Aqueous repair of a cyclobutane pyrimidine dimer (CPD) with a biomimetic artificial photolyase

ORGN 734

Chris Harrison, charris5@nd.edu1, Olaf Wiest, owiest@nd.edu1, Nicolas J. Saettel1, Radek Cibulka2, Mirjam Sax3, and Burkhard Konig2. (1) Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556-5670, (2) Naturwissenschaftliche Fakultät IV Chemie / Pharmazie, Universität Regensburg, Regensburg, Germany, (3) Universitat Regensburg, Regensburg, Germany
Repair of a cyclobutane pyrimidine dimer (CPD) was achieved by a small molecule DNA photolyase mimic consisting of a Zn-cyclen and flavin. After complexation with a binding constant of ~103 M-1, excitation with visible light resulting in a biomimetic, photoinduced electron transfer was cleanly cycloreverted in both protic and aprotic organic solvents as well as in water. Conducting the repair in water at pH 7.2, as would be most similar to the biologic reaction, gave rapid repair with ~68% conversion within 20 seconds, faster than the diffusion controlled bimolecular reaction with flavin. In order to understand the early steps of repair and more clearly establish the role in the repair, a series of control experiments suggesting a more complete description of the biomimetic repair mechanism will be presented.