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


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).


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 



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)


  1. 1.
    Barber M, Bordoli RS, Sedgewick RD, Tyler AN (1981) Fast atom bombardment of solids (F.A.B.): a new source for mass spectrometry. J Chem Soc Chem Commun 325–327Google Scholar
  2. 2.
    Aberth W, Straub KM, Burlingame AL (1982) Secondary ion mass spectrometry with cesium ion primary beam and liquid target matrix for analysis of bioorganic compounds. Anal Chem 54:2029–2034CrossRefGoogle Scholar
  3. 3.
    Torgerson DF, Skowronski RP, MacFarlane RD (1974) A new approach to the analysis of non-volatile compounds. Biochem Biophys Res Commun 60:616–618CrossRefGoogle Scholar
  4. 4.
    Jensen NJ, Tomer KB, Gross ML (1986) Fast atom bombardment and tandem mass spectrometry of phosphatidylserine and phosphatidylcholine. Lipids 21:580–588CrossRefGoogle Scholar
  5. 5.
    Jensen NJ, Tomer KB, Gross ML (1987) FAB MS/MS for phosphatidylinositol, -glycerol, -ethanolamine and other complex phospholipids. Lipids 22:480–489CrossRefGoogle Scholar
  6. 6.
    Hayashi A, Matsubara T, Morita M, Kinoshita T, Nakamura T (1989) Structural analysis of choline phospholipids by fast atom bombardment mass spectrometry and tandem mass spectrometry. J Biochem 106:264–269Google Scholar
  7. 7.
    Chen S, Kirschner G, Traldi P (1990) Positive ion fast atom bombardment mass spectrometric analysis of molecular species of glycerophosphatidylserine. Anal Biochem 191:100–105CrossRefGoogle Scholar
  8. 8.
    Bryant DK, Orlando RC, Fenselau C, Sowder RC, Henderson LE (1991) Four-sector tandem mass spectrometric analysis of complex mixtures of phosphatidylcholines present in a human immunodeficiency virus preparation. Anal Chem 63:1110–1114CrossRefGoogle Scholar
  9. 9.
    Chen S, Li KW (1994) Structural analysis of underivatized and derivatized aminophospholipids and phosphatidic acid by positive ion liquid secondary ion and collisionally induced dissociation tandem mass spectrometry. J Biochem 116:811–817Google Scholar
  10. 10.
    Chen S (1997) Tandem mass spectrometric approach for determining structure of molecular species of aminophospholipids. Lipids 32:85–100CrossRefGoogle Scholar
  11. 11.
    Kim YH, Yoo JS, Kim MS (1997) Structural determination of fatty acyl groups of phospholipids by fast atom bombardment tandem mass spectrometry of sodium adduct molecular ions. Bull Korean Chem Soc 18:874–880Google Scholar
  12. 12.
    Pittenauer E, Schmid ER, Allmaier G, Puchinger L (1996) Sample preparation for the analysis of glycerophospholipids by matrix-assisted positive and negative ion 252Cf plasma desorption time-of-flight mass spectrometry. Eur Mass Spectrom 2:247–265CrossRefGoogle Scholar
  13. 13.
    Jensen NJ, Gross ML (1988) A comparision of mass spectrometric methods for structural determination and analysis of phospholipids. Mass Spectrom Rev 7:41–69CrossRefGoogle Scholar
  14. 14.
    Murphy RC, Harrison KA (1994) Fast atom bombardment mass spectrometry of phospholipids. Mass Spectrom Rev 13:57–75CrossRefGoogle Scholar
  15. 15.
    Cheng C, Gross ML (2000) Application and mechanisms of charge-remote fragmentations. Mass Spectrom Rev 19:398–420CrossRefGoogle Scholar
  16. 16.
