title: Improved method for preparation and use of 9-anthryldiazomethane for derivatization of hydroxycarboxylic acids. Application to diarrhetic shellfish poisoning toxins.
abstract: Application of a method for the "in situ" generation of 9-anthryldiazomethane (ADAM) to the derivatization of the carboxyl function in diarrhetic shellfish poisoning (DSP) toxins revealed the formation of artifact products. Using liquid chromatography-mass spectrometry, it was determined that these artifacts were due to base-catalyzed reactions between the solvent, ethyl acetate, and the hydroxyl groups of the analyte to produce O-acetylated ADAM derivatives. Using a new formulation, with tetrahydrofuran as solvent, it was possible to eliminate these artifact reactions. Various reaction parameters have also been re-optimized to ensure quantitative derivatizations. An assessment method was developed that was useful not only for optimizing reaction parameters, but also for evaluating the reagent potency before use on important samples. Finally, application of the method to the determination of DSP toxins in plankton and mussel tissue was demonstrated.
authors.affiliation: Institute for Marine Biosciences, National Research Council of Canada, Halifax, Nova Scotia, Canada.
authors.forename: M A
authors.initials: MA
authors.lastname: Quilliam
authors.forename: A
authors.initials: A
authors.lastname: Gago-Martínez
authors.forename: J A
authors.initials: JA
authors.lastname: Rodríguez-Vázquez
mesh_terms: D000873:Anthracenes / Q000138:chemical synthesis / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D002851:Chromatography, High Pressure Liquid; D005517:Foodborne Diseases; D007202:Indicators and Reagents; D007700:Kinetics; D008387:Marine Toxins / Q000032:analysis*; D012758:Shellfish / Q000032:analysis*; D013050:Spectrometry, Fluorescence; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000873:Anthracenes; D002264:Carboxylic Acids; D007202:Indicators and Reagents; D008387:Marine Toxins; C027347:9-diazomethylanthracene