Metal Ion-Mediated Pro-oxidative Reactions of Different Lipid Molecules:Revealed by Nontargeted Lipidomic Approaches

摘要

Unsaturated fatty acids are easily affected by metal ions,leading to the changes of their flavor,nutrition,and safety through lipid oxidation.Nevertheless,there is a lack of comprehensive evaluation of the pro-oxidative ability of different metal ions,which have different effects on different lipids.Thus,in this work,crude lipids extracted from abalone were incubated with different metal ions,and the comprehensive lipid oxidation products were analyzed by nontargeted lipidomics approaches using an ultra-high-performance liquid chromatography-Q-Exactive HF-X Orbitrap Mass Spectrometer(UPLC-Q-Exactive HF-X).Results showed that the overall pro-oxidative ability from strong to weak was Fe~(3+),Fe~(2+),Cu~(2+),Zn~(2+),Mn~(2+),Mg~(2+),Na~+,and K~+.Among th em,Fe and Fe~(2+) could promote the accumulation of oxidation intermediates and branched fatty acid esters of hydroxy fatty acids.Na~+,K~+,Cu~(2+),and Mg~(2+) could accelerate the oxidation of N-acyl efhanolamines and ceramides.K~+ and Na~+ had more influences on the free fatty acids than Zn~(2+) and Mn~(2+).Slow oxidation of triglyceride may be attributed to its long distance from the oil-water interface and the restriction of the polar headgroups of phospholipids on free radicals.