Screening of cyclic imine and paralytic shellfish toxins in isolates of the genus Alexandrium (Dinophyceae) from Atlantic Canada

Qiu, Jiangbing; Rafuse, Cheryl; Lewis, N. I.; Li, Aifeng; Meng, Fanping; Beach, Daniel G.; McCarron, Pearse

doi:10.1016/j.hal.2018.05.005

Cited by 22 publications

(16 citation statements)

References 45 publications

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“…Therefore, SPXs, PnTXs, and PtTXs have similar structures and related m/z ions. The m/z 164 fragment ion (C 11 H 18 N + ) is common to all reported pinnatoxins and pteriatoxins in addition to the majority of spirolides, and a m/z 572 fragment ion can be utilized as a PnTX-and PtTX-specific product ion for selected reaction monitoring (SRM) detection and confirmation of these toxins in samples [26,29]. In relation to GYMs, both the m/z 136 (C 9 H 14 N + ) and the m/z 162 (C 11 H 16 N + ), fragment ions with the CI moiety, can also be used for the screening of gymnodimine analogs [30,33].…”

Section: Adjustment Of Lc-ms/ms To the Analysis Of Cismentioning

confidence: 99%

“…The availability of certified reference materials for CIs as GYM-A, SPX-1, and PnTX-G ( Figure 1) has allowed them to be included with other groups of marine lipophilic toxins that are currently legislated for the purpose of presently available reference methods [22][23][24][25]. In addition, because CIs include a long list of compounds and most of them are without commercially available standard solutions, LC-MS/MS methods based on fragmentation pathways of reference toxins have been proposed in order to study their occurrence [17,26]. This work was focused on the application of LC-MS/MS for the analysis of GYMs, SPXs, PnTXs, and PtTXs in mussels (Mytilus galloprovincialis) from Galician Rias in order to allow for the confirmation of PnTX-G and SPX-1 using standard solutions, as well as the detection of PnTX-A based on fragmentation pathways and key m/z ions.…”

Section: Introductionmentioning

confidence: 99%

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Analysis of Cyclic Imines in Mussels (Mytilus galloprovincialis) from Galicia (NW Spain) by LC-MS/MS

Moreiras

Leão

Gago-Martı́nez

2019

IJERPH

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Cyclic imines (CIs) are being considered as emerging toxins in the European Union, and a scientific opinion has been published by the European Food Safety Authority (EFSA) in which an assessment of the risks to human health related to their consumption has been carried out. Recommendations on the EFSA opinion include the search for data occurrence of CIs in shellfish and using confirmatory methods by liquid chromatography-tandem mass spectrometry (LC-MS/MS), which need to be developed and optimized. The aim of this work is the application of LC-MS/MS to the analysis of gymnodimines (GYMs), spirolides (SPXs), pinnatoxins (PnTXs), and pteriatoxins (PtTXs) in mussels from Galician Rias, northwest Spain, the main production area in Europe, and therefore a representative emplacement for their evaluation. Conditions were adjusted using commercially available certified reference standards of GYM-A, SPX-1, and PnTX-G and evaluated through quality control studies. The EU-Harmonised Standard Operating Procedure for determination of lipophilic marine biotoxins in molluscs by LC-MS/MS was followed, and the results obtained from the analysis of eighteen samples from three different locations that showed the presence of PnTXs and SPXs are presented and discussed. Concentrations of PnTX-G and SPX-1 ranged from 1.8 to 3.1 µg/kg and 1.2 to 6.9 µg/kg, respectively, and PnTX-A was detected in the group of samples with higher levels of PnTX-G after a solid phase extraction (SPE) step used for the concentration of extracts.

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Section: Adjustment Of Lc-ms/ms To the Analysis Of Cismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Analysis of Cyclic Imines in Mussels (Mytilus galloprovincialis) from Galicia (NW Spain) by LC-MS/MS

Moreiras

Leão

Gago-Martı́nez

2019

IJERPH

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“…To date, 15 SPX of microalgal origin have been structurally elucidated ( Table 1 ) and many others identified based on their characteristic collision induced dissociation (CID) spectra from various regions across the world. While some strains primarily produce SPX 1 [ 7 , 9 , 20 , 26 ], other strains have SPX A [ 22 ], SPX C [ 17 ], 20-methyl SPX G [ 12 , 26 ] or 13,19-didesmethyl SPX C [ 15 ] as their major component. Next to their major SPX, the vast majority of strains also contain minor constituents, which hardly have been characterized.…”

