Protein-Ligand Binding and Structural Modelling Studies of Pheromone-Binding Protein-like Sol g 2.1 from Solenopsis geminata Fire Ant Venom.

Sol g 2 is the major protein in Solenopsis geminata fire ant venom. It shares the highest sequence identity with Sol i 2 (S. invicta) and shares high structural homology with LmaPBP (pheromone-binding protein (PBP) from the cockroach Leucophaea maderae). We examined the specific Sol g 2 protein ligands from fire ant venom. The results revealed that the protein naturally formed complexes with hydrocarbons, including decane, undecane, dodecane, and tridecane, in aqueous venom solutions. Decane showed the highest affinity binding (Kd) with the recombinant Sol g 2.1 protein (rSol g 2.1). Surprisingly, the mixture of alkanes exhibited a higher binding affinity with the rSol g 2.1 protein compared to a single one, which is related to molecular docking simulations, revealing allosteric binding sites in the Sol g 2.1 protein model. In the trail-following bioassay, we observed that a mixture of the protein sol g 2.1 and hydrocarbons elicited S. geminata worker ants to follow trails for a longer time and distance compared to a mixture containing only hydrocarbons. This suggests that Sol g 2.1 protein may delay the evaporation of the hydrocarbons. Interestingly, the piperidine alkaloids extracted have the highest attraction to the ants. Therefore, the mixture of hydrocarbons and piperidines had a synergistic effect on the trail-following of ants when both were added to the protein.

(R)-(+)-γ-Decalactone is Conserved in North America as a Pheromone Component of Osmoderma eremicola (Coleoptera: Scarabaeidae) and a Kairomone of Elater abruptus (Coleoptera: Elateridae).

The scarab genus Osmoderma (Coleoptera: Scarabaeidae) includes several large species called hermit beetles that develop within dead and decaying hardwood trees. Males of at least three Palearctic species produce the aggregation-sex pheromone (R)-(+)-γ-decalactone, including the endangered O. eremita (Scopoli). However, hermit beetles have received less attention in the western hemisphere, resulting in a large gap in our knowledge of the chemical ecology of Nearctic species. Here, we identify (R)-( +)-γ-decalactone as the primary component of the aggregation-sex pheromone of the North American species Osmoderma eremicola (Knoch). Field trials at sites in Wisconsin and Illinois revealed that both sexes were attracted to lures containing (R)-(+)-γ-decalactone or the racemate, but only males of O. eremicola produced the pheromone in laboratory bioassays, alongside an occasional trace of the chain-length analog γ-dodecalactone. Females of the congener O. scabra (Palisot de Beauvois) were also significantly attracted by γ-decalactone, suggesting further conservation of the pheromone, as were females of the click beetle Elater abruptus Say (Coleoptera: Elateridae), suggesting that this compound may have widespread kairomonal activity. Further research is needed to explore the behavioral roles of both lactones in mediating behavioral and ecological interactions among these beetle species.

Structure, Synthesis, and Bioassays of Sex Pheromone for Pyrausta machaeralis (Lepidoptera: Crambidae).

The leaf skeletonizer, Pyrausta machaeralis (Lepidoptera: Crambidae), is a serious insect pest of teak (Tectona grandis) in China. The application of insect pheromones is widely applied as an environmentally friendly technology for integrated pest management (IPM). In the present study, crude extracts of sex pheromone glands of calling P. machaeralis females were collected and then analyzed using gas chromatography/electroantennographic detection (GC/EAD) and gas chromatography-mass spectrometry (GC-MS). The combination of infrared spectroscopy (IR) and nuclear magnetic resonance (NMR) spectrometry was used for structure identification. Afterward, their electrophysiological and behavioral activity was evaluated in the laboratory and field. Herein, we eventually determined two active components, E-11-tetradecenyl acetate (E11-14:Ac) and Z-11-tetradecenyl acetate (Z11-14:Ac), at a ratio of 96:4, as the sex pheromone of P. machaeralis. The identification of sex pheromones would facilitate the development of efficient strategies for monitoring and controlling the field populations of P. machaeralis.

