Interactions Between Host-plant Volatiles and the Sex Pheromones of the Bird Cherry-oat Aphid, <Emphasis Type="Italic">Rhopalosiphum padi</Emphasis> and the Damson-hop Aphid, <Emphasis Type="Italic">Phorodon humuli</Emphasis>

The bird cherry-oat aphid, Rhopalosiphum padi (L.), and the damson-hop aphid, Phorodon humuli (Schrank), migrate at the same time of year and colonize closely related Prunus spp. as primary hosts, but utilize (1R,4aS,7S,7aR)-nepetalactol and (1RS,4aR,7S,7aS)-nepetalactol, respectively, as sex pheromones. Interactions between these sex pheromones and benzaldehyde and methyl salicylate, plant volatiles common to primary hosts of both species, were investigated to assess whether they confer reproductive isolation between these species. Female autumn migrants (gynoparae) and males of these two species were caught in the field with water traps baited with their respective sex pheromones. Rhopalosiphum padi gynoparae and males also responded positively to benzaldehyde. Release of either benzaldehyde or methyl salicylate with the conspecific sex pheromone increased catches of both species of aphid. However, releasing both plant volatiles with the sex pheromone of R. padi increased catches of gynoparae and males, but reduced those with the sex pheromone of P. humuli. These results support the hypothesis that specific plant volatiles synergize responses of autumn migrating aphids to their sex pheromone. Because these interactions are species-specific, they may be important in allowing males to discriminate between conspecific sexual females (oviparae) and those of other aphid species.     

Sex Pheromone Stereochemistry and Purity Affect Field Catches of Male Aphids

Male blackberry-cereal aphids, Sitobion fragariae (Walker), were caught in the ield by water traps releasing synthetic (4aS, 7S, 7aR)-nepetalactone, the major sex pheromone component. The presence of the enantiomer (4aR,7R,7aS)-nepetalactone reduced catches and a plant-extracted (4aS,7S,7aR)-nepetalactone was less effective than the 99% (7S)-lactone. A more extensive trial with the bird cherry-oat aphid, Rhopalosiphum padi, involving the pheromone comprising the stereochemically related (4aS,7S,7aR)-nepetalactol showed a similar trend. The (7R)-isomer caught fewer males than the (7S)-isomer, but in this case the addition of high-purity (7S)-lactol to make a 50% blend caught as many males as pure (7S)-lactol. With plant-derived lactol, further purification did not significantly increase the catch. It is suggested that trace compounds associated with reduced enantiomeric purity in terms of the (7S)-configuration or from plant sources reduce activity of the sex pheromone components. Male damson-hop aphids, Phorodon humuli (Schrank), were also caught in the synthetic lactol traps, and it is suggested that this is due to traces of the (4aR,7S,7aS)-nepetalactols, which comprise the sex pheromone for this species. The significance for aphid chemical ecology studies and pest control strategies is discussed.     

Sex Pheromone of the Peach Aphid, Tuberocephalus momonis, and Optimal Blends for Trapping Males and Females in the Field

Chemical analysis of the volatiles released by sexual females (oviparae) of the peach aphid, Tuberocephalus momonis, identified two ubiquitous aphid sex pheromone components, (4aS,7S,7aR)-nepetalactone and (4aS,7S,7aR)-nepetalactol, in a ratio of 4 : 1. In field trials in Korea, employing traps releasing the two compounds in differing ratios, the most effective sex pheromone blend for trapping male T. momonis was found to be 85 : 15 nepetalactone–nepetalactol. Surprisingly, large numbers of presexual females (gynoparae) of this species were also collected when the catching rates were highest. In addition to T. momonis, over 20 other species of aphids were caught, particularly Myzus lythri, M. dycei, Lachnus tropicalis and M. persicae, in descending order of abundance.     

