Charge Transfer between [4Fe4S] Proteins and DNA Is Unidirectional: Implications for Biomolecular Signaling.

Charge Transfer between [4Fe4S] Proteins and DNA Is Unidirectional: Implications for Biomolecular Signaling.
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[4Fe4S] 蛋白质和 DNA 之间的电荷转移是单向的:对生物分子信号传导的影响。

DOI:
10.1016/j.chempr.2018.09.026
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发表时间:
2019
期刊:
影响因子:
23.5
通讯作者:
Migliore,Agostino
Migliore,Agostino
中科院分区:
化学1区
文献类型:
--
作者:
Teo,RuijieD;Rousseau,BenjaminJG;Smithwick,ElizabethR;DiFelice,Rosa;Beratan,DavidN;Migliore,Agostino

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最近的实验表明,DNA介导的电荷传输可能使人类DNA引发酶和聚合酶α的C-末端结构域中的[4Fe 4S]簇之间的信号传导,以及其他复制和修复高电位[4Fe 4S]蛋白之间的信号传导。我们的理论研究表明,氧化还原信号不能完全由DNA介导的电荷传输完成,因为部分电荷转移链具有不利的自由能分布。我们发现,空穴或过量的电子转移之间的[4Fe 4S]集群和核酸双链体通过蛋白质介质可以发生在微秒内在一个方向上,而它是在相反的方向动力学受阻。我们提出了一套信号机制,可能会发生与氧化剂或还原剂的协助下,使用允许的电荷转移过程。这些机制将使[4Fe 4S]蛋白对DNA的协调作用,参与蛋白-DNA结合亲和力的[4Fe 4S]氧化态依赖性。
Recent experiments suggest that DNA-mediated charge transport might enable signaling between the [4Fe4S] clusters in the C-terminal domains of human DNA primase and polymerase α, as well as the signaling between other replication and repair high-potential [4Fe4S] proteins. Our theoretical study demonstrates that the redox signaling cannot be accomplished exclusively by DNA-mediated charge transport because part of the charge-transfer chain has an unfavorable free energy profile. We show that hole or excess electron transfer between a [4Fe4S] cluster and a nucleic acid duplex through a protein medium can occur within microseconds in one direction while it is kinetically hindered in the opposite direction. We present a set of signaling mechanisms that may occur with the assistance of oxidants or reductants, using the allowed charge-transfer processes. These mechanisms would enable the coordinated action of [4Fe4S] proteins on DNA, engaging the [4Fe4S] oxidation state dependence of the protein-DNA binding affinity.
第一原理在天然和大小扩展的DNA中用于孔转移的有效电子耦合。
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