Caterpillars Detoxify Diterpenoid from Nepeta stewartiana by the Molting Hormone Gene CYP306A1.

Herbivorous insects are well known for detoxifying a broad range of the defense compounds produced by the plants that they feed on, but knowledge of the mechanisms of detoxification is still very limited. Here, we describe a system in which two species of lepidopteran caterpillars metabolize an abietane diterpene from the plants of Nepeta stewartiana Diels to an oxygenated derivative that is less active biologically. We found that this transformation could be catalyzed by a cytochrome P450 enzyme in caterpillars, which are associated with molting. Most interestingly, abietane diterpene targets the molting-associated gene CYP306A1 to alter the content of molting hormones in the insect at specific developmental stages and competitively inhibit molting hormone metabolism. These findings identify the mechanism by which caterpillars are able to detoxify abietane diterpenoid through hydroxylation at the C-19 position, which may be opening up exciting research questions into the mechanisms of interaction between plants and insects.

Thermally Induced Actinidine Production in Biological Samples.

Actinidine, a methylcyclopentane monoterpenoid pyridine alkaloid, has been found in many iridoid-rich plants and insect species. In a recent research on a well-known actinidine- and iridoid-producing ant species, Tapinoma melanocephalum (Fabricius) (Hymenoptera: Formicidae), no actinidine was detected in its hexane extracts by gas chromatography-mass spectrometry analysis using a common sample injection method, but a significant amount of actinidine was detected when a solid injection technique with a thermal separation probe was used. This result led us to hypothesize that heat can induce the production of actinidine in iridoid-rich organisms. To test our hypothesis, the occurrence of actinidine was investigated in four iridoid-rich organisms under different sample preparation temperatures, including two ant species, T. melanocephalum and Iridomyrmex anceps Roger (Hymenoptera: Formicidae), and two plant species, Actinidia polygama Maxim (Ericales: Actinidiaceae) and Nepeta cataria L. (Lamiales: Lamiaceae). Within a temperature range of 50, 100, 150, 200, and 250 °C, no actinidine was detected at 50 °C, but it appeared at temperatures above 100 °C for all four species. A positive relationship was observed between the heating temperature and actinidine production. The results indicate that actinidine could be generated at high temperatures. We also found that the presence of methylcyclopentane monoterpenoid iridoids (iridodials and nepetalactone) was needed for thermally induced actinidine production in all tested samples. These results suggest that the presence of actinidine in iridoid-rich plants and ants might be a consequence of using high temperatures during sample preparation.

The evolutionary origins of the cat attractant nepetalactone in catnip.

Catnip or catmint (Nepeta spp.) is a flowering plant in the mint family (Lamiaceae) famed for its ability to attract cats. This phenomenon is caused by the compound nepetalactone, a volatile iridoid that also repels insects. Iridoids are present in many Lamiaceae species but were lost in the ancestor of the Nepetoideae, the subfamily containing Nepeta. Using comparative genomics, ancestral sequence reconstructions, and phylogenetic analyses, we probed the re-emergence of iridoid biosynthesis in Nepeta. The results of these investigations revealed mechanisms for the loss and subsequent re-evolution of iridoid biosynthesis in the Nepeta lineage. We present evidence for a chronology of events that led to the formation of nepetalactone biosynthesis and its metabolic gene cluster. This study provides insights into the interplay between enzyme and genome evolution in the origins, loss, and re-emergence of plant chemical diversity.

Plant-Based Natural Product Chemistry for Integrated Pest Management of Drosophila suzukii.

Since the first reports of damage by Drosophila suzukii, the spotted-wing Drosophila (SWD), over a decade ago in Europe, widespread efforts have been made to understand both the ecology and the evolution of this insect pest, especially due to its phylogenetic proximity to one of the original model organisms, D. melanogaster. In addition, researchers have sought to find economically viable solutions for the monitoring and management of this agricultural pest, which has now swept across much of Europe, North America and Asia. In a new direction of study, we present an investigation of plant-based chemistry, where we search for natural compounds that are structurally similar to known olfactory cues from parasitoid wasps that in turn are well-described ovipositional avoidance cues for many Drosophila species. Here we test 11 plant species across two plant genera, Nepeta and Actinidia, and while we find iridoid compounds in both, only those odorants from Actinidia are noted to be detected by the insect antenna, and in addition, found to be behaviorally active. Moreover, the Actinidia extracts resulted in oviposition avoidance when they were added to fruit samples in the laboratory. Thus we propose the possible efficacy of these plants or their extracted chemistry as a novel means for establishing a cost-effective integrated pest management strategy towards the control of this pest fly.

Uncoupled activation and cyclization in catmint reductive terpenoid biosynthesis.

