is a benthic dinoflagellate known for producing pinnatoxins, pteriatoxins, portimines and kabirimine. In this study, we aimed to identify unknown analogs of these emerging toxins in mussels collected in the Ingril lagoon, France. First, untargeted data acquisitions were conducted by means of liquid chromatography coupled to hybrid quadrupole-orbitrap mass spectrometry. Data processing involved a molecular networking approach, and a workflow dedicated to the identification of biotransformed metabolites. Additionally, targeted analyses by liquid chromatography coupled to triple quadrupole mass spectrometry were also implemented to further investigate and confirm the identification of new compounds. For the first time, a series of 13--acyl esters of portimine-A ( = 13) were identified, with fatty acid chains ranging between C12:0 and C22:6. The profile was dominated by the palmitic acid conjugation. This discovery was supported by fractionation experiments combined with the implementation of a hydrolysis reaction, providing further evidence of the metabolite identities. Furthermore, several analogs were semi-synthesized, definitively confirming the discovery of these metabolization products. A new analog of pinnatoxin, with a molecular formula of CHNO, was also identified across the year 2018, with the highest concentration observed in August (4.5 μg/kg). The MS/MS data collected for this compound exhibited strong structural similarities with PnTX-A and PnTX-G, likely indicating a substituent CHO in the side chain at C33. The discovery of these new analogs will contribute to deeper knowledge of the chemodiversity of toxins produced by or resulting from shellfish metabolism, thereby improving our ability to characterize the risks associated with these emerging toxins.

中文翻译：

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在贻贝中发现了一系列Portimine-A脂肪酸酯

是一种底栖甲藻，以产生羽衣藻毒素、翼藻毒素、波替胺和卡比胺而闻名。在这项研究中，我们的目的是在法国英格里尔泻湖收集的贻贝中鉴定这些新出现的毒素的未知类似物。首先，通过与混合四极杆轨道阱质谱联用的液相色谱法进行非目标数据采集。数据处理涉及分子网络方法和致力于识别生物转化代谢物的工作流程。此外，还进行了液相色谱与三重四极杆质谱联用的靶向分析，以进一步研究和确认新化合物的鉴定。首次鉴定了一系列 13-酰基 Portimine-A (= 13) 酯，其脂肪酸链范围在 C12:0 和 C22:6 之间。该谱主要由棕榈酸缀合决定。这一发现得到了分馏实验与水解反应相结合的支持，为代谢物特性提供了进一步的证据。此外，还半合成了几种类似物，明确证实了这些代谢产物的发现。 2018 年还发现了一种新的羽衣藻毒素类似物，其分子式为 CHNO，其浓度在 8 月份达到最高浓度（4.5 μg/kg）。该化合物收集的 MS/MS 数据与 PnTX-A 和 PnTX-G 具有很强的结构相似性，可能表明 C33 侧链上有取代基 CHO。这些新类似物的发现将有助于更深入地了解贝类代谢产生的毒素的化学多样性，从而提高我们描述与这些新兴毒素相关的风险的能力。