Host-Induced Plant Volatiles Mediate Ability of the Parasitoid Microplitis croceipes to Discriminate Between Unparasitized and Parasitized Heliothis virescens Larvae and Avoid Superparasitism.

In solitary endoparasitoids, oviposition in a host previously parasitized by a conspecific (superparasitism) leads to intraspecific competition, resulting in the elimination of all but one parasitoid offspring. Therefore, avoidance of parasitized hosts presents a strong selective advantage for such parasitoid species. Parasitoids use herbivore-induced plant volatiles (HIPVs) to find their hosts. In this study, we evaluated the ability of Microplitis croceipes (Hymenoptera: Braconidae) to discriminate between unparasitized and parasitized Heliothis virescens (Lepidoptera: Noctuidae) larvae using cotton plant odors as cues. A combination of behavioral and analytical techniques were used to test two hypotheses: (i) parasitoids will show preference for plant odors induced by unparasitized hosts over odors induced by parasitized hosts, and (ii) the parasitism status of herbivores affects HIPV emission in plants. Heliothis virescens larvae were parasitized for varying durations (0, 2 and 6-days after parasitism (DAP)). In four-choice olfactometer bioassays, female M. croceipes showed greater attraction to plant odors induced by unparasitized hosts compared to plant odors induced by parasitized hosts (2 and 6-DAP). Comparative gas chromatography-mass spectrometry analyses of cotton volatiles indicated reduced emission of 10 out of 21 identified compounds from plants infested by parasitized hosts compared with plants infested by unparasitized hosts. The results suggest that changes in plant volatile emission due to the parasitism status of infesting herbivores affect recruitment of parasitoids. Avoidance of superparasitism using plant odors optimizes host foraging in M. croceipes, and this strategy may be widespread in solitary parasitoid species.

Pseudacteon Phorid Flies: Host Specificity and Impacts on Solenopsis Fire Ants.

Human commerce has resulted in the spread of the imported fire ants, Solenopsis species, worldwide. Six species of parasitic Pseudacteon phorid flies that are highly host specific to the Solenopsis saevissima complex of Solenopsis fire ants have been successfully released in the southern United States. The presence of Pseudacteon phorid flies, in addition to having direct mortality effects on their host ants, modifies foraging behavior and disrupts interspecific competition between host species and other ant species in the community. Fire ant workers have evolved effective methods to cope with parasitism pressure, which may relieve population-level impacts of introduced phorid flies. This review focuses on the mechanisms underlying host location, host preference, and host-size selection of Pseudacteon phorid flies and highlights their direct and indirect effects on fire ant populations. Knowledge gained from parasitoid-ant interactions will enhance use of natural enemies as biological control agents for invasive social insects.

Rhizobacteria activates (+)-δ-cadinene synthase genes and induces systemic resistance in cotton against beet armyworm (Spodoptera exigua).

Gossypol is an important allelochemical produced by the subepidermal glands of some cotton varieties and important for their ability to respond to changing biotic stress by exhibiting antibiosis against some cotton pests. Plant growth-promoting rhizobacteria (PGPR) are root-colonizing bacteria that increase plant growth and often elicit defence against plant pathogens and insect pests. Little is known about the effect of PGPR on cotton plant-insect interactions and the potential biochemical and molecular mechanisms by which PGPR enhance cotton plant defence. Here, we report that PGPR (Bacillus spp.) treated cotton plants showed significantly higher levels of gossypol compared with untreated plants. Similarly, the transcript levels of the genes (i.e. (+)-δ-cadinene synthase gene family) involved in the biosynthesis of gossypol were higher in PGPR-treated plants than in untreated plants. Furthermore, the levels of jasmonic acid, an octadecanoid-derived defence-related phytohormone and the transcript level of jasmonic acid responsive genes were higher in PGPR-treated plants than in untreated plants. Most intriguingly, Spodoptera exigua showed reduced larval feeding and development on PGPR-treated plants. These findings demonstrate that treatment of plants with rhizobacteria may induce significant biochemical and molecular changes with potential ramifications for plant-insect interactions.

