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Structural elucidation of palytoxin analogs produced by the dinoflagellate Ostreopsis ovata IK2 strain by complementary use of positive and negative ion liquid chromatography/quadrupole time-of-flight mass spectrometry

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Abstract

RATIONALE

The ovatoxins are palytoxin analogs of a dinoflagellate origin implicated in human intoxication. The structures of ovatoxin-a, ovatoxin-d, and ovatoxin-e produced by the IK2 strain of Ostreopsis ovata collected in Japan were elucidated using liquid chromatography/quadrupole time-of-flight mass spectrometry (LC/QTOFMS). The novel structures and a new insight into the spectral data are presented.

METHODS

The structural elucidations were carried out by complementary use of positive and negative ion LC/QTOFMS. Ostreocin-D (C127H219N3O53), another palytoxin congener previously elucidated by negative fast-atom bombardment collision-induced tandem mass spectrometry (FAB CID MS/MS), was used as a reference.

RESULTS

Positive ion spectra allowed deduction of hydroxyl positions based on the conjugated polyene structures produced, while the negative ion spectra allowed assignments of cleavage sites of C–C bonds. The analysis could be performed using a small sample without extensive purification.

CONCLUSIONS

Ovatoxin-a IK2 (C129H223N3O52), ovatoxin-d IK2 (C129H223N3O53), and ovatoxin-e IK2 (C129H223N3O53) were tentatively assigned to 42-hydroxy-17,44,70-trideoxypalytoxin, 42-hydroxy-17,70-dideoxypalytoxin and 42,82-dihydroxy-17,44,70-trideoxypalytoxin, respectively. The wide applicability of the method was suggested. Copyright © 2013 John Wiley & Sons, Ltd.

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