title: Reaction of superoxide radicals with glycosaminoglycan chloramides: a kinetic study.
abstract: Hypochlorous acid and its acid-base counterpart, hypochlorite ions, produced under inflammatory conditions, may produce chloramides of glycosaminoglycans, perhaps through the binding of myeloperoxidase directly to the glycosaminoglycans. The N-Cl group in the chloramides is a potential target for reducing species such as Cu(I) and superoxide radicals. Laser flash photolysis has been used here to obtain, for the first time, the rate constants for the direct reaction of superoxide radicals with the chloramides of hyaluronan and heparin. The rate constants were in the range 2.2-2.7 × 10(3)M(-1)s(-1). The rate constant for the reaction with the amino acid taurine was found to be much lower, at 3.5-4.0 × 10(2)M(-1)s(-1). This demonstration that superoxide anion radicals react directly with hyaluronan and heparin chloramides may support the mechanism first proposed by M.D. Rees et al. (Biochem. J.381, 175-184, 2004) for an efficient fragmentation of these glycosaminoglycans in the extracellular matrix under inflammatory conditions.
authors.affiliation: Faculty of Health and Social Sciences, Leeds Metropolitan University, Leeds LS1 3HE, UK. Electronic address: b.parsons@leedsmet.ac.uk.
authors.forename: B J
authors.initials: BJ
authors.lastname: Parsons
authors.affiliation: Faculty of Health and Social Sciences, Leeds Metropolitan University, Leeds LS1 3HE, UK.
authors.forename: S
authors.initials: S
authors.lastname: Sibanda
authors.affiliation: Faculty of Life Science, Manchester Institute of Biotechnology, Manchester M1 7DN, UK.
authors.forename: D J
authors.initials: DJ
authors.lastname: Heyes
authors.affiliation: Faculty of Health and Social Sciences, Leeds Metropolitan University, Leeds LS1 3HE, UK.
authors.forename: A W J
authors.initials: AW
authors.lastname: Paterson
mesh_terms: D003300:Copper / Q000737:chemistry; D045304:Cytochromes c / Q000737:chemistry; D006025:Glycosaminoglycans / Q000737:chemistry*; D007700:Kinetics; D010782:Photolysis; D013481:Superoxides / Q000737:chemistry*; D013654:Taurine / Q000031:analogs & derivatives / Q000737:chemistry
chemical_list: D006025:Glycosaminoglycans; D013481:Superoxides; D013654:Taurine; C043410:N-chlorotaurine; D003300:Copper; D045304:Cytochromes c
keywords: Chloramide; Extracellular matrix; Free radicals; Glycosaminoglycan; Kinetics; Laser flash photolysis; Superoxide