title: Oxidative damage of aromatic dipeptides by the environmental oxidants NO2˙ and O3.
abstract: Irreversible oxidative damage at both aromatic side chains and dipeptide linkage occurs in the aromatic N- and C-protected dipeptides 7-11 upon exposure to the environmental pollutants NO2˙ and O3. The reaction proceeds through initial oxidation of the aromatic ring by in situ generated NO3˙, or by NO2˙, respectively, which leads to formation of nitroaromatic products. The indole ring in Phe-Trp undergoes oxidative cyclization to a pyrroloindoline. An important reaction pathway for dipeptides with less oxidisable aromatic side chains proceeds through fragmentation of the peptide bond with concomitant acyl migration. This process is likely initiated by an ionic reaction of the amide nitrogen with the NO2˙ dimer, N2O4.
authors.affiliation: School of Chemistry and Bio21 Institute, ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, The University of Melbourne, 30 Flemington Road, Parkville, VIC 3010, Australia. uwille@unimelb.edu.au.
authors.forename: L F
authors.initials: LF
authors.lastname: Gamon
authors.forename: J M
authors.initials: JM
authors.lastname: White
authors.forename: U
authors.initials: U
authors.lastname: Wille
mesh_terms: D004151:Dipeptides / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009585:Nitrogen Dioxide / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry*; D010084:Oxidation-Reduction; D010126:Ozone / Q000737:chemistry*
chemical_list: D004151:Dipeptides; D005609:Free Radicals; D016877:Oxidants; D010126:Ozone; D009585:Nitrogen Dioxide