Formation of oligomeric alkenylperoxides during the oxidation of unsaturated fatty acids: an electrospray ionization tandem mass spectrometry study

authors	Villaverde, JJ; Santos, SAO; Maciel, E; Simoes, MMQ; Neto, CP; Domingues, MRM; Silvestre, AJD
nationality	International
journal	JOURNAL OF MASS SPECTROMETRY
author keywords	Fenton's and Fe2+; O2 systems; unsaturated fatty acids; oligomeric alkenylperoxides; oxidation; mass spectrometry
keywords	EPOXIDIZED VEGETABLE-OILS; LIQUID-LIQUID SYSTEMS; OXIRANE RING; HYDROPEROXIDES; DEGRADATION; IDENTIFICATION; MECHANISMS; CHEMISTRY; PRODUCTS; HYDROXY
abstract	This study reports the identification of oligomeric alkenylperoxides by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS2), during the oxidation of oleic, linoleic and linolenic acids with Fenton's (Fe2+/H2O2) and Fe2+/O2 systems. The reactions were followed by ferrous oxidation-xylenol orange method together with GC-MS and GC-FID, allowing to observe that both oxidation systems are different in terms of hydroperoxide evolution, probably due to the presence of different intermediate reactive species: perferryl ion and OH radical responsible for the decomposition of lipid hydroperoxides and formation of new compounds. The analysis of ESI-MS in the negative mode, obtained after oxidation of each fatty acid, confirmed the presence of the monomeric oxidation products together with other compounds at high mass region above m/z 550. These new ions were attributed to oligomeric structures, identified by the fragmentation pathways observed in the tandem mass spectra. Copyright (C) 2012 John Wiley & Sons, Ltd.
publisher	WILEY-BLACKWELL
issn	1076-5174
year published	2012
volume	47
issue	2
beginning page	163
ending page	172
digital object identifier (doi)	10.1002/jms.2047
web of science category	Biochemical Research Methods; Chemistry, Analytical; Spectroscopy
subject category	Biochemistry & Molecular Biology; Chemistry; Spectroscopy
unique article identifier	WOS:000300694100003