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Comparative electron impact, chemical ionization and field desorption mass spectra of some thioether metabolites of acetaminophen
Author(s) -
Nelson S. D.,
Vaishnav Y.,
Kambara H.,
Baillie T. A.
Publication year - 1981
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.1200080604
Subject(s) - chemistry , field desorption , mass spectrometry , electron ionization , thioether , adduct , desorption , dissociation (chemistry) , fragmentation (computing) , fast atom bombardment , chemical ionization , reagent , ionization , analytical chemistry (journal) , ion , chromatography , organic chemistry , adsorption , computer science , operating system
The mass spectra of several thioether conjugates of the widely used analgesic, acetaminophen (4′‐hydroxyacetanilide), have been recorded under various ionization conditions. Conjugates were obtained from both in vitro and in vivo sources and purified by high performance liquid chromatography. Some standards were chemically synthesized. Of the thioethers examined, only the methylthio and mercapturic acid conjrgates provided parent ions under electron impact conditions. In the chemical ionization mode, using isobutane as the reagent gas, the cysteinyl conjugate gave a pseudomolecular ion as well, although relatively large quantities (10–20 μg) of this amino acid adduct were required. Because of the highly polar nature and thermal instability of the cysteinyl and glutathionyl conjugates, these two thioethers were most successfully analyzed by field desorption techniques. Field desorption mass spectrometry was well suited for direct analysis of these two adducts where prominent [M] +. , [MH] + or [M+Na] + ions were observed. Furthermore, by application of the field desorption/collision induced dissociation and linked ( B / E ) scan technique, structurally informative fragmentation patterns were generated. In addition, field desorption mass spectrometry was used successfully to characterize the glucuronide conjugate of acetaminophen but not the sulfate conjugate.