Reactions of Dichioride Anion Radicals with Aliphatic Peptides in Aqueous Solutions
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Rate constants for the reactions of dichioride anion radicals with aliphatic peptides were determined by a conventional flash photolysis of 1 M solutions of potassium chloride containing aliphatic peptides. The rate constants were found to increase with increasing number of C-H bond. Partial rate constants were assigned to each C-H bond of the aliphatic peptides, as estimated for the reactions of hydroxyl radicals with the same substrates. Trend in the partial rate constants and the effect of a protonated amino group on the reactivity indicate a reaction mechanism, hydrogen atom abstraction, similar to hydroxyl radicals. Dichioride anion radical (Cl2) is a transient oxidant produced in photolysis or in radiolysis of aqueous chloride and its reactions with biomolecules have been investigated from the viewpoint of high reactivity toward aromatic amino acids, in particular, tryptophan. 1-3) On the other hand, the reaction rates with aliphatic compounds were found to be much slower than those for aromatic compounds. 4) In a previous study, 5) we determined the rate constants for reactions of dichloride anion radicals with aliphatic amino acids in aqueous neutral solutions by a conventional flash photolysis and discussed them in comparison with the reactivity of hydroxyl radicals toward the same substrates. In the reactions of hydroxyl radicals, partial rate constants were assigned satisfactorily to each C-H bond of the aliphatic amino acids. 6)
- 日本放射線影響学会の論文
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