title: Photosensitized splitting of thymine dimer or oxetane unit by a covalently N-linked carbazole via electron transfer in different marcus regions.
abstract: Although many similarities exist between the two classes of enzymes, cyclobutane photolyases and (6-4) photolyases have certain important differences. The most significant difference is in their repair quantum yields, cyclobutane photolyases with a uniformly high efficiency (0.7-0.98) and very low repair efficiency for (6-4) photolyases (0.05-0.1). To understand the significant difference, we prepared two classes of model compounds, covalently N-linked dimer- (1) or oxetane-carbazole (2) compounds with a dimethylene or trimethylene group as a linker. Under light irradiation, the dimer or oxetane unit of model compounds can be sensitized to split by the excited carbazole via an intramolecular electron transfer. The splitting reaction of dimer or oxetane unit in model compounds is strongly solvent dependent. In nonpolar solvents, such as cyclohexane or THF, no fluorescence quenching of the carbazole moiety of model compounds relative to a free carbazole, N-methylcarbazole, was observed and thus no splitting occurred. In polar solvents, two classes of model compounds reveal two reverse solvent effects on the splitting quantum yield. One is an inverse relation between the quantum yield and the polarity of the solvent for dimer-model systems, and another is a normal relation for oxetane-model systems. This phenomenon was also observed with another two classes of model compounds, covalently linked dimer- or oxetane-indole. Based on Marcus theory and thermodynamic data, it has been rationalized that the two reverse solvent effects derive from back electron transfer in the splitting process lying in the different Marcus regions. Back electron transfer lies in the Marcus inverted region for dimer-model systems and the normal region for oxetane-model systems. From repair solvent behavior of the two classes of model compounds, we gained some insights into the major difference in the repair efficiency for the two classes of photolyases.
authors.affiliation: Department of Chemistry, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Qing-Qing
authors.initials: QQ
authors.lastname: Wu
authors.forename: Qin-Hua
authors.initials: QH
authors.lastname: Song
mesh_terms: D002227:Carbazoles / Q000737:chemistry*; D004255:Deoxyribodipyrimidine Photo-Lyase / Q000737:chemistry / Q000378:metabolism; D004579:Electron Transport; D004988:Ethers, Cyclic / Q000737:chemistry*; D017319:Photosensitizing Agents / Q000737:chemistry*; D011740:Pyrimidine Dimers / Q000737:chemistry*; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry
chemical_list: D002227:Carbazoles; D004988:Ethers, Cyclic; D017319:Photosensitizing Agents; D011740:Pyrimidine Dimers; D012997:Solvents; C038545:N-methylcarbazole; D004255:Deoxyribodipyrimidine Photo-Lyase; C005287:oxetane