QUANTUM YIELDS AND SECONDARY PHOTOREACTIONS OF THE PHOTOPRODUCTS OF dTpdT, dTpdC AND dTpdU

Abstract

Abstract— The photoproducts of the dinucleoside monophosphates, dTpdT, dTpdC and dTpdU, have been purified by high performance liquid chromatography and characterized by UV absorption spectroscopy, fast atom bombardment mass spectrometry and by secondary thermal and photoreactions. Four types of photoproducts were analyzed: (1) cyclobutane dimers including cis‐syn isomers and two diastereomers of the trans‐syn isomers; (2) 6‐4 photoadducts and the corresponding Dewar valence isomers; (3) photohydrates comprising two diastereomers and (4) a new photoproduct resembling nucleobase amine adducts, which occurs only for dTpdC. The quantum yields of formation of these photoproducts and for some secondary photoreactions were measured by kinetic analysis of the photoproduct yield as a function of photon fluence. These results indicate that cis‐syn cyclobutane dimers are the photoproducts formed with highest efficiency with dT[p]dC dimers being formed with 50–75% the efficiency of dT[p]dT dimers. The 6‐4 photoadducts are formed with 5–10% the efficiency of cis‐syn cyclobutane dimers and the 6‐4 photoadduct of dTpdC is formed two to three times more efficiently than that of dTpdT. Photohydrates are also formed efficiently due to an equilibrium between stacked and unstacked complexes of the dinucleoside monophosphates. It is shown that three of these photoproducts, namely the cyclobutane dimers of dTpdC, the 6‐4 photoadducts and the possible nucleobase amine adduct, undergo photolysis in the UV‐B region resulting in either photoreversion or secondary photoreaction.