CHARACTERIZATION OF THE REACTIVE INTERMEDIATES IN LASER FLASH-PHOTOLYSIS OF ADENINE, ADENOSINE AND DAMP USING ACETONE AS PHOTOSENSITIZER

Transient absorption spectra of adenine, adenosine and 2'-deoxyadenosine 5'-monophosphate (dAMP) arising from 248 nm laser flash photolysis using acetone as a photosensitizer have been observed. The intermediates recorded are assigned to the excited triplet states and dehydrogenated radicals of adenine and its nucleoside and nucleotide. The excited triplet states of adenine and its derivatives are produced via triplet-triplet excitation transfer and observed for the first time, while the dehydrogenated radicals stemming from the interaction of triplet acetone with adenine and its derivatives via electron transfer through a five-member-ring electron donor-acceptor intermediate. The site of dehydrogenation is suggested to be the hydrogen atom on C(8) of the adenine moiety. Moreover, three sets of kinetic parameters of the triplet decay have been determined. The rate constants of the unimolecular decay (k(o)), the triplet quenching by the ground state (k(sq)) and by the triplet quencher Mn2+ (k(q)) are 1.1 X 10(5), 7.9 X 10(4), 3.7 X 10(4) s(-1), 6.9 X 10(8), 8.3 X 10(8), 3.6 X 10(8) dm(3) mol(-1) s(-1) and 4.2 X 10(8), 3.5 X 10(8), 6.0 X 10(8) dm(3) mol(-1) s(-1) respectively for adenine, adenosine and dAMP.