Partial Reactivities Observed in the Hydrogen Abstraction Reactions of Hydroxyl Radicals from Aliphatic Amino Acids

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Rate constants for the hydrogen abstraction reactions of hydroxyl radicals from aliphatic amino acids were determined by the p-nitrosodimethylaniline method in gamma-irradiated aqueous solutions. Partial reactivities for the hydrogen abstraction reactions were estimated for C-H bonds found in molecules of aliphatic amino acids, on the basis of the rate constants of glycine, alanine, valine, and leucine and also by assumption of the linear relationship between the position of carbon atom and natural logarithm of the difference in activation energy. The calculated rate constants from the estimated partial reactivities were found to be in good agreement with the observed ones. The hydrogen abstraction reaction of hydroxyl radicals from a C-H bond of an aliphatic molecule has been well established. Anbar, Meyerstein and Neta determined rate constants for the reactions of hydroxyl radicals with aliphatic alcohols and carboxylic acids and proposed partial reactivities, which correspond to primary, secondary, and tertiary hydrogen bound to α- or β-carbon respectively, for the purpose of interpreting whole reactivity. Recently, Asmus, Mockel and Henglein investigated the reaction site of the hydroxyl radical on aliphatic alcohol by means of pulse radiolysis and found that the relative possibilities for hydrogen abstraction from other than a position increase with increasing number of carbon atoms.
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