Fragmentation Behavior and Gas-Phase Structures of Cationized Glycosphingolipids in Ozone-Induced Dissociation Mass Spectrometry.

摘要: The role of cationization in the fragmentation behavior glycoconjugates is amply documented collisional activation techniques but remains less explored ozone-induced dissociation mass spectrometry (OzID-MS). OzID-MS has been used to elucidate location carbon-carbon double bonds unsaturated lipids. Previously, we demonstrated structural analysis glycosphingolipids using by mass-selecting [M+Na]+ adduct for fragmentation. In this work, aimed examine effect different adducts, namely [M+Na]+, [M+Li]+, and [M+H]+ on a representative glycosphingolipid, LacCer d18:1/18:1(9Z). Our data show that primarily undergoes dehydration followed collision-induced dissociation-like loss headgroup, while [M+Li]+ dissociate at albeit with slightly intensities resulting fragments. Using molecular mechanics theoretical calculations semiempirical level, report first time gas-phase structure cationized glycosphingolipids, which helps rationalize observed bond cleavage. findings highlight type adducts can influence ion subsequently affect their OzID-MS. This study contributes growing body knowledge structures ionized lipids have potential be extended other more complex glycoconjugates.