Response of The Lacewing Chrysopa cognata to Pheromones of its Aphid Prey

The lacewing Chrysopa cognata, one of the principal predators of aphids in Korea, was tested for responses to the aphid sex pheromone components (4aS,7S,7aR)-nepetalactone and (1R,4aS,7S,7aR)-nepetalactol and the aphid alarm pheromone (E)--farnesene. Electroantennogram responses were obtained to the sex pheromone components but not to (E)--farnesene. The sex pheromone components were attractive in a Y-tube olfactometer assay and in field trials with water traps, but no attraction was observed to (E)--farnesene.     

Dolichodial: A New Aphid Sex Pheromone Component?

The sex pheromones of many aphid species from the subfamily Aphididae comprise a mixture of the iridoids (cyclopentanoids) (1R,4aS,7S,7aR)-nepetalactol and (4aS,7S,7aR)-nepetalactone. In this paper, we investigate whether other chemicals, in addition to nepetalactol and nepetalactone, are released from Dysaphis plantaginea (rosy apple aphid) oviparae as part of their sex pheromone. Four compounds present in an air entrainment sample collected from D. plantaginea oviparae feeding on apple (Malus silvestris c.v. Braburn) elicited electrophysiological responses from male D. plantaginea. Active peaks were tentatively identified by gas chromatography (GC) coupled with mass spectrometry, with identification confirmed by peak enhancement with authentic compounds on GC columns of different polarities. The electroantennography-active chemicals were (1R,4aS,7S,7aR)-nepetalactol, (4aS,7S,7aR)-nepetalactone, (1S,2R,3S)-dolichodial, and phenylacetonitrile. (1S,2R,3S)-Dolichodial elicited a behavioral response from male D. plantaginea and naïve-mated female parasitoids, Aphidius ervi. This is the first report of electrophysiological and behavioral responses from any aphid morph to (1S,2R,3S)-dolichodial. Whether or not (1S,2R,3S)-dolichodial is a third component of the aphid sex pheromone is discussed.     

Characterization of (1'R,4S,4aR,7S,7aR)-dihydronepetalactol as a semiochemical for lacewings,including Chrysopa spp. and Peyerimhoffina gracilis

The enantiomerically pure diastereoisomers (1R,4S,4aR,7S,7aR)- (1) and (1R,4R,4aR,7S,7aR)-dihydronepetalactol (2) were synthesized diastereoselectively from a renewable resource, (4aS,7S,7aR)-nepetalactone (3), isolated as the main constituent of the essential oil of the catmint plant Nepeta cataria. The stereochemistry of the compounds was determined by NMR spectroscopy and X-ray crystallography, and the compounds were identified, respectively, as neomatatabiol and isoneomatatabiol, natural products from Actinidia polygama, for which the lactol stereochemistry was previously incompletely defined. Compound 1 was found to catch significant numbers of three species of lacewing in the field: in Korea, Chrysopa cognata, and in the United Kingdom, Nineta vittata and most notably Peyerimhoffina gracilis. All species caught in significant numbers were found more frequently in traps releasing 1 than 2, while more C. cognata, C. formosa, and C. phyllochroma were found in traps releasing (1R,4aS,7S,7aR)-nepetalactol (4). The catch of P. gracilis with 1 is of particular interest as this lacewing has only recently been recorded in the United Kingdom. Where sexed, the lacewings of all species trapped were found to be male, implying a possible pheromonal role for these or structurally related compounds.     

Comparative Responses of Parasitoids to Synthetic and Plant-Extracted Nepetalactone Component of Aphid Sex Pheromones

The responses of aphid parasitoids to completely synthetic and plant-extracted nepetalactone, a component of aphid sex pheromones, were investigated. In wind tunnel tests, Praon volucre and Aphidius ervi responded equally strongly to both plant-extracted and 99% pure synthetic (4aS,7S,7aR)-nepetalactone. In the field, aphid-infested cereal trap plants were used to test the attractiveness of plant-extracted and synthetic (4aS,7S,7aR)-nepetalactone, as well as the synthetic enantiomer (4aR,7R,7aS)-nepetalactone. There was no significant difference in parasitisation levels by Praon spp. between plants baited with the synthetic or with the plant-extracted 7S isomers. However, the 7R isomer was unattractive alone and rendered the synthetic 7S isomer unattractive when combined to form a 50% blend of the two. It is concluded that the response of aphid parasitoids to nepetalactone is influenced more by enantiomeric purity rather than the possible presence of plant-related contaminants associated with plant extraction. The results are compared with data on male aphid responses to the compounds, which indicate that plant-derived contaminants can reduce attractancy, and the implications for the manipulation of parasitoids in the field are discussed.     