Section: Introductionmentioning

confidence: 99%

Mass Spectrometry-Based Characterization of New Spirolides from Alexandrium ostenfeldii (Dinophyceae)

et al. 2020

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Spirolides belong to a group of marine phycotoxins produced by the marine planktonic dinophyte Alexandrium ostenfeldii. Composed of an imine moiety and a spiroketal ring system within a macrocylcle, spirolides are highly diverse with toxin types that vary among different strains. This study aims to characterize the spirolides from clonal A. ostenfeldii strains collected from the Netherlands, Greenland and Norway by mass spectral techniques. The structural characterization of unknown spirolides as inferred from high-resolution mass spectrometry (HR-MS) and collision induced dissociation (CID) spectra revealed the presence of nine novel spirolides that have the pseudo-molecular ions m/z 670 (1), m/z 666 (2), m/z 696 (3), m/z 678 (4), m/z 694 (5), m/z 708 (6), m/z 720 (7), m/z 722 (8) and m/z 738 (9). Of the nine new spirolides proposed in this study, compound 1 was suggested to have a truncated side chain in lieu of the commonly observed butenolide ring in spirolides. Moreover, there is indication that compound 5 might belong to new spirolide subclasses with a trispiroketal ring configuration having a 6:5:6 trispiroketal ring system. On the other hand, the other compounds were proposed as C- and G-type SPX, respectively. Compound 7 is proposed as the first G-type SPX with a 10-hydroxylation as usually observed in C-type SPX. This mass spectrometry-based study thus demonstrates that structural variability of spirolides is larger than previously known and does not only include the presence or absence of certain functional groups but also involves the triketal ring system.

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“…Recently, trace amounts of several M-toxins were also reported in the PST-producing dinoflagellates Alexandrium spp. [8,9] and cyanobacteria of the genus Aphanizomenon [10]. They have also been formed through chemical degradation, [7] adding further uncertainty and complexity to their origin and formation.…”

Section: Introductionmentioning

confidence: 99%

“…Currently, the most common instrumental analytical techniques used for PST analysis are liquid chromatography coupled with fluorescence detection (LC-FLD) [11][12][13], and liquid chromatography-mass spectrometry (LC-MS) [14][15][16][17][18] LC-FLD uses strong ion pair agents to allow retention of highly polar PSTs in reverse-phase LC and is sensitive for C-toxins, GTXs and STXs, but responds poorly to M-toxins [3]. LC-MS methods are typically based on hydrophilic interaction liquid chromatography (HILIC) and have generally used a selected reaction monitoring (SRM) scan mode on triple quadrupole mass spectrometers (HILIC-MS/MS) [14][15][16][17]19] or more recently involve less targeted approaches using high-resolution MS (HILIC-HRMS) [8,9,20]. The development of targeted LC-MS/MS methods is highly dependent on the availability of authentic standards since electrospray ionization (ESI) source parameters and MS/MS conditions need to be optimized for each analyte and high variability is observed in ESI sensitivity [21].…”

Section: Introductionmentioning

confidence: 99%

Semiquantitation of Paralytic Shellfish Toxins by Hydrophilic Interaction Liquid Chromatography-Mass Spectrometry Using Relative Molar Response Factors

Qiu

Wright

Thomas

et al. 2020

Toxins

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Paralytic shellfish toxins (PSTs) are a complex class of analogs of the potent neurotoxin saxitoxin (STX). Since calibration standards are not available for many PSTs, including C-11 hydroxyl analogs called M-toxins, accurate quantitation by liquid chromatography–mass spectrometry (LC-MS) can be challenging. In the absence of standards, PSTs are often semiquantitated using standards of a different analog (e.g., STX), an approach with a high degree of uncertainty due to the highly variable sensitivity between analytes in electrospray ionization. Here, relative molar response factors (RMRs) were investigated for a broad range of PSTs using common LC-MS approaches in order to improve the quantitation of PSTs for which standards are unavailable. First, several M-toxins (M1-M6, M9 and dcM6) were semipurified from shellfish using preparative gel filtration chromatography and quantitated using LC-charged aerosol detection (LC-CAD). The RMRs of PST certified reference materials (CRMs) and M-toxins were then determined using selective reaction monitoring LC-MS/MS and full scan LC-high-resolution MS (LC-HRMS) methods in positive and negative electrospray ionization. In general, RMRs for PSTs with similar chemical structures were comparable, but varied significantly between subclasses, with M-toxins showing the lowest sensitivity. For example, STX showed a greater than 50-fold higher RMR than M4 and M6 by LC-HRMS. The MS instrument, scan mode and polarity also had significant impacts on RMRs and should be carefully considered when semiquantitating PSTs by LC-MS. As a demonstration of their utility, the RMRs determined were applied to the semiquantitation of PSTs in contaminated mussels, showing good agreement with results from calibration with CRMs.

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Screening of cyclic imine and paralytic shellfish toxins in isolates of the genus Alexandrium (Dinophyceae) from Atlantic Canada

Cited by 22 publications

References 45 publications

Analysis of Cyclic Imines in Mussels (Mytilus galloprovincialis) from Galicia (NW Spain) by LC-MS/MS

Analysis of Cyclic Imines in Mussels (Mytilus galloprovincialis) from Galicia (NW Spain) by LC-MS/MS

Mass Spectrometry-Based Characterization of New Spirolides from Alexandrium ostenfeldii (Dinophyceae)

Semiquantitation of Paralytic Shellfish Toxins by Hydrophilic Interaction Liquid Chromatography-Mass Spectrometry Using Relative Molar Response Factors

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