title: Electrochemistry coupled online to liquid chromatography-mass spectrometry for fast simulation of biotransformation reactions of the insecticide chlorpyrifos.
abstract: An automated method is presented for fast simulation of (bio)transformation products (TPs) of the organophosphate insecticide chlorpyrifos (CPF) based on electrochemistry coupled online to liquid chromatography-mass spectrometry (EC-LC-MS). Oxidative TPs were produced by a boron doped diamond (BDD) electrode, separated by reversed phase HPLC and online detected by electrospray ionization-mass spectrometry (ESI-MS). Furthermore, EC oxidative TPs were investigated by HPLC-tandem mass spectrometry (LC-MS/MS) and FT-ICR high resolution mass spectrometry (HRMS) and compared to in vitro assay metabolites (rat and human liver microsomes). Main phase I metabolites of CPF: chlorpyrifos oxon (CPF oxon), trichloropyridinol (TCP), diethylthiophosphate (DETP), diethylphosphate (DEP), desethyl chlorpyrifos (De-CPF), and desethyl chlorpyrifos oxon (De-CPF oxon), were successfully identified by the developed EC-LC-MS method. The EC-LC-MS method showed similar metabolites compared to the in vitro assay with possibilities of determining reactive species. Our results reveal that online EC-(LC)-MS brings an advantage on time of analysis by eliminating sample preparation steps and matrix complexity compared to conventional in vivo or in vitro methods.
authors.affiliation: Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489, Berlin, Germany.|Humboldt-Universität zu Berlin, School of Analytical Sciences Adlershof (SALSA), Albert-Einstein-Str. 5-9, 12489, Berlin, Germany.
authors.forename: Tessema F
authors.initials: TF
authors.lastname: Mekonnen
authors.affiliation: Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489, Berlin, Germany.|Humboldt-Universität zu Berlin, School of Analytical Sciences Adlershof (SALSA), Albert-Einstein-Str. 5-9, 12489, Berlin, Germany.
authors.forename: Ulrich
authors.initials: U
authors.lastname: Panne
authors.affiliation: Bundesanstalt für Materialforschung und -prüfung (BAM), Richard-Willstätter-Str. 11, 12489, Berlin, Germany. Matthias.Koch@bam.de.
authors.forename: Matthias
authors.initials: M
authors.lastname: Koch
mesh_terms: D004390:Chlorpyrifos / Q000737:chemistry* / Q000378:metabolism*; D002853:Chromatography, Liquid / Q000379:methods*; D003198:Computer Simulation; D055664:Electrochemical Techniques / Q000379:methods*; D013058:Mass Spectrometry / Q000379:methods*; D008956:Models, Chemical; D010084:Oxidation-Reduction
chemical_list: D004390:Chlorpyrifos
keywords: EC-LC-MS; Electrochemical oxidation; In vitro; LC-MS/MS; Metabolism; Organophosphate agrochemicals