The major component of the trail pheromone of the leaf-cutting ant,Atta sexdens rubropilosa forel

The major component of the trail pheromone of the South American leaf-cutting ant,Atta sexdens rubropilosa Forel, is 3-ethyl-2,5-dimethylpyrazine (II). Methyl and ethyl phenylacetate and methyl 4-methylpyrrole-2-carboxylate (I), which is the major component of the trail pheromone ofA. texana (Buckley) andA. cephalotes (L.), were also identified and may be minor components. The pheromone is stored in the poison gland.Atta sexdens sexdens (L.) also responds strongly to the pyrazine, which in large amounts evokes a weak response fromA. texana, A. cephalotes, andAcromyrmex octospinosus (Reich). Foraging workers ofAtta sexdens rubropilosa did not preferentially pick up baits impregnated with the pyrazine. The pyrazine was puffed into the nests ofA. cephalotes, and a particular response called milling was noted.     

Comparative deterrency of two terpenoids to two genera of attine ants

Caryophyllene and caryophyllene epoxide are two terpenoids found in neotropical plants and known to be deterrent to leafcutter ants. To estimate the variation in deterrent activity of these compounds toward the generaAtta andAcromyrmex, behavioral bioassays were conducted over a range of concentrations. The responses of four captive colonies ofAtta cephalotes and two captive colonies ofAcromyrmex octospinosus, all from a single locality in Costa Rica, were studied. Although specific patterns of deterrency differed in the two genera, in both cases caryophyllene epoxide concentrations of 0.70 mg/g or greater, and caryophyllene concentrations of 7.0 mg/g or greater, significantly deterred the harvest of potential substrates. Individual colonies within each genus did not differ significantly in their responses to caryophyllene epoxide. The mean response of the two genera to caryophyllene epoxide differed significantly, but responses to caryophyllene did not.Acromyrmex octospinosus was more sensitive to low concentrations and less sensitive to high concentrations of caryophyllene epoxide than wasAtta cephalotes.     

The Mandibular Gland Secretions of the Leaf-Cutting Ants Atta sexdens sexdens and Atta opaciceps Exhibit Intercaste and Intercolony Variations

The mandibular gland secretions of worker castes from wild colonies of the leaf-cutting ants Atta sexdens sexdens and Atta opaciceps were analyzed quantitatively by gas chromatography–mass spectrometry. The secretions comprised a complex mixture of volatile, mainly oxygenated compounds, and their profiles exhibited considerable qualitative and quantitative variations among species and castes. The known alarm pheromone 4-methyl-3-heptanone was common to both species. The elevated relative proportions of this ketone found in the secretions of gardeners and generalists suggest that such castes are primarily responsible for the production and release of the alarm pheromone. Quantitative variations (but no qualitative differences) in the profiles of secretions of soldiers from different colonies of A. sexdens sexdens were detected, supporting the view that intraspecific colony recognition is mediated through mandibular gland secretions. Subsequent laboratory assays showed that, among the compounds identified by GC–MS, 4-methyl-3-heptanone elicited a strong alarm response in workers of A. sexdens sexdens and A. opaciceps.     

Diterpene composition of defense secretion of four west AfricanTrinervitermes soldiers

The diterpene composition of the defensive secretions of minor and major soldiers is described for four sympatricTrinervitermes from the Ivory Coast. The degree of intra- and interspecific similarity between the secretions is assessed and related to available information on soldier behavior. A significant chemical dimorphism is observed between minor and major soldiers ofT. geminatus andT. togoensis. Both species build extensive foraging trails in the open air. During these excursions, the workers are protected by numerous minor soldiers, but only a few major ones. Internest comparison inT. geminatus suggests that the differences between minor and major soldiers is as large within a nest as between different nests. By, contrast, inT. trinervius andT. oeconomus both types of soldiers produce very similar secretions. The foraging habits of those species are far more cryptic. The first species builds earthen tunnels, and the second one forages in close proximity to its nest under cover of vegetation.Maître de Recherche du Fonds National de la Recherche Scientifique de Belgique.     

