Behavioral correlates for minor volatile compounds from stink bugs (Heteroptera: Pentatomidae)

Many terrestrial Heteroptera have small, but functional, dorsal abdominal glands as adults. The chemistry, and associated intra- and inter-specific behavior, for dorsal abdominal gland secretions from 10 species representing four genera of Pentatomidae was investigated. Eighteen volatile compounds were identified in species-specific blends from the dorsal abdominal gland secretions ofEuschistus, Acrosternum, andEurydema adults, including aliphatic, aromatic, and terpenoid constituents. Evidence from bioassays is presented that parasitic Tachinidae (Diptera) and Scelionidae (Hymenoptera) use these secretions as kairomones. A field experiment was performed to test the hypothesis that minor volatiles increase the specificity of the main pheromone component from NearcticEuschistus species, methyl (2E,4Z)-decadienoate. However, significantly fewer individuals ofE. tristigmus were captured in traps baited with the complete blend for this species than in traps baited with methyl (2E,4Z)-decadienoate alone. Thus, at the concentrations tested, these kinds of dorsal abdominal gland secretions may be epideictic, promoting spacing in the natural habitat.     

Macrocyclic lactones and isopentenyl esters in the Dufour's gland secretion of halictine bees (Hymenoptera: Halictidae)

The volatile components of the Dufour's gland secretion of female halictid bees have been examined in 18 Nearctic species belonging toAgapostemon, Augochlora, Augochlorella, Augochloropsis, Dialictus, Evylaeus, Halictus, andLasioglossum. Nine saturated and unsaturated macrocyclic lactones ranging from C₁₈ to C₂₆ have been identified. Four of these compounds, the saturated C₂₆ and the unsaturated C₂₀, C₂₂, and C₂₄ lactones, are new natural products reported for halictine bees. A series of eight esters containing branched C₅-alkenols and fatty acids has been identified in several species. The cell linings and pollen ball inAugochlora pura pura contain the same major lactones as the Dufour's gland. A discussion of the significance of the Dufour's gland secretion for apoid systematics and its function in the Halictidae is presented.     

Chemical Defense in the Stink Bug Cosmopepla bimaculata

Adult Cosmopepla bimaculata discharge a volatile secretion from paired ventral metathoracic glands (MTG) when disturbed. Collected volatiles were similar in both sexes and consisted of n-tridecane (67%), (E)-2-decenal (12%), (E)-2-decenyl acetate (12%), (E)-2-hexenal (3%), hexyl acetate (2%), n-dodecane (2%), a tridecene isomer (1%), and n-undecane, n-tetradecane, and n-pentadecane (all <1%). In addition, undisturbed males produced a novel insect compound, (E)-8-heneicosene, whose function is unknown. The MTG secretion emerges as an enlarging droplet, which is held in place by a cuticular projection and a pleural scent area consisting of specialized rough cuticle surrounding the gland opening. Insects can selectively discharge from either the right or left gland or both glands simultaneously, can control the amount of fluid ejected, and can resorb the ejected secretion droplet back into the gland reservoir. In feeding trials, killdeer (Charadrius vociferous), starlings (Sturnus vulgaris), robins (Turdus migratorius), and anole lizards (Anolis carolinensis) rejected or demonstrated aversion to feeding on the bugs. Furthermore, bugs that lacked the secretion were more susceptible to predation than bugs with secretion, suggesting that the secretion functions in defense against predators.     

Sex pheromone of the woodbine leafroller moth,Sparganothis sp.

The sex pheromone of the woodbine leafroller,Sparganothis sp., includes (E)-11-tetradecen-1-ol, (Z)-11-tetradecen-1-ol, and (E)-11-tetradecen-1-yl acetate, based on chemical analysis of gland extracts, electroantennogram tests, and field trapping. Highest trap catches were obtained when these compounds were dispensed in the relative proportions observed in the female gland. (Z)-11-Tetradecen-1-yl acetate also was found in gland extracts, but significantly reduced trap catches. The saturated compounds tetradecan-1-ol and tetradecan-1-yl acetate were found in gland extracts as well, but were not tested. The amounts of these compounds per female gland were 127, 93, 17, 20, 25, and 3 ng, in the order named.Lepidoptera: Tortricidae.Supported by National Science Foundation Grant PCM 78-13241.     

