Photoinduced spin-polarized radical pair formation in a DNA photolyase.substrate complex at low temperature.

Electron spin polarization is a phenomenon characterized by anomalous line intensities (emission or enhanced absorption) in the EPR spectrum. It is highly diagnostic of radical pairs, such as those formed in photoinduced electron transfer reactions. Electron spin polarization behavior (E/A pattern) is observed in light-modulated EPR spectra obtained at 4 K with fully reduced DNA photolyase.substrate complexes. Similar results are obtained with complexes formed with native enzyme or reconstituted enzyme containing fully reduced flavin as its only chromophore. No signal is observed for fully reduced enzyme or substrate alone. The results suggest that the electron spin polarization signal is due to photoinduced formation of a flavin/substrate radical pair (FADH./T < > T.-); splitting of T < > T.- does not occur at 4 K, and the radical pair can only undergo back-electron-transfer reactions. The data are consistent with the proposal that electron transfer initiates DNA repair in the photolyase reaction.