Cuticular lipid profiles of selected species of cyclocephaline beetles (Melolonthidae, Cyclocephalini).

Neotropical cyclocephaline beetles, a diverse group of flower-loving insects, significantly impact natural and agricultural ecosystems. In particular, the genus Cyclocephala, with over 350 species, displays polymorphism and cryptic complexes. Lacking a comprehensive DNA barcoding framework, accessible tools for species differentiation are needed for research in taxonomy, ecology, and crop management. Moreover, cuticular hydrocarbons are believed to be involved in sexual recognition mechanisms in these beetles. In the present study we examined the cuticular chemical profiles of six species from the genus Cyclocephala and two populations of Erioscelis emarginata and assessed their efficiency in population, species, and sex differentiation. Overall we identified 74 compounds in cuticular extracts of the selected taxa. Linear alkanes and unsaturated hydrocarbons were prominent, with ten compounds between them explaining 85.6% of species dissimilarity. Although the cuticular chemical profiles efficiently differentiated all investigated taxa, only C. ohausiana showed significant cuticular profile differences between sexes. Our analysis also revealed two E. emarginata clades within a larger group of 'Cyclocephala' species, but they were not aligned with the two studied populations. Our research underscores the significance of cuticular lipid profiles in distinguishing selected cyclocephaline beetle species and contemplates their potential impact as contact pheromones on sexual segregation and speciation.

The Trail-Following Communication in Stylotermes faveolus and S. halumicus (Blattodea, Isoptera, Stylotermitidae).

Stylotermitidae appear peculiar among all termites, feeding in trunks of living trees in South Asia only. The difficulty to collect them limits the ability to study them, and they thus still belong to critically unknown groups in respect to their biology. We used a combination of microscopic observations, chemical analysis and behavioural tests, to determine the source and chemical nature of the trail-following pheromone of Stylotermes faveolus from India and S. halumicus from Taiwan. The sternal gland located at the 5th abdominal segment was the exclusive source of the trail-following pheromone in both S. faveolus and S. halumicus, and it is made up of class I, II and III secretory cells. Using gas chromatography coupled mass spectrometry, (3Z)-dodec-3-en-1-ol (DOE) was identified as the trail-following pheromone which elicits strong behavioural responses in workers at a threshold around 10- 4 ng/cm and 0.1 ng/gland. Our results confirm the switch from complex aldehyde trail-following pheromones occurring in the basal groups to simpler linear alcohols in the ancestor of Kalotermitidae and Neoisoptera.

Natural genetic variation in the pheromone production of C. elegans.

From bacterial quorum sensing to human language, communication is essential for social interactions. Nematodes produce and sense pheromones to communicate among individuals and respond to environmental changes. These signals are encoded by different types and mixtures of ascarosides, whose modular structures further enhance the diversity of this nematode pheromone language. Interspecific and intraspecific differences in this ascaroside pheromone language have been described previously, but the genetic basis and molecular mechanisms underlying the variation remain largely unknown. Here, we analyzed natural variation in the production of 44 ascarosides across 95 wild Caenorhabditis elegans strains using high-performance liquid chromatography coupled to high-resolution mass spectrometry. We discovered wild strains defective in the production of specific subsets of ascarosides (e.g., the aggregation pheromone icas#9) or short- and medium-chain ascarosides, as well as inversely correlated patterns between the production of two major classes of ascarosides. We investigated genetic variants that are significantly associated with the natural differences in the composition of the pheromone bouquet, including rare genetic variants in key enzymes participating in ascaroside biosynthesis, such as the peroxisomal 3-ketoacyl-CoA thiolase, daf-22, and the carboxylesterase cest-3. Genome-wide association mappings revealed genomic loci harboring common variants that affect ascaroside profiles. Our study yields a valuable dataset for investigating the genetic mechanisms underlying the evolution of chemical communication.

Chemical signatures of egg maternity and Dufour's gland in Vespine wasps.

