Biomimetic nitration of the linoleic acid metabolite 13-hydroxyoctadecadienoic acid: isolation and spectral characterization of novel chain-rearranged epoxy nitro derivatives.
Nitration of unsaturated fatty acids is a (patho)physiologically important pathway of lipid modification induced by nitric oxide-derived species. We report herein on the unexpected chain rearrangement undergone by (13S,9Z,11E)-13-hydroxyoctadeca-9,11-dienoic acid (1), a linoleic acid metabolite, when exposed to nitrating agents of biological relevance. At pH 7.4 and at room temperature, reaction of 1 with peroxynitrite (ONOO-) as well as Fe2+-EDTA/H2O2/NO2- and horseradish peroxidase/H2O2/NO2- led to the formation of two nitration products, which could be isolated as the methyl esters and were identified as diastereoisomeric methyl (12S)-10,11-epoxy-12-hydroxy-9-nitromethylheptadecanoates by extensive 1H, 13C, 15N NMR and MS analysis.
Manini
Paola
P
Department of Organic Chemistry and Biochemistry, University of Naples Federico II, Via Cintia 4, Naples, Italy.
Camera
Emanuela
E
Picardo
Mauro
M
Napolitano
Alessandra
A
d'Ischia
Marco
M
D032701:Biomimetics; D002851:Chromatography, High Pressure Liquid; D008401:Gas Chromatography-Mass Spectrometry; D006735:Horseradish Peroxidase / Q000378:metabolism; D008041:Linoleic Acids / Q000737:chemistry* / Q000378:metabolism; D009574:Nitro Compounds / Q000737:chemistry* / Q000378:metabolism; D019906:Nuclear Magnetic Resonance, Biomolecular; D030421:Peroxynitrous Acid / Q000737:chemistry
D008041:Linoleic Acids; D009574:Nitro Compounds; D030421:Peroxynitrous Acid; C024348:13-hydroxy-9,11-octadecadienoic acid; D006735:Horseradish Peroxidase