Volatile glandular secretions of three species of new world army ants,Eciton burchelli,Labidus coecus,andLabidus praedator

The Dufour glands of workers ofEciton burchelli contain a mixture of small quantities of oxygenated compounds, some of which are derived from terpenes, and C₁₇-C₂₅ hydrocarbons. The secretion of the Dufour glands of soldiers was either similar to that of workers, with geranylacetone a significant component, or they contained geranyllinalool in large amounts. The glands of workers and soldiers ofLabidus praedator andLabidus coecus contained (E)--ocimene, a new substance for the Dufour glands of ants. 4-Methyl-3-heptanone was the dominant compound in the mandibular glands ofE. burchelli andL. coecus. Skatole and indole were found in the gasters ofL. praedator, and skatole was present in the venom glands of some soldiers ofE. burchelli.     

Chemical defense secretions of some species of Malaysian rhinotermitidae (Isoptera,Rhinotermitidae)

The defense secretions of the soldiers of the Malaysian rhinotermitid,Parrhinotermes aequalis (Havilandi) andP. pygmaeus (John),Termitogeton planus (Havilandi) andSchedorhinotermes malaccensis (Holmgren) consist mainly of vinyl ketones, whereas that ofProrhinotermes flavus (Bugnion & Popoff) gives (E)-1-nitropentadecene. The chemistry of the defense secretions ofParrhinotermes andTermitogeton is documented and based on their chemical relationships;Termitogeton shows a closer affinity to the Rhinotermitinae than Heterotermitinae.     

Variation with caste of the mandibular gland secretion in the leaf-cutting antAtta sexdens rubropilosa

InAtta sexdens rubropilosa, a strongly polyethic and polymorphic species of myrmicine ant, the contents of the mandibular gland vary with caste. Small workers of head width 0.5–1.8 mm, those generally engaged in duties inside the nest, contain chiefly 4-methyl-3-heptanone. Larger workers, those chiefly engaged in foraging, and the soldier caste contain a mixture dominated by neral and geranial, with very little of the ketone of the smaller workers. The soldiers have massive glands containing milligram amounts of neral and geranial. Virgin and mated females contain essentially only 4-methyl-3-heptanone, the amount increasing after mating, while virgin males have 4-methyl-3-heptanone and 4-methyl-3-heptanol in approximately equal proportions. Mated males have less secretion and lose the 4-methyl-3-heptanol.     

Mandibular Gland Secretion in Different Castes of the Leaf-Cutter Ant Atta laevigata

Gas chromatography analyses and behavioral assays showed that Atta laevigata, a highly polymorphic ant species, has a mandibular gland secretion that varies with castes. All castes contain 4-methyl-3-heptanone as the main component and its concentration is proportional to head size. Small workers and soldiers, but not medium size workers, also contain 4-methyl-3-heptanol. Queens show variations in their chemical composition after mating, as virgin males contain a secretion dominated by 4-methyl-3-heptanol, and, in a lesser proportion, 4-methyl-3-heptanone. In mated males these proportions are inverted. The compounds 4-methyl-6-hepten-3-one, 4-methyl-4-hepten-3-one, 6-methyl-tetradecene, and 2,6-dimethyl-2-dodecene are found only in queens. The behavioral response elicited by the secretion is mainly alarm, which is elicited more strongly by glands of larger workers. The results suggest that chemical castes, behavioral castes, and morphological castes overlap in this species.     

