Free radical oxidation of coriolic acid (13-(S)-hydroxy-9Z,11E- octadecadienoic acid)

P. Manini, E. Camera, M. Picardo, A. Napolitano, M. D'Ischia

Research output: Contribution to journalArticlepeer-review

Abstract

The reaction of (13S,9Z,11E)-13-hydroxy-9,11-octadecadienoic acid (1a), one of the major peroxidation products of linoleic acid and an important physiological mediator, with the Fenton reagent (Fe2+/EDTA/H 2O2) was investigated. In phosphate buffer, pH 7.4, the reaction proceeded with >80% substrate consumption after 4 h to give a defined pattern of products, the major of which were isolated as methyl esters and were subjected to complete spectral characterization. The less polar product was identified as (9Z,11E)-13-oxo-9,11-octadecadienoate (2) methyl ester (40% yield). Based on 2D NMR analysis the other two major products were formulated as (11E)-9,10-epoxy-13-hydroxy-11-octadecenoate (3) methyl ester (15% yield) and (10E)-9-hydroxy-13-oxo-10-octadecenoate (4) methyl ester (10% yield). Mechanistic experiments, including deuterium labeling, were consistent with a free radical oxidation pathway involving as the primary event H-atom abstraction at C-13, as inferred from loss of the original S configuration in the reaction products. Overall, these results provide the first insight into the products formed by oxidation of 1a with the Fenton reagent, and hint at novel formation pathways of the hydroxyepoxide 3 and hydroxyketone 4 of potential (patho)physiological relevance in settings of oxidative stress.

Original languageEnglish
Pages (from-to)161-171
Number of pages11
JournalChemistry and Physics of Lipids
Volume134
Issue number2
DOIs
Publication statusPublished - Apr 2005

Keywords

  • (1/2)D NMR
  • Deuterium labeling
  • Fenton reagent
  • Linoleic acid
  • Lipid peroxidation

ASJC Scopus subject areas

  • Biochemistry
  • Biophysics

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