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Electrospray and chemical ionization mass spectrometry of di‐ n ‐butyl sulfate. Unimolecular chemistry of its protonated form and quantification method by liquid chromatography/electrospray ionization tandem mass spectrometry
Author(s) -
Rondeau David,
Bouchoux Guy,
Vogel René,
Müller Etienne
Publication year - 2000
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/1097-0231(20000815)14:15<1410::aid-rcm40>3.0.co;2-s
Subject(s) - chemistry , electrospray ionization , mass spectrometry , electrospray , tandem mass spectrometry , protonation , ion , ionization , analytical chemistry (journal) , chromatography , chemical ionization , organic chemistry
Di‐ n ‐butyl sulfate (DNBS) has been studied by electrospray (ESI) and chemical (CI) ionization mass spectrometry. The use of methanol as solvent in electrospray ionization allows observation of relatively abundant [DNBS + CH 3 OH + H] + ions ( m/z 243) which upon collision dissociate to [DNBS + H] + ions ( m/z 211). In both ESI and CI experiments, it is found that [DNBS + H] + ions lead to m/z 113 daughter ions. The composition of this m/z 113 fragment ion and its mechanism of formation have been established by high resolution measurements and CID‐MIKE experiments. An ‘internal substitution’ reaction involving an ion‐neutral intermediate is proposed to explain the formation of a [C 8 H 17 ] + ion ( m/z 113) by loss of a H 2 SO 4 molecule. Finally, a LC/ESI‐MS/MS quantification method is proposed in which a detection limit of di‐ n ‐butyl sulfate in the ppm range is obtained. It is suggested that the quantification method might be extended to higher dialkyl sulfates. Copyright © 2000 John Wiley & Sons, Ltd.