Cuticular hydrocarbons and defensive compounds ofReticulitermes flavipes (Kollar) andR. santonensis (feytaud): Polymorphism and chemotaxonomy

Colonies ofReticulitermes flavipes andR. santonensis were collected from the southeastern United States (Georgia) and the southwest of France (Charente-maritime). Defensive compounds and cuticular hydrocarbons were identified by gas chromatography-mass spectrometry and quantified by gas chromatography using an internal standard for each caste and all colonies. These analyses show that although the cuticular hydrocarbons ofR. santonensis in Europe andR. flavipes in Georgia are identical, their relative proportions are different. However, the defensive compounds synthesized by their soldiers are different. A strong chemical polymorphism between sympatric colonies ofR. flavipes in the SW United States was detected in terms of both the hydrocarbons of the workers and soldiers and in the defensive secretions of the soldiers. The six defensive secretion phenotypes are based on the presence or absence of terpenes whereas the cuticular hydrocarbon phenotypes are based on significant differences in the proportions of the various components. A multivariate analysis (analysis of principal components) clearly permitted discrimination of four phenotypes (three inR. flavipes and one inR. santonensis) without intermediates. The hydrocarbons responsible for these variations were identified, and it was shown that the variations are neither seasonal nor geographic. The phenotypes of the cuticular hydrocarbons (workers and soldiers) and defensive compounds are linked in each colony, forming in three groups inR. flavipes Georgia, one subdivided into four subgroups according to the defensive secretion phenotypes. The role of these polymorphisms is discussed and ethological tests indicate that the chemical polymorphism do not determine aggressive behavior. The taxonomic significance of these results is considered and two hypothesis are formulated: (1) We only detected a strong genetic polymorphism in one unique species, and we believe thatR. santonensis was introduced into Europe in the last century from oneR. flavipes colony. (2) Chemical variability characterizes the sibling species that can be grouped into the same subspeciesR. flavipes. Unknown mechanisms of reproductive isolation separate them.     

Chemical defense secretions of the termite soldiers ofAcorhinotermes andRhinotermes (Isoptera,Rhinotermitinae)

The defense secretions of advanced nasutoid rhinotermitine soldiers from the New World contain enolic -ketoaldehydes as the major components. The secretions of minor soldiers ofRhinotermes hispidus (Emerson) andR. marginalis (Emerson) consist primarily of 3-keto-13-tetradecenal and 3-ketotetradecanal, but possess in addition C₁₃, C₁₄, C₁₅, and C₁₇ saturated and unsaturated ketones. Major soldiers lacked these compounds and in fact had virtually no frontal gland secretion. The defense secretion of the monomorphic soldiers ofAcorhinotermes subfusciceps (Emerson) contains mostly 3-keto-(Z)-9-hexadecenal and (Z)-8-pentadecen-2-one. Biosynthetic origins and interrelationships are postulated for these compounds, and the concomitant evolution of chemical weaponry and the modified labral brush is discussed.Fellow of the Alfred P. Sloan Foundation (1981–1983).     

Toxicity of lignans to symbiotic fungus of leaf-cutting ants

Lignans fromVirola sebifera Aubl.,Virola sp., andOtoba parvifolia (Mkfg.) A. Gentry (Myristicaceae) inhibited the in vitro growth of the fungus cultivated by leaf-cutting ants of the speciesAtta sexdens rubropilosa Forel (Hymenoptera: Formicidae). A comparison of activity among the lignans was obtained.     

Metapleural Gland Secretion of the Leaf-cutter Ant Acromyrmex octospinosus: New Compounds and Their Functional Significance

Ants of the myrmicine tribe Attini live in symbiosis with a fungus that provides them with food. In return the ants maintain optimal growth conditions for the fungus, weed out competing microorganisms, and inhibit the growth conditions of these competitors by chemical means. We present a comprehensive analysis of metapleural gland secretions of Acromyrmex octospinosus, using a recently developed method for the analysis of polar compounds by gas chromatography and mass spectrometry. We show that the chemical identity and quantitative recovery of different compounds in the metapleural gland secretion depends upon the method used and the type of colony from which the samples are taken. In addition to the two compounds previously recorded in the metapleural gland secretion of Acromyrmex ants (indolacetic acid and myrmicacin), 20 new compounds were detected in the secretion of a random sample of workers from two laboratory colonies and two field colonies. These compounds span the whole range of carboxylic acids from acetic acid to the long-chain fatty acids but comprise also some alcohols, lactones, and keto acids. The possible function of this highly complex secretion mixture is discussed.     

