Identification of a drimenol synthase and drimenol oxidase from Persicaria hydropiper, involved in the biosynthesis of insect deterrent drimanes

Abstract

SUMMARYThe sesquiterpenoid polygodial, which belongs to the drimane family, has been shown to be an antifeedant for a number of herbivorous insects. It is presumed to be synthesized from farnesyl diphosphate via drimenol, subsequent C-12 hydroxylation and further oxidations at both C-11 and C-12 to form a dialdehyde. Here, we have identified a drimenol synthase (PhDS) and a cytochrome P450 drimenol oxidase (PhDOX1) from Persicaria hydropiper. Expression of PhDS in yeast and plants resulted in production of drimenol alone. Co-expression of PhDS with PhDOX1 in yeast yielded drimendiol, the 12-hydroxylation product of drimenol, as a major product, and cinnamolide. When PhDS and PhDOX1 were transiently expressed by agro-infiltration in Nicotiana benthamiana leaves, drimenol was almost completely converted into cinnamolide and several additional drimenol derivatives were observed. In vitro assays showed that PhDOX1 only catalyses the conversion from drimenol to drimendiol, and not the further oxidation into an aldehyde. In yeast and heterologous plant hosts, the C-12 position of drimendiol is therefore likely to be further oxidized by endogenous enzymes into an aldehyde and subsequently converted to cinnamolide, presumably by spontaneous hemiacetal formation with the C-11 hydroxyl group followed by oxidation. Purified cinnamolide was confirmed by NMR and shown to be deterrent with an effective deterrent dose (ED 50 ) of about 200-400 lg g À1 fresh weight against both whiteflies and aphids. The putative additional physiological and biochemical requirements for polygodial biosynthesis and stable storage in plant tissues are discussed.

Antioxidant, α-amylase, and acetylcholinesterase inhibitory activities of Hertia cheirifolia essential oils: Influence of plant organs and seasonal variation

“…In fact, the molecular ion peak (M + ) of m/z 234, corresponding to C 15 H 22 O 2 as the molecular formula structure, and the base peak of m/z 109 are the main characteristics of drimane-type sesquiterpene lactone components. [27,28] The total essential oil composition and the occurrence of the drimane-type sesquiterpene lactone and drimenin, observed in our study, are not in line with the few previous studies reported on the species. In fact, Hertia cheirifolia growing in Algeria was characterized by its richness in drimenin (67.5%) and 1,2-Di (2-pyridinyl)-1,2-ethanediol (11.2%).…”

Insecticidal and Antifeedant Activities of Malagasy Medicinal Plant (Cinnamosma sp.) Extracts and Drimane-Type Sesquiterpenes against Aedes aegypti Mosquitoes

“…However, the antifeedant efficacy of 4 was similar to 1 , 9 , and 10 . Moreover, in the hemipteran pests Bemisia tabaci and Myzus persicae , 4 was antifeedant, albeit with apparent less potency than 9 [72]. Thus, our results suggest that the mechanism of 4 ’s antifeedant activity is distinct from 1 , 9 , and 10 , and remains to be elucidated.…”

Chemical Diversity and Biosynthesis of Drimane‐Type Sesquiterpenes in the Fungal Kingdom

“…[14] The in vitro activity of the isolated HAD-like enzyme, DrtB, demonstrated the formation of drimenol. This implies that, similar to plant terpene cyclases involved in polygodial biosynthesis, [15] DrtB is self-sufficient and produces drimenol by catalysing both dephosphorylation and cyclization of FPP (Figure 1). This explained the biosynthesis of the known DTSs and novel structures named calidoustenes A (3), B (4), and C (5), identified from A. calidoustus.…”