Olfactory Reactions of the Twelve-Spotted Lady Beetle, Coleomegilla maculata and the Green Lacewing, Chrysoperla carnea to Semiochemicals Released from Their Prey and Host Plant: Electroantennogram and Behavioral Responses

Electroantennograms (EAGs) were recorded from two predatory insect species, the twelve-spotted lady beetle, Coleomegilla maculata and the green lacewing, Chrysoperla carnea in response to semiochemicals emitted from one of their prey species, the pea aphid Acyrthosiphon pisum and their host plant. EAG responses were also recorded from C. maculata in response to extracts from individuals of the opposite sex and to extracts from an herbaceous plant, catnip Nepeta cataria. Extracts of catnip and two sex pheromone components of aphids, (4aS,7S,7aR)-nepetalactone and (1R,4aS,7S,7aR)-nepetalactol, elicited significant EAG responses from the antennae of both predatory species. Of 10 corn volatile compounds tested, C. carnea adults responded most strongly to 2-phenylethanol and (E)--farnesene. A significant difference in EAG response to extracts of corn leaf collections was observed between male and female C. carnea. In C. maculata, significant EAG responses were elicited by most of the tested corn volatile compounds, except -pinene and (E)-2-hexenal. The highest EAG responses were observed in response to (E)--farnesene, -terpineol, 2-phenylethanol, and -caryophyllene. Sexual differences in EAG responses of C. maculata were only found in response to 1-octen-3-ol. Male antennae of C. maculata produced significant EAG responses to extracts from conspecific females, but not to males, which indicates that some chemicals from females could be involved in sexual communication. A significant EAG response also was recorded in response to the extracts of fluids produced during reflex bleeding. Male and female antennae of both species exhibited similar dose–response curves to most of the selected compounds, although female C. maculata antennae exhibited higher thresholds in response to several compounds including -terpineol, (Z)-3-hexenol, and (4aS,7S,7aR)-nepetalactone. Field tests showed that 2-phenylethanol was highly attractive to both sexes of the two investigated species. Only C. maculata was attracted to traps baited with -terpineol.     

Kairomonal Effects of Sawfly Sex Pheromones on Egg Parasitoids

The response of the two eulophid egg parasitoid species Chrysonotomyia ruforum and Dipriocampe diprioni to sex pheromones of their sawfly hosts Diprion pini and Neodiprion sertifer was studied in olfactometer bioassays. Females of C. ruforum were arrested when exposed to odor of the tested major sex pheromone components of Diprion pini [acetate and propionate of (2S,3R,7R)-3,7–dimethyl-2–tridecanol] or Neodiprion sertifer [(2S,3S,7S)-3,7–dimethyl-2–pentadecyl acetate]. This behavioral response of C. ruforum was observed whether (1) parasitoid females had oviposition experience with D. pini eggs or not, (2) parasitoid females emerged from D. pini eggs of a French population or from N. sertifer eggs of a Finnish population, and (3) the tested sex pheromone concentration was low (1 ng/l hexane) or high (100 ng/l hexane). However, C. ruforum did not behaviorally respond to a stereoisomer of the major sex pheromone component of N. sertifer, which is known to act as a sex pheromone antagonist [antagonist = (2S,3R,7R)-3,7–dimethyl-2–pentadecyl acetate]. Thus, C. ruforum responded stereospecifically to the S,S,S configured pheromone of N. sertifer, but not to the S,R,R configuration. Females of the parasitoid D. diprioni were also arrested by the tested major sex pheromone components of the host D. pini. The kairomonal effects of diprionid host sex pheromones on these egg parasitoids are compared to known responses of egg parasitoids to lepidopteran sex pheromones.     

