Experimental evidence that electrospray-produced sodiated lysophosphatidyl ester structures exist essentially as protonated salts.

Sodiated lysoglycerophosphatidylethanolamine (LGPE) and lysoglycerophosphatidylcholine (LGPC) species dissociate under low collision energy by covalent bond cleavage resulting in product ions with either sodium retention or without sodium retention. For explaining these fragmentations, sodium chelation by heteroatoms (as charge-solvated structures) is often considered, and consequently, under keV collision conditions, sodium is "spectator" of cleavages (charge remote fragmentation). However, cleavage of such charge-solvated forms under low-energy conditions should result in sodium desolvation rather than covalent bond cleavage. In the present study, protonated salts are proposed as the main representative structures of the sodiated LGPE and LGPC forms. These structures are generated from sodiation of zwitterionic and betaine forms of LGPE and LGPC molecules, respectively. Experimental evidence to determine which structure is involved in the dissociations is provided, especially by comparing the dissociation of LGPL sodiated forms with that of sodiated polyethylene glycols. Energy-resolved mass spectrometry breakdown experiments were performed on a quadrupole time-of-flight instrument to demonstrate that both LGPE and LGPC sodiated forms exist as protonated salt structures. From such structures, proton migration by prototropy can result in different bond cleavages whereas the salt moiety remains spectator of these processes.