title: Studies on azaspiracid biotoxins. II. Mass spectral behavior and structural elucidation of azaspiracid analogs.
abstract: In this report, the mass spectral analysis of azaspiracid biotoxins is described. Specifically, the collision-induced dissociation (CID) behavior and differences between CID spectra obtained on a triple-quadrupole, a quadrupole time-of-flight, and an ion-trap mass spectrometer are addressed here. The CID spectra obtained on the triple-quadrupole mass spectrometer allowed the classification of the major product ions of the five investigated compounds (AZA 1-5) into five distinct fragment ion groups, according to the backbone cleavage positions. Although the identification of unknown azaspiracids was difficult based on CID alone, the spectra provided sufficient structural information to allow confirmation of known azaspiracids in marine samples. Furthermore, we were able to detect two new azaspiracid analogs (AZA 1b and 6) in our samples and provide a preliminary structural analysis. The proposed dissociation pathways under tandem mass spectrometry (MS/MS) conditions were confirmed by a comparison with accurate mass data from electrospray quadrupole time-of-flight MS/MS experiments. Regular sequential MS(n) analysis on an ion-trap mass spectrometer was more restricted in comparison to the triple-quadrupole mass spectrometer, because the azaspiracids underwent multiple [M + H - nH(2)O](+) (n = 1-6) losses from the precursor ion under CID. Thus, the structural information obtained from MS(n) experiments was somewhat limited. To overcome this limitation, we developed a wide-range excitation technique using a 180-u window that provided results comparable to the triple-quadrupole instrument. To demonstrate the potential of the method, we applied it to the analysis of degraded azaspiracids from mussel tissue extracts.
authors.affiliation: Institute for Marine Biosciences, National Research Council, 1411 Oxford Street, Halifax, Nova Scotia B3H 3Z1, Canada.
authors.forename: Stephan
authors.initials: S
authors.lastname: Brombacher
authors.forename: Suzanne
authors.initials: S
authors.lastname: Edmonds
authors.forename: Dietrich A
authors.initials: DA
authors.lastname: Volmer
mesh_terms: D000818:Animals; D049872:Bivalvia / Q000737:chemistry*; D008387:Marine Toxins / Q000737:chemistry*; D013058:Mass Spectrometry / Q000379:methods*; D015394:Molecular Structure; D013141:Spiro Compounds / Q000737:chemistry*; D014020:Tissue Extracts / Q000737:chemistry; D000095702:Polyether Toxins
chemical_list: D008387:Marine Toxins; D013141:Spiro Compounds; D014020:Tissue Extracts; C406592:azaspiracid; D000095702:Polyether Toxins