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Capillary electrophoresis/mass spectrometry: a promising tool for the control of some physiologically hazardous compounds. I—Derivatives of 3‐quinuclidinol
Author(s) -
Bednář Petr,
Lemr Karel,
Barták Petr,
Ševčík Juraj,
Hlaváč Jan,
Stýskala Jakub,
Wiedermannová Iveta,
Stránský Zdeněk
Publication year - 2002
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.380
Subject(s) - chemistry , mass spectrometry , isopropyl , chromatography , capillary electrophoresis , alkyl , analytical chemistry (journal) , organic chemistry
A method based on the coupling of capillary electrophoresis with mass spectrometry (CE/MS) was developed for the monitoring of 3‐quinuclidinol and its four N ‐alkyl derivatives (methyl, ethyl, propyl and isopropyl derivatives). A fragmentation study (collision‐induced dissociation of ions in an ion trap) and optimization of the ion optics set‐up for CE/MS experiments using direct infusion of a methanolic solution of the standards into the mass spectrometer were carried out in advance. Molecular ions of all quaternary compounds and the quasi‐molecular ion [M + H] + of free 3‐quinuclidinol prevail in the mass spectra. In the MS/MS of propyl and isopropyl derivatives, the elimination of the alkyl chain dominates, leading to the ion at m / z 128. The fragmentation of the other compounds is more complex. Previous CE separation of the mixture of isobaric propyl and isopropyl derivatives is necessary for their unambiguous identification. A 10 m M ammonium acetate buffer (pH 4.0) is the optimum running electrolyte, allowing the CE separation of methyl, ethyl, propyl and isopropyl derivatives. A 0.5% (v/v) solution of acetic acid in methanol provides sufficient detection sensitivity when used as the sheath liquid. Limits of detection of 0.1 ppm for 3‐quinuclidinol and 0.05 ppm for quaternary derivatives were achieved under the optimum conditions. The optimized method was applied to the determination of 3‐quinuclidinol and related quaternary derivatives spiked into a sample of pond water. The experimental set‐up for CE/MS/MS was investigated, which strongly increases the identification capability of the technique. Copyright © 2002 John Wiley & Sons, Ltd.