanol, ethanol, diethyl ether, triethyl-o-formate, cyclohexanol, and cyclohexane oxidation in the presence of electrochemically generated radical cations of 2,5-dimethyl-, 2,3,5,6-tetramethyl-, 2,3-dimethyl-5,6-cyclohexa-, and 3-phenyl-5,6-cyclohexapyrazin-di-N-oxydes as mediators was studied by cyclic voltammetry, ESR-electrolysis, and gas chromatography. The studies were carried out at glassy-carbon-, Pt-, and Au-electrodes in 0.1 M LiClO4 solutions in acetonitrile and methanol, the alcohol being used as a solvent and substrate simultaneously. ESR-spectra of the radical cations of the pyrazin-di-N-oxydes were recorded. Effects of temperature, oxygen, admixtures of water and acid, and the nature of substrate and solvent on the shape of the cyclic voltammograms and intensity of the ESR-spectra of the pyrazin-di-N-oxydes are elucidated. By comparing experimental and calculated voltammograms, the rate constants for the interaction between the pyrazin-di-N-oxydes and the substrates C-H-bonds are determined. Mechanism of the ultimate two-electron catalytic oxidation of the organics as a constituent of complexes, formed with the radical cations of the mediators (pyrazin-di-N-oxydes), is suggested.

Electrochemical and ESR studies of au-protein from Micrococcus luteus

Au-protein from Micrococcus luteus, with and without Au inactive center, and chloroauric acid (HAu IIICl4·4H2O) with the addition of rutin, catechol, and riboflavin have been studied by means of electrochemistry and ESR. The redox potentials for Au-protein, as well as for the complexes Au-rutin and Au-catechol, have been measured, and ESR spectra of complexes Au-rutin and Au-catechol have been recorded. It has been shown that the Au atom binds to Au-protein via OH-groups of rutin. Flavin does not participatein gold binding. Au-protein is characterized by two peaks of cyclic voltammogram, −0.37 and −0.54 V. Au-protein with these potentials is able to function in the electron-transport chain of membranes between flavoproteins and quinones.

Electrochemical and ESR study of the mechanism of oxidation of phenazine-di-N-oxide in the presence of cyclohexanol on glassy carbon and single-walled carbon nanotube electrodes

The mechanism of oxidation of phenazine-di-N-oxide in the presence of cyclohexanol was studied by cyclic voltammetry on glassy carbon (GC) and single-walled carbon nanotube (SWCNT) electrodes in 0.1 M LiClO4 solutions in acetonitrile. The effect of cyclohexanol on the shape of the cyclic voltammograms of phenazine-di-N-oxide and the intensity of the ESR signal of its radical cation was investigated. It was shown by ESR that the products of the one-electron oxidation and reduction of phenazine-di-N-oxide were radical cations and anions. The catalytic currents were recorded during the oxidation of phenazine-di-N-oxide on the SWCNT and GC electrodes in the presence of cyclohexanol. The results were explained in terms of the E1C1E2C2 mechanism of the two-stage electrode process characterized by the catalytic current recorded at the second electrode stage. The overall two-electron catalytic oxidation of cyclohexanol in the complex with the phenazine-di-N-oxide radical cation was assumed to occur. It was shown that SWCNT electrodes can be used in the electrocatalytic oxidation of organic compounds in the presence of the electrochemically generated phenazine-di-N-oxide radical cation.

Electrochemical and ESR studies of the oxidation mechanism of pyrazine-di-N-oxides in the presence of methanol and its deuterated derivatives

The mechanism of oxidation of pyrazine-, 2,5-di-Me-, and 2,3,5,6-tetra-Me-pyrazine-di-N-oxides in the presence of methanol and its deuterated derivatives (CH3OD, CD3OD), i.e., compounds exhibiting the high energy of C-H bond dissociation, is studied by the methods of cyclic voltammetry, ESR electrolysis, and quantum chemical modeling. The study is carried out on a glassy carbon (GC) electrode in acetonitrile and on an Au electrode in solutions of different alcohols (methanol and its deuterated derivatives CH3OD, CD3OD). In alcohol solutions, the ESR spectra of radical cations and radical anions of the tested aromatic di-N-oxides are observed. The quantum chemical simulation of the reaction of the pyrazine-di-N-oxide radical cation with the MeOH C-H bond is carried out. The results obtained are explained within the framework of the E1C1E2C2 mechanism for a two-stage electrode process determined by the catalytic current of the second electrode stage. The overall two-electron catalytic oxidation of an alcohol within its complex with the pyrazine-di-N-oxide radical cation is proposed.

Electrochemical study of Au(III)-luteolin flavonoid system in tris-buffer

The Au(III)-luteolin system was studied by means of cyclic voltammetry, spectrometry, and quantum chemical simulation. The mutual effect of luteolin to Au(III) reduction and Au(III) to luteolin oxidation was studied by means of cyclic voltammetry on Pt and carbon glass electrodes in 0.05 M tris-buffer solution (pH 8) containing ethyl alcohol. The absorption spectra of luteolin were recorded with and without Au(III) in 0.05 M tris-buffer solution (pH 8) containing ethyl alcohol. The quantum chemical simulation of Au(III)-tris, Au(III)-luteolin, and Au(III)-tris-luteolin systems was carried out. On the basis of the collected data, formation of Au(III)-tris-luteolin complex in 0.05 M tris-buffer solution (pH 8) in the presence of ethanol was suggested.

Gold(III) reduction in a tris-HCl buffer: Effect of riboflavin, rutin, 1,1-dipyridyl, and 1-naphthol

Reduction of chloroauric acid on platinum and gold electrodes in a 0.1 M tris-HCl buffer of pH 8 containing riboflavin, rutin, 1,1-dipyridyl, or 1-naphthol is studied by cyclic voltammetry and in situ ESR methods. On the basis of the obtained data it is assumed that in the buffer there occurs the reduction of Au(III) to Au(I). In the presence of 1,1-dipyridyl, there occurs the reduction of complex [Au(III)-1,1-dipyridyl]. The reduction of Au(III) in the presence of 1-naphthol is realized in the composition of complex [Au(III)-tris-1-naphthol]. The hampering of the electrode process of the Au(III) reduction in the presence of 1-naphthol is caused by the adsorption of the [tris-1-naphthol] associates at the electrode surface. The presence of Au(III) does not exert any influence on the process of electroreduction of riboflavin. The obtained results make it possible to presume that the resistance of gold-accumulating cells Micrococcus luteus toward toxic compounds that are inhibitors of the respiratory chain, such as 1,1-dipyridyl and 1-naphthol, is caused by their binding in gold-containing complexes in the composition of Au-protein.