Chemical Defense in Harvestmen (Arachnida,Opiliones): Do Benzoquinone Secretions Deter Invertebrate and Vertebrate Predators?

Two alkylated 1,4-benzoquinones were identified from the defensive secretion produced by the neotropical harvestman Goniosoma longipes (Gonyleptidae). They were characterized as 2,3-dimethyl-1,4-benzoquinone and 2-ethyl-3-methyl-1,4-benzoquinone. We tested the effectiveness of these benzoquinone secretions against several predator types, including invertebrates and vertebrates. Different predators were exposed to the harvestmen's gland secretion or to distilled water in laboratory bioassays. Our results indicate that secretions containing the 1,4-benzoquinones released by G. longipes can be an effective defense against predation, and that the effectiveness of the secretion is dependent on the predator type. The scent gland secretion repelled seven ant species, two species of large wandering spiders, and one frog species, but was not an effective defense against an opossum. Our study also demonstrates that the scent gland secretion of G. longipes can work as a chemical shield preventing the approach of three large predatory ants for at least 10 min. The chemical shield may protect the harvestman against successive attacks of the same ant worker and also allow the harvestman to flee before massive ant recruitment. Our data support the suggestion that chemical defenses may increase survival with some but not all potential predators. This variation in defense effectiveness may result from many interacting factors, including the attack strategy, size, learning ability, and physiology of the predators, as well as the chemical nature of the defensive compounds, type of emission, and amount of effluent released by the prey.     

Mandibular gland allomones ofDasymutilla occidentalis and other mutillid wasps

The mandibular gland secretion of the mutillid wasp,Dasymutilla occidentalis, possesses three short-chained ketones-4-methyl-3-heptanone (4MH), 4,6-dimethyl-3-nonanone (4,6DMN), 4,6-dimethyl-3-octanone (4,6DMO)—and several unidentified compounds. This is the first report of 4,6DMN as a natural product and its synthesis is described. These ketones, which are either known to be ant alarm pheromones or are structurally very similar to ant alarm pheromones, appear to function as allomones against ants, major potential predators of mutillid wasps. The major secretory component, 4-methyl-3-heptanone, which was identified in females and/ or males of the species analyzed within the generaDasymutilla, Timulla, Traumatomutilla, andPappognatha, appears to constitute a chemical character of the defensive secretions of these genera.     

Effect of Volatile Constituents from <Emphasis Type="Italic">Securidaca</Emphasis><Emphasis Type="Italic">Longepedunculata</Emphasis> on Insect pests Of Stored Grain

Securidaca longepedunculata Fers (Polygalaceae) is commonly used as a traditional medicine in many parts of Africa as well as against a number of invertebrate pests, including insects infesting stored grain. The present study showed that S. longepedunculata root powder, its methanol extract, and the main volatile component, methyl salicylate, exhibit repellent and toxic properties to Sitophilus zeamais adults. Adult S. zeamais that were given a choice between untreated maize and maize treated with root powder, extract, or synthetic methyl salicylate in a four-way choice olfactometer significantly preferred the control maize. Methyl salicylate vapor also had a dose-dependant fumigant effect against S. zeamais, Rhyzopertha dominica, and Prostephanus truncates, with a LD₁₀₀ achieved with a 60 l dose in a 1-l container against all three insect species after 24 hr of exposure. Probit analyses estimated LD₅₀ values between 34 and 36 l (95% CI) for all insect species. Furthermore, prolonged exposure for 6 days showed that lower amounts (30 l) of methyl salicylate vapor were able to induce 100% adult mortality of the three insect species. The implications are discussed in the context of improving stored product pest control by small-scale subsistence farmers in Africa.     

Effects of elevated CO<Subscript>2</Subscript> on foliar quality and herbivore damage in a scrub oak ecosystem

Atmospheric CO₂ concentrations have increased exponentially over the last century and continuing increases are expected to have significant effects on ecosystems. We investigated the interactions among atmospheric CO₂, foliar quality, and herbivory within a scrub oak community at the Kennedy Space Center, Florida. Sixteen plots of open-top chambers were followed; eight of which were exposed to ambient levels of CO₂ (350 ppm), and eight of which were exposed to elevated levels of CO₂ (700 ppm). We focused on three oak species, Quercus geminata, Quercus myrtifolia, Quercus chapmanii, and one nitrogen fixing legume, Galactia elliottii. There were declines in overall nitrogen and increases in C:N ratios under elevated CO₂. Total carbon, phenolics (condensed tannins, hydrolyzable tannins, total phenolics) and fiber (cellulose, hemicellulose, lignin) did not change under elevated CO₂ across plant species. Plant species differed in their relative foliar chemistries over time, however, the only consistent differences were higher nitrogen concentrations and lower C:N ratios in the nitrogen fixer when compared to the oak species. Under elevated CO₂, damage by herbivores decreased for four of the six insect groups investigated. The overall declines in both foliar quality and herbivory under elevated CO₂ treatments suggest that damage to plants may decline as atmospheric CO₂ levels continue to rise.     

