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Sweet Poisons: Honeys Contaminated with Glycosides of the Neurotoxin Tutin

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    Sweet Poisons: Honeys Contaminated with Glycosides of the Neurotoxin Tutin
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    † The New Zealand Institute for Plant and Food Research Limited, Department of Chemistry, University of Otago, P.O. Box 56, Dunedin, New Zealand
    ‡ The New Zealand Institute for Plant and Food Research Limited, Private Bag 4704, Christchurch, New Zealand
    § The New Zealand Institute for Plant and Food Research Limited, Hamilton 3214, New Zealand
    *Tel: + 64 3 479 8354. E-mail: [email protected]
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    Journal of Natural Products

    Cite this: J. Nat. Prod. 2015, 78, 6, 1363–1369
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    https://doi.org/10.1021/acs.jnatprod.5b00241
    Published May 21, 2015
    Copyright © 2015 The American Chemical Society and American Society of Pharmacognosy
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    Abstract

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    Poisonings due to consumption of honeys containing plant toxins have been reported widely. One cause is the neurotoxin tutin, an oxygenated sesquiterpene picrotoxane, traced back to honeybees (Apis mellifera) collecting honeydew produced by passionvine hoppers (Scolypopa australis) feeding on sap of the poisonous shrub tutu (Coriaria spp.). However, a pharmacokinetic study suggested that unidentified conjugates of tutin were also present in such honeys. We now report the discovery, using ion trap LC-MS, of two tutin glycosides and their purification and structure determination as 2-(β-d-glucopyranosyl)tutin (4) and 2-[6′-(α-d-glucopyranosyl)-β-d-glucopyranosyl]tutin (5). These compounds were used to develop a quantitative triple quadrupole LC-MS method for honey analysis, which showed the presence of tutin (3.6 ± 0.1 μg/g honey), hyenanchin (19.3 ± 0.5), tutin glycoside (4) (4.9 ± 0.4), and tutin diglycoside (5) (4.9 ± 0.1) in one toxic honey. The ratios of 4 and 5 to tutin varied widely in other tutin-containing honeys. The glycosidation of tutin may represent detoxification by one or both of the insects involved in the food chain from plant to honey.

    Copyright © 2015 The American Chemical Society and American Society of Pharmacognosy

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    Supporting Information

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    Copies of NMR and mass spectra for tutin glycosides 4–7, LC-MS traces for analytical standards and one toxic honey, table of LC-MS quantitation of tutin and derivatives in toxic honeys from a variety of locations, and table of MRM transitions used for detection and quantitation of tutin and related compounds. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jnatprod.5b00241.

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    Journal of Natural Products

    Cite this: J. Nat. Prod. 2015, 78, 6, 1363–1369
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jnatprod.5b00241
    Published May 21, 2015
    Copyright © 2015 The American Chemical Society and American Society of Pharmacognosy
    Request reuse permissions

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