Identification of Key Plant-Associated Volatiles Emitted by Heliothis virescens Larvae that Attract the Parasitoid, Microplitis croceipes: Implications for Parasitoid Perception of Odor Blends.

Herbivores emit plant-associated volatile organic compounds (VOCs) after feeding on plants. These plant-associated VOCs can be used by parasitoids to locate their hosts. It is hypothesized that certain compounds play key roles in the attractiveness of host-associated odor blends. The larval parasitoid, Microplitis croceipes (Hymenoptera: Braconidae) and its herbivore host, Heliothis virescens (Lepidoptera: Noctuidae), a major pest of cotton plant were used as model species to identify key compounds mediating attraction of parasitoids to hosts. Comparative GC/MS analyses of cotton-fed vs. artificial diet-fed hosts indicated that 12 of 17 compounds in the headspace of H. virescens larvae were exclusive to plant-fed hosts, and thus considered to be plant-associated. In order to identify key attractive compounds, a full blend of 15 commercially available synthetic compounds was modified by removing each of the 10 plant-associated compounds emitted by host larvae. In Y-tube olfactometer bioassays testing parasitoid responses to modified blends, 1-octen-3-ol, decanal, (E)-ß-caryophyllene, α-humulene, α-farnesene, and ß-pinene were identified as key compounds contributing to attractiveness of the natural blend of VOCs emitted by cotton-fed hosts. The results showed that while various host-associated compounds act in concert to serve as useful host location cues, only a fraction of the natural blend mediates attraction in parasitoids. Furthermore, the role of a compound is better assessed in the context of other compounds, and odor blends are better perceived as a whole rather than as individual components.

Management of Yellowmargined Leaf Beetle Microtheca ochroloma (Coleoptera: Chrysomelidae) Using Turnip as a Trap Crop.

The yellowmargined leaf beetle, Microtheca ochroloma Stål, is a major pest of cruciferous vegetable crops in organic production systems. Very few organically acceptable management options are currently available for this pest. Field studies were conducted at a research station in Alabama and at a commercial organic vegetable farm in Florida to investigate the effectiveness of turnip, Brassica rapa rapa, as a trap crop for M. ochroloma. In the research station trial with cabbage planted as the cash crop, perimeter planting of turnip as a trap crop effectively reduced beetle numbers and crop damage below levels recorded in the control. During the first season of our on-farm trial, with napa cabbage and mustard as the cash crops, using turnip as a trap crop effectively reduced both beetle numbers and cash crop damage below levels found in the control plots, but economic damage was still high. In the second season, beetle populations were too low for significant differences in damage levels to occur between the trap crop and control plots. Together, these results suggest that turnip planted as a trap crop can be an effective control tactic for cruciferous crops, like cabbage, that are much less attractive to M. ochroloma than turnip. In crops, like mustard and napa cabbage, that are equally or only slightly less attractive than turnip, planting turnip as a trap crop would have to be used in combination with other tactics to manage M. ochroloma.

Secretions from the ventral eversible gland of Spodoptera exigua caterpillars activate defense-related genes and induce emission of volatile organic compounds in tomato, Solanum lycopersicum.

