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Discovery of fatty acid ester metabolites of spirolide toxins in mussels from Norway using liquid chromatography/tandem mass spectrometry
Author(s) -
Aasen John A. B.,
Hardstaff William,
Aune Tore,
Quilliam Michael A.
Publication year - 2006
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.2501
Subject(s) - chemistry , chromatography , liquid chromatography–mass spectrometry , tandem mass spectrometry , mass spectrometry , marine toxin , tandem , biochemistry , toxin , materials science , composite material
Cultured mussels sampled in the spring of 2002 and 2003 from Skjer, a location in the Sognefjord, Norway, tested positive in the mouse bioassay for lipophilic toxins. In a previous report, it was established that a number of spirolides, cyclic imine toxins produced by the phytoplankton Alexandrium ostenfeldii , were present in the mussels and were responsible for the observed toxicity. The main toxin proved to be a new compound named 20‐methyl spirolide G. In subsequent studies, a delayed onset of spirolide‐like symptoms in the mouse bioassay exceeding the usual time limit of 20 min was observed in some samples, with symptoms and death appearing as long as 45–50 min after injection. It is well known that shellfish can extensively metabolize other toxins, such as okadaic acid and the dinophysistoxins, to fatty acid acyl esters and it is also known that a delayed onset of toxic symptoms with such metabolites can occur. Analyses performed with liquid chromatography/tandem mass spectrometry (LC/MS/MS) have revealed a complex mixture of esters of 20‐methyl spirolide G in the contaminated mussels. Precursor ion scanning has delineated the range of fatty acid esters involved, while product ion scanning has provided information on structure. Identity was also supported through reaction of 20‐methyl spirolide G with palmitic anhydride, which produced a derivative with a retention time and spectrum identical with one putative metabolite, 17‐ O ‐palmitoyl‐20‐methyl spirolide G. Copyright © 2006 Crown in the right of Canada. Published by John Wiley & Sons, Ltd.