Journal
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
Volume 13, Issue 6, Pages 680-695Publisher
ELSEVIER SCIENCE INC
DOI: 10.1016/S1044-0305(02)00362-8
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Funding
- NCRR NIH HHS [P41-RR-00954] Funding Source: Medline
- NHLBI NIH HHS [P01-HL-57-278] Funding Source: Medline
- NIDDK NIH HHS [R37-DK-34388, P60-DK-20579] Funding Source: Medline
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We applied electrospray ionization (ESI) tandem quadrupole mass spectrometry to establish the fragmentation pathways of ceramides under low energy collisional-activated dissociation (CAD) by studding more than thirty compounds in nine subclasses. The product-ion spectra of the [M + Li](+) ions of ceramides contain abundant fragment ions that identify the fatty acyl substituent and the long-chain base (LCB) of the molecules, and thus, the structure of ceramides can be easily determined. Fragment ions specific to each ceramide subclasses are also observed. These feature ions permit differentiation among different ceramide subclasses. The ion series arising from the classical C-C bond cleavages that were reported in the fast-atom bombardment (FAB)-high energy tandem mass spectrometry is not observable; however, the product-ion spectra contain multiple fragment ions informative for structural characterization and isomer identification. We also investigated the tandem mass spectra of the fragment ions generated by in-source CAD (pseudo-MS3) and of the deuterium-labeling molecular species obtained by H/D exchange to support the ion structure assignments and the proposed fragmentation pathways that lead to the ion formation. (J Am Soc Mass Spectrom 2002, 13, 680-695) (C) 2002 American Society for Mass Spectrometry.
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