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含胸腺嘧啶碱基的合成聚合物上的光化学反应。

Photochemical reactions on the synthetic polymers containing thymine bases.

作者信息

Kita Y, Uno T, Inaki Y, Takemoto K

出版信息

Nucleic Acids Symp Ser. 1979(6):s63-6.

PMID:547242
Abstract

Photodimerizations of N-2-isobutyloxyethyl thymine (T-M), bis[2-(5-methyl-1-pyrimidinyl)ethyl]glutarate (T-T), poly-N-2-methacryloyloxethyl thymine (P-MAOT) and poly-N-2-acryloyloxyethyl thymine (P-AOT) were studied in dimethylformamide solution. Quantum efficiencies of intramolecular photodimerizations were determined to be 0.0012 for T-T, 0.0084 for P-MAOT and 0.010 for P-AOT. In the case of T-M, however, intermolecular photodimerization did not occur under the reaction condition used. Quenching studies by using isoprene suggest that the photodimerization of T-T occurs predominantly through an excited triplet state, while that of P-MAOT and P-AOT occur through both singlet and triplet states. For the effect of adding model compounds containing adenine bases on this reaction, adenine derivatives acts as an inhibitor against this reaction by quenching the excited singlet state of thymine. The photodimers of T-T, P-MAOT and P-AOT were concluded to be two syn-fused cyclobutane- type dimers (cis-syn and trans-syn).

摘要

在二甲基甲酰胺溶液中研究了N - 2 - 异丁氧基乙基胸腺嘧啶(T - M)、双[2 - (5 - 甲基 - 1 - 嘧啶基)乙基]戊二酸酯(T - T)、聚N - 2 - 甲基丙烯酰氧基乙基胸腺嘧啶(P - MAOT)和聚N - 2 - 丙烯酰氧基乙基胸腺嘧啶(P - AOT)的光二聚反应。测定了分子内光二聚反应的量子产率,T - T为0.0012,P - MAOT为0.0084,P - AOT为0.010。然而,在所用反应条件下,T - M未发生分子间光二聚反应。用异戊二烯进行的猝灭研究表明,T - T的光二聚反应主要通过激发三重态发生,而P - MAOT和P - AOT的光二聚反应则通过单重态和三重态发生。对于添加含腺嘌呤碱基的模型化合物对该反应的影响,腺嘌呤衍生物通过猝灭胸腺嘧啶的激发单重态而对该反应起抑制作用。得出结论,T - T、P - MAOT和P - AOT的光二聚体为两种顺式稠合环丁烷型二聚体(顺式 - 顺式和反式 - 顺式)。

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