Dioxygen reactivity of a biomimetic [4Fe-4S] compound exhibits [4Fe-4S] to [2Fe-2S] cluster conversion
Dioxygen reactivity of a biomimetic [4Fe-4S] compound exhibits [4Fe-4S] to [2Fe-2S] cluster conversion
复制标题
仿生 [4Fe-4S] 化合物的分子氧反应性表现出 [4Fe-4S] 到 [2Fe-2S] 簇的转化
DOI：
10.1016/j.jinorgbio.2022.111714
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发表时间：
2022
影响因子：
3.9
通讯作者：
Kim, Eunsuk
中科院分区：
文献类型：
--
作者：
Oakley, Kady M.;Lehane, Ryan L.;Zhao, Ziyi;Kim, Eunsuk
富马酸盐和硝酸盐还原酶（FNR）是一种控制大肠杆菌厌氧到有氧呼吸的基因调控蛋白，其中o2作为一个控制开关，通过将[4Fe-4S]辅因子转化为[2Fe-2S]簇来诱导蛋白质结构变化。尽管仿生模型可以帮助理解其蛋白质对应物的复杂功能，但离散[Fe-S]分子对有氧条件的固有敏感性对模拟FNR的o2感知能力提出了独特的挑战。在此，我们报道了一种离散的[4Fe-4S]配合物[Fe4S4(SPhF)4]2−(1)的前所未有的仿生O2反应活性，其中sphfi是4-氟噻吩酸盐，其中1在硫代酸盐存在下与O2(g)反应产生[2Fe-2S]类似物[Fe2S2(SPhF)4]2−(2)，在室温下。在相同的反应条件下，用二硫化物作为氧化剂也可以实现1到2的团簇转化。o2对[4Fe-4S]到[2Fe-2S]簇的转化速度明显快于二硫化物，而与二硫化物的反应产率更高。
Fumarate and nitrate reductase (FNR) is a gene regulatory protein that controls anaerobic to aerobic respiration inEscherichia coli, for which O2serves as a control switch to induce a protein structural change by converting [4Fe-4S] cofactors to [2Fe-2S] clusters. Although biomimetic models can aid in understanding the complex functions of their protein counterparts, the inherent sensitivity of discrete [Fe-S] molecules to aerobic conditions poses a unique challenge to mimic the O2-sensing capability of FNR. Herein, we report unprecedented biomimetic O2reactivity of a discrete [4Fe-4S] complex, [Fe4S4(SPhF)4]2−(1) where SPhFis 4-fluorothiophenolate, in which the reaction of1with O2(g)in the presence of thiolate produces its [2Fe-2S] analogue, [Fe2S2(SPhF)4]2−(2), at room temperature. The cluster conversion of1to2can also be achieved by employing disulfide as an oxidant under the same reaction conditions. The [4Fe-4S] to [2Fe-2S] cluster conversion by O2was found to be significantly faster than that by disulfide, while the reaction with disulfide produced higher yields of2.