Identification of gymnodimine D and presence of gymnodimine variants in the dinoflagellate Alexandrium ostenfeldii from the Baltic Sea

• Published in: Toxicon (Oxford) 2016-03, Vol.112, p.68-76
• Main Authors: Harju, Kirsi, Koskela, Harri, Kremp, Anke, Suikkanen, Sanna, de la Iglesia, Pablo, Miles, Christopher O., Krock, Bernd, Vanninen, Paula
• Format: Article
• Language: English
• Subjects: Alexandrium ostenfeldii; Atlantic Ocean; Carbon; Cells, Cultured; Chromatography; Chromatography, High Pressure Liquid; Clone Cells; Culture; Dinoflagellate; Dinoflagellates; Dinoflagellida - chemistry; Dinoflagellida - cytology; Dinoflagellida - growth & development; Dinoflagellida - metabolism; Gymnodimine; Harmful Algal Bloom; Heterocyclic Compounds, 3-Ring - chemistry; Heterocyclic Compounds, 3-Ring - isolation & purification; Heterocyclic Compounds, 3-Ring - metabolism; Heterocyclic Compounds, 4 or More Rings - chemistry; Heterocyclic Compounds, 4 or More Rings - isolation & purification; Heterocyclic Compounds, 4 or More Rings - metabolism; High resolution mass spectrometry; Hydrocarbons, Cyclic - chemistry; Hydrocarbons, Cyclic - isolation & purification; Hydrocarbons, Cyclic - metabolism; Imines; Imines - chemistry; Imines - isolation & purification; Imines - metabolism; Karenia; Liquid chromatography–mass spectrometry; Liquids; Marine Toxins - chemistry; Marine Toxins - isolation & purification; Marine Toxins - metabolism; Mass spectrometry; Methylation; Molecular Structure; Nuclear magnetic resonance; Nuclear Magnetic Resonance, Biomolecular; Spectrometry, Mass, Electrospray Ionization; Stereoisomerism; Sweden; Tandem Mass Spectrometry
• ISSN: 0041-0101; 1879-3150
• DOI: 10.1016/j.toxicon.2016.01.064

Gymnodimines are lipophilic toxins produced by the marine dinoflagellates Karenia selliformis and Alexandrium ostenfeldii. Currently four gymnodimine analogues are known and characterized. Here we describe a novel gymnodimine and a range of gymnodimine related compounds found in an A. ostenfeldii isolate from the northern Baltic Sea. Gymnodimine D (1) was extracted and purified from clonal cultures, and characterized by liquid chromatography–tandem mass spectrometry (LC–MS/MS), nuclear magnetic resonance (NMR) spectroscopy, and liquid chromatography–high resolution mass spectrometry (LC–HRMS) experiments. The structure of 1 is related to known gymnodimines (2–5) with a six-membered cyclic imine ring and several other fragments typical of gymnodimines. However, the carbon chain in the gymnodimine macrocyclic ring differs from the known gymnodimines in having two tetrahydrofuran rings in the macrocyclic ring. •A novel gymnodimine was found in the cultured A. ostenfeldii dinoflagellate isolated from the Baltic Sea.•The structure of gymnodimine D was determined with LC–MS/MS and NMR studies.•Other gymnodimine variants were also detected in A. ostenfeldii from the Baltic Sea.