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Analytical and Bioanalytical Chemistry

, Volume 407, Issue 17, pp 5079–5089 | Cite as

Collision-induced dissociation of aminophospholipids (PE, MMPE, DMPE, PS): an apparently known fragmentation process revisited

  • Ernst Pittenauer
  • Pavel Rehulka
  • Wolfgang Winkler
  • Günter AllmaierEmail author
Research Paper
Part of the following topical collections:
  1. Lipidomics

Abstract

A new type of low-mass substituted 4-oxazolin product ions of [M + H]+ precursor ions of aminophospholipids (glycerophosphatidylethanolamine, glycerophosphatidyl-N-methylethanolamine, glycerophosphatidyl-N,N-dimethylethanolamine, glycerophosphatidylserine) resulting from high-energy collision-induced dissociation (matrix-assisted laser desorption/ionization time-of-flight/reflectron time-of-flight mass spectrometry) and low-energy collision-induced dissociation (e.g., electrospray ionization quadrupole reflectron time-of-flight mass spectrometry) with accurate mass determination is described; these were previously misidentified as CHO-containing radical cationic product ions. The mechanism for the formation of these ions is proposed to be via rapid loss of water followed by cyclization to an 11-membered-ring transition state for the sn-1 fatty acid substituent and to a ten-membered-ring transition state for the sn-2 fatty acid substituent, and via final loss of monoacylglycerol phosphate, leading to substituted 4-oxazolin product ions. The minimum structural requirement for this interesting skeletal rearrangement fragmentation is an amino group linked to at least one hydrogen atom (i.e., ethanolamine, N-methylethanolamine, serine). Therefore, N,N-dimethylethanolamine derivates do not exhibit this type of fragmentation. The analytical value of these product ions is given by the fact that by post source decay and particularly high-energy collision-induced dissociation achieved via matrix-assisted laser desorption/ionization time-of-flight/reflectron time-of-flight mass spectrometry, the sn-2-related substituted 4-oxazolin product ion is always significantly more abundant than the sn-1-related one, which is quite helpful for detailed structural analysis of complex lipids. All other important product ions found are described in detail (following our previously published glycerophospholipid product ion nomenclature; Pittenauer and Allmaier, Int. J. Mass. Spectrom. 301:90–1012, 2011).

Keywords

High-energy collision-induced dissociation Matrix-assisted laser desorption/ionization time-of-flight/reflectron time-of-flight mass spectrometry Low-energy collision-induced dissociation Electrospray ionization quadrupole reflectron time-of-flight mass spectrometry Aminophospholipids Substituted 4-oxazolin product ions 

Notes

Acknowledgments

The authors thank Omar Belgacem and Matthew Openshaw (both from Shimadzu Kratos Analytical, Manchester, UK) for giving us the opportunity to acquire MALDI-MS spectra using the MALDI-7090 instrument. The desorption ESI/ESI/intermediate pressure MALDI ion mobility QRTOF mass spectrometer was made available by the UniInfra IV program (to G.A.) of the Austrian Federal Ministry of Science. The experiments performed in the Czech Republic were supported by the long-term organization plan (1011) from the Faculty of Military Health Sciences, University of Defence.

Supplementary material

216_2015_8470_MOESM1_ESM.pdf (409 kb)
ESM 1 (PDF 409 kb)

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Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  • Ernst Pittenauer
    • 1
  • Pavel Rehulka
    • 2
  • Wolfgang Winkler
    • 1
  • Günter Allmaier
    • 1
    Email author
  1. 1.Institute of Chemical Technologies and AnalyticsVienna University of TechnologyViennaAustria
  2. 2.Institute of Molecular Pathology, Faculty of Military Health SciencesUniversity of DefenseHradec KraloveCzech Republic

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