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Intraspecific phytochemical variation across a landscape can cascade up trophic levels, potentially mediating the composition of entire insect communities. Surprisingly, we have little understanding of the processes that regulate and maintain phytochemical variation within species, likely because these processes are complex and operate simultaneously both temporally and spatially. To assess how phytochemistry varies within species, we tested the degree to which resource availability, contrasting soil type, and herbivory generate intraspecific chemical variation in growth and defense of the tropical shrub, Piper imperiale (Piperaceae). We quantified changes in both growth (e.g., nutritional protein, above- and below-ground biomass) and defense (e.g., imide chemicals) of individual plants using a well-replicated fully factorial shade-house experiment in Costa Rica. We found that plants grown in high light, nutrient- and richer old alluvial soil had increased biomass. High light was also important for increasing foliar protein. Thus, investment into growth was determined by resource availability and soil composition. Surprisingly, we found that chemical defenses decreased in response to herbivory. We also found that changes in plant protein were more plastic compared to plant defense, indicating that constitutive defenses may be relatively fixed, and thus an adaptation to chronic herbivory that is common in tropical forests. We demonstrate that intraspecific phytochemical variation of P. imperiale is shaped by resource availability from light and soil type. Because environmental heterogeneity occurs over small spatial scales (tens of meters), herbivores may be faced with a complex phytochemical landscape that may regulate how much damage any individual plant sustains., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Six new nostocyclophanes and four known compounds have been isolated from Nostoc linckia (Nostocaceae) cyanobacterial strain UTEX B1932. The new compounds, nostocyclophanes E-J ( 1 - 6 ), were characterized by NMR and MS techniques. The known compounds were nostocyclophanes B-D, previously isolated from this strain, and dedichloronostocyclophane D. Structural modifications on the new [7.7]paracyclophane analogs 1 - 5 , isolated from the 80% methanol fraction, range from simple changes such as the lack of methylation or halogenation to more unusual modifications such as those seen in nostocyclophane H ( 4 ), in which the exocyclic alkyl chains are of different length; this is the first time this modification has been observed in this family of natural products. In addition, nostocyclophane J ( 6 ) is a linear analog in which C-20 is chlorinated in preparation for the presumed enzymatic Friedel-Craft cyclization needed to form the final ring structure, analogous to the biosynthesis of the related cylindrocyclophanes. Nostocyclophane D, dedichloronostocyclophane D, and nostocyclophanes E-J demonstrated moderate to weak growth inhibition against MDA-MB-231 breast cancer cells.

Nectar chemistry can influence the behavior of pollinators in ways that affect pollen transfer, yet basic questions about how nectar chemical diversity impacts plant-pollinator relationships remain unexplored. For example, plants' capacity to produce neurotransmitters and endocrine disruptors may offer a means to manipulate pollinator behavior. We surveyed 15 plant species and discovered that two insect neurotransmitters, octopamine and tyramine, were widely distributed in floral nectar. We detected the highest concentration of these chemicals in Citrus , alongside the well-studied alkaloid caffeine. We explored the separate and interactive effects of these chemicals on insect pollinators in a series of behavioral experiments on bumblebees ( Bombus impatiens ). We found that octopamine and tyramine interacted with caffeine to alter key aspects of bee behavior relevant to plant fitness (sucrose responsiveness, long-term memory, and floral preferences). These results provide evidence for a means by which synergistic or antagonistic nectar chemistry might influence pollinators., Competing Interests: The authors declare no competing interests., (© 2022 The Author(s).)

Foundational hypotheses addressing plant-insect codiversification and plant defense theory typically assume a macroevolutionary pattern whereby closely related plants have similar chemical profiles. However, numerous studies have documented variation in the degree of phytochemical trait lability, raising the possibility that phytochemical evolution is more nuanced than initially assumed. We utilize proton nuclear magnetic resonance ( 1 H NMR) data, chemical classification, and double digest restriction-site associated DNA sequencing (ddRADseq) to resolve evolutionary relationships and characterize the evolution of secondary chemistry in the Neotropical plant clade Radula (Piper; Piperaceae). Sequencing data substantially improved phylogenetic resolution relative to past studies, and spectroscopic characterization revealed the presence of 35 metabolite classes. Metabolite classes displayed phylogenetic signal, whereas the crude 1 H NMR spectra featured little evidence of phylogenetic signal in multivariate tests of chemical resonances. Evolutionary correlations were detected in two pairs of compound classes (flavonoids with chalcones; p-alkenyl phenols with kavalactones), where the gain or loss of a class was dependent on the other's state. Overall, the evolution of secondary chemistry in Radula is characterized by strong phylogenetic signal of traditional compound classes and weak phylogenetic signal of specialized chemical motifs, consistent with both classic evolutionary hypotheses and recent examinations of phytochemical evolution in young lineages., (© 2021. The Author(s).)

Identifying the interactions of functional, biotic, and abiotic factors that define plant-insect communities has long been a goal of community ecologists. Metabolomics approaches facilitate a broader understanding of how phytochemistry mediates the functional interactions among ecological factors. Ceanothus velutinus communities are a relatively unstudied system for investigating chemically mediated interactions. Ceanothus are nitrogen-fixing, fire-adapted plants that establish early post-fire, and produce antimicrobial cyclic peptides, linear peptides, and flavonoids. This study takes a metabolomic approach to understanding how the diversity and variation of C. velutinus phytochemistry influences associated herbivore and parasitoid communities at multiple spatiotemporal scales. Herbivores and foliar samples were collected over three collection times at two sites on the east slope of the Sierra Nevada Mountain range. Foliar tissue was subjected to LC-MS metabolomic analysis, and several novel statistical analyses were applied to summarize, quantify, and annotate variation in the C. velutinus metabolome. We found that phytochemistry played an important role in plant-insect community structure across an elevational gradient. Flavonoids were found to mediate biotic and abiotic influences on herbivores and associated parasitoids, while foliar oligopeptides played a significant positive role in herbivore abundance, even more than abundance of host plants and leaf abundance. The importance of nutritional and defense chemistry in mediating ecological interactions in C. velutinus plant-herbivore communities was established, justifying larger scale studies of this plant system that incorporate other mediators of phytochemistry such as genetic and metageomic contributions.

