The temperature dependence of the cage effect in liquid-phase reactions

Khloplyankina, M.S.; Бучаченко, А. Л.; Vasil'eva, A. G.; Neiman, M. B.

doi:10.1007/bf00847919

Cited by 5 publications

(7 citation statements)

References 4 publications

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“…A similar kinetic sequence is observed for hydrocar bons (RH) with the difference that reaction (2) then occurs as detachment: + RH → ROOH + [5,6].…”

Section: Introductionsupporting

confidence: 57%

“…The table shows that the transition from oxygen to air decreases the rate of oxi dation for various by much less than five times. According to [1][2][3][4][5][6], this allows us to suggest that nitroxyl radicals react with both and The kinetic curves of (III) consumption at various [ (III)] 0 and [O 2 ] 0 are shown in Figs. 2 and 3, respectively.…”

Section: Resultsmentioning

confidence: 99%

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The kinetics and mechanism of reactions of aliphatic stable nitroxyl radicals with alkyl and peroxide radicals during styrene oxidation

Плисс

Тихонов

Русаков

2012

Russ. J. Phys. Chem. B

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A kinetic study (EPR, microvolumometry), quantum chemical analysis (DFT B3LYP/6 31G*), and kinetic simulation of the antioxidant activity of aliphatic stable nitroxyl radicals during styrene oxidation was performed. The key reactions constituting the detailed mechanism of the process were analyzed. It was shown that the inhibiting action of nitroxyl radicals was caused by their reaction not only with alkyl radicals but also with substrate peroxy radicals, which resulted in the regeneration of nitroxyl radicals in chain termi nation steps.

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“…A similar kinetic sequence is observed for hydrocar bons (RH) with the difference that reaction (2) then occurs as detachment: + RH → ROOH + [5,6].…”

Section: Introductionsupporting

confidence: 57%

Section: Resultsmentioning

confidence: 99%

The kinetics and mechanism of reactions of aliphatic stable nitroxyl radicals with alkyl and peroxide radicals during styrene oxidation

Плисс

Тихонов

Русаков

2012

Russ. J. Phys. Chem. B

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“…Stable nitroxide free radicals are widely used in biophysical studies and have previously been reported to react with various free radicals (Khloplyankina et al, 1965; Brownlie & Ingold, 1967; Robbins & Eastman, 1970;Rigo et al, 1977; Mehlhorn & Packer, 1984; Belkin et al, 1987). Superoxide radicals (02-) were found to reduce the five-membered ring nitroxide 2-ethyl-2,5,5-trimethyl-3-oxazolidineoxyl (OXANO)1 to its corresponding hydroxylamine, 2-ethyl-l-hydroxy-2,5,5-trimethyl-3-oxazolidine (OXANOH) (Samuni et al, 1989):…”

mentioning

confidence: 99%

Nitroxides block DNA scission and protect cells from oxidative damage

Samuni¹,

Godinger²,

Aronovitch³

et al. 1991

Biochemistry

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The protective effect of cyclic stable nitroxide free radicals, having SOD-like activity, against oxidative damage was studied by using Escherichia coli xthA DNA repair-deficient mutant hypersensitive to H2O2. Oxidative damage induced by H2O2 was assayed by monitoring cell survival. The metal chelator 1,10-phenanthroline (OP), which readily intercalates into DNA, potentiated the H2O2-induced damage. The extent of in vivo DNA scission and degradation was studied and compared with the loss of cell viability. The extent of DNA breakage correlated with cell killing, supporting previous suggestions that DNA is the crucial cellular target of H2O2 cytotoxicity. The xthA cells were protected by catalase but not by superoxide dismutase (SOD). Both five- and six-membered ring nitroxides, having SOD-like activity, protected growing and resting cells from H2O2 toxicity, without lowering H2O2 concentration. To check whether nitroxides protect against O2.(-)-independent injury also, experiments were repeated under hypoxia. These nitroxides also protected hypoxic cells against H2O2, suggesting alternative modes of protection. Since nitroxides were found to reoxidize DNA-bound iron(II), the present results suggest that nitroxides protect by oxidizing reduced transition metals, thus interfering with the Fenton reaction.

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“…On this hypothesis, it was shown 40 , 59 , 60 that the introduction of stable iminoxy-radicals, which are powerful free radical acceptors 61 , into hydroperoxide -aliphatic phosphite [triethyl phosphite (TEP), tripropyl phosphite (TPP), and iso-octyl diphenyl phosphite] systems leads to their destruction §. This implies that free radicals are formed in the reaction between hydroperoxides and phosphites.…”

Section: ίη''mentioning

confidence: 99%

Kinetics and Mechanism of the Reaction of Peroxy-compounds with Phosphites, Sulphides, and Aromatic Amines

Pobedimskii¹

1971

Russ. Chem. Rev.

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The studies dealing with the elucidation of the detailed mechanism and quantitative kinetics of the reactions of peroxycompounds with phosphites, sulphides, and aromatic amines are reviewed. It is shown how evidence has been obtained, by ESR of the existence of the one-electron amine oxidation stage, i.e. the stage involving the formation of radicalcations. The consecutive reactions of the radical-cations formed initially and their relation to the behaviour of the amines as polymerisation initiators are analysed. The characteristics of the detection of free radicals in reactions of phosphites and sulphides with hydroperoxides are examined and certain criteria of the latent, radical nature of these reactions are formulated. In the last section correlations of the Hammett equation type for rates of the reactions under consideration and also the correlation between the rate constants on the one hand and the ionisation potentials and electron affinities on the other are discussed within the framework of the one-electron oxidation-reduction mechanism. The bibliography includes 96 references. CONTENTS

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The temperature dependence of the cage effect in liquid-phase reactions

Cited by 5 publications

References 4 publications

The kinetics and mechanism of reactions of aliphatic stable nitroxyl radicals with alkyl and peroxide radicals during styrene oxidation

The kinetics and mechanism of reactions of aliphatic stable nitroxyl radicals with alkyl and peroxide radicals during styrene oxidation

Nitroxides block DNA scission and protect cells from oxidative damage

Kinetics and Mechanism of the Reaction of Peroxy-compounds with Phosphites, Sulphides, and Aromatic Amines

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