    Fenwick GR, Eagles J, Self R (1983) Fast atom bombardment mass spectrometry of intact phospholipids and related compounds. Biomed Mass Spectrom 10:382–386CrossRefGoogle Scholar
  17. 17.
    Yamashita M, Fenn J (1984) Electrospray ion source. Another variation on the free-jet theme. J Phys Chem 88:4451–4459CrossRefGoogle Scholar
  18. 18.
    Tanaka K, Waki H, Ido Y, Akita S, Yoshida Y, Yoshida T (1988) Protein and polymer analyses up to m/z 100 000 by laser ionization time-of-flight mass spectrometry. Rapid Commun Mass Spectrom 2:151–153CrossRefGoogle Scholar
  19. 19.
    Karas M, Hillenkamp F (1988) Laser desorption ionization of proteins with molecular masses exceeding 10.000 daltons. Anal Chem 60:2299–2301CrossRefGoogle Scholar
  20. 20.
    Pittenauer E, Allmaier G (2009) The renaissance of high-energy CID for structural elucidation of complex lipids: MALDI-TOF/RTOF-MS of alkali cationized triacylglycerols. J Am Soc Mass Spectrom 20:1037–1047CrossRefGoogle Scholar
  21. 21.
    Pittenauer E, Allmaier G (2011) A universal product ion nomenclature for [M-H], [M + H]+ and [M + nNa-(n-1)H]+ (n = 1–3) glycerophospholipid precursor ions based on high-energy CID by MALDI-TOF/RTOF mass spectrometry. Int J Mass Spectrom 301:90–101CrossRefGoogle Scholar
  22. 22.
    Kubo A, Satoh T, Itoh Y, Hashimoto M, Tamura J, Cody RB (2013) Structural analysis of triacylglycerols by using a MALDI TOF/TOF system with monoisotopic precursor selection. J Am Soc Mass Spectrom 24:684–689CrossRefGoogle Scholar
  23. 23.
    Nishikawa K, Hashimoto M, Itoh Y, Hiroi S, Kusai A, Hirata F, Sakamoto T, Iwaya K (2014) Detection of changes in the structure and distribution map of triacylglycerols in fatty liver model by MALDI-SpiralTOF. FEBS Open Bio 4:179–184CrossRefGoogle Scholar
  24. 24.
    Shimma S, Kubo A, Satoh T, Toyoda M (2012) Detailed structural analysis of lipids directly on tissue specimens using a MALDI-SpiralTOF-reflectron TOF mass spectrometer. PLoS ONE 7:e37107CrossRefGoogle Scholar
  25. 25.
    Satoh T, Kubo A, Shimma S, Toyoda M (2013) Mass spectrometry imaging and structural analysis of lipids directly on tissue specimens by using a spiral orbit type tandem time-of-flight mass spectrometer, SpiralTOF-TOF. Mass Spectrom (Tokyo) 1(2):A0013Google Scholar
  26. 26.
    Stübiger G, Belgacem O, Rehulka P, Bicker W, Binder BR, Bochkov V (2010) Analysis of oxidized phospholipids by MALDI mass spectrometry using 6-aza-2-thiothymine together with matrix additives and disposable target surfaces. Anal Chem 82:5502–5510CrossRefGoogle Scholar
  27. 27.
    Belgacem O, Bowdler A, Brookhouse I, Brancia FL, Raptakis E (2006) Dissociation of biomolecules using a ultraviolet matrix-assisted laser desorption/ionisation time-of-flight/curved field reflectron tandem mass spectrometer equipped with a differential-pumped collision cell. Rapid Commun Mass Spectrom 20:1653–1660CrossRefGoogle Scholar
  28. 28.
    Angel PM, Spraggins JM, Baldwin HS, Caprioli R (2012) Enhanced sensitivity for high spatial resolution lipid analysis by negative ion mode matrix assisted laser desorption ionization imaging mass spectrometry. Anal Chem 84:1557–1564CrossRefGoogle Scholar
  29. 29.
    Hsu FF, Turk J (2000) Characterization of phosphatidylethanolamine as a lithiated adduct by triple quadrupole tandem mass spectrometry with electrospray ionization. J Mass Spectrom 35:596–606CrossRefGoogle Scholar

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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