Bifurcating electron-transfer pathways in DNA photolyases determine the repair quantum yield.

Bifurcating electron-transfer pathways in DNA photolyases determine the repair quantum yield.
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DOI:
10.1126/science.aah6071
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发表时间:
2016-10-14
期刊:
Science (New York, N.Y.)
影响因子:
--
通讯作者:
Zhong D
Zhong D
中科院分区:
其他
文献类型:
--
作者:
Zhang M;Wang L;Shu S;Sancar A;Zhong D

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光裂合酶是一种蓝光激活的酶,其修复以环丁烷嘧啶二聚体(CPD)和嘧啶-嘧啶酮(6-4)光产物的形式发生的紫外线诱导的DNA损伤。以前对微生物光解酶的研究揭示了一个电子隧穿途径,这对修复机制至关重要。在这项研究中,我们使用飞秒光谱deconvolute七个电子转移反应在10个基本步骤中的所有类别的CPD光解酶。我们报告了一个统一的电子传递途径,通过一个保守的结构配置,分叉有利于直接隧道在原核生物和真核生物中的两步跳跃机制。两个分叉路线是可操作的,但它们的相对贡献,由黄素辅因子和底物的还原电位决定,决定了修复的整体量子产率。
Photolyase is a blue-light–activated enzyme that repairs ultraviolet-induced DNA damage that occurs in the form of cyclobutane pyrimidine dimers (CPDs) and pyrimidine-pyrimidone (6–4) photoproducts. Previous studies on microbial photolyases have revealed an electron-tunneling pathway that is critical for the repair mechanism. In this study, we used femtosecond spectroscopy to deconvolute seven electron-transfer reactions in 10 elementary steps in all classes of CPD photolyases. We report a unified electron-transfer pathway through a conserved structural configuration that bifurcates to favor direct tunneling in prokaryotes and a two-step hopping mechanism in eukaryotes. Both bifurcation routes are operative, but their relative contributions, dictated by the reduction potentials of the flavin cofactor and the substrate, determine the overall quantum yield of repair.
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