Dihydroperoxidation facilitates the conversion of lipids to aldehydic products via alkoxyl radicals

The mechanisms of formation of many aldehydic lipid oxidation products remain unclear, and the involvement of peroxyl radical additions in some cases was recently suggested. Here, the effect of α-tocopherol, a peroxyl radical trap, on the formation of aldehydic phospholipids from a phosphatidylcholine hydroperoxide was studied by electrospray ionization mass spectroscopy (ESI-MS). Based on the observed differential enhancement or suppression of formation of different aldehydes, new pathways are deduced for aldehyde formation via alkoxyl radicals derived from dihydroperoxy derivatives.