Food Res Int 2026 May 31;238:119453. doi: 10.1016/j.foodres.2026.119453.

Elucidating the oxidation mechanism of phospholipid-based marine oils during storage: A new insight based on the analysis of oxidized phospholipids.

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Marine oils rich in phospholipid-bound polyunsaturated fatty acids are susceptible to oxidation; however, traditional evaluation indices poorly capture their complex degradation pathways. This study employed reversed-phase high-performance liquid chromatography-tandem mass spectrometry to profile oxidized phospholipids (oxPLs) in Antarctic krill oil (AKO), Sea cucumber oil (SCO), and Mussel oil (MO) during storage at 40 °C. Sixty-nine oxPL molecular species were identified, with compositional dynamics closely linked to native PL profiles: oxPCs dominated in AKO (accounting for 58.3% of total oxPLs), oxPEs in MO (62.7%), and oxidized plasmalogen-PEs in SCO (41.5%). The dihydroxy-to-epoxy oxPL ratio emerged as a robust kinetic indicator, exhibiting a logarithmic growth across all oils and enabling prediction of oxidation progression (R2 = 0.8305-0.8814). Pro-oxidation experiments revealed distinct transformation pathways: directly oxygenated intermediates (PL-OH and PL-OOH) peaked early (at 12-24 h) and then declined, while carboxyl-type oxPLs accumulated continuously, indicating that chain cleavage predominates at later stages. This work establishes oxPL profiling as a precise tool for mechanistic insight and quality control of PL-based marine oils.

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