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Structural study of spirolide marine toxins by mass spectrometry

Part I. Fragmentation pathways of 13-desmethyl spirolide C by collision-induced dissociation and infrared multiphoton dissociation mass spectrometry

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Abstract

A novel group of toxins, the spirolides, has been investigated by several mass spectrometric (MS) methods to enable structure elucidation and metabolite identification. These macrocyclic compounds, produced by the dinoflagellate Alexandrium ostenfeldii, are a new class of marine phycotoxin with characteristic spiro-linked tricyclic ether and imine moieties. A crude phytoplankton extract has been shown to contain known spirolides and several unknown compounds, present at low yet significant levels. This study has focused on mass spectrometric characterization of the main component of this extract, 13-desmethyl spirolide C. Collision-induced dissociation (CID) spectra were collected on triple-quadrupole and quadrupole linear ion-trap instruments. High-resolution Fourier-transform ion cyclotron resonance MS data revealed the accurate masses of the protonated molecule and the product ions formed by infrared multiphoton dissociation. A fragmentation scheme for this toxin has been proposed to explain the formation of the collision-induced fragments. Charge-remote fragmentations dominate the CID spectra, because there is only one predominantly basic site in this molecule, and prove to be structurally informative. Extensive MS characterization of 13-desmethyl spirolide C will undoubtedly be useful in the characterization of known and unknown spirolides and other related compounds.

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Acknowledgements

The authors wish to thank Dr Michael Chalmers and Dr Alan Marshall at the NHMFL in Tallahassee, FL, USA, for the FTICR data (work supported in part by the NSF National High-Field FTICR MS Facility, CHE-99-09502). LS acknowledges financial assistance received from le Fonds Quebecois de la recherche sur la nature et les technologies (FCAR), the National Research Council’s Graduate Student Scholarship Supplement Program (GSSSP) and Dr Alan Cembella at the National Research Council’s Institute for Marine Biosciences. We would also like to thank Dr Stuart Grossert (Dalhousie University, Halifax, NS) for helpful discussions.

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  1. Institute for Marine Biosciences, National Research Council, 1411 Oxford Street, Halifax, Nova Scotia, B3H 3Z1, Canada

    Lekha Sleno, Anthony J Windust & Dietrich A Volmer

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  1. Lekha Sleno
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  2. Anthony J Windust
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  3. Dietrich A Volmer
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Correspondence to Dietrich A Volmer.

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Sleno, L., Windust, A.J. & Volmer, D.A. Structural study of spirolide marine toxins by mass spectrometry. Anal Bioanal Chem 378, 969–976 (2004). https://doi.org/10.1007/s00216-003-2297-z

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  • DOI: https://doi.org/10.1007/s00216-003-2297-z

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