Double-bond location in monounsaturated fatty acids by dimethyl disulfide derivatization and mass spectrometry: Application to analysis of fatty acids in pheromone glands of four lepidoptera

A rapid analytical procedure for the determination of the position of double bonds in mixtures of monounsaturated fatty acid methyl esters has been developed. The method is based on direct capillary GC-MS-EI analysis of dimethyl disulfide adducts. The procedure was applied to mixtures of monounsaturated fatty esters from pheromone gland extracts of three tortricids from theChoristoneura genus,C. fumiferana, C. occidentalis, andC. pinus pinus, and one noctuid from the Plusiinae subfamily,Plusia chalcites. A correlation was found between the known major pheromone components in the four species with the corresponding fatty acids. Some of the additional fatty acids may be precursors to as yet unidentified minor pheromone components, present in extremely small quantities, in these species.On sabbatical leave from the Institute of Plant Protection, Volcani Center, Bet Dagan 50 250, Israel.     

Sex pheromone components of the buck moth Hemileuca maia

The sex attractant pheromone blend of Hemileuca maia (Lepidoptera: Saturniidae) from the vicinity of Baton Rouge, Louisiana, has been identified. The major component of the blend is (E10,Z12)-hexadeca-10,12-dienal (E10,Z12–16:Ald), in combination with the minor components (E10,Z12)-hexadeca-10,12-dien-1-ol (E10,Z12–16:OH), and (E10,Z12)-hexadeca-10,12-dien-1-yl acetate (E10,Z12–16:Ac). Ratios of the compounds in extracts of female pheromone glands varied around a mean of 100:7.4:6.3. None of the three components were attractive to male moths when tested as single components. Several other compounds were tentatively identified from female pheromone gland extracts, including E10,E12–16:Ald, E10,E12–16:OH, and E10,E12–16:Ac, but addition of these components, either alone or in combination, at biologically relevant rates, did not significantly increase the attractiveness of lures. The saturated analogs, hexadecanal, hexadecanol, and hexadecyl acetate, also were identified in gland extracts, but had no apparent effect as pheromone components.     

Responses by canids to scent gland secretions of the western diamondback rattlesnake (Crotalus atrox)

Many snakes discharge malodorous fluids from paired scent glands in the base of the tail when they are disturbed. A number of authors suggest that these secretions repel predators. Scent gland secretions of the western diamondback rattlesnake (Crotalus atrox), or dichloromethane extracts of them, were presented to coyotes (Canis latrans) in three field tests, and to domestic dogs (Canis familiaris) in two kennel tests, to determine whether responses of possible benefit to snakes are elicited. Free-ranging coyotes visited and rubbed and rolled at stations containing scent gland secretions in perforated plastic capsules more frequently than at those containing untreated or dichloromethane-treated capsules. Responses to dichloromethane extracts of scent gland secretions subjected to rotary evaporation were not significantly different from those to dichloromethane. Pure and mixed breeds of dogs presented with filter papers treated with dichloromethane or a dichloromethane extract of scent gland secretions mouthed (licked, bit, or ate) secretion-treated papers more frequently. Staffordshire terriers presented with filter papers treated with dichloromethane or dichloromethane extracts of snake scent gland and alligator (Alligator mississippiensis) paracloacal gland secretions exhibited urination postures to snake secretion-treated papers more frequently than to dichloromethane-treated papers, but responses to snake- and alligator-treated papers did not differ significantly. There was no indication that canids are repelled by scent gland secretions.     

Virgin Queen Mandibular Gland Signals of Apis mellifera capensis Change with Age and Affect Honeybee Worker Responses

The mandibular gland secretions of Apis mellifera capensis virgin queens were analyzed by gas chromatography–mass spectroscopy. Changes in the patterns of the mandibular gland volatiles of A. m. capensis virgin queens were followed from emergence until 14-d old. Ontogenetic changes in the mandibular gland secretions were largely quantitative in nature, delineating the age categories (global R = 0.612, P = 0.001), except for 7- and 14-d-old queens, which cannot be separated on their mandibular gland profiles (P = 0.2). (E)-9-Oxodec-2-enoic acid (9ODA) contributes most and most consistently to the dissimilarity between groups as well as the similarity within groups. Worker reactions to introduced virgin queens of various ages were recorded. Workers showed a significant increase in hostile reactions as queens aged (r = 0.615, N = 20, P < 0.05). Consequently, worker reactions and relative 9ODA production exhibit a positive queen age-dependent response.     

