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• W2146261645 endingPage "7770" @default.
• W2146261645 startingPage "7762" @default.
• W2146261645 abstract "cis–syn Cyclobutane pyrimidine dimers, major UV-induced DNA lesions, are efficiently repaired by DNA photolyases. The key step of the repair reaction is a light-driven electron transfer from the FADH− cofactor to the dimer; the resulting radical anion splits spontaneously. Whether the splitting reaction requires considerable activation energy is still under dispute. Recent reports show that the splitting reaction of a dimer radical anion has a significant activation barrier (0.45 eV), and so photolyases have to provide considerable energy. However, these results contradict observations that cis–syn dimer radical anions split into monomers at −196 °C, and that the full process of DNA photoreactivation was fast (1.5–2 ns). To investigate the activation energies of dimer radical anions, three model compounds 1–3 were prepared. These include a covalently linked cyclobutane thymine dimer and a tryptophan residue (1) or a flavin unit (3), and the covalently linked uracil dimer and tryptophan (2). Their properties of photosensitised splitting of the dimer units by tryptophan or flavin unit were investigated over a large temperature range, −196 to 70 °C. The activation energies were obtained from the temperature dependency of splitting reactions for 1 and 2, 1.9 kJ mol−1 and 0.9 kJ mol−1 for the thymine and uracil dimer radical anions, respectively. These values are much lower than that obtained for E. coli photolyase (0.45 eV), and are surmountable at −196 °C. The activation energies provide support for previous observations that repair efficiencies for uracil dimers are higher than thymine dimers, both in enzymatic and model systems. The mechanisms of highly efficient enzymatic DNA repair are discussed." @default.
• W2146261645 created "2016-06-24" @default.
• W2146261645 creator A5008497740 @default.
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• W2146261645 creator A5048956159 @default.
• W2146261645 date "2007-09-17" @default.
• W2146261645 modified "2023-10-17" @default.
• W2146261645 title "Do Photolyases Need To Provide Considerable Activation Energy for the Splitting of Cyclobutane Pyrimidine Dimer Radical Anions?" @default.
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• W2146261645 doi "https://doi.org/10.1002/chem.200700251" @default.
• W2146261645 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/17568458" @default.
• W2146261645 hasPublicationYear "2007" @default.
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