Selected metastable peak monitoring: a new specific technique in quantitative gas chromatography mass spectrometry.

Using the combined electrostatic analyser-magnet scan facility of a double focusing mass spectrometer, the daughter ion peak for the fragmentation, [M-57]+ leads to [M-57-76]+, of a 5alpha-dihydrotestosterone tert-butyl-dimethylsilyl ether was monitored during gas chromatography mass spectrometry. The detection limit was approximately 20 pg. The steroid was detected by this method in an extract of human blood plasma.

Development of a procedure for the assay of an experimental steroid drug in dog plasma.

Studies of the estimation of 16alpha-cyano-3beta-cyclopentyloxypregn-5-en-20-one (an experimental drug) in dog plasma are described. Extraction using a salt/solvent pair (ammonium carbonate/ethyl acetate) is followed by a rapid chromatographic procedure employing Lipidex 5000, which affords a substantially purified fraction. After preparation of the t-butyldimethylsilyloxime, quantification of the drug is performed by selected ion monitoring.

Gas-liquid chromatography-mass spectrometry of phospholipid mixtures after enzymic hydrolysis.

Gas-liquid chromatography-mass spectrometry (GLC-MS), employing an open-tubular Silanox-type glass column, has been applied to the products of phospholipase C hydrolysis of natural and synthetic phospholipid mixtures. The materials studied were egg lysolecithin, synthetic L-alpha-l-stearoyl-2-oleoyl lecithin, bovine brain sphingomyelin, and phospholipids derived from human arterial tissue. l-Monoglycerides and ceramides were analysed as methaneboronates, and 1,2-diglycerides as trimethylsilyl ethers.

Applications of boronate derivatives in the study of ceramides by gas-liquid chromatography-mass spectrometry.

Methaneboronate derivatives of ceramides possess excellent gas-liquid chromatographic properties and give informative mass spectra. Molecular ions, present at high abundance where an unsaturated acyl substituent is present, are accompanied in the electron impact mass spectra by fragment ions which denote the acyl group and long-chain base. In the gas-liquid chromatographic-mass spectrometric analyses of natural ceramides, as methaneboronate derivatives, the properties of open-tubular columns are exploited to give good separations in moderate analysis times.

Trimethylsilyl group migration during electron impact and chemical ionization mass spectrometry of the trimethylsilyl ethers of 20-hydroxy-5alpha-pregnan-3-ones and 20-hydroxy-4-pregnen-3-ones.

The electron impact and chemical ionization (isobutane) mass spectra of the TMS derivatives of 20-hydroxy-5alpha-pregnan-3-ones and 20-hydroxy-4-pregnen-3-ones include ions [M--44]+-attributable to loss of a CH3CHO fragment from C-17 with migration of the TMS group to the charge-retaining fragment. Mass spectra of isotopically labelled ([3-18O], [20-18O] and [2H9-TMS]) analogues are consistent with this mechanism; [2H9-TMS] labelling further indicates that subsequent loss of a methyl group from [M--44]+-ions does not involve the TMS group. Corresponding ions are not observed at significant abundance in the spectra of 20beta-trimethylsilyloxy-5alpha-pregnane and 20beta-trimethylsilyloxy-4-pregnen-3-one 3-O-methyloxime.

New derivatives for the analysis of sphingosine long-chain bases by gas-liquid chromatography-mass spectrometry.

Cyclic derivatives formed by reaction of sphingosines with methane-, n-butane- and benzeneboronic acid have been examined by gas-liquid chromatography (GLC) and by combined GLC-mass spectrometry (MS). Analogous compounds have also been studied, in which the amino group has been protected, for example as an acetone Schiff base or N,N-dimethylaminomethylene derivative. Phytosphingosine (4D-hydroxysphinganine) yielded bis-alkaneboronates.