Metal catalyzed oxidation of tyrosine residues by different oxidation systems of copper/hydrogen peroxide.
Metal-catalysed oxidation (MCO) reactions result in the formation of reactive oxygen species (ROS) in biological systems. These ROS cause oxidative stress that contributes to a number of pathological processes leading to a variety of diseases. Tyrosine is one residue that is very susceptible to oxidative modification and the formation of dityrosine (DT) and 3,4-dihydroxyphenylalanine (DOPA) have been widely reported in a number of diseases. However, the mechanisms of MCO of tyrosine in biological systems are poorly understood and require further investigation. In this study we investigated the mechanism of DT and DOPA formation by MCO using N-acetyl tyrosine ethyl ester as a model for tyrosine in proteins and peptides. The results showed that DT formation could be observed upon Cu2+/H2O2 oxidation at pH 7.4. Our results indicate that it is unlikely to be via Fenton chemistry since Cu+/H2O2 oxidative conditions did not lead to the formation of DT.
Ali
Feda E
FE
School of Chemistry, University of Melbourne, Melbourne, VIC 3010, Australia.
Barnham
Kevin J
KJ
Barrow
Colin J
CJ
Separovic
Frances
F
D002851:Chromatography, High Pressure Liquid; D003300:Copper / Q000737:chemistry*; D004295:Dihydroxyphenylalanine / Q000737:chemistry / Q000378:metabolism; D006735:Horseradish Peroxidase / Q000378:metabolism; D006861:Hydrogen Peroxide / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D010084:Oxidation-Reduction; D013050:Spectrometry, Fluorescence; D021241:Spectrometry, Mass, Electrospray Ionization; D013056:Spectrophotometry, Ultraviolet; D014443:Tyrosine / Q000031:analogs & derivatives* / Q000737:chemistry* / Q000378:metabolism*
D014443:Tyrosine; D004295:Dihydroxyphenylalanine; D003300:Copper; C007651:ethyl N-alpha-acetyl-tyrosinate; D006861:Hydrogen Peroxide; C007543:dityrosine; D006735:Horseradish Peroxidase