Cuticular hydrocarbons (CHCs) are often used in the chemical communication among social insects. CHCs can be used in nestmate recognition and as queen pheromones, the latter allows the regulation of the reproductive division of labor. In the common wasp Vespula vulgaris, CHCs and egg-marking hydrocarbons are caste-specific, being hydrocarbon queen pheromones and egg maternity signals. Whether these compounds are conserved among other Vespinae wasps remains unknown. Queens, virgin queens, reproductive workers, and workers belonging to four different wasp species, Dolichovespula media, Dolichovespula saxonica, Vespa crabro, and Vespula germanica, were collected and studied. The cuticular hydrocarbons, egg surface, and Dufour's gland composition were characterized and it was found that chemical compounds are caste-specific in the four species. Quantitative and qualitative differences were detected in the cuticle, eggs, and Dufour's gland. Some specific hydrocarbons that were shown to be overproduced in the cuticle of queens were also present in higher quantities in queen-laid eggs and in their Dufour's gland. These hydrocarbons can be indicated as putative fertility signals that regulate the division of reproductive labor in these Vespine societies. Our results are in line with the literature for V. vulgaris and D. saxonica, in which hydrocarbons were shown to be conserved queen signals. This work presents correlative evidence that queen chemical compounds are found not only over the body surface of females but also in other sources, such as the Dufour's gland and eggs.

Nematode Pheromones: Structures and Functions.

Pheromones are chemical signals secreted by one individual that can affect the behaviors of other individuals within the same species. Ascaroside is an evolutionarily conserved family of nematode pheromones that play an integral role in the development, lifespan, propagation, and stress response of nematodes. Their general structure comprises the dideoxysugar ascarylose and fatty-acid-like side chains. Ascarosides can vary structurally and functionally according to the lengths of their side chains and how they are derivatized with different moieties. In this review, we mainly describe the chemical structures of ascarosides and their different effects on the development, mating, and aggregation of nematodes, as well as how they are synthesized and regulated. In addition, we discuss their influences on other species in various aspects. This review provides a reference for the functions and structures of ascarosides and enables their better application.

Impact of Marine Chemical Ecology Research on the Discovery and Development of New Pharmaceuticals.

Diverse ecologically important metabolites, such as allelochemicals, infochemicals and volatile organic chemicals, are involved in marine organismal interactions. Chemically mediated interactions between intra- and interspecific organisms can have a significant impact on community organization, population structure and ecosystem functioning. Advances in analytical techniques, microscopy and genomics are providing insights on the chemistry and functional roles of the metabolites involved in such interactions. This review highlights the targeted translational value of several marine chemical ecology-driven research studies and their impact on the sustainable discovery of novel therapeutic agents. These chemical ecology-based approaches include activated defense, allelochemicals arising from organismal interactions, spatio-temporal variations of allelochemicals and phylogeny-based approaches. In addition, innovative analytical techniques used in the mapping of surface metabolites as well as in metabolite translocation within marine holobionts are summarized. Chemical information related to the maintenance of the marine symbioses and biosyntheses of specialized compounds can be harnessed for biomedical applications, particularly in microbial fermentation and compound production. Furthermore, the impact of climate change on the chemical ecology of marine organisms-especially on the production, functionality and perception of allelochemicals-and its implications on drug discovery efforts will be presented.

Volatile Organic Compounds: A Promising Tool for Bed Bug Detection.

