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Pyrimidinone: versatile Trojan horse in DNA photodamage?
Mathias Micheel1, Christian Torres Ziegenbein, Peter Gilch
1Institut für Physikalische Chemie, Heinrich-Heine-Universität Düsseldorf, Universitätstr. 1, D-40225 Düsseldorf, Germany. gilch@hhu.de.
Abstract:
(6-4) Photolesions between adjacent pyrimidine DNA bases are prone to secondary photochemistry. It has been shown that singlet excited (6-4) moieties form Dewar valence isomers as well as triplet excitations. We here report on the triplet state of a minimal model for the (6-4) photolesion, 1-methyl-2(1H)-pyrimidinone. Emphasis is laid on its ability to abstract hydrogen atoms from alcohols and carbohydrates. Steady-state and time-resolved experiments consistently yield bimolecular rate constants of ∼10(4) M(-1) s(-1) for the hydrogen abstraction. The process also occurs intramolecularly as experiments on zebularine (1-(β-d-ribofuranosyl)-2(1H)-pyrimidinone) show.
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