Glycosides of the Neurotoxin Tutin in Toxic Honeys Are from Coriaria arborea Phloem Sap, Not Insect Metabolism

Some honeys contain the neurotoxin tutin (1) plus hyenanchin (2), 2-(β-d-glucopyranosyl)­tutin (3), and 2-[6′-(α-d-glucopyranosyl)-β-d-glucopyranosyl]­tutin (4). These honeys are made by bees collecting honeydew from passionvine hoppers feeding on the sap of tutu plants (Coriaria spp.). We report a LC-MS study showing that all these picrotoxanes are of plant, not insect, origin. Hyenanchin was barely detectable and the diglucoside was not detectable in C. arborea leaves, but tutu phloem sap contained all four compounds at concentrations up to the highest found in honeydew. It is proposed that the diglucoside may function as a transport form of tutin, analogous to sucrose transport in phloem.