Meliaceae and rutaceae limonoids as termite antifeedants evaluated usingReticulitermes speratus kolbe (Isoptera: Rhinotermitidae)

Four limonoids were evaluated by a no-choice bioassay method as termite antifeedants usingReticulitermes speratus Kolbe. Obacunone showed the highest degree of antifeeding potency (PC₉₅=1133 ppm w/w), followed by nomilin (PC₉₅=4475 ppm), azadirachtin (PC₉₅=65,293 ppm), and limonin (with PC⁹⁵ estimates beyond the bioassay limits), which was the least potent. None of the four limonoids exhibited any evidence of acute toxicity towardsR. speratus, although termites fed on obacunone and nomilin at concentrations higher than their PC₉₅ estimates tend to die faster than those in the unfed treatment. Obacunone and nomilin also showed a drastic antifeedant consumption (AC) reduction effect at concentrations higher than 510 and 1360 ppm, respectively. With azadirachtin and limonin, such an effect was not observed. The present data suggest that both obacunone and nomilin have an absolute antifeeding activity towardsR. speratus.     

Do Enemies of Herbivores Influence Plant Growth and Chemistry? Evidence from a Seminatural Experiment

It is predicted that enemies of insect herbivores may influence the effects of herbivores on their host plants by affecting the choice of plant genotypes. To examine the effect of predators, we conducted two experiments, each with a different caterpillar species (Junonia coenia and Pyrrharctia isabella). Under seminatural conditions, we provided a choice between two genotypes of plantain (Plantago lanceolata) with different levels of iridoid glycosides and used Podisus maculiventris stinkbugs as predators. There were four treatments: no herbivores and no predators, low density of herbivores and no predators, high density of herbivores and no predators, and high density of herbivores plus predators. The caterpillars had little effect on plant growth but did influence the iridoid glycoside concentration. For the Junonia experiment, the concentration of iridoid glycosides was less for plots with a low density of caterpillars (with no predators) compared to the other treatments of caterpillar density. In the Pyrrharctia experiment, catalpol was induced by a high density of caterpillars (with no predators). There were no increases in total iridoid glycosides associated with either herbivore species. The presence of predators had no effect on plant growth or total iridoid glycoside pattern. The lack of effect by predators seems to reflect the relatively large variation in iridoid glycoside concentration among leaf ages, and the herbivores ability to respond to that variation, such that the difference in iridoid glycoside concentrations in the plant genotypes was less important.     

GC-MS detected difunctional carboxylic acids released by driedCladophora at the pH of lake ontario and the st. lawrence river

A study to identify the acidic components ofCladophora glomeata active againstAedes triseriatus larvae was extended to a mixture obtained by extracting the dried powdered alga in aqueous suspension at pH 8.5. The presence of 1,9-nonanedioic, 1,10-decanedioic, 1,11-undecanedioic and 4-ketononanoic acids was determined by GC-EIMS and GC-CIMS and confirmed by analytical coinjection GC. The presence of 5-pentyldihydro-2(3H)-furanone, a minor component, was also indicated. The group of major acidic constituents is different from those obtained by extracting driedCladophora with methanol. In contrast to the C₁₀–C₁₄ monocarboxylic acids, which hadLD ₅₀ values<20 ppm againstA. triseriatus, none of the dicarboxylic acids of the series G₄–C₁₄, C₁₆, and C₂₂ were active; nor were 4-ketononanoic acid and 5-pentyldihydro-2(3H)-furanone active.     