Odor correspondence betweenMelitta females and males of their nest parasiteNomada flavopicta K. (Hymenoptera: Apoidea)

Analyses have been performed with the help of combined capillary gas chromatography and mass spectrometry on volatile secretions emanating from the Dufour glands of femaleMelitta haemorrhoidalis andM. leporina and heads of maleNomada flavopicta, a nest parasite of theMelitta species. It was found that the cephalic secretions ofN. flavopicta males have definite similarities with the Dufour gland secretions of the two species ofMelitta. They all contain octadecyl butyrate as a major component. Monounsaturated alcohols of different chain lengths are also present in the secretions. Beside these compounds,Melitta has some other esters, notably C₁₂-, C₁₄-, C₁₆-, and C₂₀-butyrates as well as C₁₂- and C₁₆-acetates.     

Volatile secretions of old world army antAenictus rotundatus and chemotaxonomic implications of army ant dufour gland chemistry

The Dufour glands ofAenictus rotundatus contain a complex mixture of terpenoids with geranylgeraniol comprising over 50% of the secretion. Some novel compounds have been tentatively identified as higher homologs of 1,3,3-trimethyl-2,7-dioxabicyclo[2,2,1]heptane based on GC-MS data. The Dufour gland secretion ofA. rotundatus is more similar in composition to the secretions of members of the subfamily Ecitoninae than to its closer relatives from the tribe Dorylini, a result that further complicates studies on the phylogeny of army ants. The mandibular glands ofA. rotundatus contain a mixture of 4-methyl-3-heptanone and limonene in trace amounts, and the well-developed postpygidial glands contain methyl anthranilate only.     

Trail pheromone of the leaf-cutting ant,Acromyrmex octospinosus (Reich), (Formicidae: Myrmicinae)

The most active component of the trail pheromone of the leafcutting ant,Acromyrmex octospinosus, is methyl 4-methylpyrrole-2-carboxylate (I). Two pyrazine isomers (II) and (III) are present but inactive.     

Chemistry and functions of exocrine secretions of the antsTapinoma melanocephalum and T. erraticum

Volatile constituents produced by ant workers belonging to the speciesTapinoma melanocephalum andT. erraticum have been analyzed by gas chromatography-mass spectrometry. The pygidial (=anal) gland secretion ofT. melanocephalum is fortified with 6-methyl-5-hepten-2-one and actinidine (the mass spectrum of which is corrected in this paper). An unidentified compound was detected in cephalic extracts. The pygidial gland secretion ofT. erraticum was also dominated by 6-methyl-5-hepten-2-one, in addition to two isomers of iridodial, and iridomyrmecin. The sternal glands contained iridodial and C₁₅-C₂₀ hydrocarbons. Workers ofT. melanocephalum effectively utilize their pygidial gland secretions as an alarm-defense system during aggressive encounters with workers ofSolenopsis geminata. 6-Methyl-5-hepten-2-one is active as a releaser of alarm behavior, and actinidine is repellent to workers ofT. melanocephalum. Cephalic extracts possessed attractant and arrestant properties for workers of this species.     

γ-Linolenic and stearidonic acids in Mongolian Boraginaceae

Seeds of nine Central Asian species of Boraginaceae were investigated for the first time for their oil content and for the fatty acid composition of their seed oils by capillary gas chromatography. Levels of γ-linolenic acid ranged from 6.6 to 13.0% and levels of stearidonic acid ranged from 2.4 to 21.4% of total seed fatty acids. The seed oil ofHackelia deflexa exhibited the highest stearidonic acid content (21.4%) that has been found so far in nature. Other high contents of this fatty acid were in threeLappula species (17.2 to 18.1%). Seed oils ofCynoglossum divaricatum andAmblynotus rupestris contain considerable amounts ofcis-11-eicosenoic (5.3 to 5.8%) andcis-13-docosenoic acid (7.0 to 9.7%) besides γ-linolenic (10.2 to 13.0%) and stearidonic acid (2.4 to 6.5%), which distinguish these oils from those of other Boraginaceae genera. This paper was presented as a poster at 10th Minisymposium and Workshop on Plant Lipids, Sept. 3–6, 1995, in Berne, Switzerland.     

