Free-Radical-Initiated Phospholipid Oxidations at the Air-Water Interface: The Oxidation of Unsaturated and Saturated Fatty Acid Chains.

Lipid oxidations initiated by free radicals are usually considered to undergo peroxidation, a chain process starting with hydrogen abstraction by an initiator, followed by O2 uptake. While this peroxidation mechanism is widely accepted and sometimes taken for granted, here we provide evidence of the oxidation of both of the unsaturated and saturated fatty acid chains in phospholipids initiated by photoinitiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide (TMDPO) at the air-water interface, and no peroxidation products are observed in these reactions. A unique field-induced droplet ionization mass spectrometry (FIDI-MS) methodology which is capable of the selective online sampling of monolayers of molecules that reside at the air-water interface is employed to detect the products. We have shown that the double bonds on the oleyl chains of the lipids are first oxidized into epoxides, after which other saturated carbon atoms are oxidized into carbonyl groups. We anticipate that this work will draw more attention to the complexity of the lipid oxidation chemistry initiated by free radicals.