Trail-following in termites: Evidence for a multicomponent system

Several African termite species from different subfamilies and different habitats are sensitive to trail-active extracts or to naturally laid trails from other species. Using single-extract bioassays, it is shown that the response threshold for trail-following is nearly identical for all tested species (except forHodotermes mossambicus). However, when termite workers have a choice between trails from their own species and from other species, conspecific trail-following is exclusively observed. This phenomenon can be counteracted by dilution (110) of the conspecific trail-pheromone extract. Tests of the trail activity of various synthetic alcohols show that among these, the highest sensitivity of termite workers is to (Z)-3-dodecen-1-ol. Based on our experimental data, we postulate that, in addition to a generally active trail-pheromone constituent (an unsaturated primary C₁₂ alcohol) or a pool of chemically closely related alcohols, other species-specific components are present in termite trails.     

Chemical ecology ofReticulitermes flavipes (Kollar) andR. virginicus (Banks) (Rhinotermitidae)

Reticulitermes flavipes andR. virginicus have been examined for the presence and possible defense functions of soldiers specific secretions. The cephalic extracts for soldiers of both species contained the identical two major sesquiterpenes which were absent from other castes. The sesquiterpenes have been identified as ₁-cadinene (I) and the corresponding aldehyde (II) by high-resolution nuclear magnetic resonance spectrometry using homonuclear proton decoupling and by high-resolution mass spectrometry. When groups of termite soldiers were exposed to foraging parties of the sympatric native fire ant,Solenopsis geminata, the termites utilized only mechanical defenses. No evidence was obtained to indicate that the ants had been sprayed or coated with either an irritant or toxicant, and there was no evidence that an alarm had been promulgated.     

Powder and Monolith-Supported Sulphur Trap Materials Based on Modified Hydrotalcite-Derived Supports

SO _x traps were prepared using hydrotalcite materials of different composition and their SO _x storage properties were monitored during temperature cycling (50–600 °C) under continuous feed streams (50 ppm SO₂, 6 vol.% O₂, 5 vol.% CO₂, 100 ppm NO) at a space velocity of 144,000 L/(kg h). A comparison is made with non-hydrotalcite mixed oxide supports as well as pure alumina. The most promising material NaMnO _x /Al₂O₃ was wash-coated on a cordierite core and its SO _x trap capacity was compared with the performance of the powder and the slurry. The slurry as well as the monolith-supported material showed an SO₂ uptake of 93% over 7 h time-on-stream corresponding to 20 wt.% sulphate. DRIFT spectroscopy revealed the prevailing sulphate formation on Mn-related sites and Na. Regeneration of the trap with CO/H₂ (λ = 0.99) at 600 °C was not completely possible.     

Defensive role ofAllium sulfur compounds for leek mothAcrolepiopsis assectella Z. (Lepidoptera) against generalist predators

It has been shown previously that sulfur volatiles produced byAllium plants affect the behavior of their specialist phytophages and of their specialist entomophages. The action of these compounds in protecting the leek mothAcrolepiopsis assectella against generalist entomophages was studied in comparison to the proposed original defensive role of these compounds against generalist herbivorous insects. Two ants species,Formica selysi andF. fusca, were used as generalist predators. Six behavioral criteria of the predatory behavior of the ants were studied in presence of the last-instar caterpillars (C₅). C₅ reared on artificial diets with or without leek components were tested, as well as C₅ soaked in frass of leek-reared caterpillars or disulfide solutions. In addition, the response of the ants to pure chemicals found in leek was studied using honey solutions with or without sulfur compounds. The sulfur allelochemicals ofAllium plants have a negative action on predatory ants. Interestingly, the nonvolatile precursors of sulfur volatiles ofAllium plants seem to have a protective role for their phytophagous insects against generalist entomophages.     

Correlation of 1-octen-3-one with antixenotic resistance in subterranean clover cotyledons to red-legged earth mite,Halotydeus destructor (Acarina: Penthaleidae)

Artificially damaged cotyledons of subterranean clover (Trifolium subterraneum L.) released several volatile metabolites, including 1-octen-3-one, arising from lipid peroxidation. The amount of 1-octen-3-one produced was negatively correlated with feeding damage caused by the red-legged earth mite (Halotydeus destructor) in nine out of 10 resistant and susceptibleT. subterraneum varieties tested. The EC₅₀ of this compound in deterring mites from feeding in a membrane bioassay was 50 ppm. Cotyledon toughness was also involved in resistance. The resistant variety, S3615D, which has the lowest toughness value among the resistant varieties, produced the highest amount of 1-octen-3-one recovered from the headspace in 1 hr. Artificially damaged cotyledons of both susceptible Dalkeith and resistant DG1007, growing in shade, showed lower toughness, but had enhanced production of C₈ volatile compounds and were avoided by mites during a 3-hr feeding test. When both 1-octen-3-one content and cotyledon toughness value were taken as cofactors in resistance, the resultant multiplication value yielded a more significantly negative correlation with mite feeding damage scores within the 10 varieties than either factor alone. We conclude that 1-octen-3-one has a role in resistance of subclover cotyledon to the mite.     

