| Autor: |
Randolph CE; Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-2084, United States., Shenault DM; Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-2084, United States., Blanksby SJ; Central Analytical Research Facility, Institute for Future Environments, Queensland University of Technology, Brisbane, QLD 4000, Australia., McLuckey SA; Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-2084, United States. |
| Jazyk: |
angličtina |
| Zdroj: |
Journal of the American Society for Mass Spectrometry [J Am Soc Mass Spectrom] 2020 May 06; Vol. 31 (5), pp. 1093-1103. Date of Electronic Publication: 2020 Apr 14. |
| DOI: |
10.1021/jasms.0c00025 |
| Abstrakt: |
Ether lipids represent a unique subclass of glycerophospholipid (GPL) that possesses a 1- O -alkyl (i.e., plasmanyl subclass) or a 1- O -alk-1'-enyl (i.e., plasmenyl subclass) group linked at the sn -1 position of the glycerol backbone. As changes in ether GPL composition and abundance are associated with numerous human pathologies, analytical strategies capable of providing high-level structural detail are desirable. While mass spectrometry (MS) has emerged as a prominent tool for lipid structural elucidation in biological extracts, distinctions between the various isomeric forms of ether-linked GPLs have remained a significant challenge for tandem MS, principally due to similarities in the conventional tandem mass spectra obtained from the two ether-linked subclasses. To distinguish plasmanyl and plasmenyl GPLs, a multistage (i.e., MS n where n = 3 or 4) mass spectrometric approach reliant on low-energy collision-induced dissociation (CID) is required. While this method facilitates assignment of the sn -1 bond type (i.e., 1- O -alkyl versus 1- O -alk-1'-enyl), a composite distribution of isomers is left unresolved, as carbon-carbon double-bond (C=C) positions cannot be localized in the sn -2 fatty acyl substituent. In this study, we combine a systematic MS n approach with two unique gas-phase charge inversion ion/ion chemistries to elucidate ether GPL structures with high-level detail. Ultimately, we assign both the sn -1 bond type and sites of unsaturation in the sn -2 fatty acyl substituent using an entirely gas-phase MS-based workflow. Application of this workflow to human blood plasma extract permitted isomeric resolution and in-depth structural identification of major and, in some cases, minor isomeric contributors to ether GPLs that have been previously unresolved when examined via conventional methods. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
|
