Preparation and tandem mass spectrometric analyses of deuterium-labeled cysteine-containing leukotrienes

Leukotrienes (LT) C4, E4 and N-acetyl-E4, their respective monomethyl esters and 14,15-2H2 analogs have been synthesized. The collisionally activated decompositions of the [M + H]+ and [M - H]- ions formed by fast atom bombardment (FAB) have been studied by tandem mass spectrometry using a hybrid se...

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Bibliographic Details
Published inBiomedical & environmental mass spectrometry Vol. 19; no. 8; p. 465
Main Authors Raftery, M J, Thorne, G C, Orkiszewski, R S, Gaskell, S J
Format Journal Article
LanguageEnglish
Published England 01.08.1990
Subjects
Cysteine - analysis
Cysteine - chemistry
Deuterium
Indicators and Reagents
Isotope Labeling
Mass Spectrometry
SRS-A - analysis
SRS-A - chemistry
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Summary:Leukotrienes (LT) C4, E4 and N-acetyl-E4, their respective monomethyl esters and 14,15-2H2 analogs have been synthesized. The collisionally activated decompositions of the [M + H]+ and [M - H]- ions formed by fast atom bombardment (FAB) have been studied by tandem mass spectrometry using a hybrid sector/quadrupole instrument. Structurally informative product ion spectra were obtained for each analyte; the fragmentation pathways proposed are consistent with the parallel data obtained for labeled and derivatized species. Fragmentation of [M + H]+ ions occurs prominently via cleavage of the thioether linkage with charge retention on the cysteine-containing (predominant for LTC4) or lipid-derived (predominant for LTE4) moieties. More pronounced differences were observed between the fragmentations of [M - H]- ions derived from LTC4 and LTE4; the preference for charge retention, however, parallels that observed for the fragmentation of [M + H]+ ions. Selected ion monitoring during continuous-flow FAB mass spectrometric analysis of authentic LTC4 indicated a low-picogram detection limit.
ISSN:0887-6134
DOI:10.1002/bms.1200190804