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Charge-remote fragmentations are energy-dependent processes

C Cheng1, E Pittenauer, M L Gross

  • 1Department of Chemistry, Washington University, St. Louis, Missouri, USA.

Journal of the American Society for Mass Spectrometry
|August 6, 1998
PubMed
Summary
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Charge-remote fragmentations (CRFs) in lipids are complex. Different ionization methods yield distinct fragmentation patterns, influenced by internal energy and applied energies, revealing multiple simultaneous pathways.

Area of Science:

  • Analytical Chemistry
  • Mass Spectrometry
  • Lipidomics

Background:

  • Charge-remote fragmentations (CRFs) are crucial for analyzing lipids.
  • Previous studies indicate complex and unresolved mechanisms and energetics of CRFs.

Purpose of the Study:

  • To investigate the fragmentation mechanisms of tristearoylglycerol and fatty acids using different ionization techniques.
  • To elucidate the factors influencing CRF pathways and product ion distributions.

Main Methods:

  • Utilizing fast atom bombardment (FAB) and electrospray ionization (ESI) mass spectrometry.
  • Analyzing product ions from tristearoylglycerol, stearic acid, and nervonic acid.

Main Results:

  • FAB-produced ions yielded one series of product ions (CnH2n + 2 losses).

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  • ESI-produced ions yielded two series of product ions (CnH2n + 2 and CnH2n + 1 losses).
  • Multiple fragmentation pathways operate simultaneously in CRFs.

    • Conclusions:

    • CRF mechanisms are intricate and depend on ionization methods.
    • The internal energy of the molecule and applied ionization/activation energies dictate preferred fragmentation pathways (CnH2n + 1 vs. CnH2n + 2 losses).