Enantioselective fractionation of fluoroquinolones in the aqueous environment using chiral liquid chromatography coupled with tandem mass spectrometry

Abstract

This paper aims to examine the multiresidue enantiomeric profiling of (fluoro)quinolones and their metabolites in solid and liquid environmental matrices using chiral HPLC-MS/MS method and a CHIRALCEL OZ-RH column. Simultaneous chiral separation was obtained for chiral ofloxacin and its main metabolites ofloxacin-N-oxide and desmethyl-ofloxacin; moxifloxacin; the prodrug prulifloxacin and its active compound ulifloxacin; flumequine; nadifloxacin and R-(+)-besifloxacin. Achiral antibiotics (ciprofloxacin, norfloxacin and nalidixic acid) were also included in the method to enable the analysis of all targeted quinolones within one analytical run. Satisfactory enantiomeric resolution (Rs ≥ 1) was obtained for five out of eight chiral drugs enabling quantitative analysis. The overall performance of the method was satisfactory with a method precision <20%, relative recoveries >70% for most of the analytes and method detection limits (MDL) at low ng L levels (0.1 < MDL (ng L)< 6.4, 0.1 < MDL (ng L)< 6.6 and 0.1 < MDL (ng L)< 7.0 in influent, effluent and river waters for 83% compounds, 0.01 < MDL (ng g)< 4.9 in solids for 91% compounds). Enantiomeric profiling from a week-long monitoring campaign in the UK showed that (±)-ofloxacin was found to be racemic in upstream waters but it was enriched with S-(-)-enantiomer in wastewater and in receiving waters. This could be due to the fact that ofloxacin can be used both as a racemate and as a S-(-)-enantiomer. Its consumption was further confirmed by the chiral signature of the investigated ofloxacin metabolites. As a result, alterations in the enantiomeric composition of antibiotics could influence not only their activity and toxicity in the environment, but also could induce changes in the microbial communities constantly exposed to them.

Analysis, fate and toxicity of chiral non-steroidal anti-inflammatory drugs in wastewaters and the environment: a review

“…A well-known issue of environmental analysis using electrospray ionization in LC-MS applications is the effect of co-extracted matrix components on analyte signal strength (Cappiello et al 2008;Furey et al 2013;Petrović et al 2005). This can lead to enhancement or suppression of signal strength, which can also be enantioselective Kasprzyk-Hordern 2015, 2017;Camacho-Muñoz et al 2016;Castrignanò et al 2018;López-Serna et al 2013). Such effects can be easily corrected using deuterated surrogates in the analysis process.…”

Enantioseparation and determination of flumequine enantiomers in multiple food matrices with chiral liquid chromatography coupled with tandem mass spectrometry

“…Nevertheless, a few papers have reported on the enantioselective quantification of flumequine in different matrices, including in rat plasma, sediment, and different water samples. [22][23][24][25] But, to our best knowledge, no literature has been published on enantioselective determination of flumequine in multiple food matrices by LC-MS/MS. Therefore, this study aimed to develop a new robust method for the enantioselective determination of flumequine in multiple matrices (milk, yogurt, honey, egg, chicken, and beef) using a reversed-phase HPLC-MS/MS with the Chiralpak IC column.…”

“…In the present, there is a trend on enantioselective determination of chiral drugs in various matrices. Nevertheless, a few papers have reported on the enantioselective quantification of flumequine in different matrices, including in rat plasma, sediment, and different water samples . But, to our best knowledge, no literature has been published on enantioselective determination of flumequine in multiple food matrices by LC‐MS/MS.…”

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“…Moxifloxacin is chemically known as [1-Cyclopropyl-b-fluoro-1, 4-dihydro-8-methoxy-7-[(4aS, 7aS)-octahydro-6H-pyrrolo [3,[4][5][6] pyridine-6-yl]-4-oxo-3-quinoline carboxylic acid, is a fluoroquinolone broad-spectrum antibiotic agent and used in conjunctivitis. A few analytical techniques have been constructed for quantification of several drugs based on literature survey such as UV Spectrophotometry [33][34][35][36] RP-HPLC [37][38][39][40] , HPLC [41][42] , HPLC-MS [43][44] , LC-MS 45 , LC 46 , chemiluminescence 47 , Tanden mass spectrometry 48 methods for determination of Moxifloxacin have been reported.…”