Nitrosylation of Nitric-Oxide-Sensing Regulatory Proteins Containing [4Fe-4S] Clusters Gives Rise to Multiple Iron-Nitrosyl Complexes
Nitrosylation of Nitric-Oxide-Sensing Regulatory Proteins Containing [4Fe-4S] Clusters Gives Rise to Multiple Iron-Nitrosyl Complexes
复制标题
含有 [4Fe-4S] 簇的一氧化氮感应调节蛋白的亚硝基化产生多个铁-亚硝酰基复合物
DOI：
10.1002/ange.201607033
复制
发表时间：
2016
影响因子：
--
通讯作者：
Serrano P
中科院分区：
文献类型：
--
作者：
Serrano P
蛋白质结合的铁硫 (Fe-S) 簇与一氧化氮 (NO) 的反应在 NO 介导的毒性和信号传导中发挥着关键作用。由于缺乏所形成的亚硝酰铁产物的性质信息，NO 与含有 Fe-S 簇的 DNA 调节蛋白的反应机制的阐明受到了阻碍。在此，我们报告了核共振振动光谱（NRVS）和密度泛函理论（DFT）计算，这些计算识别了WhiD和NsrR中的NO反应产物，这些调节蛋白使用[4Fe-4S]簇来感知NO。这项工作揭示了亚硝基化产生了多种结构上与 Roussin 红酯 (RRE, [Fe2(NO)4(Cys)2]) 和 Roussin 黑盐 (RBS, [Fe4(NO)7S3]) 相关的产物。在后一种情况下，NRVS 光谱 Fe−S 区域中缺乏 32S/34S 位移表明存在一个新物种，Roussin 黑酯 可以形成(RBE)，其中一个或多个硫化物配体被Cys硫醇盐取代。
The reaction of protein‐bound iron–sulfur (Fe‐S) clusters with nitric oxide (NO) plays key roles in NO‐mediated toxicity and signaling. Elucidation of the mechanism of the reaction of NO with DNA regulatory proteins that contain Fe‐S clusters has been hampered by a lack of information about the nature of the iron‐nitrosyl products formed. Herein, we report nuclear resonance vibrational spectroscopy (NRVS) and density functional theory (DFT) calculations that identify NO reaction products in WhiD and NsrR, regulatory proteins that use a [4Fe‐4S] cluster to sense NO. This work reveals that nitrosylation yields multiple products structurally related to Roussin's Red Ester (RRE, [Fe2(NO)4(Cys)2]) and Roussin's Black Salt (RBS, [Fe4(NO)7S3]. In the latter case, the absence of32S/34S shifts in the Fe−S region of the NRVS spectra suggest that a new species, Roussin's Black Ester (RBE), may be formed, in which one or more of the sulfide ligands is replaced by Cys thiolates.