The reaction of hyaluronic acid and its monomers, glucuronic acid and N-acetylglucosamine, with reactive oxygen species.
Synovial fluid is a approximately 0.15% (w/v) aqueous solution of hyaluronic acid (HA), a polysaccharide consisting of alternating units of GlcA and GlcNAc. In synovial fluid of patients suffering from rheumatoid arthritis, HA is thought to be degraded either by radicals generated by Fenton chemistry (Fe2+/H2O2) or by NaOCl generated by myeloperoxidase. We investigated the course of model reactions of these two reactants in physiological buffer with HA, and with the corresponding monomers GlcA and GlcNAc. meso-Tartaric acid, arabinuronic acid, arabinaric acid and glucaric acid were identified by GC-MS as oxidation products of glucuronic acid. When GlcNAc was oxidised, erythronic acid, arabinonic acid, 2-acetamido-2-deoxy-gluconic acid, glyceric acid, erythrose and arabinose were formed. NaOCl oxidation of HA yielded meso-tartaric acid; in addition, arabinaric acid and glucaric acid were obtained by oxidation with Fe2+/H2O2. These results indicate that oxidative degradation of HA proceeds primarily at glucuronic acid residues. meso-Tartaric acid may be a useful biomarker of hyaluronate oxidation since it is produced by both NaOCl and Fenton chemistry.
Jahn
M
M
Lehrstuhl Organische Chemie I, Universität Bayreuth, Germany.
Baynes
J W
JW
Spiteller
G
G
D000117:Acetylglucosamine / Q000737:chemistry*; D001089:Arabinose / Q000031:analogs & derivatives; D008401:Gas Chromatography-Mass Spectrometry; D005937:Glucaric Acid / Q000032:analysis; D020723:Glucuronic Acid / Q000737:chemistry*; D006801:Humans; D006820:Hyaluronic Acid / Q000737:chemistry* / Q000378:metabolism; D006861:Hydrogen Peroxide / Q000737:chemistry; D006997:Hypochlorous Acid / Q000737:chemistry; D007501:Iron / Q000737:chemistry; D007700:Kinetics; D017382:Reactive Oxygen Species; D013644:Tartrates / Q000032:analysis; D014574:Uronic Acids / Q000032:analysis
C045076:Fenton's reagent; D017382:Reactive Oxygen Species; D013644:Tartrates; D014574:Uronic Acids; D006997:Hypochlorous Acid; D020723:Glucuronic Acid; D006820:Hyaluronic Acid; D001089:Arabinose; D006861:Hydrogen Peroxide; D007501:Iron; D005937:Glucaric Acid; D000117:Acetylglucosamine; C029768:tartaric acid