BACKGROUND: Plant induced defense against herbivory are generally associated with metabolic costs that result in the allocation of photosynthates from growth and reproduction to the synthesis of defense compounds. Therefore, it is essential that plants are capable of sensing and differentiating mechanical injury from herbivore injury. Studies have shown that oral secretions (OS) from caterpillars contain elicitors of induced plant responses. However, studies that shows whether these elicitors originated from salivary glands or from other organs associated with feeding, such as the ventral eversible gland (VEG) are limited. Here, we tested the hypothesis that the secretions from the VEG gland of Spodoptera exigua caterpillars contain elicitors that induce plant defenses by regulating the expression of genes involved in the biosynthesis of volatile organic compounds (VOCs) and other defense-related genes. To test this hypothesis, we quantified and compared the activity of defense-related enzymes, transcript levels of defense-related genes and VOC emission in tomato plants damaged by S. exigua caterpillars with the VEG intact (VEGI) versus plants damaged by caterpillars with the VEG ablated (VEGA). RESULTS: The quantified defense-related enzymes (i.e. peroxidase, polyphenol oxidase, and lipoxigenase) were expressed in significantly higher amounts in plants damaged by VEGI caterpillars than in plants damaged by VEGA caterpillars. Similarly, the genes that encode for the key enzymes involved in the biosynthesis of jasmonic acid and terpene synthase genes that regulate production of terpene VOCs, were up-regulated in plants damaged by VEGI caterpillars. Moreover, the OS of VEGA caterpillars were less active in inducing the expression of defense genes in tomato plants. Increased emissions of VOCs were detected in the headspace of plants damaged by VEGI caterpillars compared to plants damaged by VEGA caterpillars. CONCLUSION: These results suggest that the VEG of S. exigua caterpillars contains elicitors of late plant defense signaling in tomato which trigger defense-related enzymatic activity, regulate expression of defense-related genes, and induce emission of plant VOCs. These signaling cascades may have important ramifications for plant-insect and tritrophic interactions.

Duration of plant damage by host larvae affects attraction of two parasitoid species (Microplitis croceipes and Cotesia marginiventris) to cotton: implications for interspecific competition.

Volatile organic compounds (VOCs) released by herbivore-damaged plants can guide parasitoids to their hosts. The quantity and quality of VOC blends emitted by plants may be affected by the duration of plant damage by herbivores, which could have potential ramifications on the recruitment of competing parasitoids. We used two parasitoid species, Microplitis croceipes and Cotesia marginiventris (Hymenoptera: Braconidae), to address the question of whether duration of plant damage affects parasitoid use of plant VOCs for host location. Both wasp species are larval endoparasitoids of Heliothis virescens (Lepidoptera: Noctuidae), an important pest of cotton. Attraction of the two parasitoid species to odors emitted by undamaged (UD), fresh (6 h infestation) damage (FD), and old (24 h infestation) damage (OD) cotton plants infested by H. virescens larvae was investigated using a headspace volatile collection system coupled with four-choice olfactometer bioassay. Both sexes of M. croceipes showed a preference for FD- and OD-plant odors over UD-plants. On the other hand, more C. marginiventris females were attracted to UD- and FD-plants than to OD-plants. GC/MS analyses showed qualitative and quantitative differences in the VOC profiles of UD, FD, and OD-plants, which may explain the observed preferences of the parasitoids. These results suggest a temporal partitioning in the recruitment of M. croceipes and C. marginiventris to H. virescens-damaged cotton, and may have potential implications for interspecific competition between the two parasitoid species.

On the formation of a protic ionic liquid in nature.

The practical utility of ionic liquids (ILs) makes the absence (heretofore) of reported examples from nature quite puzzling, given the facility with which nature produces many other types of exotic but utilitarian substances. In that vein, we report here the identification and characterization of a naturally occurring protic IL. It can be formed during confrontations between the ants S. invicta and N. fulva. After being sprayed with alkaloid-based S. invicta venom, N. fulva detoxifies by grooming with its own venom, formic acid. The mixture is a viscous liquid manifestly different from either of the constituents. Further, we find that the change results as a consequence of formic acid protonation of the N centers of the S. invicta venom alkaloids. The resulting mixed-cation ammonium formate milieu has properties consistent with its classification as a protic IL.

Toxicity of cockroach gel baits to the oothecal parasitoid Aprostocetus hagenowii (Hymenoptera: Eulophidae) and implications for cockroach integrated pest management.

