Hypochlorous acid reacts with the N-terminal methionines of proteins to give dehydromethionine, a potential biomarker for neutrophil-induced oxidative stress.
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.
Department of Chemistry and Biochemistry, University of Oklahoma, Norman, Oklahoma 73019, USA.
Jennifer L
JL
Beal
Steven B
SB
Foster
Michael T
MT
Ashby
D015415:Biomarkers / Q000032:analysis / Q000737:chemistry; D005978:Glutathione / Q000031:analogs & derivatives / Q000737:chemistry; D019803:Glutathione Disulfide / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry; D006997:Hypochlorous Acid / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008715:Methionine / Q000031:analogs & derivatives / Q000737:chemistry*; D008954:Models, Biological; D008956:Models, Chemical; D009504:Neutrophils / Q000201:enzymology / Q000378:metabolism*; D016877:Oxidants / Q000737:chemistry; D010084:Oxidation-Reduction; D018384:Oxidative Stress; D010446:Peptide Fragments / Q000737:chemistry; D009195:Peroxidase / Q000378:metabolism; D011506:Proteins / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D013450:Sulfones / Q000737:chemistry; D013844:Thiazoles / Q000032:analysis / Q000737:chemistry*; D025801:Ubiquitin / Q000737:chemistry; D014598:Uteroglobin / Q000737:chemistry
D015415:Biomarkers; D016877:Oxidants; D010446:Peptide Fragments; D011506:Proteins; D013450:Sulfones; D013844:Thiazoles; D025801:Ubiquitin; C430906:glutathione sulfonamide; C064645:antiflammin P1; C057796:dehydromethionine; D006997:Hypochlorous Acid; D014598:Uteroglobin; D008715:Methionine; D006861:Hydrogen Peroxide; D009195:Peroxidase; D005978:Glutathione; D019803:Glutathione Disulfide; C013111:methionine sulfoxide