Reactions of dichloride anion radicals with pyrimidine and its derivatives.
Rate constants for the reactions of dichloride anion radicals with pyrimidine and its derivatives were determined by a conventional flash photolysis. Kinetic treatment was carried out by assuming that second-order self decay of the anion radicals and the reaction with a substrate proceed simultaneously. Values of the rate constants were found within 1.1 × 107 to 4.1 × 109 M-1 s-1; the lowest reactivity was observed for pyrimidine and the highest for 2, 4, 6triaminopyrimidine. Comparison of the rate constants with those for hydroxyl radicals suggests that the dichloride anion radicals undergo a different reaction with pyrimidine bases from that of the hydroxyl radicals. A transient absorption due to an intermediate produced in the reaction with the anion radicals was observed for 5-aminouracil. This is only a case where relatively long-lived absorption was observed. The absorption was used to determine the rate constants for the reactions with the anion radicals.
Comparison of reactivities of dibromide anion radical and dichloride anion radical in neutral aqueous solution.
Rate constants of reactions of dibromide anion radical with some aliphatic dipeptides or unsaturated compounds including pyrimidine bases have been determined by flash photolysis. Difference in activation energy between, dibromide and dichloride anion radicals has been estimated by comparing rate constants obtained for common substrates.
Some aspects of the destruction of lysine under conditions of acid and enzymic hydrolysis of protein materials containing carbohydrates.
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