Oxidation of Glutathione by [FeIV(O)(N4Py)]2+: Characterization of an [FeIII(SG)(N4Py)]2+ Intermediate

被引:17
作者
Campanali, Ashley A. [1 ]
Kwiecien, Timothy D. [1 ]
Hryhorczuk, Lew [1 ]
Kodanko, Jeremy J. [1 ]
机构
[1] Wayne State Univ, Dept Chem, Detroit, MI 48202 USA
关键词
NONHEME OXOIRON(IV) COMPLEX; MYOGLOBIN; CYTOCHROME-P-450; REACTIVITY; CHEMISTRY; LIGANDS; ENZYMES; MODELS; REDOX;
D O I
10.1021/ic100439n
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The mechanism of glutathione (GSH) oxidation by a nonheme ferryl species has been investigated. The reaction of [Fe-IV(O)(N4Py)](2+) (1) with GSH in an aqueous solution leads to the rapid formation of a green intermediate, characterized as the low-spin ferric complex [Fe-III(SG)(N4Py)](2+) (2) by UV-vis and electron paramagnetic resonance spectroscopies and by high-resolution time-of-flight mass spectrometry. Intermediate 2 decays to form the final products [Fe-II(OH2)(N4Py)](2+) and the disulfide GSSG over time. The overall reaction was fit to a three-step process involving rapid quenching of the ferryl by GSH, followed by the formation and decay of 2, which are both second-order processes.
引用
收藏
页码:4759 / 4761
页数:3
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