Fragmentation behavior and gas-phase structures of cationized glycosphingolipids in ozone-induced dissociation mass spectrometry
| Autor: | Rodell C. Barrientos, Qibin Zhang |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
Double bond 010401 analytical chemistry Glycosphingolipid 010402 general chemistry Mass spectrometry 01 natural sciences Dissociation (chemistry) Article 0104 chemical sciences Adduct Ion Crystallography chemistry.chemical_compound Fragmentation (mass spectrometry) chemistry Structural Biology lipids (amino acids peptides and proteins) Spectroscopy Bond cleavage |
| Zdroj: | J Am Soc Mass Spectrom |
| Popis: | The role of cationization in the fragmentation behavior of glycoconjugates is amply documented in collisional activation techniques but remains less explored in ozone-induced dissociation mass spectrometry (OzID-MS). OzID-MS has been used to elucidate the location of carbon-carbon double bonds in unsaturated lipids. Previously, we demonstrated the structural analysis of unsaturated glycosphingolipids using OzID-MS by mass-selecting the [M+Na](+) adduct for fragmentation. In this work, we aimed to examine the effect of different adducts, namely [M+Na](+), [M+Li](+) and [M+H](+) on the OzID-MS fragmentation behavior of a representative unsaturated glycosphingolipid, LacCer d18:1/18:1(9Z). Our data show that [M+H](+) primarily undergoes dehydration followed by collision-induced dissociation-like loss of the headgroup, while [M+Li](+) and [M+Na](+) dissociate at the double bonds albeit with slightly different intensities of the resulting fragments. Using molecular mechanics and theoretical calculations at the semi-empirical level, we report for the first time the gas-phase structure of cationized glycosphingolipids, which helps to rationalize the observed bond cleavage. Our findings highlight that the type of adducts can influence gas-phase ion structure of glycosphingolipids and subsequently affect their fragmentation in OzID-MS. This study contributes to the growing body of knowledge on OzID-MS and gas-phase structures of ionized lipids and the findings have potential to be extended to other more complex glycoconjugates. |
| Databáze: | OpenAIRE |
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