FN Archimer Export Format PT J TI Characterization of maitotoxin‐4 (MTX4) using electrospray positive mode ionization high‐resolution mass spectrometry and UV spectroscopy BT AF Pisapia, Francesco Sibat, Manoella Watanabe, Ryuichi Roullier, Catherine Suzuki, Toshiyuki Hess, Philipp Herrenknecht, Christine AS 1:1;2:1;3:2;4:3;5:2;6:1;7:3; FF 1:PDG-ODE-DYNECO-PHYC;2:PDG-ODE-DYNECO-PHYC;3:;4:;5:;6:PDG-ODE-DYNECO-PHYC;7:; C1 Ifremer, DYNECO Rue de l'Île d'Yeu 44311 Nantes, France NRIFS, Japan Fisheries Research and Education Agency 2‐12‐4 Fukuura, Kanazawa‐ku Yokohama Kanagawa 236‐8648, Japan Université de Nantes, MMS EA2160, Faculté de Pharmacie 9 rue Bias, 44035 Nantes, France C2 IFREMER, FRANCE NRIFS, JAPAN UNIV NANTES, FRANCE SI NANTES SE PDG-ODE-DYNECO-PHYC IN WOS Ifremer UPR copubli-france copubli-univ-france copubli-int-hors-europe IF 2.419 TC 7 UR https://archimer.ifremer.fr/doc/00633/74524/74355.pdf LA English DT Article AB Rationale The dinoflagellate genera Gambierdiscus and Fukuyoa are producers of toxins responsible for Ciguatera Poisoning (CP). Although having very low oral potency, maitotoxins (MTXs) are very toxic following intraperitoneal injection and feeding studies have shown they may accumulate in fish muscle. To date, six MTX congeners have been described but two congeners (MTX2 and MTX4) have not yet been structurally elucidated. The aim of the present study was to further characterize MTX4. Methods Chemical analysis was performed using Liquid Chromatography coupled to a Diode Array Detector (DAD) and positive ionization mode High Resolution Mass Spectrometry (LC/HRMS) on partially purified extracts of G. excentricus (strain VGO792). HRMS/MS studies were also carried out to tentatively explain the fragmentation pathways of MTX and MTX4. Results The comparison of UV and HRMS (ESI+) spectra between MTX and MTX4 led us to propose the elemental formula of MTX4 (C157H241NO68S2, as unsalted molecule). The comparison of the theoretical and measured m/z values of the doubly charged ions of the isotopic profile in ESI+ were coherent with the proposed elemental formula of MTX4. The study of HRMS/MS spectra on the tri‐ammoniated adduct ([M–H+3NH4]2+) of both molecules gave additional information about structural features. The cleavage observed, probably located at C99–C100 in both MTX and MTX4, highlighted the same A‐side product ion shared by the two molecules. Conclusion All these investigations on the characterization of MTX4 contribute to highlighting that MTX4 belongs to the same structural family of MTXs. However to accomplish a complete structural elucidation of MTX4, NMR‐based study and LC/HRMSn investigation will have to be carried out. PY 2020 PD OCT SO Rapid Communications In Mass Spectrometry SN 0951-4198 PU Wiley VL 34 IS 19 UT 000571215700004 DI 10.1002/rcm.8859 ID 74524 ER EF