The recent decades' resurgence of bed bugs as a public health concern in industrialized countries has driven an increased interest on new sustainable insecticide-free methods to monitor and control these ectoparasites. Current methods of detection rely mainly on visual inspection or canine scent detection, which are methods that are time-consuming, require experience, are non-specific or require costly mission repetitions. Volatile organic compounds (VOCs) are considered an environmentally friendly alternative and a promising approach for bed bug detection. An overview of the released literature on VOCs, their chemical characteristics and their role in bed bugs' intra- and inter-species communications allowed us to highlight the identification of 49 VOCs in Cimex lectularius (23 molecules) and C. hemipterus (26), which are emitted by both sexes during diverse compartments including aggregation (46), mating (11), defense (4), etc., and all life stages including exuviae or dead bed bugs as a principal indicator of infestation. The latter has a great importance for application of these semiochemicals in successful detection and control management of bed bugs and to prevent their further dispersion. This approach has the advantage of more reliability compared to conventional detection methods with no need for repeated inspections, household furniture moving or resident rehousing for bed bugs' VOC detection, which are commonly performed by active or passive sampling with absorbing tubes and analyzed by gas chromatography-based analytical platforms.

Development of a New Sex Attractant via the Peripheral Coding of Pheromones in Mythimna loreyi.

Sex pheromones play an essential role when moths are searching for mates. Male olfactory receptor neurons (ORNs) are the primary determinant during peripheral pheromone recognition. Here, we identified the sex pheromones of a global agricultural pest, Mythimna loreyi, using gas chromatography coupled with mass spectrometry and electroantennographic detection. Nine pheromone components were identified, including (Z)-9-tetradecen-1-yl acetate (Z9-14:OAc), (Z)-7-dodecen-1-yl acetate (Z7-12:OAc), and (Z)-11-hexadecen-1-yl acetate (Z11-16:OAc), and the first two elicited electrophysiological activities in the male antennae. Trichoid sensilla were classified into four functional types on the basis of neuronal responses to pheromones by single sensillum recording. Five functional ORNs were involved in recognizing pheromones and pheromone analogues. Finally, a field bioassay revealed that a blend of Z9-14:OAc, Z7-12:OAc, and Z11-16:OAc at a ratio of 100:8.8:19.7 was highly efficient for trapping males. Our results uncover the pheromone recognition mechanism in M. loreyi and provide a novel angle for developing efficient sex attractants of pests on the basis of screening the peripheral olfactory neurons.

The Alarm Pheromone and Alarm Response of the Clonal Raider Ant.

Ants communicate via an arsenal of different pheromones produced in a variety of exocrine glands. For example, ants release alarm pheromones in response to danger to alert their nestmates and to trigger behavioral alarm responses. Here we characterize the alarm pheromone and the alarm response of the clonal raider ant Ooceraea biroi, a species that is amenable to laboratory studies but for which no pheromones have been identified. During an alarm response, ants quickly become unsettled, leave their nest pile, and are sometimes initially attracted to the source of alarm, but ultimately move away from it. We find that the alarm pheromone is released from the head of the ant and identify the putative alarm pheromone as a blend of two compounds found in the head, 4-methyl-3-heptanone and 4-methyl-3-heptanol. These compounds are sufficient to induce alarm behavior alone and in combination. They elicit similar, though slightly different behavioral features of the alarm response, with 4-methyl-3-heptanone being immediately repulsive and 4-methyl-3-heptanol being initially attractive before causing ants to move away. The behavioral response to these compounds in combination is dose-dependent, with ants becoming unsettled and attracted to the source of alarm pheromone at low concentrations and repulsed at high concentrations. While 4-methyl-3-heptanone and 4-methyl-3-heptanol are known alarm pheromones in other more distantly related ant species, this is the first report of the chemical identity of a pheromone in O. biroi, and the first alarm pheromone identified in the genus Ooceraea. Identification of a pheromone that triggers a robust, consistent, and conserved behavior, like the alarm pheromone, provides an avenue to dissect the behavioral and neuronal mechanisms underpinning chemical communication.

Recent advances in the synthesis of insect pheromones: an overview from 2013 to 2022.

