Premium
Gas chromatography chemical ionization mass spectrometry of prostaglandin F α cyclic boronate derivatives
Author(s) -
Smith Andrew G.,
Brooks Charles J. W.
Publication year - 1977
Publication title -
biomedical mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0306-042X
DOI - 10.1002/bms.1200040413
Subject(s) - chemistry , trimethylsilyl , electron ionization , chemical ionization , mass spectrum , gas chromatography , fragmentation (computing) , ion , mass spectrometry , cyclohexane , ionization , prostaglandin , polyatomic ion , medicinal chemistry , analytical chemistry (journal) , organic chemistry , chromatography , computer science , operating system , biochemistry
The electron impact mass spectra of prostaglandins F 1α , F 2α and F 3α methyl ester cyclic 9,11‐methane‐, n ‐butane‐, cyclohexane‐ and benzeneboronate 15‐trimethylsilyl ethers show base peaks corresponding to [M – (C‐16—C‐20)] + , i.e. [M ‐ 71] + for prostaglandins F 1α and F 2α but [M ‐ 69] + for prostaglandin F 3α yielding identical ions in the latter two cases. Derivatives of prostaglandin F 2α and F 3α are difficult to separate by gas chromatography, so that the use of this ion type for single ion monitoring of either prostaglandin (as has been reported) is ambiguous. The chemical ionization mass spectra of these cyclic boronates, however, show distinctive base peaks for prostaglandins F 1α , F 2α and F 3α at m / e 317, 315 and 313 respectively, corresponding to [M ‐ RBO 2 H 2 ‐ TMSO] + . Fragmentation patterns have been investigated by the use of [3,3,4,4‐ 2 H 4 ]prostaglandin F 2α and by the formation of [ 2 H 9 ]trimethylsilyl ethers and a [ 2 H 3 ]methyl ester. Cleavage of the C‐15—C‐16 bond is of minor importance under chemical ionization conditions. The possible value of the [M ‐ RBO 2 H 2 – TMSO] + ions for single ion monitoring is explored: specificity is aided by the formation of the same ions from a series of boronates of characteristic retention indices.