Chemical Profiles of Scent Gland Secretions in the Cyphophthalmid Opilionid Harvestmen, <Emphasis Type="Italic">Siro duricorius</Emphasis> and <Emphasis Type="Italic">S. exilis</Emphasis>

Gas chromatographic–mass spectrometric analyses of the scent gland secretions of Siro duricorius and S. exilis (Opiliones, Cyphophthalmi, Sironidae) revealed a set of 24 components, comprising a series of saturated and unsaturated methyl ketones (C11–C15) and four naphthoquinones. Whereas the scent gland secretions of S. duricorius, collected in Austria, and S. exilis from USA were qualitatively nearly indistinguishable (with the exception of acetophenone that was specific to S. duricorius), they distinctly differed in their relative quantitative compositions: major components of the secretion of S. duricorius were 7-tridecen-2-one, tridecan-2-one, undecan-2-one, 1,4-naphthoquinone, 6-methyl-1,4-naphthoquinone (tentatively identified only), and 4-chloro-1,2-naphthoquinone. In contrast, in S. exilis a compound tentatively identified as 6-methyl-4-chloro-1,2-naphthoquinone was present in large amounts (in S. duricorius a trace component), whereas undecan-2-one only occurred in minor quantities. Secretion profiles of juveniles and adults (both sexes) of each species showed high correspondence.This is the first report on the chemistry of scent gland secretions of the opilionid suborder Cyphophthalmi. 4-Chloro-1,2-naphthoquinone was identified as a new exocrine product of arthropods, whereas 1,4-naphthoquinone and the tentatively identified 6-methyl-1,4-naphthoquinone are known constituents of exocrine secretions from one species of palpatorid opilionids, Phalangium opilio. In contrast, all ketones identified were new for opilionid scent glands, although similar ketones are characteristic of scent gland secretions of palpatorid genera Leiobunum and Hadrobunus. With regard to the near-basic position of Cyphophthalmi in currently proposed phylogenetic trees of Opiliones, naphthoquinones and ketones from Siro may represent the condition ancestral to the (derived) naphthoquinone- and ketone-rich secretions in phalangid Palpatores.     

(7<Emphasis Type="Italic">Z</Emphasis>,9<Emphasis Type="Italic">E</Emphasis>)-2-Methyl-7,9-Octadecadiene: A Sex Pheromone Component of <Emphasis Type="Italic">Lymantria Bantaizana</Emphasis>

Our objective was to identify the sex pheromone of Lymantria bantaizana (Lepidoptera: Lymantriidae) whose larvae feed exclusively on walnut, Juglans spp., in China, and Japan. Coupled gas chromatographic–electroantennographic detection (GC-EAD) analyses of pheromone gland extracts revealed a single EAD-active component. Retention index calculations of this compound on four GC columns suggested that it was a methyl-branched octadecadiene with conjugated double bonds. In GC-EAD analyses of 2-methyloctadecenes, (Z)-2-methyl-7-octadecene and (E)-2-methyl-7-octadecene elicited the strongest antennal responses, suggesting that the double bond positions were at C7 and C9. In comparative GC-EAD analyses of pheromone gland extract and stereoselectively synthesized isomers (E,E; E,Z; Z,E; Z,Z) of 2-methyl-7,9-octadecadiene, the (E,Z)- and (Z,E)-isomer had retention times identical to that of the candidate pheromone, but only the latter isomer elicited strong EAD activity. Results of field experiments in Japan substantiated that (7Z,9E)-2-methyl-7,9-octadecadiene is the L. bantaizana sex pheromone, a compound previously unknown in the Lepidoptera. Detection surveys in North America for exotic Eurasian forest defoliators could include traps baited with the L. bantaizana pheromone.     

Volatile male-specific natural products of a coreid bug (Hemiptera: Heteroptera)

The large coreid bug,Pachylis laticornis (Hemiptera: Coreidae), feeds on several mimosaceous trees in Guanacaste, Costa Rica. In addition to the presumably defensive metathoracic exocrine glands that occur in both sexes of this species, the adult males also possess a ventral abdominal gland, opening midventrally in the 7–8th abdominal intersegmental membrane, that releases volatile compounds. Two esters, (E)-2-hexenyl tiglate and (E)-2-hexenyl (E)-2-hexenoate, account for over 90% of the total volatiles in the ventral abdominal gland secretion of males. (E)-2-Octenyl tiglate and (E)-2-hexenyl benzoate are present at low concentrations, as are at least three other unidentified compounds. The biological role for this fragrant male-specific exudate is unknown.     