Covering: 2013 to June 2022Pheromones are usually produced by insects in sub-microgram amounts, which prevents the elucidation of their structures by nuclear magnetic resonance (NMR). Instead, a synthetic reference material is needed to confirm the structure of the natural compounds. In addition, the provision of synthetic pheromones enables large-scale field trials for the development of environmentally friendly pest management tools. Because of these potential applications in pest control, insect pheromones are attractive targets for the development of synthetic procedures and the synthesis of these intraspecific chemical messengers has been at the core of numerous research efforts in the field of pheromone chemistry. The present review is a quick reference guide for the syntheses of insect pheromones published from 2013 to mid-2022, listing the synthesized compounds and highlighting current methodologies in organic synthesis, such as carbon-carbon coupling reactions, organo-transition metal chemistry including ring-closing olefin metathesis, asymmetric epoxidations and dihydroxylations, and enzymatic reactions.

The volatile chemistry of orchid pollination.

Covering: up to September 2022Orchids are renowned not only for their diversity of floral forms, but also for their many and often highly specialised pollination strategies. Volatile semiochemicals play a crucial role in the attraction of a wide variety of insect pollinators of orchids. The compounds produced by orchid flowers are as diverse as the pollinators they attract, and here we summarise some of the chemical diversity found across orchid taxa and pollination strategies. We focus on compounds that have been experimentally demonstrated to underpin pollinator attraction. We also highlight the structural elucidation and synthesis of a select subset of important orchid pollinator attractants, and discuss the ecological significance of the discoveries, the gaps in our current knowledge of orchid pollination chemistry, and some opportunities for future research in this field.

Allelochemical run-off from the invasive terrestrial plant Impatiens glandulifera decreases defensibility in Daphnia.

Invasive species are a major threat for native ecosystems and organisms living within. They are reducing the biodiversity in invaded ecosystems, by outcompeting native species with e. g. novel substances. Invasive terrestrial plants can release allelochemicals, thereby reducing biodiversity due to the suppression of growth of native plants in invaded habitats. Aside from negative effects on plants, allelochemicals can affect other organisms such as mycorrhiza fungi and invertebrates in terrestrial ecosystems. When invasive plants grow in riparian zones, it is very likely that terrestrial borne allelochemicals can leach into the aquatic ecosystem. There, the often highly reactive compounds may not only elicit toxic effects to aquatic organisms, but they may also interfere with biotic interactions. Here we show that the allelochemical 2-methoxy-1,4-naphthoquinone (2-MNQ), produced by the ubiquitously occurring invasive terrestrial plant Impatiens glandulifera, interferes with the ability of Daphnia to defend itself against predators with morphological defences. Daphnia magna and Daphnia longicephala responded with morphological defences induced by chemical cues released by their corresponding predators, Triops cancriformis or Notonecta sp. However, predator cues in combination with 2-MNQ led to a reduction in the morphological defensive traits, body- and tail-spine length, in D. magna. In D. longicephala all tested inducible defensive traits were not significantly affected by 2-MNQ but indicate similar patterns, highlighting the importance to study different species to assess the risks for aquatic ecosystems. Since it is essential for Daphnia to adapt defences to the current predation risk, a maladaptation in defensive traits when simultaneously exposed to allelochemicals released by I. glandulifera, may therefore have knock-on effects on population dynamics across multiple trophic levels, as Daphnia is a key species in lentic ecosystems.

Honeybee queen mandibular pheromone induces a starvation response in Drosophila melanogaster.

Eusocial insect societies are defined by the reproductive division of labour, a social structure that is generally enforced by the reproductive dominant(s) or 'queen(s)'. Reproductive dominance is maintained through behavioural dominance or production of queen pheromones, or a mixture of both. Queen mandibular pheromone (QMP) is a queen pheromone produced by queen honeybees (Apis mellifera) which represses reproduction in worker honeybees. How QMP acts to repress worker reproduction, the mechanisms by which this repression is induced, and how it has evolved this activity, remain poorly understood. Surprisingly, QMP is capable of repressing reproduction in non-target arthropods. Here we show that in Drosophila melanogaster QMP treatment mimics the starvation response, disrupting reproduction. QMP exposure induces an increase in food consumption and activation of checkpoints in the ovary that reduce fecundity and depresses insulin signalling. The magnitude of these effects is indistinguishable between QMP-treated and starved individuals. As QMP triggers a starvation response in an insect diverged from honeybees, we propose that QMP originally evolved by co-opting nutrition signalling pathways to regulate reproduction.

