UV-Induced Structural Changes of Model DNA Helices Probed by Optical Spectroscopy†

Chemical alterations of DNA, if not repaired, may lead to carcinogenic mutations. Structural modifications of the helix around the lesion enable its recognition by repair enzymes. We have used absorption spectroscopy and mass spectrometry to detect structural changes provoked by cyclobutane thymine dimers, the major lesion induced by UV radiation. We found that formation of a cyclobutane dimer in the model duplex (dA)20·(dT)20 destroys base stacking on the adenine strand. The physical background of this novel approach is the existence of charge-transfer states among neighboring bases, whose contribution to the hypochromism of the helix disappears following destacking.