Abstract:
:The oxidizing power of the thiyl radical (GS*) produced on oxidation of glutathione (GSH) was determined as the mid-point electrode potential (reduction potential) of the one-electron couple E(m)(GS*,H+/GSH) in water, as a function of pH over the physiological range. The method involved measuring the equilibrium constants for electron-transfer equilibria with aniline or phenothiazine redox indicators of known electrode potential. Thiyl and indicator radicals were generated in microseconds by pulse radiolysis, and the position of equilibrium measured by fast kinetic spectrophotometry. The electrode potential E(m)(GS*,H+/GSH) showed the expected decrease by approximately 0.06 V/pH as pH was increased from approximately 6 to 8, reflecting thiol/thiolate dissociation and yielding a value of the reduction potential of GS*=0.92+/-0.03 V at pH 7.4. An apparently almost invariant potential between pH approximately 3 and 6, with potentials significantly lower than expected, is ascribed at least in part to errors arising from radical decay during the approach to the redox equilibrium and slow electron transfer of thiol compared to thiolate.
journal_name
Arch Biochem Biophysjournal_title
Archives of biochemistry and biophysicsauthors
Madej E,Wardman Pdoi
10.1016/j.abb.2007.03.002subject
Has Abstractpub_date
2007-06-01 00:00:00pages
94-102issue
1eissn
0003-9861issn
1096-0384pii
S0003-9861(07)00123-3journal_volume
462pub_type
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