Structural characterization of product ions by electrospray ionization and quadrupole time-of-flight mass spectrometry to support regulatory analysis of veterinary drug residues in foods

RATIONALE Monitoring of veterinary drug residues in foods is often conducted using liquid chromatography/tandem mass spectrometry (LC/MS/MS). Results have high economic stakes for producers, but the ions monitored are usually selected due to signal intensities without structural interpretation. In this study, the ion transitions were characterized by high-resolution mass spectrometry. METHODS The 62 veterinary drugs from the LC/MS/MS method consisted of sulfonamides, beta-lactams, phenicols, macrolides, tetracyclines, fluoroquinolones, non-steroidal anti-inflammatory drugs (NSAIDs), and corticosteroids. They were individually infused into a quadrupole time-of-flight (Q-TOF) mass spectrometer using electrospray ionization (ESI) operated in positive mode. The MS and collision-induced dissociation (CID) MS/MS spectra for each analyte were obtained for structural elucidation. The Q-TOF instrument was calibrated to obtain a mass accuracy error RESULTS The use of high-resolution ESI-Q-TOF-MS for the generation of the MS/MS product ions allowed for the determination of chemical formulae for the analytes, some of which led to new findings. Assigned structures were based on rational interpretation of the most stable possible products with comparison with the scientific literature. In difficult cases, isotopically labeled drugs or hydrogen/deuterium (H/D) exchange experiments were used to help confirm the structures of the product ions. CONCLUSIONS The use of ESI-Q-TOF-MS in this study has allowed structure elucidation of 186 MS/MS product ions previously selected for the LC/MS/MS analysis of 62 veterinary drugs. This serves to reduce the chances of false positives and negatives in the monitoring program, and provides justification and defense in regulatory enforcement actions. Published in 2014. This article is a US Government work and is in the public domain in the USA.