Biochemical and behavioral evidence foe hybridization between fire ants,Solenopsis invicta andSolenopsis richteri (Hymenoptera: Formicidae)

Behavioral and biochemical evidence is presented for hybridization between the fire ants,Solenopsis richteri andS. invicta. The response of the two species to extracts of their trail pheromones presented as a point source is clearly species-specific; however, hybrid workers responded to parental Dufour's gland extracts and parental workers responded to Dufour's gland extracts of the hybrid. The behavioral evidence for hybridization was confirmed by gas Chromatograph comparison of the Dufour's gland extracts of the three fire ant forms, which showed a pattern for the hybrid that was intermediate to the two parental species.     

Trail-Following Pheromones in Basal Termites, with Special Reference to Mastotermes darwiniensis

In the framework of an evolutionary study, trail pheromones have been studied in the most basal extant termite, Mastotermes darwiniensis (Mastotermitidae), and two other basal termites, the Termopsidae Porotermes adamsoni (Porotermitinae) and Stolotermes victoriensis (Stolotermitinae). Although workers of M. darwiniensis do not walk in single file while exploring a new environment under experimental conditions and are unable to follow artificial trails in ‘open field’ experiments, they do secrete a trail-following pheromone from their sternal glands. This unique behavior might reflect a primitive function of communication of the sternal gland. The major component of the pheromone appears to be the same in the three basal species: the norsesquiterpene alcohol (E)-2,6,10-trimethyl-5,9-undecadien-1-ol. This represents a new chemical category of trail-following pheromones for termites. The quantity of pheromone was estimated as 20 pg/individual in M. darwiniensis, 700 pg/individual in P. adamsoni, and 4 pg/individual in S. victoriensis. The activity threshold was 1 ng/cm in M. darwiniensis and 10 pg/cm in P. adamsoni. In M. darwiniensis, the trail pheromone was secreted by sternal gland 4 and to a lesser degree by sternal gland 3, sternal gland 5 being almost inactive. This study highlighted phylogenetic relationships between the Mastotermitidae and two subfamilies of the Termopsidae, the Porotermitinae and the Stolotermitinae. Furthermore, it indicated a heterogeneity within the Termopsidae, with Porotermitinae and Stolotermitinae on one hand, and Termopsinae on the other. Finally, Mastotermitidae and Termopsidae, with C14 trail pheromones, are clearly separated from the Kalotermitidae, Rhinotermitidae, and Termitidae that secrete C12 or C20 trail pheromones.     

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.     

N,N-dimethyluracil and actinidine,two pheromones of the ponerine antMegaponera foetens (Fab.) (Hymenoptera: Formicidae)

By means of gas chromatographic, mass spectrometric, and micro-preparative methodsN,N-dimethyluracil and actinidine were identified as two ethologically active compounds in the ponerine antMegaponera foetens. The synthesized poison gland compoundN,N-dimethyluracil released trail-following behavior, whereas actinidine, found in the pygidial gland, stimulated ants to leave the nest, possibly in an alarm reaction. Biological activity of the synthetic samples were confirmed by behavioral experiments and electroantennogram responses with worker antennae.Kern, F, and Bestmann, H.J. 1994. Pheromones 99. Pheromones 98:Z. Naturforsch. 49c:865–870.     

Enantiomers of (Z,Z)-6,9-Heneicosadien-11-OL: Sex Pheromone Components of Orgyia detrita

(6Z,9Z,11S)-6,9-Heneicosadien-11-ol (Z6Z9-11S-ol-C21) and (6Z,9Z,11R)-6,9-heneicosadien-11-ol (Z6Z9-11R-ol-C21) were identified as major sex pheromone components of female tussock moths, Orgyia detritaGuérin-Méneville (Lepidoptera: Lymantriidae), on the basis of (1) analyses of pheromone gland extracts of female O. detrita by coupled gas chromatographic-electroantennographic detection (GC-EAD) and GC mass spectrometry, and (2) field trapping experiments with synthetic standards. Z6Z9-11S-ol-C21 and Z6Z9-11R-ol-C21 in combination, but not singly, attracted significant numbers of male moths. Racemic Z6Z9-11-ol-C21 was more attractive than the 1:3.5 (R:S) blend ratio found in pheromone gland extracts from female moths. Lower and higher homologues of Z6Z9-11-ol-C21 were also detected in GC-EAD recordings of pheromone extracts, and the racemic compounds enhanced attractiveness of Z6Z9-11-ol-C21 in field experiments. Because of trace amounts of these homologues in extracts, their enantiomeric composition could not be determined. This is the first report of secondary alcohols as pheromone components in the ditrysian (advanced) Lepidoptera.     

