Biomimetic nitration of the linoleic acid metabolite 13-hydroxyoctadecadienoic acid: isolation and spectral characterization of novel chain-rearranged epoxy nitro derivatives

Paola Manini, Emanuela Camera, Mauro Picardo, Alessandra Napolitano, Marco d'Ischia

Research output: Contribution to journalArticle

Abstract

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.

Original languageEnglish
Pages (from-to)51-61
Number of pages11
JournalChemistry and Physics of Lipids
Volume151
Issue number1
DOIs
Publication statusPublished - Jan 2008

Fingerprint

Nitration
Biomimetics
Peroxynitrous Acid
Linoleic Acid
Horseradish Peroxidase
Metabolites
Unsaturated Fatty Acids
Edetic Acid
Nitric Oxide
Esters
Derivatives
Lipids
Temperature
Acids
Nuclear magnetic resonance
Carbon-13 Magnetic Resonance Spectroscopy
13-hydroxy-9,11-octadecadienoic acid

Keywords

  • Fenton reagent
  • Linoleic acid
  • Lipid peroxidation
  • Peroxynitrite

ASJC Scopus subject areas

  • Biochemistry
  • Biophysics

Cite this

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title = "Biomimetic nitration of the linoleic acid metabolite 13-hydroxyoctadecadienoic acid: isolation and spectral characterization of novel chain-rearranged epoxy nitro derivatives",
abstract = "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.",
keywords = "Fenton reagent, Linoleic acid, Lipid peroxidation, Peroxynitrite",
author = "Paola Manini and Emanuela Camera and Mauro Picardo and Alessandra Napolitano and Marco d'Ischia",
year = "2008",
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language = "English",
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T1 - Biomimetic nitration of the linoleic acid metabolite 13-hydroxyoctadecadienoic acid

T2 - isolation and spectral characterization of novel chain-rearranged epoxy nitro derivatives

AU - Manini, Paola

AU - Camera, Emanuela

AU - Picardo, Mauro

AU - Napolitano, Alessandra

AU - d'Ischia, Marco

PY - 2008/1

Y1 - 2008/1

N2 - 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.

AB - 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.

KW - Fenton reagent

KW - Linoleic acid

KW - Lipid peroxidation

KW - Peroxynitrite

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