title: Optimization of hydrophilic interaction liquid chromatography/mass spectrometry and development of solid-phase extraction for the determination of paralytic shellfish poisoning toxins.
abstract: The combination of hydrophilic interaction liquid chromatography (HILIC) and liquid chromatography/mass spectrometry (LC/MS) for the determination of paralytic shellfish poisoning (PSP) toxins has been proposed for use in routine monitoring of shellfish. In this study, methods for the detection of multiple PSP toxins [saxitoxin (STX), neosaxitoxin (NEO), decarbamoyl saxitoxin (dcSTX), decarbamoyl neosaxitoxin (dcNEO), gonyautoxins 1-5 (GTX1, GTX2, GTX3, GTX4, GTX5), decarbamoyl gonyautoxins (dcGTX2 and dcGTX3), and the N-sulfocarbamoyl C toxins (C1 and C2)] were optimized using single (MS) and triple quadrupole (MS/MS) instruments. Chromatographic separation of the toxins was achieved by using a TSK-gel Amide-80 analytical column, although superior chromatography was observed through application of a ZIC-HILIC column. Preparative procedures used to clean up shellfish extracts and concentrate PSP toxins prior to analysis were investigated. The capacity of computationally designed polymeric (CDP) materials and HILIC solid-phase extraction (SPE) cartridges to retain highly polar PSP toxins was explored. Three CDP materials and 2 HILIC cartridges were assessed for the extraction of PSP toxins from aqueous solution. Screening of the CDPs showed that all tested polymers adsorbed PSP toxins. A variety of elution procedures were examined, with dilute 0.01% acetic acid providing optimum recovery from a CDP based on 2-(trifluoromethyl)acrylic acid as the monomer. ZIC-HILIC SPE cartridges were superior to the PolyLC equivalent, with recoveries ranging from 70 to 112% (ZIC-HILIC) and 0 to 90% (PolyLC) depending on the PSP toxin. It is proposed that optimized SPE and HILIC-MS methods can be applied for the quantitative determination of PSP toxins in shellfish.
authors.affiliation: Fisheries Research Services, 375 Victoria Rd, Aberdeen AB11 9DB, United Kingdom. turrelle@marlab.ac.uk
authors.forename: Elizabeth
authors.initials: E
authors.lastname: Turrell
authors.forename: Lesley
authors.initials: L
authors.lastname: Stobo
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Lacaze
authors.forename: Sergey
authors.initials: S
authors.lastname: Piletsky
authors.forename: Elena
authors.initials: E
authors.lastname: Piletska
mesh_terms: D000818:Animals; D002138:Calibration; D002851:Chromatography, High Pressure Liquid; D007474:Ion Exchange; D008387:Marine Toxins / Q000032:analysis*; D013058:Mass Spectrometry; D008958:Models, Molecular; D049878:Mytilus / Q000737:chemistry; D015203:Reproducibility of Results; D012530:Saxitoxin / Q000031:analogs & derivatives* / Q000032:analysis*; D012758:Shellfish / Q000032:analysis*; D052616:Solid Phase Extraction
chemical_list: D008387:Marine Toxins; D012530:Saxitoxin