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High‐performance liquid chromatography/thermospray mass spectrometry of some prostaglandins of the F series
Author(s) -
Abián J.,
Gelpí E.
Publication year - 1995
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1190300412
Subject(s) - chemistry , thermospray , mass spectrum , mass spectrometry , ion , moiety , chromatography , deuterium , polyatomic ion , fragmentation (computing) , hydrolysis , detection limit , column chromatography , analytical chemistry (journal) , stereochemistry , organic chemistry , tandem mass spectrometry , selected reaction monitoring , physics , quantum mechanics , computer science , operating system
Thermospray (TSP) mass spectra and chromatographic characteristics of the prostanoids PGF 2α , 6‐keto‐PGF 1α , 2,3‐dinor‐6‐keto‐PGF 1α , and their methyl esters and methoximes are reported. The spectra of these compounds are dominated by ions of the type [M + H + x NH 3 ‐ n H 2 O] + in the positive‐ion mode and [M ‐ H + x AcOH – n H 2 O] − in the negative‐ion mode ( n ranges from 0–4 and x is 0 or 1). The relative abundances of these ions depend on the particular structure, source and interface temperatures and eluent composition. In addition, these compounds show losses of 44 mass units, mainly due to the loss of the C‐10–C‐11 moiety, as demonstrated by deuterium labelling of PGF 2α . Methoximated derivatives of 6‐keto‐PGF 1α also show low‐abundance ions due to fragmentation in the position α to the methoxime group. The liquid‐phase equilibria of tautomers of 2,3‐dinor‐6‐keto‐PGF 1α or products thereof which direct its particular chromatographic behavior, can be effectively blocked by methoximation of the keto group thus improving its detectability. Detection limits of 20 ng on‐column may be obtained for this derivative. Adsorption and hydrolysis in the interface are the principal factors responsible for this relatively high detection limit.