Premating Behavior of Bombus Confusus Males and Analysis of Their Labial Gland Secretion

Premating behavior in the bumblebee Bombus confusus was studied. Visual searching for females is not the only premating strategy of this species, as was believed earlier. Males of B. confusus have a normally developed labial gland and its secretion is used to mark a perch from which they visually search for females. The labial gland secretion contains geranylcitronellol and (Z)-9-octadecenyl acetate as the main components.     

Sex Pheromones of Thysanoplusia intermixta and T. orichalcea: Identification and Field Tests

Thysanoplusia intermixta, which inhabits the temperate zone in Japan, is a defoliator of plants in the family Compositae, Apiaceae, and others. By GC-MS analysis, (Z)-7-dodecenyl acetate, (Z)-7-dodecen-l-ol, (5E, 7Z)-5,7-dodecadienyl acetate and (5E, 7Z)-5,7-dodecadien-l-ol were identified from a pheromone gland extract of the virgin females in a ratio of 18:3:100:13. A lure baited only with the major diene acetate could attract male moths of T. intermixta in the field. Other minor components had a synergistic effect on the attraction of the diene acetate. The same four components were included in a very different ratio of 100:6:11:1 in the gland extract of Thysanoplusia orichalcea, a closely related subtropical species. The monoene and diene acetates are essential for field attraction, and a 100:11 mixture is an optimum lure for T. orichalcea males. However, this mixture, including the diene acetate as a minor component, captured very few T. intermixta males, suggesting the possibility that these two Thysanoplusia species are reproductively isolated from each other by pheromonal communication.     

Beyond 9-ODA: SEX Pheromone Communication in the European Honey Bee Apis mellifera L.

The major component of the mandibular gland secretion of queen honeybees (Apis mellifera L.), 9-ODA ((2E)-9-oxodecenoic acid), has been known for more than 40 yr to function as a long-range sex pheromone, attracting drones at congregation areas and drone flyways. Tests of other mandibular gland components failed to demonstrate attraction. It remained unclear whether these components served any function in mating behavior. We performed dual-choice experiments, using a rotating drone carousel, to test the attractiveness of 9-ODA compared to mixtures of 9-ODA with three other most abundant components in virgin queen mandibular gland secretions: (2E)-9-hydroxydecenoic acid (9-HDA), (2E)-10-hydroxydecenoic acid (10-HDA), and p-hydroxybenzoate (HOB). We found no differences in the number of drones attracted to 9-ODA or the respective mixtures over a distance. However, adding 9-HDA and 10-HDA, or 9-HDA, 10-HDA, and HOB to 9-ODA increased the number of drones making contact with the baited dummy. On the basis of these results, we suggest that at least 9-HDA and 10-HDA are additional components of the sex pheromone blend of A. mellifera.     

Activity of volatile compounds in glandular trichomes ofLycopersicon species against two insect herbivores

Several major chemicals in the glandular heads of type VI trichomes ofLycopersicon species were identified and quantified by gas chromatography and mass spectrometry. Two normal odd-chained ketones, 2-undecanone (47 ng) and 2-tridecanone (146 ng), and one unknown sesquiterpene (5 ng), comprised approximately 95% of the contents of a gland ofL.hirsutum f.glabratum Mull. In a closely related plant,L.hirsutum Humb. & Bonpl. (LA 361), two unknown insecticidal sesquiterpenes accounted for 6% of the gland contents. Additionally, small amounts of one unknown monoterpene and another unknown sesquiterpene were found in type VI glands of a commercial tomato variety,L.esculentum Mill. Bioassays comparing the gland exudate (by direct contact) and isooctane extracts of glands to neonate larvae ofKeiferia lycopersicella (Walsingham) (Lepidoptera: Gelechiidae) andSpodoptera exigua (Hübner) (Lepidoptera: Noctuidae) indicated that: (1) 2-tridecanone and 2-undecanone were the major insecticidal compounds inL.hirsutum f.glabratum, (2) the two unknown sesquiterpenes inL.hirsutum were acutely toxic to both species, and (3) gland contents in the commercial tomato variety provided only a physical barrier toK.lycopersicella, and were not detrimental toS.exigua. In topical bioassay trials, synthetic mixtures of 2-tridecanone and 2-undecanone (3 1) demonstrated potentiation. Concentrations of these chemicals decreased as trichomes aged. Quantities of insecticidal chemicals and density of type VI trichomes varied with plant age and location within plants.