Field response of maritime pine scale,Matsucoccus feytaudi duc. (Homoptera: Margarodidae), to synthetic sex pheromone stereoisomers

The absolute configuration of the primary component of the maritime pine scale (Matsucoccus feytaudi) pheromone (i.e., (8E, 10E)-3,7,9-trimethyl-8,10-dodecadien-6-one) was determined as 3S,7R by field-trapping experiments using synthetic stereoisomers and according to previous NMR considerations. The 3R,7R isomer showed similar activity to 3S,7R, whereasM. feytaudi males responded very weakly to the two other candidates (3R,7S and 3S,7S). Further studies were conducted to optimize scale trapping for monitoring scale populations. Results of these studies showed that the trapping efficiency was related to pheromone dose, trap area, and wind speed but not to trap height.     

Optical isomers of 3,13-dimethylheptadecane: Sex pheromone components of the western false hemlock looper,Nepytia freemani (Lepidoptera: Geometridae)

(3S, 13R)-3, 13-Dimethylheptadecane [(3S, 13R)-3, 13-dime-17Hy] is the major pheromone component of the western false hemlock looper (WFHL),Nepytia freemani. In comparative gas chromotographic-electroantennographic detection (GC-EAD) analyses of stereoselectively synthesized isomers, 1 pg of (3S, 13R)-dime-17Hy elicited significantly stronger electrophysiological responses by male WFHL antennae than did 1 pg of separately injected (3R, 13R)-, (3R, 13S)- or (3S, 13S)-3, 13-dime-17Hy. In field experiments with individually tested stereoisomers. (3S, 13R)-3, 13-dime-17Hy was the only stereoisomer to attract males, but the four-stereoisomer blend was 3.6 times more attractive. Quaternary and all binary combinations of (3S, 13R)-3, 13-dime-17Hy with the other stereoisomers were equally attractive, suggesting that synergisytic behavioral activity in WFHL resided with either one of (3R, 13R)-, (3R, 13S)-, or (3S, 13S)-3, 13-dime-17Hy. Because optical isomers of (di)methylhydrocarbons do not separate on currently available columns, it remains unknown whether female WFHL also produce a four-stereoisomer pheromone blend. Substitutionality of pheromone stereoisomers without loss of behavioural activity has not previously been reported, but favorably compares with the concept of pheromone redundancy that was first suggested for the multiple pheromone component blend of the cabbage looper moth,Trichoplusia ni.     

Identification and synthesis of insect pheromone

(Z,Z)-3,13-Octadecadien-1-ol1a is identified as the sex pheromone from the poplar pole clearwing moth,Sphecia siningensis Hsu, by GCMS analysis, synthesis, EAG, and field bioassay. Species isolation among Sesiidae by pheromone is also discussed.Studies on the identification and synthesis of insect pheromone XXVII. Stereoselective synthesis of (5R, 6S)-(–)- and (5S, 6R)-(+)-mosquito oviposition attractant pheromone and stereochemistry of asymmetric addition of a chiral sulfoxide to a chiral aldehyde. Zhou, W.S., Cheng, J.F. and Lin, G.Q.,Acta Chemica Sinica 46:274, 1985.     

Chirality of synergistic sex pheromone components of the western hemlock looperLambdina fiscellaria lugubrosa (HULST) (Lepidoptera: Geometridae)