Aprostocetus hagenowii (Ratzeburg) is a parasitoid wasp that parasitizes the oothecae of peridomestic pest cockroaches. A. hagenowii has been used in integrated pest management (IPM) programs for cockroach control but little is known about how this parasitoid responds to the insecticides commonly used for cockroach management. Five insecticidal gel bait products containing indoxacarb, clothianidin, fipronil, dinotefuran, or abamectin B1 were tested for their toxicity towards A. hagenowii and the American cockroach, Periplaneta americana (L.; Blattodea: Blattidae), a host of A. hagenowii and a common pest. All baits were tested as fresh and 1-d aged deposits. Indoxacarb was the only active ingredient that did not cause significant (P < 0.05) A. hagenowii mortality compared to the control in both the fresh and aged gel experiments (Median survival time [MST]s: 168 h fresh, 72 h aged). Clothianidin caused the lowest A. hagenowii MSTs across experiments (24 h, fresh and aged). All baits caused significant P. americana mortality as fresh and 1-d aged deposits (P < 0.05). Indoxacarb appears most compatible with A. hagenowii in cockroach IPM.

Species and sexual differences in antennal lobe architecture and glomerular organization in two parasitoids with different degree of host specificity, Microplitis croceipes and Cotesia marginiventris.

The endoparasitic wasps (Hymenoptera: Braconidae), Microplitis croceipes (specialist) and Cotesia marginiventris (generalist), are parasitoids of lepidopteran larvae and differ in their degree of host specificity. Recent studies have reported key differences between the two species in the abundance of antennal olfactory sensilla and their response to host-related volatiles. Here, we have compared antennal lobe architecture and glomerular organization in the two parasitoid species by using a combination of axonal tract tracing techniques and confocal microscopy. In M. croceipes, the medial half of the antennal lobe is larger with a greater number of glomeruli compared with the lateral half, whereas in C. marginiventris, the lateral half is larger than the median half. The volume of the antennal lobe is approximately 2.5 times greater in M. croceipes than in C. marginiventris. However, the number of glomeruli per antennal lobe is only slightly higher in M. croceipes (females: 219-222; males: 220-224) than in C. marginiventris (females: 192-194; males: 193-196). A comparison of males and females within each species demonstrated a striking sexual difference in terms of an enlarged glomerulus (macroglomerulus or MG) at the entrance of the antennal nerve and of a complex of 3-4 MG (CMG) in the posterior region of the antennal lobe of males of both species. Being specific to males, both the MG and CMG might be involved in the detection of female-related odor.

Potential of the oothecal parasitoid Aprostocetus hagenowii (Hymenoptera: Eulophidae) as a biological control agent for the Turkestan cockroach (Blattodea: Blattidae).

The Turkestan cockroach, Blatta lateralis (Walker), is a peridomestic pest of growing concern in the US Southwest. The parasitoid Aprostocetus hagenowii (Ratzburg) is used in IPM programs targeting other blattid cockroach species and may aid in B. lateralis suppression. Information about the ability of A. hagenowii to parasitize B. lateralis is lacking. A no-choice host-switching experiment was used to test A. hagenowii acceptance of B. lateralis oothecae, and a multigenerational no-choice experiment was used to determine the suitability of B. lateralis as a host for A. hagenowii over several months of rearing. Periplaneta americana (L.) (Blattodea: Blattidae), the preferred host of A. hagenowii, and Blatta orientalis L., a known host and relative of B. lateralis, were used for comparison. Development time was similar among hosts and generations (P > 0.05). Parasitism success and proportion of female progeny declined significantly with subsequent generations on both Blatta spp. (parasitism success: χ2 = 14.916; df = 2; P = 0.001; proportion female: H = 6.364; df = 2; P = 0.041). These results suggest that A. hagenowii may initially aid in suppression of B. lateralis, but an overall decline in fitness will require repeated releases or provisioning of P. americana oothecae. Development of a strain more suitable for B. lateralis control may be possible via selection from laboratory strains or through use of wild A. hagenowii from areas where B. lateralis is present.

Effects of Food Source Availability, Host Egg:Parasitoid Ratios, and Host Exposure Times on the Developmental Biology of Megacopta cribraria Egg Parasitoids.

