Liquid chromatography/electrospray ionization quadrupole time-of-flight mass spectrometry for the analysis of sulfaquinoxaline byproducts formed in water upon solar light irradiation
Article first published online: 17 FEB 2013
Copyright © 2013 John Wiley & Sons, Ltd.
Rapid Communications in Mass Spectrometry
Volume 27, Issue 6, pages 722–730, 30 March 2013
How to Cite
Le Fur, C., Legeret, B., de Sainte Claire, P., Wong-Wah-Chung, P. and Sarakha, M. (2013), Liquid chromatography/electrospray ionization quadrupole time-of-flight mass spectrometry for the analysis of sulfaquinoxaline byproducts formed in water upon solar light irradiation. Rapid Commun. Mass Spectrom., 27: 722–730. doi: 10.1002/rcm.6507
- Issue published online: 17 FEB 2013
- Article first published online: 17 FEB 2013
- Manuscript Revised: 14 JAN 2013
- Manuscript Accepted: 14 JAN 2013
- Manuscript Received: 30 NOV 2012
Sulfonamides such as sulfaquinoxaline (SQX) are among the most important antibiotic families due to their extensive use in veterinary medicine. The prediction of their fate under solar irradiation through the identification of the generated metabolites is required. However, unambiguous structural characterizations often remain a challenge particularly when several isomers could match with the same MS2 data.
Liquid chromatography/electrospray ionization quadrupole time-of-flight mass spectrometry (LC/ESI-Q-TOFMS) in the positive ion mode, leading to the formation of the protonated forms of the studied compounds, [M + H+] ions, was employed. Collision-induced dissociation tandem mass spectrometry (CID-MS/MS) of the protonated molecules was carried out, and the effect of the collision energy as well as the elemental compositions of the product ions were used to propose chemical structures. Validation of the hypothesized structures was performed by the calculation of key fragmentation pathway energies using density functional theory (DFT) calculations (B3LYP/6-31 G (d,p)).
The photoproducts were identified as 2-aminoquinoxaline, SQX isomers, 2-(N-parabenzoquinoneimine)quinoxaline and isomers resulting from SO2 extrusion. The direct fragmentations of [SQX + H]+ and its protonated isomers mostly occurred through the loss of 2-aminoquinoxaline and/or the 4-sulfoaniline radical ion, while their rearrangements involved the migration of H and/or O atoms. For the desulfonated byproducts in their protonated forms, the main neutral losses were of the quinoxaline radical, aminoquinoxaline and NH3. The fragmentation of the protonated 2-aminoquinoxaline mainly involved the elimination of NH3 and HCN.
LC/ESI-Q-TOFMS and DFT calculations have been shown to be useful and complementary methods for the identification of unknown isomeric compounds and the elucidation of fragmentation patterns, in the case of the sulfaquinoxaline veterinary antibiotic. Copyright © 2013 John Wiley & Sons, Ltd.