Chemical defense in Platyphora kollari Baly and Leptinotarsa behrensi Harold (Coleoptera: Chrysomelidae). Hypotheses on the origin and evolution of leaf beetles toxins

Summary. The defensive secretions of Platyphora kollari beetles (Chrysomelidae) from Brazil contained one oleanene glycoside. This was identified as 3-O-g-D-glucopyranosyl-(l̆)-g-D-glucuronopyranosyl-hederagenin (8), by a combination of 1D and 2D NMR methods (COSY, HMQC, MBC) and SIMS. There were also several amino acid derivatives, including the known non-protein amino acid (Z)-2-amino-3,5-hexadienoic acid (1), the new dipeptide L-n-glutamyl-2-amino-(3Z)-hexenoic acid (4), ethanolamine (7), and a mixture of phosphatidylcholines. Compounds 1 and 7 have already been identified in several leaf beetle taxa. Secretions of Leptinotarsa behrensi contained as major triterpene glycoside 3-O-g-d-glucopyranosyl-(l̅)-g-d-glucuronopyranosyl-oleanolic acid-28-O-g-d-glucopyranoside (9), already isolated from Platyphora opima. Although the host plants of these beetles were devoid of these triterpene glycosides, g-amyrin was shown to be present in three plants on which different species of triterpene-producing chrysomelids had been fed (Mikania micrantha, Ipomoea batatas and Convolvulus arvensis). This suggests that these insects are able to use g-amyrin from their food plant as a precursor to their oleanolic- and hydroxyoleanolic acid glycosides. The distribution of toxins already identified in leaf beetles suggests that amino acid derivatives could be a plesiomorphic character, considering their wide distribution, whereas the secretion of triterpene saponins, probably derived from ubiquitous plant triterpenes, could be an apomorphic character shared by some Doryphorina. The secretion of cardenolides derived from ubiquitous plant phytosterols would be another apomorphic character shared by other Doryphorina and Chrysolinina.