In situ formation of C-glycosides during electrospray ionization tandem mass spectrometry of a series of synthetic amphiphilic cholesteryl polyethoxy neoglycolipids containing N-acetyl-D-glucosamine

  • Joseph Banoub
  • Paul Boullanger
  • Dominique Lafont
  • Alejandro Cohen
  • Anas El Aneed
  • Elizabeth Rowlands
Short Communication

Abstract

In this communication, the structural analysis of six synthetic O-Linked amphiphilic cholesteryl polyethoxy neoglycolipids containing N-acetyl-D-glucosamine was performed by electrospray ionization mass spectrometry in the positive ion mode, with a QqTOF-MS/MS hybrid instrument. The MS/MS analyses provided evidence for the “in situ” formation, in the collision cell of the tandem mass spectrometer, of an unexpected and unique [C-glycoside]+ product ion, resulting from an ion-molecule reaction between the N-acetyl-D-glucosamine oxonium ion and the neutral cholesta-3,5-diene molecule. Quasi MS3 analysis of this ion resulted in the dissociation of the precursor [C-glycoside]+ ion, which produced the expected third generation N-acetyl-D-glucosamine oxonium and the protonated cholesta-3,5-diene product ions.

References

  1. 1.
    Kemoun, R.; Gelhausen, M.; Besson, F.; Lafont, D.; Buchet, R.; Boullanger, P.; Roux, B. Interactions of Egg Yolk Phosphatidylcholine with Cholesteryl Polyethoxy Neoglycolipids Containing N-Acetyl-D-Glucosamine. J.Mol. Struct. 1998, 10, 395–404.Google Scholar
  2. 2.
    Lafont, D.; Boullanger, P.; Chierici, S.; Gelhausen, M.; Roux, B. Cholesteryl Polyethoxyethylene Glycols as D-Glucosamine Anchors into Phospholipid Bilayers. New J. Chem. 1996, 20, 1093–1101.Google Scholar
  3. 3.
    Duffels, A.; Green, L. G.; Ley, S. V.; Miller, A. D. Synthesis of High-Mannose Type Neoglycolipids: Active Targeting of Liposomes to Macrophages in Gene Therapy. Chemistry 2000, 6, 1416–1430.CrossRefGoogle Scholar
  4. 4.
    Xu, Z.; Jayaseharan, J.; Marchant, R. E. Synthesis and Characterization of Oligomaltose-Grafted Lipids with Application to Liposomes. J. Colloid Interface Sci. 2002, 252, 57–65.CrossRefGoogle Scholar
  5. 5.
    Perouzel, E.; Jorgensen, M. R.; Keller, M.; Miller, A. D. Synthesis and Formulation of Neoglycolipids for the Functionalization of Liposomes and Lipoplexes. Bioconjug. Chem. 2003, 14, 884–898.CrossRefGoogle Scholar
  6. 6.
    El Aneed, A. Current Strategies in Cancer Gene Therapy. J. Control Release 2004, 94, 1–14.CrossRefGoogle Scholar
  7. 7.
    Hanessian, S.; Banoub, J. Innovations in Synthetic Carbohydrate Chemistry—Practical and Conceptual Approaches to Glycoside Synthesis. A. C. S. Symp. Ser. 1976, 39, 36–63.Google Scholar
  8. 8.
    Banoub, J.; Boullanger, P.; Lafont, D. Synthesis of Oligosaccharides of 2-Amino-2-Deoxy Sugars. Chem. Rev. 1992, 92(6), 1167–1195.CrossRefGoogle Scholar
  9. 9.
    Hanessian, S.; Luo, B. Stereocontrolled Glycosyl Transfer Reactions with Unprotected Glycosyl Donors. Chem. Rev. 2000, 100(12), 4443–4464.CrossRefGoogle Scholar
  10. 10.
    Vidasky, I.; Chorush, R. A.; Longevialle, P.; McLafferty, F. W. Funtional Group Migration in Ionized Long-Chain Compounds. J. Am. Chem. Soc. 1994, 116, 5865–5872.CrossRefGoogle Scholar
  11. 11.
    Cerda, B. A.; Horn, D. H. M.; Breuker, K.; McLafferty, F. W. Sequencing of Specific Copolymer Oligomers by Electron Capture-Dissociaton Mass Spectrometry. J. Am. Chem. Soc. 2002, 124, 9287–9291.CrossRefGoogle Scholar
  12. 12.
    Longevialle, P.; Lefèvre, O.; Mollova, N.; Bouchoux, G. Further Arguments Concerning a ‘Rotational Effect’ in the Unimolecular Fragmentations of Organic Ions in the Gas Phase. Rapid Commun. Mass Spectrom. 1998, 12, 57–60.CrossRefGoogle Scholar
  13. 13.
    Brüll, L. P.; Heerma, W.; Thomas-Oates, J. E.; Haverkamp, J.; Kovácik, V.; Kovác, P. Loss of Internal 1 → 6 Substituted Monosaccharide Residues and Per-O-Methylated Trisaccharides. J. Am. Soc. Mass Spectrom. 1997, 8, 43–49.CrossRefGoogle Scholar
  14. 14.
    Brüll, L. P.; Kovácik, V.; Thomas-Oates, J. E.; Heerma, W.; Haverkamp, J. Sodium-Cationized Oligosaccharides Do Not Appear to Undergo “Internal Residue Loss” Rearrangement Processes on Tandem Mass Spectrometry. Rapid Commun. Mass Spectrom. 1998, 12, 1520–1532.CrossRefGoogle Scholar
  15. 15.
    Allen, M. H.; Vestal, M. L. Design and Performance of a Novel Electrospray Interface. J. Am. Soc. Mass Spectrom. 1992, 3, 18–26.CrossRefGoogle Scholar
  16. 16.
    Beau, J. M.; Gallagher, T. Nucleophilic C-Glycosyl Donors for C-Glycoside Synthesis. Topics in Current Chemistry 1997, 187, 1–54.CrossRefGoogle Scholar

Copyright information

© American Society for Mass Spectrometry 2005

Authors and Affiliations

  • Joseph Banoub
    • 1
    • 4
  • Paul Boullanger
    • 3
  • Dominique Lafont
    • 3
  • Alejandro Cohen
    • 4
  • Anas El Aneed
    • 4
  • Elizabeth Rowlands
    • 4
  1. 1.Special Projects, Science BranchDepartment of Fisheries and OceansSt. John’sCanada
  2. 2.Northwest Atlantic Fisheries Center, Fisheries and Oceans CanadaMemorial University of NewfoundlandSt. John’sCanada
  3. 3.Laboratoire de Chimie Organique 2Université Claude BernardVilleurbanneFrance
  4. 4.Biochemistry DepartmentMemorial University of NewfoundlandSt. John’sCanada

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