glutathione-sulfonamide and methionine-sulfoxide

Electrophilic halogenating agents, including hypohalous acids and haloamines, oxidize free methionine and the N-terminal methionines of peptides and proteins (e.g., Met-1 of anti-inflammatory peptide 1 and ubiquitin) to produce dehydromethionine (a five-membered isothiazolidinium heterocycle). Amide derivatives of methionine are oxidized to the corresponding sulfoxide derivatives under the same reaction conditions (e.g., Met-3 of anti-inflammatory peptide 1). Other biological oxidants, including hydrogen peroxide and peroxynitrite, also produce only the corresponding sulfoxides. Hypothiocyanite does not react with methionine residues. We suggest that dehydromethionine may be a useful biomarker for the myeloperoxidase-induced oxidative stress associated with many inflammatory diseases.

Topics: Biomarkers; Glutathione; Glutathione Disulfide; Hydrogen Peroxide; Hypochlorous Acid; Magnetic Resonance Spectroscopy; Methionine; Models, Biological; Models, Chemical; Neutrophils; Oxidants; Oxidation-Reduction; Oxidative Stress; Peptide Fragments; Peroxidase; Proteins; Spectrometry, Mass, Electrospray Ionization; Sulfones; Thiazoles; Ubiquitin; Uteroglobin