Photo-CIDNP study of the splitting of the dinucleotidecis,syn-thymine dimer with reduced flavin as a sensitizer: Evidence for a thymine radical anion intermediate |
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Authors: | P J W Pouwels R Kaptein |
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Institution: | 1. Bijvoet Center for Biomolecular Research, Utrecht University, Padualaan 8, 3584 CH, Utrecht, The Netherlands
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Abstract: | Photochemically induced dynamic nuclear polarization (photo-CIDNP) studies were performed on the splitting ofcis,syn 2′-deoxythymidylyl-(3′→5′)-2′-deoxythymidine cyclobutane dimer (cs-dTp dT), using reduced flavin as a sensitizer. This system serves as a model for the light-induced repair mechanism of thymine dimers in DNA by the enzyme photolyase. The CIDNP spectrum shows enhanced absorption of the two C6-H protons of the corresponding monomer dTpdT, which demonstrates that a thymine radical anion is involved in the splitting of the dimer. This is supported by a similar CIDNP spectrum that is obtained with the electron-donorN α-acetyl tryptophan as a sensitizer. This result suggests that the light-induced splitting of thymine dimers in DNA by photolyase also proceedsvia the thymine radical anion. The small difference in intensity of the two CIDNP signals belonging to the C6-H protons shows that the unpaired electron in the monomer radical has a slight preference for the thymine moiety at the 5′ terminus. |
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