Flavonoid Metabolites in the Hemolymph of European Pine Sawfly (Neodiprion sertifer) Larvae

Flavonoids in the hemolymph of European pine sawfly (Neodiprion sertifer) larvae that were feeding on Pinus sylvestris needles were identified. HPLC–ESI–MS analysis revealed that the main components in the hemolymph were flavonol di- and triglucosides and a catechin monoglucoside. These compounds were isolated from the larval hemolymph and their structures were established by HPLC–MS, GC–MS, and NMR spectroscopy. The isolated flavonoids were identified as (+)-catechin 7-O-β-glucoside, isorhamnetin 3,7,4′-tri-O-β-glucoside, kaempferol 3,7,4′-tri-O-β-glucoside, and quercetin 3,7,4′-tri-O-β-glucoside. The combined concentration of these four compounds in the hemolymph was 3.7 mg/ml. None of these compounds was present in the needles of P. sylvestris. Therefore, we propose that the flavonoid glucosides were produced by the larvae from flavonoid monoglucosides and (+)-catechin obtained from the pine needles.