Formation of oligomeric alkenylperoxides during the oxidation of unsaturated fatty acids: an electrospray ionization tandem mass spectrometry study
Article first published online: 20 FEB 2012
Copyright © 2012 John Wiley & Sons, Ltd.
Journal of Mass Spectrometry
Volume 47, Issue 2, pages 163–172, February 2012
How to Cite
Villaverde, J. J., Santos, S. A. O., Maciel, E., Simões, M. M. Q., Neto, C. P., Domingues, M. R. M. and Silvestre, A. J. D. (2012), Formation of oligomeric alkenylperoxides during the oxidation of unsaturated fatty acids: an electrospray ionization tandem mass spectrometry study. J. Mass Spectrom., 47: 163–172. doi: 10.1002/jms.2047
- Issue published online: 20 FEB 2012
- Article first published online: 20 FEB 2012
- Manuscript Accepted: 12 DEC 2011
- Manuscript Revised: 9 DEC 2011
- Manuscript Received: 26 OCT 2011
- Fenton's and Fe2+/O2 systems;
- unsaturated fatty acids;
- oligomeric alkenylperoxides;
- mass spectrometry
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 © 2012 John Wiley & Sons, Ltd.