Investigations into the performance of travelling wave enabled conventional and cyclic ion mobility systems to characterise protomers of fluoroquinolone antibiotic residues. (18th February 2019) - McCullagh, Michael
Abstract : Rationale: Fluoroquinolones (FLQs) have been shown to form protomers with distinctive fragment profiles. Experimental parameters affect protomer formation, impacting observed conventional tandem mass spectrometric (MS/MS) dissociation and multiple reaction monitoring (MRM) transition reproducibility. Collision cross section (CCS) measurement can provide an additional identification metric and improved ion mobility (IM) separation strategies could provide further understanding of fluctuations in fragmentation when using electrospray ionisation (ESI). Methods: Porcine muscle tissue was fortified with nine fluoroquinolone antibiotics. Extracts were cleaned using QuEChERS dispersive extraction. Separation was achieved via ultra‐high‐performance liquid chromatography (UHPLC) and analysis performed using positive ion ESI coupled with linear T‐wave IM (N2 and CO2 drift gas) and cyclic IM‐MS (calibrated to perform accurate mass and CCS measurement). Results: IM‐resolved protomeric species have been observed for nine FLQs (uniquely three for danofloxacin). Long‐term reproducibility and cross‐platform T‐wave/cIM studies have demonstrated CCS metric errors <1.5% when compared with a FLQ protomer reference CCS library. When comparing FLQ protomer separation using a standard, linear T‐wave IM separator (N2 /CO2 ) and using a high‐resolution cyclic T‐wave device (N2 ), protomer peak‐to‐peak resolution ranged between Rs = 1 to Rs = 6 for the IM strategies utilised. Conclusions: CCS is a reliable cross platform metric; specific FLQ CCS identification fingerprints have been produced, illustrating the potential to compliment MS/MS specificity or provide an alternative identification metric. Using cIM there is opportunity to correlate the erratic nature of protomer formation with the analytical conditions used and to gain further understanding of ionisation/dissociation mechanisms taking place during routine analyses.