Ultraviolet-induced reactions of thymine and uracil in the presence of cysteine

Abstract —Ultraviolet‐radiation photolysis of thymine in the presence of cysteine gives rise to four isomeric dimers, dihydrothymine, and at least five cysteine addition products. Similar reactions occur for uracil but the products have not all been characterized in detail. The addition reactions arise from the triplet state of the pyrimidine. The initial step is production of a hydropyrimidine radical, which then reacts with cysteine to give the addition products. The triplet is quenched by cysteine with a rate constant of about 2 times 10 8 M ‐1 s ‐1 for thymine and 2–9 times 10 8 for uracil. The total yield of products gives a lower‐limit estimate of the triplet yield and hence of the intersystem‐crossing efficiency. These studies, combined with earlier determinations of dimer yields, show that 93% of the thymine triplets which interact with another thymine molecule are quenched without forming stable dimers. For uracil, the corresponding figure is 75%.