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Kinetics of the reduction of cystine and related dithio acids by reversible oxidation-reduction systems


, : Kinetics of the reduction of cystine and related dithio acids by reversible oxidation-reduction systems. Jour Biol Chem 87(3): 767-784

Dithio (R-S-S-R) acids were reduced by reversible oxidation-reduction systems of high reducing intensity and reaction rates were obtained which resembled approximately those of 2nd order reactions. These results serve as a criterion for the exclusion of certain reduction reactions as the predominating mechanisms. The reduction rates differed fcfr the various acids studied and seemed to depend on the position and nature of the groups attached to the -S-S- linkage, the rates being higher in those cases in which the -COOH or [alpha] -NH2 group was adjacent to the -S-S- linkage. The reduction rates decreased as the acidity was increased. Temperature coefficients calculated for certain of the reactions were rather unusual and certain unexpected results were obtained for the effect on the reaction rates of the potential of the reversible reagent employed for the reduction; the rate of reduction was not affected by an alteration of the potential of the reagent employed when the oxidant-reductant ratio was changed, but the use of another system of different E[omicron] value did alter the rate of the reduction. The results led to certain conclusions regarding the possible nature of the apparent reversibility of the change R-S-S-R to R-S-H and a comparison of this system to other oxidation and reduction systems has been presented to assist in classifying this reaction.

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