Direct Mass Spectrometric Analysis of Ozonides: Application to Unsaturated Glycerophosphocholine Lipids

Abstract

The reaction of ozone with double bonds present in glycerophosphocholine lipids results in formation of ozonides that can be directly analyzed by mass spectrometry as either positive or negative molecular ion species generated by electrospray ionization. Polyunsaturated fatty acyl groups esterified to the phospholipid yielded a mixture of ozonide species with the maximum number of ozone molecules added equal to the total number of double bonds. Ozonide decomposition resulted in omega-aldehyde and omega-carboxylic acid products as revealed by ESI-MS. Collisional activation of the ozone adducts for mono- and polyunsaturated phospholipids gave rise to fragment ions indicative of the position of the double bonds in these molecules. The major decomposition pathway for either positive or negative ozonide ion species involved charge remote fragmentation of the ozonide initiated by homolytic cleavage of the peroxide bridge followed by rearrangement to form the omega-aldehyde and omega-carboxylate acyl species. The reaction of ozone with phospholipids containing polyunsaturated fatty acyl groups is a useful method to probe the position of double bonds by electrospray ionization mass spectrometry.