Many DNA-processing enzymes have been shown to contain a [4Fe4S] cluster, a common redox cofactor in biology. Using DNA electrochemistry, we find that binding of the DNA polyanion promotes a negative shift in [4Fe4S] cluster potential, which corresponds thermodynamically to a ∼500-fold increase in DNA-binding affinity for the oxidized [4Fe4S]3+ cluster versus the reduced [4Fe4S]2+ cluster. This redox switch can be activated from a distance using DNA charge transport (DNA CT) chemistry. DNA-processing proteins containing the [4Fe4S] cluster are enumerated, with possible roles for the redox switch highlighted. A model is described where repair proteins may signal one another using DNA-mediated charge transport as a first step in their search for lesions. The redox switch in eukaryotic DNA primases appears to regulate polymerase handoff, and in DNA polymerase δ, the redox switch provides a means to modulate replication in response to oxidative stress. We thus describe redox signaling interactions of DNA-processing [4Fe4S] enzymes, as well as the most interesting potential players to consider in delineating new DNA-mediated redox signaling networks.

中文翻译：

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基因组中的氧化还原化学：[4Fe4S] 辅助因子在修复和复制中的出现。


许多 DNA 加工酶已被证明含有 [4Fe4S] 簇，这是生物学中常见的氧化还原辅助因子。使用DNA电化学，我们发现DNA聚阴离子的结合促进了[4Fe4S]簇电位的负移，这在热力学上对应于氧化的[4Fe4S]3+簇的DNA结合亲和力比还原的[4Fe4S]3+簇的DNA结合亲和力增加约500倍。 [4Fe4S]2+簇。该氧化还原开关可以使用 DNA 电荷传输 (DNA CT) 化学物质从远处激活。列举了含有 [4Fe4S] 簇的 DNA 加工蛋白，并突出显示了氧化还原开关的可能作用。描述了一种模型，其中修复蛋白可以使用 DNA 介导的电荷传输相互发出信号，作为寻找病变的第一步。真核 DNA 引物酶中的氧化还原开关似乎可以调节聚合酶交接，而在 DNA 聚合酶 δ 中，氧化还原开关提供了一种调节复制以响应氧化应激的方法。因此，我们描述了 DNA 加工 [4Fe4S] 酶的氧化还原信号相互作用，以及在描绘新的 DNA 介导的氧化还原信号网络时需要考虑的最有趣的潜在参与者。