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Updated: Jun 9, 2025

Profiling Thiol Redox Proteome Using Isotope Tagging Mass Spectrometry
Published on: March 24, 2012
Proton-Coupled Electron Transfer between a Pendant Thiol and a Ferrous Dioxygen Adduct
Souvik Dinda1, Triparna Roy1, Soumya Samanta1
1School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A & B Raja S C Mullick Road, Kolkata, WB 700032, India.
Abstract:
The mechanism of thiol oxidation by O2, as catalyzed by ferrous porphyrins, is investigated by trapping intermediates of the transformation at low temperatures and subsequently characterizing them using continuous wave and pulsed electron paramagnetic resonance and resonance Raman spectroscopy. A Fe(III)-O2•- species is initially formed in an iron porphyrin with a pendant thiol functional group, which undergoes proton-coupled electron transfer (PCET) (not HAT) to form an Fe(III)-OOH species. Following O-O bond homolysis, this forms a Fe(IV)═O species with concomitant oxidation of the thiol to an RSO3H group.
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