Characterization of iron dinitrosyl species formed in the reaction of nitric oxide with a biological Rieske center.

Characterization of iron dinitrosyl species formed in the reaction of nitric oxide with a biological Rieske center.
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DOI:
10.1021/ja106290p
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发表时间:
2010-12-29
影响因子:
15
通讯作者:
Lippard SJ
Lippard SJ
中科院分区:
化学1区
文献类型:
--
作者:
Tinberg CE;Tonzetich ZJ;Wang H;Do LH;Yoda Y;Cramer SP;Lippard SJ

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一氧化氮与半胱氨酸连接的铁硫簇蛋白的反应通常导致铁硫核心的分解和二亚硝酰铁络合物(DNIC)的形成。在这里,我们报告的第一个证据表明,DNIC也形成在NO与Rieske型[2Fe-2S]团簇反应。在用稍微过量的NO(g)或NO-产生剂S-亚硝基-N-乙酰基-D,L-藜芦胺(SNAP)和二乙胺NONOate(DEANO)处理来自假单胞菌属OX 1的甲苯/邻二甲苯单加氧酶(ToMOC)的组分C的Rieske蛋白时,[2Fe-2S]簇的吸收带消失,并被在367 nm处缓慢生长的新特征所取代。通过EPR、穆斯堡尔和NRVS光谱分析反应产物表明,反应的主要产物是硫醇根桥联的二铁四亚硝酰基物质,[Fe 2(μ-SCys)2(NO)4],其分子式为铁蛋白红酯(RRE),单核DNIC仅占亚硝酰基化铁的一小部分。用连二亚硫酸钠还原该RRE反应产物,产生在640和960 nm处具有吸收的单电子还原的胭脂红酯(rRRE)。这些结果表明,NO反应很容易与蛋白质中的Rieske中心,并建议双核RRE物种,而不是单核DNIC,可能是主要的铁二亚硝酰基物种负责在生物学中这样的系统中的一氧化氮的病理和生理作用。
Reactions of nitric oxide with cysteine-ligated iron-sulfur cluster proteins typically result in disassembly of the iron-sulfur core and formation of dinitrosyl iron complexes (DNICs). Here we report the first evidence that DNICs also form in the reaction of NO with Rieske-type [2Fe-2S] clusters. Upon treatment of a Rieske protein, component C of toluene/o-xylene monooxygenase (ToMOC) from Pseudomonas sp. OX1, with a slight excess of NO (g) or NO-generators S-nitroso-N-acetyl-D,L-pencillamine (SNAP) and diethylamine NONOate (DEANO), the absorbance bands of the [2Fe-2S] cluster are epxtinguished and replaced by a new feature that slowly grows in at 367 nm. Analysis of the reaction products by EPR, Mössbauer, and NRVS spectroscopy reveals that the primary product of the reaction is a thiolate-bridged diiron tetranitrosyl species, [Fe2(μ-SCys)2(NO)4] having a Roussin's red ester (RRE) formula, and that mononuclear DNICs account for only a minor fraction of nitrosylated iron. Reduction of this RRE reaction product with sodium dithionite produces the one-electron reduced Roussin's red ester (rRRE) having absorbtions at 640 and 960 nm. These results demonstrate that NO reacts readily with Rieske centers in protein and suggest that dinuclear RRE species, not mononuclear DNICs, may be the primary iron dinitrosyl species responsible for the pathological and physiological effects of nitric oxide in such systems in biology.
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发表时间: 2009-02-03
期刊: BIOCHEMISTRY
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影响因子: --
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