Explore the vast range of titles available.

Scytonemin, a UV-protective pigment produced by cyanobacteria, is essential for microbial survival under extreme solar radiation. Recent studies suggest its structural analog, scytonemin imine, may serve as a biosynthetic marker for cyanobacteria exposed to intense light. Here, we present a structural revision, revealing scytonemin imine as a cyclic hydropyrrolo[2,3- b ]indole, rather than the previously proposed primary imine. This reassignment is supported by 1D and 2D NMR, Q-TOF mass spectrometry, confirmatory synthesis, and DFT calculations. Our synthesis demonstrates that scytonemin converts to scytonemin imine under mild conditions–ammonia and acetone exposure–suggesting the imine adduct is likely an artifact of isolation. However, our findings also indicate that this artifact may reveal a previously unrecognized in-vivo state of scytonemin, which is released upon condensation with acetone. This reactivity uncovers a new chromism within the scytonemin scaffold, supporting the idea that biogenic scytonemin analogs may filter visible light to regulate photosynthesis and protect against ROS-mediated photodamage during high light exposure or desiccation. This chromatic transformation highlights scytonemin’s structural adaptability, offering insight into its role as a protective pigment in ancient and modern cyanobacteria and its relevance for understanding microbial adaptation to extreme environments.

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.

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.

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.

In the original publication [...]

Phytochemical diversity is increasingly appreciated as an important attribute of plants that affects their interactions with other organisms and can have substantial effects on arthropod communities, but this axis of diversity is less studied for agricultural plants. For both managed and natural systems, understanding how extreme weather events, such as droughts, floods, and extreme wind, affect phytochemical diversity is an important part of predicting responses of plant–arthropod interactions to climate change. In an outdoor field experiment with two distinct varieties of hemp (Cannabis sativa L., Cannabaceae), we investigated the effects of simulated water stress from reduced water availability and flooding, along with an unplanned extreme wind event on phytochemical diversity and cannabinoid profiles. We also examined how changes in chemistry affected the diversity of the associated arthropods. Our results indicate that both genetic variety and environmental stress have substantial effects on variation in hemp phytochemical diversity and cannabinoid composition, and these effects cascaded to alter the arthropod communities on flowers. The largest differences in chemistry were found between different varieties, which accounted for over 10% of the variation in phytochemical diversity. Stress from wind and floods reduced the phytochemical diversity of flowers, wind had negative effects on cannabidiol (CBD) concentrations, and both water deficit and flooding caused subtle shifts in cannabinoid composition. The subsequent cascading effects of chemistry depended on how it was characterized, with increases in CBD causing higher arthropod richness, while increased phytochemical diversity reduced arthropod diversity. These results provide insights into the potential effects of extreme weather on hemp chemistry, as well as the consequences of hemp phytochemical diversity on colonizing arthropods.

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. We use modern metabolomic profiling to dissect the complexity of phytochemistry affecting the development and survival of a specialist caterpillar on a novel host plant. A diversity of effects are uncovered, including positive and negative consequences of variation in metabolites with a range of function. Associations among plant traits are discussed in the context of the evolution of this plant‐insect interaction.

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.

Studies of herbivores and secondary consumer communities rarely incorporate a comprehensive characterization of primary producer trait variation, thus limiting our understanding of how plants mediate community assembly of consumers. We took advantage of recent technological developments for efficient generation of phytochemical, microbial and genomic data to characterize individual alfalfa plants (Medicago sativa; Fabaceae) growing in an old‐field, semi‐naturalized state for 770 traits (including 753 chemical features). Using random forest modelling, we investigated the effect of variation in these traits on arthropod and fungal assemblages while accounting for plant genetic structure. We found that traits indicative of plant vigour, including size, percentage of flowering stems and leaf area, were positively associated with arthropod richness and abundance. Most phytochemicals were, by comparison, poor predictors, although phytochemical diversity and several individual phenolic compounds were important. Plants with a higher proportion of flowering stems were hotspots of intertrophic interactions with higher species richness of secondary consumers. The effects of many traits on plant‐associated assemblages were best modelled as nonlinear functions, often incorporating threshold effects. Foliar fungal richness was not well predicted by our models, suggesting we have much to learn regarding the role of plant traits on phyllosphere fungi at small spatial scales. Our results support the need for characterization of multiple axes of plant phenotypes in studies of plant‐arthropod‐microbe communities and demonstrate the value of modern analytical techniques for understanding the nonlinear ways in which plant traits mediate the structure of associated biotic communities. A plain language summary is available for this article. Plain Language Summary