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The radiation chemistry of thymine in aqueous solution. Some reactions of the thymine-electron adduct.

SummaryThe electron and OH adducts of thymine formed on irradiation of thymine in aqueous solutions containing O2 react rapidly with the dissolved O2 : k(TOH + O2) = 1·5 × 109 M−1 sec−1 and k(T− + O2) = 8 × 109 M−1 sec−1. In both reactions O2 adds to the thymine radical, producing T(OH)O2 and TO2−. It is shown that TO2− is ultimately converted into H2O2 and thymine, when the OH radicals are scavenged by a second organic solute. In the absence of O2 and in the presence of formate or isopropanol evidence is presented that the thymine negative ion (or its protonated form) disproportionates, producing thymine and dihydrothymine. In low dose-rate, steady-state radiolysis, CO2− radicals destroy the chromophore of thymine in competition with a radical-radical combination reaction of CO2−. With the high dose-rates used in pulse-radiolysis only these radical—radical reactions can occur.