High Value-Added Application of Natural Products in Crop Protection: Discovery and Exploration of Caffeoyl and Flavonoid Derivatives from Clematis brevicaudata DC. as Novel Insecticide Candidates

Abstract

Nine caffeoyl derivatives (1−9), including two new dicaffeoyl glycosides, brevicaudatosides A and B (1 and 2), and six flavonoids (10−15), were identified from overground Clematis brevicaudata DC. Compounds 1 and 13 exhibited significant oral toxicities against Acyrthosiphon pisum Harris with LC 50 (half-lethal concentration) values of 0.12 and 0.28 mM, respectively. Meanwhile, compounds 1, 8, 10, 13, and 15 showed remarkable repellent effects against A. pisum with the repellent indexes valued at 1.00 under 50−200 μg/mL at 24 h. Compounds 1 and 8 also displayed moderate antifeedant activities against Plutella xylostella L. The shrunken bodies, especially for wizened cauda, and the ultrastructural damages of microvilli, mitochondrion, nucleus, and endoplasmic reticulum in midgut were toxic symptoms of A. pisum caused by 1 and 13. The inhibition of Chitinase was the main reason for their potent insecticidal activities. This study provided valuable pieces of evidence for the high value-added application of caffeoyl and flavonoid derivatives from C. brevicaudata as novel plant-origin biopesticides for crop protection.