Plasma desorption mass spectrometric study of UV-induced lesions within DNA model compounds

Positive and negative plasma desorption (PD) mass spectra of the di-deoxyribonucleoside monophosphate d(TpT) and of its biologically relevant ultraviolet-induced intramolecular photodimers are examined and discussed. The photodimers which were analysed by PD mass spectrometry include the cis-syn and trans-syn cyclobutyl isomers d(T[p]T), the pyrimidine-pyrimidone photoadduct (6-4)d(TpT) and its Dewar valence isomer. Molecular ions, quasi-molecular ions and several fragment ions are observed in all cases. It is shown that, despite the absence of mass differences between these dinucleoside monophosphates, the fragmentation pattern differs significantly between the two main classes: cyclobutane dimers and (6-4) adducts. PD mass spectrometry can therefore be envisaged for characterizing their formation within short DNA fragments.