Discovery of fatty acid ester metabolites of spirolide toxins in mussels from Norway using liquid chromatography/tandem mass spectrometry
Discovery of fatty acid ester metabolites of spirolide toxins in mussels from Norway using liquid chromatography/tandem mass spectrometry
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DOI：
10.1002/rcm.2501
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发表时间：
2006-01-01
影响因子：
2
通讯作者：
Quilliam, Michael A.
中科院分区：
文献类型：
--
作者：
Aasen, John A. B.;Hardstaff, William;Quilliam, Michael A.
2002年和2003年春天，在挪威索内峡湾的Skjer地区采集的养殖贻贝在小鼠亲脂毒素生物测定中呈阳性。在以前的一份报告中，已经确定贻贝中存在许多螺内酯，即浮游植物亚历山大藻产生的环亚胺毒素，并且是观察到的毒性的原因。经证实，主要毒素是一种名为20-甲基螺环内酯g的新化合物。在随后的研究中，在一些样品中观察到，在小鼠生物测定中，螺环内酯样症状的延迟发作超过了通常的20分钟的时间限制，在注射后45-50分钟内出现症状和死亡。众所周知，贝类可以将其他毒素，如冈田酸和甲藻毒素，广泛代谢为脂肪酸酰基酯，而且这些代谢物可能会导致中毒症状的延迟发作。液相色谱/串联质谱（LC/MS/MS）分析显示，污染贻贝中含有20-甲基螺内酯G酯的复杂混合物。前体离子扫描描绘了所涉及的脂肪酸酯的范围，而产物离子扫描提供了结构信息。20-甲基螺环内酯G与棕榈酸酐的反应也证实了其特性，该反应产生的衍生物的保留时间和光谱与一种推测的代谢物17- o -棕榈酰-20-甲基螺环内酯G相同。版权所有(c) 2006 Crown，加拿大所有。约翰·威利父子有限公司出版。
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 (c) 2006 Crown in the right of Canada. Published by John Wiley & Sons, Ltd.