Dedicated to Dr. Robert Boyd on the occasion of his retirement as Editor-in-Chief of Rapid Communications in Mass Spectrometry.
Discovery of fatty acid ester metabolites of spirolide toxins in mussels from Norway using liquid chromatography/tandem mass spectrometry†
Article first published online: 20 APR 2006
Copyright © 2006 Crown in the right of Canada. Published by John Wiley & Sons, Ltd.
Rapid Communications in Mass Spectrometry
Volume 20, Issue 10, pages 1531–1537, 30 May 2006
How to Cite
Aasen, J. A. B., Hardstaff, W., Aune, T. and Quilliam, M. A. (2006), Discovery of fatty acid ester metabolites of spirolide toxins in mussels from Norway using liquid chromatography/tandem mass spectrometry. Rapid Commun. Mass Spectrom., 20: 1531–1537. doi: 10.1002/rcm.2501
- Issue published online: 20 APR 2006
- Article first published online: 20 APR 2006
- Manuscript Revised: 23 MAR 2006
- Manuscript Accepted: 23 MAR 2006
- Manuscript Received: 1 JAN 2006
- Research Council of Norway. Grant Number: 139593/140
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.