Insecticidal activity of hypericin towardsManduca sexta larvae

The toxic effect of hypericin (HYP), a photodynamic quinone that occurs in certain species of the genusHypericum, towardsManduca sexta third-instar larvae was investigated. The LD₅₀ of purified hypericin was 16 g/g larval initial fresh weight in constant light (22 W/m²). Reduced irradiance resulted in decreased mortality. Sublethal applications retarded larval growth (body fresh weight) in a dose-dependent manner. Toxicity had an absolute light dependence at the dose levels used, the active wavelengths being >500 nm. The phototoxic effect was rapidly lost when larvae were maintained in darkness (>8 hr) prior to irradiation. However, the potential for light-dependent mortality was retained if larvae were starved prior to irradiation.     

Shield Defense of a Larval Tortoise Beetle

Larvae of the folivorous tortoise beetle, Plagiometriona clavata, carry shields formed from feces and exuviae above their bodies. We used an ecologically relevant predatory ant, Formica subsericea, in a bioassay to determine if shields functioned as simple barriers, as previous studies indicated, or whether they were chemical defenses. Shields were necessary for larval survival; shield removal rendered larvae vulnerable. Shields produced by larvae reared on a substitute diet failed to provide protection. Solvent-leached shields also failed to deter ants, indicating the shield had a host-derived chemical component likely located in the feces, not in the exuviae. Solanum dulcamara, the larval host plant, contained free phytol, steroidal glycoalkaloids, and saponins. Shields contained partially deglycosylated metabolites of host steroidal glycoalkaloids and saponins, a suite of fatty acids, and derivatives of phytol, which together formed a deterrent barrier against ant attack. We compared the mobile shield of P. clavata to the stationary shield of another S. dulcamara-feeding leaf beetle, Lema trilinea. Both larval shield defenses were formed from a very similar array of host-derived compounds with deterrent properties. We concluded that convergent patterns of limited chemical transformation and selective incorporation of particular deterrent metabolites in shield defenses of two unrelated taxa represented responses to selection from invertebrate predators.     

Insect antifeedant activity of clerodane diterpenoids against larvae ofSpodoptera Littoralis (Boisd.) (Lepidoptera)

Antifeedant activities of nine clerodane diterpenoids, isolated in this laboratory from different species ofAjuga plants, have been studied against larvae of Egyptian cotton leafwormSpodoptera littoralis (Boisd.) (Lepidoptera) by application of the leaf disk method. Evaluation of activity was carried out by calculating, at different time intervals, the feeding ratio (FR) from the relationship between the consumed areas of treated disks (CTD) and control disks (CCD); for comparison purposes a FR₅₀ defined as the FR at a CCD of 50% was established. Some compounds exhibited activity at a 0.01 g/cm² dose (0.3 ppm). Structure-activity relationships are discussed     

Consequences of Enriched Atmospheric CO2 and Defoliation for Foliar Chemistry and Gypsy Moth Performance

Elevated concentrations of atmospheric CO₂ are likely to interact with other factors affecting plant physiology to alter plant chemical profiles and plant–herbivore interactions. We evaluated the independent and interactive effects of enriched CO₂ and artificial defoliation on foliar chemistry of quaking aspen (Populus tremuloides) and sugar maple (Acer saccharum), and the consequences of such changes for short-term performance of the gypsy moth (Lymantria dispar). We grew aspen and maple seedlings in ambient (~360 ppm) and enriched (650 ppm) CO₂ environments at the University of Wisconsin Biotron. Seven weeks after budbreak, trees in half of the rooms were subjected to 50% defoliation. Afterwards, foliage was collected for chemical analyses, and feeding trials were conducted with fourth-stadium gypsy moths. Enriched CO₂ altered foliar levels of water, nitrogen, carbohydrates, and phenolics, and responses generally differed between the two tree species. Defoliation induced chemical changes only in aspen. We found no significant interactions between CO₂ and defoliation for levels of carbon-based defenses (phenolic glycosides and tannins). CO₂ treatment altered the performance of larvae fed aspen, but not maple, whereas defoliation had little effect on performance of insects. In general, results from this experimental system do not support the hypothesis that induction of carbon-based chemical defenses, and attendant effects on insects, will be stronger in a CO₂-enriched world.     

