6. チミン誘導体水溶液の超音波分解反応
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Biological effect of ultrasonic is believed to originate from either homolysis or heterolysis of intracellular waters at high temperature and pressure by cavitation to produce toxic hydroxyl (OH) radicals. Ionizing radiation exerts similar effects with a different mechanism for generation of OH radicals. There has been a hypothesis that OH radicals are generated densely in small cavities upon sonolysis, while homogeneously at much lower concentration upon radiolysis. For better understanding of the sonochemical reaction characteristics, sonolytic and radiolytic hydroxylations of thymine derivatives (la: thymine; lb: 1,3-dimethylthymine; 3: 1,3-di(thymin-1-yl)propan-2-one) leading to cis- and trans-thymine glycol structures (2a: 5,6-dihydroxy-5,6-dihydrothymine; 2b: 1,3-dimethyl-5,6-dihydroxy-5,6-dmydrothymine; 4: 1-(thymin-1-yl)-3-(5,6-dihydroxy-5,6-dihydrothymin-1-yl)propan-2-one; 5: 1,3-di((5,6-dihydroxy-5,6-dihydrothymin-1-yl)propan-2-one) in aqueous solutions have been compared. In the sonolysis of lb in aqueous solution under Ar-bubbling, cis-2h was obtained in 4.3-times higher yield than trans-2b. Addition of KBr to this sonolysis system enhanced the formation of trans-2b relative to cis-2b. These reaction characteristics were substantially the same as in the radiolysis. In both sonolysis and radiolysis of aqueous solutions containing KBr, a dimeric thymine derivative 3 underwent hydroxyiation to a mono-glycol product 4 which was successively converted to a di-glycol product 5. The sonolysis and radiolysis in the absence of KBr are also being investigated. Based on these results, we discuss mechanistic details of the sonolytic hydroxyiation of thymines.
- 日本ソノケミストリー学会の論文
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- 6. チミン誘導体水溶液の超音波分解反応