Interspecific variation of diterpene composition ofCubitermes soldier defense secretions

Soldiers of the humivorous termite generaCubitermes andCrenetermes (Isoptera: Termitidae: Termitinae) secrete a mixture of unusual diterpene hydrocarbons from the fontanellar opening of the frontal gland. The defense secretions of sixCubitermes species and oneCrenetermes species show species-specific distributions of the five chemically identified major components and 12 unidentified minor components. The secretion is also present with its characteric terpene distribution in white presoldiers and newly molted soldiers, but is completely absent in workers.Fellow of the Alfred P. Sloan Foundation (1981–85) and Camille and Henry Dreyfus Teacher-Scholar (1981–86).     

Repellency to two-spotted spider mite,Tetranychus urticae Koch,as related to leaf surface chemistry ofLycopersicon hirsutum accessions

Bioassays employingTetranychus urticae Koch were used to examine repellency of leaves and trichome secretions of one cultivar of tomato,Lycopersicon esculentum, and 11 accessions ofL. hirsutum consisting of seven accessions ofL. hirsutum f.typicum and four accessions ofL. hirsutum f.glabratum. Leaves of f.typicum were more repellent to mites than were those of f.glabratum orL. esculentum. Removal of trichomes and their secretions by wiping leaves of f.typicum accessions with 95% ethanol rendered them less repellent, indicating that trichomes or their secretions were potentially responsible for repellency. Gas and thin-layer chromatography of leaflet washes obtained by steeping leaflets in hexane indicated that the chemical composition of the washes differed among accessions. The main difference between botanical forms was the presence in leaflet washes from f.typicum accessions of compounds eluting late on the gas Chromatograph and migrating further on reverse-phase thin-layer chromatography; compounds having these characteristics were absent in washes of f.glabratum andL. esculentum. The compositions of secretions taken directly from type I, type IV, and type VI trichomes were similar to that of the leaflet wash obtained from the same f.typicum plant, indicating that leaflet washes contained mainly compounds of trichomal origin. Leaflet washes from f.typicum plants were generally more repellent toT. urticae than were washes from f.glabratum when tested by choice and nonchoice bioassays. Taken together, the data indicate that trichome secretions of f.typicum are likely responsible for potent repellency to two-spotted spider mites observed in this taxon; the likely active compounds are sesquiterpene acids or other polar constituents of trichome secretions.     

Defensive secretions of three species ofAcilius (Coleoptera: Dytiscidae) and their seasonal variations as determined by high-pressure liquid chromatography

A rapid, sensitive, stable, and quantitative high-pressure liquid chromatographic technique was developed for the analysis of defensive secretions obtained from the pygidial and prothoracic glands of dytiscids. Methods were developed for both normal phase (Porasil) and reverse phase (Bondapak C₁₈) columns. The applicability of this technique was demonstrated when defensive compounds ofAcilius semiculcatus, A. sylvanus andA. mediatus were isolated, identified, and quantitated. No major differences were found in the composition of the defensive secretions between the three species. The seasonal defensive titer ofA. semisulcatus was determined from June through October 1977. The pygidial defensive agents (benzoic acid,p-hydroxybenzaldehyde, and methylp-hydroxybenzoate varied from 9.0 to 67.8 g and exhibited a maximum in July, and a steroid from the prothoracic gland varied from 7.1 to 33.2 g and was maximum in October.