Enantioselective simultaneous analysis of selected pharmaceuticals in environmental samples by ultrahigh performance supercritical fluid based chromatography tandem mass spectrometry

Abstract

In order to assess the true impact of each single enantiomer of pharmacologically active compounds (PACs) in the environment, highly efficient, fast and sensitive analytical methods are needed. For the first time this paper focuses on the use of ultrahigh performance supercritical fluid based chromatography coupled to a triple quadrupole mass spectrometer to develop multi-residue enantioselective methods for chiral PACs in environmental matrices. This technique exploits the advantages of supercritical fluid chromatography, ultrahigh performance liquid chromatography and mass spectrometry. Two coated modified 2.5 μm-polysaccharide-based chiral stationary phases were investigated: an amylose tris-3,5-dimethylphenylcarbamate column and a cellulose tris-3-chloro-4-methylphenylcarbamate column. The effect of different chromatographic variables on chiral recognition is highlighted. This novel approach resulted in the baseline resolution of 13 enantiomers PACs (aminorex, carprofen, chloramphenicol, 3-N-dechloroethylifosfamide, flurbiprofen, 2-hydroxyibuprofen, ifosfamide, imazalil, naproxen, ofloxacin, omeprazole, praziquantel and tetramisole) and partial resolution of 2 enantiomers PACs (ibuprofen and indoprofen) under fast-gradient conditions (<10 min analysis time). The overall performance of the methods was satisfactory. The applicability of the methods was tested on influent and effluent wastewater samples. To the best of our knowledge, this is the first feasibility study on the simultaneous separation of chemically diverse chiral PACs in environmental matrices using ultrahigh performance supercritical fluid based chromatography coupled with tandem mass spectrometry.

Determination of cannabinoid and synthetic cannabinoid metabolites in wastewater by liquid–liquid extraction and ultra‐high performance supercritical fluid chromatography‐tandem mass spectrometry

“…[8] The non-toxic and non-reactive properties of this gas entail, compared to LC, lower environmental impact, improved health and safety conditions, and reduced costs associated with solvent disposal. [9] The main aim of this work was, therefore, to optimize and validate a new UHPSFC-MS/MS method to determine Δ9-tetrahydrocannabinol (THC), three of its major human metabolites, and four JWH-type synthetic cannabinoid metabolites in wastewater. To the best of the authors' knowledge, this technique has been used for the analysis of some of these substances in urine, [10] plant products, [11] and seized drugs, [12] but not for the analysis of wastewater in search of drug residues.…”

Occurrence of Chiral Bioactive Compounds in the Aquatic Environment: A Review

“…GC-MS/MS was employed in the first works reporting enantioselective environmental analysis by indirect methods using enantiomerically-pure derivatizing reagents [9,60], or by direct methods using CSPs [61,85]. Despite indirect [70,83] and direct methods [67,80,89] remaining in some studies, LC-MS/MS has been the analytical technique of election for illicit drugs and pharmaceutical while GC-MS and GC-ECD have been the most used for pesticides [13,54,55,57,62,[64][65][66][67][68][69][71][72][73][74][75][76][77][80][81][82]84,87,88,[90][91][92]95,[100][101][102][103][104][105]. Although much less used, LC-DAD, LC-UV and LC-FD detection have been used in some of the studies [11,26,27,…”

“…Since 2010, a trend is being verified for the use of three types of CSPs: protein-based [68,69,[74][75][76][77]81,82,100,101], polysaccharide-based [54,55,78,79,102] and macrocyclic antibiotic-based CSPs [13,26,27,63,64,71-73, 76,78,88,91,103]. The first reports describing the use of macrocyclic antibiotic-based CSPs for environmental analysis were published in 2006-2007 [84,104], but its application was later intensely reported from 2010 [13,26,27,57,[71][72][73]76,78,86,87,90,93,94,103,105].…”

“…Only a few illicit drugs and some therapeutic classes of pharmaceuticals such as beta-blockers, antidepressants and its metabolites, antifungals, and NSAIDs have been enantioselectively analyzed in environmental matrices (Table 1) [9,11,13,26,27,54,55,57,[60][61][62][63][64]95,[100][101][102][103][104][105]117].…”

“…Two studies focused on the enantioselective determination of 11 chiral veterinary and human pharmaceuticals in environmental water samples [101] and another including 15 pharmaceuticals [102] showed respectively, an EF of 0.5 and 0.6 for an anti-helminthic tetramisole, which is administrated in the (S)-form as veterinary drug, suggesting its enantiomerization or its use as adulterant in illicit cocaine production. Kasprzyk-Hordern and co-workers published recently a multi-residue method for enantioselective separation of chiral pharmaceuticals using teicoplanin as chiral selector for the simultaneous enantioresolution of carboxyibuprofen, chloramphenicol, 2-hydroxyibuprofen, ibuprofen, ifosfamide, indoprofen, ketoprofen, naproxen and praziquantel.…”