The scent chemistry of butterflies.

Covering: 1990 up to 2022 Contrary to popular opinion, butterflies exhibit a rich chemistry and elaborate use of volatile compounds, especially for sexual communication, but also for defence. In contrast to night flying moths, in which commonly females are the producers of pheromones, male scent emission is prevalent in butterflies. While visual signals are generally important for long-range attraction, butterfly scent signals are often active only within a short range. Another feature of butterfly scent chemistry is the wide variety of compounds used, including alkaloids, terpenoids, fatty acid derivatives and aromatic compounds, sometimes with unique structures. This contrasts the strucutrally more restricted pheromone chemistry of moths. In this review, the compounds emitted predominately from male butterflies will be discussed and their ecological function explained, if known. The review includes material from 1990 to date, but will also cover older material to provide a necessary background.

No Evidence of Responding Individuals Constraining the Evolution of the Pheromone Signal in the Pine Engraver Ips avulsus.

Chemical signals are important mediators of interactions within forest ecosystems. In insects, pheromone signals mediate intraspecific interactions such as mate location and acceptance. The evolution of pheromones in insects has been mostly studied from a theoretical perspective in the Lepidoptera. With this study, we aimed to broaden our understanding of pheromone communication in bark beetles. We first demonstrated that the enantiomeric ratios of ipsdienol produced by male I. avulsus, showed little variation. Subsequently, with field trapping trials we characterized the influence of the enantiomeric ratio of ipsdienol (pheromone component of I. avulsus) on I. avulsus captures and observed a great amount of variation in the receiver preference function. Most importantly, we demonstrated that responding individuals responded indiscriminately to all the enantiomeric ratios produced by the emitting individuals. These observations are consistent with the asymmetric tracking model which postulates that if the limiting sex is the emitting sex, responding individuals should not discriminate between emitted ratios. Consequently, responding individuals do not constrain the evolution of the signal. Our data suggest that, in I. avulsus, the composition of the aggregation pheromone signal might be more responsive to external selection forces, such as predation and metabolic constraints, as suggested by the asymmetric tracking model.

Quick and In Situ Detection of Different Polar Allelochemicals in Taxus Soil by Microdialysis Combined with UPLC-MS/MS.

The action of allelopathy need that allelochemicals exist in the soil and reach a certain concentration. Also, the detection of allelochemicals in the soil is one of the most important research topics in the process of exploring allelopathy. To solve the problem of the simultaneous detection of allelochemicals with low concentrations and different polarities, a novel strategy for the quick detection of the allelochemicals in Taxus soil by microdialysis combined with UPLC-MS/MS on the basis of in situ detection without destroying the original structure of soil was developed for the first time in the work. The dialysis conditions were optimized by the Box-Behnken design (BBD): 70% methanol, 3 µL/min flow rate, and 3 cm long membrane tube. A reliable UPLC-MS/MS program was systematically optimized for the simultaneous detection of nine allelochemicals with different polarities. The results proved the differences in the contents and distributions of nine allelochemicals in three different Taxus soils.

[Research progress on insect single sensillum recording.] / æ˜†è™«å•ä¸ªæ„Ÿè§‰å™¨è®°å½•æŠ€æœ¯ç ”ç©¶è¿›å±•.

Single sensillum recording is an insect extracellular electrophysiological technique, which can measure the electrophysiological responses of a single sensillum to stimuli in insects. It can help explore the electrophysiologi-cal response mechanism of insect olfactory and taste receptors to different semiochemicals. Combined with other techniques, it can be used to understand the molecular genetic mechanisms of olfactory responses, as well as to develop behavior regulators and volatile organic compound biosensors. In this review, we proposed the basic structure and the principle of single sensillum recording, and summarized its applications in insect studies, aiming to provide the foundation for understanding the mechanisms and applications in insect perception of semiochemicals.