Mechanisms for the formation of major oxidation products of adenine upon 365-nm irradiation with 2-methyl-1,4-naphthoquinone as a sensitizer.

Recently we reported the isolation and characterization of N6-formyl- and N6-acetyladenine from 365-nm irradiation of dinucleoside monophosphates d(ApA), d(ApC), and d(CpA) in the presence of 2-methyl-1,4-naphthoquinone (menadione) (Wang et al. Biochem. Biophys. Res. Commun. 2002, 291, 1252-7). In this article we investigated the mechanisms for the formation of the two major products by carrying out photoirradiation with isotopically labeled menadione and 2,3-dimethyl-1,4-naphthoquinone. HPLC and electrospray ionization (ESI)-mass spectrometry (MS) and tandem MS studies of the products unambiguously established that the carbonyl group in the products arises from the photosensitizer: The N6-formyl group comes from oxidation of the methyl group and the N6-acetyl group stems from the methyl group and the adjacent ring carbon in menadione. From above results, we proposed mechanisms for the formation of the two products.