Modern metabolomic approaches that generate more comprehensive phytochemical profiles than were previously available are providing new opportunities for understanding plant-animal interactions. Specifically, we can characterize the phytochemical landscape by asking how a larger number of individual compounds affect herbivores and how compounds covary among plants. Here we use the recent colonization of alfalfa ( Medicago sativa ) by the Melissa blue butterfly ( Lycaeides melissa ) to investigate the effects of indivdiual compounds and suites of covarying phytochemicals on caterpillar performance. We find that survival, development time, and adult weight are all associated with variation in nutrition and toxicity, including biomolecules associated with plant cell function as well as putative anti-herbivore action. The plant-insect interface is complex, with clusters of covarying compounds in many cases encompassing divergent effects on different aspects of caterpillar performance. Individual compounds with the strongest associations are largely specialized metabolites, including alkaloids, phenolic glycosides, and saponins. The saponins are represented in our data by more than 25 individual compounds with beneficial and detrimental effects on L. melissa caterpillars, which highlights the value of metabolomic data as opposed to approaches that rely on total concentrations within broad defensive classes., Competing Interests: The authors declare no competing interests., (© 2020 The Authors. Ecology and Evolution published by John Wiley & Sons Ltd.)

Tolyporphins L-R ( 2 - 8 ) have been isolated from a mixed cyanobacterium-microbial culture. The structures of tolyporphins L and M have been revised to four constitutional isomers, isolated as two mixtures of dioxobacteriochlorins ( 2 / 3 and 4 / 5 ). In contrast, tolyporphin P ( 6 ) is a fully oxidized tetrapyrrole, while tolyporphins Q and R ( 7 and 8 ) are oxochlorins. X-ray structures are reported for the first time for tolyporphins A ( 1 ), R ( 8 ), and E ( 9 ), revealing unexpected stereochemical variation within the series.

Herbivorous insects can defend themselves against pathogens via an immune response, which is influenced by the nutritional quality and phytochemistry of the host plant. However, it is unclear how these aspects of diet interact to influence the insect immune response and what role is played by ingested foliar microbes. We examined dietary protein, phytochemistry, and the caterpillar microbiome to understand variation in immune response of the Melissa blue butterfly, Lycaeides melissa. We also asked if these factors have host plant-specific effects by measuring L. melissa immune response when reared on a recently colonized exotic host plant (Medicago sativa) as compared to the immune response on an ancestral, native host (Astragalus canadensis). L. melissa did not experience immunological benefits directly related to consumption of the novel plant M. sativa. However, we did find negative, direct effects of phytochemical diversity and negative, direct effects of diet-derived microbial diversity on constitutive immune response for caterpillars fed M. sativa, as measured by phenoloxidase activity. Foliar protein did not directly influence the immune response, but did do so indirectly by increasing weight gain. Our results highlight the important effects of host diet on caterpillar physiology and raise the possibility that foliar microbiota, despite being rapidly passed through the gut, can affect the caterpillar immune response.

Plant-insect interactions are ubiquitous, and have been studied intensely because of their relevance to damage and pollination in agricultural plants, and to the ecology and evolution of biodiversity. Variation within species can affect the outcome of these interactions. Specific genes and chemicals that mediate these interactions have been identified, but genome- or metabolome-scale studies might be necessary to better understand the ecological and evolutionary consequences of intraspecific variation for plant-insect interactions. Here, we present such a study. Specifically, we assess the consequences of genome-wide genetic variation in the model plant Medicago truncatula for Lycaeides melissa caterpillar growth and survival (larval performance). Using a rearing experiment and a whole-genome SNP data set (>5 million SNPs), we found that polygenic variation in M. truncatula explains 9%-41% of the observed variation in caterpillar growth and survival. Genetic correlations among caterpillar performance and other plant traits, including structural defences and some anonymous chemical features, suggest that multiple M. truncatula alleles have pleiotropic effects on plant traits and caterpillar performance (or that substantial linkage disequilibrium exists among distinct loci affecting subsets of these traits). A moderate proportion of the genetic effect of M. truncatula alleles on L. melissa performance can be explained by the effect of these alleles on the plant traits we measured, especially leaf toughness. Taken together, our results show that intraspecific genetic variation in M. truncatula has a substantial effect on the successful development of L. melissa caterpillars (i.e., on a plant-insect interaction), and further point toward traits potentially mediating this genetic effect., (© 2019 John Wiley & Sons Ltd.)

Prenylflavonoids are an unique class of phytochemicals found in the inflorescences of the hop plant (Humulus lupulus). These flavonoids have demonstrated a wide range of biological activities, which may be influenced by their stereochemical configuration. Additionally, recent studies suggest that hop prenylflavonoids are subject to biotransformations which could alter or enrich their stereochemistry. In order to facilitate studies of the stereoisomers of flavanones, a facile method was developed for resolving the diastereomeric esters of flavanones via reversed-phase HPLC. Herein, a method for forming the tri-(1S)-(-)-camphanic acid esters of the 4',5,7-trihydroxy flavanones naringenin, 8-prenylnaringenin and 6-prenylnaringenin, is described. The respective diastereomers were separated using analytical reversed-phase HPLC. Diastereomeric esters were isolated by preparative HPLC to >98% d.e. based on HPLC, with their absolute configurations established by application of CD spectrometry.