Parasitoids forage for hosts in dynamic ecosystems and generally have a short period of time to access hosts. The current study examined the optimal reproductive attributes of two egg parasitoids, Paratelenomus saccharalis Dodd (Hymenoptera: Platygastridae) and Ooencyrtus nezarae Ishii (Hymenoptera: Encyrtidae), of the kudzu bug, Megacopta cribraria Fabricius (Hemiptera: Plataspidae). The proportion of O. nezarae and P. saccharalis adult offspring that emerged from M. cribraria eggs and the sex ratio of the parasitoid offspring were compared among treatments for the effects of different adult parasitoid food sources, host egg-to-adult parasitoid ratios, and host exposure times. Our results suggest that honey solution as a food source, a 21:7 host-to-parasitoid ratio, and three-to-five days of exposure time optimized the production of female O. nezarae offspring. For P. saccharalis, honey solution as a food source, a 21:7 host-to-parasitoid ratio, and one day were optimal for maximizing female offspring production. These findings provide new information about the biology of these egg parasitoids.

Similarity in venom alkaloid chemistry of alate queens of imported fire ants: implication for hybridization between Solenopsis richteri and S. invicta in the Southern United States.

Both cis- and trans-2-methyl-6-undecylpiperidines, MC11P, have been previously reported as the major components of the venom of alate queens of the imported fire ants, Solenopsis richteri (black) and S. invicta (red). To identify the minor components of venom alkaloids from alate queens and compare the venom alkaloid chemistry of alate queen of their hybrid (S. richteri×S. invicta) with that of the two parental fire ant species (S. richteri and S. invicta), silica-gel short-column chromatography was utilized for separating cis-stereoisomers of venom alkaloids from trans-stereoisomers. GC/MS Analyses of venom-alkaloid chemistry of alate queens demonstrated that fewer alkaloid peaks were detected in the chromatograms of the alate queens compared to those of workers. Three new compounds, 7, 12, and 13, were detected as minor components in the venom of alate queens of all three fire ant species. Alate queens of hybrid fire ants showed cis- and trans-alkaloid patterns similar to those of the parental species. Similarity in venom-alkaloid chemistry of alate queens of S. richteri and S. invicta, and their hybrid may indicate their reproductive compatibility in the hybrid zone in southern United States, where all three species occur sympatrically.

Direct and Indirect Competitive Interactions between Ooencyrtus nezarae and Paratelenomus saccharalis Parasitizing Megacopta cribraria Egg Patches.

The present study investigated egg parasitoid interspecific interactions between a generalist, Ooencyrtus nezarae Ishii (Hymenoptera: Encyrtidae) and a specialist, Paratelenomus saccharalis Dodd (Hymenoptera: Platygastridae) in a laboratory setting using kudzu bug (Megacopta cribraria Fabricius, (Hemiptera: Plataspidae)) eggs as their shared host. Three experiments were conducted to evaluate the emergence of wasps from parasitized hosts after the simultaneous and sequential release of wasps, monitor aggressive behavior of P. saccharalis, and quantify intraguild predation of O. nezarae larvae on heterospecific P. saccharalis larvae. Results showed that total host egg parasitism was higher when both wasps were released simultaneously than if wasps were released sequentially. Ooencyrtus nezarae produced more total offspring than P. saccharalis in all sequential/simultaneous treatments but produced male offspring in most cases. In the aggressive behavioral experiment, specialist, P. saccharalis used head butting to fight O. nezarae, but no other aggressions were observed. In an experiment examining intraguild predation, O. nezarae was able to develop in host eggs parasitized by P. saccharalis four days earlier, acting as a superior larval competitor. These findings shed light on the potential interspecific interactions between O. nezarae and P. saccharalis, which may determine their relative abundance and influence their compatibility in kudzu bug biological control programs.

Kudzu Bug (Megacopta cribraria) and Associated Egg Parasitoids Emergence Rates in Alabama are Predicted by Weather Indices.

