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In-depth structural characterization of phospholipids by pairing solution photochemical reaction with charge inversion ion/ion chemistry

  • Elissia T. Franklin
  • Stella K. Betancourt
  • Caitlin E. Randolph
  • Scott A. McLuckey
  • Yu Xia
Research Paper
Part of the following topical collections:
  1. Young Investigators in (Bio-)Analytical Chemistry

Abstract

Shotgun lipid analysis based on electrospray ionization-tandem mass spectrometry (ESI-MS/MS) is increasingly used in lipidomic studies. One challenge for the shotgun approach is the discrimination of lipid isomers and isobars. Gas-phase charge inversion via ion/ion reactions has been used as an effective method to identify multiple isomeric/isobaric components in a single MS peak by exploiting the distinctive functionality of different lipid classes. In doing so, fatty acyl chain information can be obtained without recourse to condensed-phase separations or derivatization. This method alone, however, cannot provide carbon–carbon double bond (C=C) location information from fatty acyl chains. Herein, we provide an enhanced method pairing photochemical derivatization of C=C via the Paternò–Büchi reaction with charge inversion ion/ion tandem mass spectrometry. This method was able to provide gas-phase separation of phosphatidylcholines and phosphatidylethanolamines, the fatty acyl compositions, and the C=C location within each fatty acyl chain. We have successfully applied this method to bovine liver lipid extracts and identified 40 molecular species of glycerophospholipids with detailed structural information including head group, fatty acyl composition, and C=C location.

Graphical Abstract

Keywords

Lipidomics The Paternò–Büchi reaction Unsaturated lipid Charge inversion Mass spectrometry 

Notes

Funding information

This research was supported by the National Institutes of Health (R01GM118484 to Y. X. and GM R37-45372 to S. A. M.) and Sciex.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

216_2018_1537_MOESM1_ESM.pdf (758 kb)
ESM 1 (PDF 758 kb)

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of ChemistryPurdue UniversityWest LafayetteUSA
  2. 2.Department of ChemistryTsinghua UniversityBeijingChina

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