Terpene synthases typically form complex molecular scaffolds by concerted activation and cyclization of linear starting materials in a single enzyme active site. Here we show that iridoid synthase, an atypical reductive terpene synthase, catalyzes the activation of its substrate 8-oxogeranial into a reactive enol intermediate, but does not catalyze the subsequent cyclization into nepetalactol. This discovery led us to identify a class of nepetalactol-related short-chain dehydrogenase enzymes (NEPS) from catmint (Nepeta mussinii) that capture this reactive intermediate and catalyze the stereoselective cyclisation into distinct nepetalactol stereoisomers. Subsequent oxidation of nepetalactols by NEPS1 provides nepetalactones, metabolites that are well known for both insect-repellent activity and euphoric effects in cats. Structural characterization of the NEPS3 cyclase reveals that it binds to NAD+ yet does not utilize it chemically for a non-oxidoreductive formal [4 + 2] cyclization. These discoveries will complement metabolic reconstructions of iridoid and monoterpene indole alkaloid biosynthesis.

Differential effects of two strains of Rhizophagus intraradices on dry biomass and essential oil yield and composition in Calamintha nepeta.

The aim of this work was to determine the effects of two geographically different strains of Rhizophagus intraradices (M3 and GA5) on the total biomass and essential oil (EO) yield and composition of Calamintha nepeta, with or without phosphorus (P) fertilization, under greenhouse conditions. The plant biomass was not significantly affected by any of the treatments, showing higher values in control plants. Strains had a differential response in their root colonization rates: M3 reduced these parameters while GA5 did not modify them. Both strains affected EO yield in absence of P fertilization: M3 promoted EO yield in C. nepeta plants and GA5 resulted in negative effects. The percentage composition of EO was not significantly modified by either strain or P fertilization. M3 strain could be a potential fungal bioinoculant for production and commercialization of C. nepeta in the aromatic plant market.

Differential effects of two strains of Rhizophagus intraradices on dry biomass and essential oil yield and composition in Calamintha nepeta / Differential effects of two strains of Rhizophagus intraradices on dry biomass and essential oil yield and composition in Calamintha nepeta.

The aim of this work was to determine the effects of two geographically different strains of Rhizophagus intraradices (M3 and GA5) on the total biomass and essential oil (EO) yield and composition of Calamintha nepeta, with or without phosphorus (P) fertilization, under greenhouse conditions. The plant biomass was not significantly affected by any of the treatments, showing higher values in control plants. Strains had a differential response in their root colonization rates: M3 reduced these parameters while GA5 did not modify them. Both strains affected EO yield in absence of P fertilization: M3 promoted EO yield in C. nepeta plants and GA5 resulted in negative effects. The percentage composition of EO was not significantly modified by either strain or P fertilization. M3 strain could be a potential fungal bioinoculant for production and commercialization of C. nepeta in the aromatic plant market.

Differential effects of two strains of Rhizophagus intraradices on dry biomass and essential oil yield and composition in Calamintha nepeta. / Differential effects of two strains of Rhizophagus intraradices on dry biomass and essential oil yield and composition in Calamintha nepeta.

The aim of this work was to determine the effects of two geographically different strains of Rhizophagus intraradices (M3 and GA5) on the total biomass and essential oil (EO) yield and composition of Calamintha nepeta, with or without phosphorus (P) fertilization, under greenhouse conditions. The plant biomass was not significantly affected by any of the treatments, showing higher values in control plants. Strains had a differential response in their root colonization rates: M3 reduced these parameters while GA5 did not modify them. Both strains affected EO yield in absence of P fertilization: M3 promoted EO yield in C. nepeta plants and GA5 resulted in negative effects. The percentage composition of EO was not significantly modified by either strain or P fertilization. M3 strain could be a potential fungal bioinoculant for production and commercialization of C. nepeta in the aromatic plant market.

Aphid sex pheromones: from discovery to commercial production.

This review charts the progress made with aphid sex pheromone chemistry, from initial identification of cyclopentanoid nepetalactones, for example (4aS,7S,7aR)-nepetalactone (1). and (1R,4aS,7S,7aR)-nepetalactol (2). to commercial production from a renewable non-food crop, the catmint, Nepeta cataria (Lamiaceae). The availability of aphid sex pheromone components is now facilitating the development of new aphid pest control strategies, incorporating the use of other semiochemicals, particularly in the manipulation of populations of aphid parasitoids and aphid predators such as lacewings, which can utilise the nepetalactones and closely related molecules to locate their hosts and prey. This is the first example of a plant resource being developed as a feedstock for the production of a commercially valuable insect pheromone. The development of a plant-based production route highlights the tremendous potential that higher plants offer as cheap and renewable resources for the production of insect semiochemicals, through the wide array of secondary metabolites that they can generate.