The kudzu bug, Megacopta cribraria (Fabricius) (Hemiptera: Plataspidae), is a major economic pest of soybean in the southeastern United States. With climate warming, this pest is expected to move northward and cause additional crop damage. Parasitoid biocontrol is a potential method of integrated pest management for kudzu bug. Two species of egg parasitoid wasps have been observed emerging from kudzu bug egg masses in the southeastern United States: Paratelenomus saccharalis (Dodd) (Hymenoptera: Platygastridae) and Ooencyrtus nezarae (Ishii) (Hymenoptera: Encyrtidae). This paper used egg mass emergence data collected between 2018 and 2020 in Alabama soybean fields and compared the data to weather indices. Indices included the number of days with minimum temperatures below zero, accumulated rainfall (mm m-2), as well as species specific metrics of accumulated growing degree days, accumulated daily minimum temperature (°C), and accumulated daily maximum temperature (°C). Emergence of the generalist parasitoid, O. nezarae, was highly correlated with kudzu bug nymph abundance, accumulated degree day, accumulated daily temperatures, and precipitation. Ooencyrtus nezarae emergence was predicted in a stepwise regression equation by aggregated degree day and date of collection, which indicates that seasonality may be a predictor of its presence. In contrast, collections of the specialist parasitoid, P. saccharalis, were near-zero throughout the collection period, suggesting that this species may no longer be a usable biocontrol agent in the southeastern United States as a result of external limiting factors.

Field evaluation of traps and lures for monitoring plum curculio (Coleoptera: Curculionidae) in Alabama peaches.

The plum curculio, Conotrachelus nenuphar (Herbst) (Coleoptera: Curculionidae), is a key pest of peaches, Prunus persica (L.) Batsch, in North America. We evaluated the effectiveness of two widely used trap types (pyramid versus Circle traps) and commercially available synthetic lures for monitoring the pest in two peach orchards in Alabama during 2008 and 2009. The lures evaluated alone or in combinations included benzaldehyde (BZ) (a component of fruit odor), plum essence (PE) (a mixture of fruit odor extracted from food grade plum), and grandisoic acid (GA) (a male-produced aggregation pheromone of plum curculio). In general, pyramid traps captured more plum curculio adults than Circle traps, particularly during the first generation. Trap performance was improved numerically by the addition of BZ, PE, or GA alone (single lures) and was significantly enhanced by the addition of the combined BZ + PE lure. In both first and second generations, the combined BZ + PE lure increased plum curculio captures (significant in some trials) over unbaited traps and traps baited with single lures by approximately 1.5-21-fold and had the highest response indices (RIs), which is indicative of high attractiveness. The combined BZ + GA lure and the three-component BZ + PE + GA lure also captured numerically more plum curculio adults than unbaited traps or traps baited with single lures but the differences were rarely significant. Analysis of ratios of interaction suggests the possibility of synergistic interactions between BZ and PE and between BZ and GA; however, additive effects were concluded due to high sample errors. These results are discussed in relation to the physicochemical properties of the lures and the potential of using baited monitoring traps to aid plum curculio management decisions in peach orchards.

Comparative Cutaneous Water Loss and Desiccation Tolerance of Four Solenopsis spp. (Hymenoptera: Formicidae) in the Southeastern United States.

The high surface area to volume ratio of terrestrial insects makes them highly susceptible to desiccation mainly through the cuticle. Cuticular permeability (CP) is usually the most important factor limiting water loss in terrestrial insects. Water loss rate, percentage of total body water (%TBW) content, CP, and desiccation tolerance were investigated in workers of four Solenopsis species in the southeastern USA. We hypothesized that tropical/subtropical ants (S. invicta and S. geminata) will have lower CP values and tolerate higher levels of desiccation than temperate ants (S. richteri and S. invicta × S. richteri). The %TBW content was similar among species. Solenopsis invicta had a 1.3-fold and 1.1-fold lower CP value than S. invicta × S. richteri and S. richteri, respectively. Solenopsis geminata had a 1.3-fold lower CP value than S. invicta × S. richteri, and a 1.2-fold lower CP value than S. richteri. The LT50 values (lethal time to kill 50% of the population) ranged from 1.5 h (small S. geminata) to 8.5 h (large S. invicta). Desiccation tolerance ranged between 36 and 50 %TBW lost at death and was not related to a species' location of origin. This study is the first report of water relations of S. invicta × S. richteri. It demonstrates that desiccation stress differentially can affect the survival of different Solenopsis species and implies that environmental stress can affect the distribution of these species in the southeastern USA.

