Oxidation of glutathione by [Fe(IV)(O)(N4Py)](2+): characterization of an [Fe(III)(SG)(N4Py)](2+) intermediate.
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)(OH(2))(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.
Campanali
Ashley A
AA
Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, Michigan 48202, USA.
Kwiecien
Timothy D
TD
Hryhorczuk
Lew
L
Kodanko
Jeremy J
JJ
D056831:Coordination Complexes / Q000737:chemistry*; D005290:Ferric Compounds / Q000737:chemistry*; D005978:Glutathione / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction
D056831:Coordination Complexes; D005290:Ferric Compounds; D005978:Glutathione