Termite predation byMegaponera foetens (FAB.) (Hymenoptera: Formicidae)

Termite predation by the ponerine ant,Megaponera foetens, is coordinated by chemicals from at least two glands. Columns of ants are guided to termite foraging areas by pheromones originating from the poison apparatus. On finding groups of termites, ants release alkyl sulfides (dimethyl disulfide and trisulfide) from their mandibular glands which attract sister workers who dig, into the termite galleries, in response to other unidentified mandibular gland pheromones.     

Significance of medium chainn-alkanes as accompanying compounds in hemipteran defensive secretions: An investigation based on the defensive secretion ofCoridius janus

A mixture oftrans-2-hexenal;n-tridecane (60:40, w/w), the natural combination present in the defensive secretion ofCoridius janus (Hemiptera; Pentatomidae) was shown by comparison with similar aldehyde mixtures having longer and shorter chainn-alkanes, to be the optimal combination as a fumigant and a repellent against three test insect species,Anoplolepis longipes, Sitotroga cerealella, andCulex quinquefasciatus. Toxic values obtained for the three insects, respectively: 1/LC₅₀, 1.72, 4.54, and 6.66 ppm while repellencies were 63%, 50%, and 69%. This study revealed that amongt-2-hexenal:n-alkane combinations those with medium carbon chains,viz C-11 and C-12, also possessed high toxicities and repellencies comparable to that of the natural combination while those with shorter and longern-alkanes possessed lower activity. Toxicities and repellencies ofn-alkane series were only moderate to low showing highest toxic values forn-tridecane at 1/LC₅₀, 0.39, 2.32, and 2.32 ppm and repellencies at 31%, 30%, and 32% for the three test insects, respectively. This series, nevertheless, showed similar variation, medium length chains, C-11, C-12, and C-13 showing comparatively higher activity than other alkanes of shorter and longer chains. This study also revealed that the fumigant property of both alkane and aldehyde are of equal importance while repellency is heavily dependent on the aldehyde.     

Response ofAedes triseriatus larvae to fatty acids ofCladophora

The activity of a methanol extract residue fromCladophora glomerata against larvae ofAedes triseriatus is confirmed. Fractionation of this residue by solubility in solvents of varying polarity is monitored by bioassay withA. triseriatus larvae. The presence of fatty acids in the active hexane soluble fraction and saponified material obtained therefrom is indicated by¹H NMR and IR. The identification of the individual fatty acids is achieved by co-injection and mass GLC of their methyl esters. Saturated and unsaturated fatty acids are screened against larvae and the LD₅₀ values of the most active acids are determined. The LD₅₀ of capric [100], lauric [120], myristic [140] and palmitoleic [161 (9c)] are 14,7, 4 and 3ppm respectively. The most active acids 120, 140 and 161 (9c) are present in all the fractions examined and are released to water by the powdered alga at pH 8.5.     

Comparison Between a Pt–Rh/Ba/Al2O3 and a Newly Formulated NOX-Trap Catalysts Under Alternate Lean–Rich Flows

In situ FT-IR spectroscopy coupled with mass spectrometry have been used to study the mechanism of nitrates formation and reduction over a common Pt–Rh/Ba/Al₂O₃ NO _x storage catalyst, compared with a different alumina-based compound.The experimental device used consists of a transmission reactor cell (having a very small dead volume) dedicated to the evolution of surface species, and of a mass spectrometer combined with a FT-IR micro-cell for gas analysis, allowing time resolved analysis in stationary and transient conditions.At the first time the nitration properties of the catalysts under a lean flow have been studied in the appropriate temperature window (473–673 K). The dynamics of nitrates formation has been pointed out, as well as the different coordination sites on the compounds surface. Then the catalysts have been alternatively exposed to rich and lean flows very close to the real exhaust composition. This has allowed the identification of reduction pathway, active sites, intermediate species and by-products for NO _X -trap reaction. In particular, we have differentiated the role of the support and of the noble metal in the mechanism, as well as of isocyanate adspecies and ammonia among the detected species. The very high NO _X storage properties and the selectivity (near 100%) in nitrogen of the newly designed catalyst have been pointed out.