Biting Rates and Onchocerca Infectivity Status of Black Flies from the Simulium damnosum Complex (Diptera: Simuliidae) in Osun State, Nigeria.

The Simulium damnosum Theobald complex transmits Onchocerca volvulus Leuckart (Spirurida: Onchocercidae), the causative agent of onchocerciasis. Recent evidence suggests that control efforts have strongly suppressed parasite populations, but vector surveillance is needed in parts of Africa where the disease remains endemic. Here, studies on biting rates and infectivity status of suspected vector species were conducted in three onchocerciasis-endemic areas, namely Iwo, Ede, and Obokun, in Osun State, Nigeria. A total of 3,035 black flies were collected between October 2014 and September 2016, and examined for parity and parasites using standard methods. A separate collection of 2,000 black flies was pool-screened for infectivity using polymerase chain reaction (PCR) amplification of the O-150 marker. Results showed that parous flies were significantly less common than nulliparous flies with overall parous rates of 8.02% in Iwo and 35.38% in Ede at the end of the study period. Obokun had a parous rate of 22.22% obtained in the first year only. None of the dissected parous flies were infected with O. volvulus and PCR assays showed no amplification of O-150 O. volvulus-specific repeats in head and body pools. However, annual biting rates exceeded the World Health Organization threshold of 1,000 bites/person/yr. Thus it appears that, with such high rates of biting, even low levels of vector infection can sustain onchocerciasis in African communities.

Re-investigation of venom chemistry of Solenopsis fire ants. I. Identification of novel alkaloids in S. richteri.

Dialkylpiperidines are characteristic of fire ants in the genus Solenopsis (Hymenoptera: Formicidae). Workers of the black imported fire ant, S. richteri produce cis and trans stereoisomers of 2,6-dialkylpiperidines with the trans isomer predominating. We used silica gel short column chromatography to separate both stereoisomers (cis and trans) of S. richteri venom alkaloids and coupled gas chromatography mass spectrometry (GC-MS) to identify novel minor components. The identities of various peaks in GC-MS analyses of the venom fractions were based on relative retention times and mass spectral data. GC profiles verified the presence of both cis and trans stereoisomers of C15:1 and C15 in S. richteri. The GC trace of the cis stereoisomers of S. richteri alkaloids was presented for the first time. In addition to the previously described components of S. richteri venom, seven novel 2,6-dialkyl-delta1,2-piperideines and 2,6-dialkyl-delta1,6-piperideines were detected. The chemical identities of these minor components were determined by comparing with fragmentations of known compounds. Possible biosynthetic pathways for the production of cis and trans solenopsins by S. richteri are discussed.

Re-investigation of venom chemistry of Solenopsis fire ants. II. Identification of novel alkaloids in S. invicta.

The venom of the red imported fire ant, Solenopsis invicta, is dominated by trans stereoisomers of 2,6-dialkylpiperidines. cis Stereoisomers of alkaloids in the venom of S. invicta were separated from trans stereoisomers by using silica gel short column chromatography and identified by coupled gas chromatography mass spectrometry (GC-MS). Seven pairs of cis and trans sterecoisomers were identified based on relative retention times and mass spectral data. The GC trace of the cis stereoisomers of S. invicta alkaloids was presented for the first time. In addition to the previously described 2,6-dialkylpiperideines, eleven novel 2,6-dialkyl-delta1,2-piperideines and 2,6-dialkyl-delta1,6-piperideines were identified from S. invicta venom. The results are discussed in relation to the evolutionary significance of these piperideines and their possible biosynthetic pathways in Solenopsis fire ants.