An enhanced LC-MRM-MS platform for sensitive and simultaneous quantification of cyclic imines in shellfish.

Cyclic imines (CIs) produced by microalgae species and accumulating in the food chain of marine organisms are novel biotoxins that do not belong to the classical group of marine biotoxins. In the past, CIs were found only in limited areas, but in recent years, rapid changes in marine ecosystems have led to widespread CIs, increasing exposure to toxic risks. Monitoring of CIs is therefore required, but still analytically challenging due to the presence of high levels of analogues and interference from other lipophilic substances. Herein, we developed the LC/MRM-MS-based quantitative platform that can selectively enrich for marine-derived CIs and monitor seven CIs simultaneously: pinnatoxin (PnTX E, PnTX F, PnTX G), gymnodimine (GYM A), and spirolide (13-desMe SPX C, 13,19-didesMe SPX C, 20-Me SPX G). In particular, the combination of chromatographic separation by the hydrophobic nature of intrinsic residues of CIs with monitoring of CI structure-specific product ions generated by CID-MS/MS significantly improves the selectivity and sensitivity for quantitative analysis. Indeed, three CIs corresponding to PnTX G, GYM A, and 13-desMe SPX C could be successfully determined at the level of part-per-trillion (ppt) in three species of shellfish collected around the Korean Peninsula. Our analysis revealed that the expression of CIs in the Korean Peninsula was more influenced by the season rather than the species. This analytical platform with high sensitivity can be applied not only to marine biology but also to various other fields requiring CI analysis. Key Contribution: A highly sensitive analytical method for the simultaneous quantitation of cyclic imines based on LC/MRM-MS has been developed.

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Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.