Mass spectrometric detection of iron nitrosyls, sulfide oxidation and mycothiolation during nitrosylation of the NO sensor [4Fe-4S] NsrR.

Mass spectrometric detection of iron nitrosyls, sulfide oxidation and mycothiolation during nitrosylation of the NO sensor [4Fe-4S] NsrR.
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NO传感器[4FE-4S] NSRR的亚硝基化过程中亚硝基素,硫化物氧化和霉菌性的质谱检测。

DOI:
10.1039/c8cc01339j
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发表时间:
2018-06-08
期刊:
Chemical communications (Cambridge, England)
影响因子:
--
通讯作者:
Le Brun NE
Le Brun NE
中科院分区:
其他
文献类型:
--
作者:
Crack JC ;Hamilton CJ ;Le Brun NE

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[4Fe-4S] NsrR亚硝基化形成的rre型铁亚硝基物种的鉴定。细菌一氧化氮(NO)感应转录调节因子NsrR结合一个[4Fe-4S]簇,使dna结合,从而抑制细胞的NO应激反应。暴露于NO后,该簇发生复杂的亚硝基化反应,产生铁-亚硝基物种的混合物,光谱研究表明,这种混合物类似于表征良好的低分子量二硝基铁配合物(DNIC)、Roussin红酯(RRE)和Roussin黑盐(RBS)。在这里,我们报告了质谱研究,使nsrr结合的rre型物种的明确鉴定,包括由簇硫化物氧化产生的过硫结合形式。在低分子量硫醇谷胱甘肽和真菌硫醇的存在下,易形成谷胱甘肽化和真菌硫醇化形式的NsrR。
Identification of RRE-type iron-nitrosyl species formed upon nitrosylation of [4Fe–4S] NsrR. The bacterial nitric oxide (NO)-sensing transcriptional regulator NsrR binds a [4Fe–4S] cluster that enables DNA-binding and thus repression of the cell's NO stress response. Upon exposure to NO, the cluster undergoes a complex nitrosylation reaction resulting in a mixture of iron-nitrosyl species, which spectroscopic studies have indicated are similar to well characterized low molecular weight dinitrosyl iron complex (DNIC), Roussin's Red Ester (RRE) and Roussin's Black Salt (RBS). Here we report mass spectrometric studies that enable the unambiguous identification of NsrR-bound RRE-type species, including a persulfide bound form that results from the oxidation of cluster sulfide. In the presence of the low molecular weight thiols glutathione and mycothiol, glutathionylated and mycothiolated forms of NsrR were readily formed.
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