Oxidative modifications to
phospholipids (
OxPL) play a major role in modulating signaling events in
inflammation and
infection, and complete understanding on the induced
biological effects can only be understood based on knowledge of the oxidative motifs present. Specific neutral losses observed in tandem mass spectrometry data (LC-MS/MS) of primary peroxidation products in oxidized palmitoyl-arachidonoyl-
phosphatidylcholines (
OxPAPC) provide information on the prevailing structural motifs regarding the oxidized acyl
carbon chain, the nature of oxidized group and the site of
carbon oxidation. The higher hydrophobicity of hydroperoxides compared to di-hydroxy derivatives under reverse-phase conditions together with specific fragmentation patterns enabled the identification of 12 structurally different
OxPAPC structural (di-hydroxy and
hydroperoxide derivatives) and positional isomers as well as the presence of poly-hydroxy together with
isoprostanes derivatives. The fragmentation patterns described in quadrupole time-of-flight and linear ion trap instruments
complement the m/z value and retention time parameters in the identification of oxidative composition in
OxPAPC products becoming a valuable tool for the exploratory screening of oxidized
phosphatidylcholines in
OxPAPC extracts, distinction of native and modified PC isobaric structures in complex samples contributing to the increased understanding of redox lipidomics in
inflammation and
infection.