Bakers' yeast reduction of (2E)-3-(2-furanyl)-2-methyl-2-propenal yielded the synthetic intermediate, (2S)-3-(2-furanyl)-2-methylpropanol, of high chiral purity (>97% ee) for the synthesis of the enantiomers of 2,5-dimethylheptadecane and 7-methylheptadecane, two synergistic sex pheromone components of the western hemlock looper (WHL),Lambdina fiscellaria lugubrosa Hulst. In electrophysiological bioassays, (7S)- but not (7R)-7-methylheptadecane elicited strong antennal responses by male WHL antennae. In field trapping experiments, addition of (7S)- but not (7R)-7-methylheptadecane to (5R,11S)-5,11-dimethylheptadecane, the major sex pheromone component of WHL, increased attraction. Attraction to (5R,11S)-5,11-dimethylheptadecane in combination with (7S)-7-methyiheptadecane was further enhanced by the addition of (5S)- but not (5R)-2,5-dimethylheptadecane. Similarly, attraction to (5R,11S)-5,11-dimethylheptadecane combined with (5S)-2,5-dimethylheptadecane increased when 7S- but not (7R)-7-methylheptadecane was added as a third component. We conclude that (7S)-7-methylheptadecane and (5S)-2,5-dimethylheptadecane are the synergistic sex pheromone components of WHL. The synthetic methodology described is applicable to the synthesis of chiral methyl-branched pheromones in other orders of the Insecta, particularly Coleoptera, Diptera and Orthoptera.     

A chiral sex pheromone system in the pea midge, Contarinia pisi

The sex pheromone of the pea midge consists of 2-acetoxytridecane, (2S,11S)-diacetoxytridecane and (2S,12S)-diacetoxytridecane. The responses of male pea midges to the corresponding stereoisomers of (2S,11S)-diacetoxytridecane and (2S,12S)-diacetoxytridecane were tested in field trapping experiments and by electroantennographic recordings. When added at 20% of the pheromone component to the sex pheromone blend, the (2S,11R)- and (2R,11S)-stereoisomers of (2S,11S)-diacetoxytridecane, were shown to have a strong inhibitory effect on male attraction in the field. At the same dose, (2R,11R)-diacetoxytridecane, (2R,12R)-diacetoxytridecane, and meso-2,12-diacetoxytridecane, did not have a significant effect on male behavior. It was also shown that substitution of either (2S,11S)-diacetoxytridecane or (2S,12S)-diacetoxytridecane with the related stereoisomers reduced trap catches to the level of blank traps. The electroantennographic recordings showed similar dose–response curves for the pheromone components and the stereoisomers shown to have an inhibitory effect. It seems likely that male antennae have receptors for both pheromone components and for inhibitory stereoisomers. Scanning electron microscopy and transmission electron microscopy of the antennae revealed three types of sensilla involved in chemoreception: sensilla circumfila, sensilla trichodea, and sensilla coeloconica. The sensilla circumfila and trichodea are both innervated by two sensory cells, whereas the sensilla coeloconica are innervated by four to five cells.     

Electroantennogram responses of grape borerXylotrechus pyrrhoderus bates (Coleoptera: Cerambycidae) to its male sex pheromone components

Electroantennograms were recorded from the grape borerXylotrechus pyrrhoderus in response to serial dilutions of male sex pheromone components, (2S,3S)-octanediol and (2S)-hydroxy-3-octanone, and to 100 g of their optical isomers and host plant substances. Female antennae always responded more strongly than male antennae. Antennae of both sexes were highly sensitive to (2S)-hydroxy-3-octanone. F/M ratio (female to male EAG value) was greater for male sex pheromone components, especially (2S,3S)-octanediol, and their optical isomers than plant substances. Antennal sensitivity to optical isomers (2R,3R-octanediol and 2S,3R-octanediol) was lower than true pheromone components.     

Identification of Epoxyhenicosadiene and Novel Diepoxy Derivatives as Sex Pheromone Components of the Clear-Winged Tussock Moth Perina nuda

Four EAG-active components (A–D) were found in the solvent extract of virgin females of the clear-winged tussock moth, Perina nuda. The most abundant component (B, ca. 250 ng/female) was identified as (3Z,6S,7R,9Z)-6,7-epoxyhenicosa-3,9-diene by GC-MS analyses of the extract, chemical derivatization, and comparative chiral HPLC. Minor components also elucidated were (3Z,9Z)-cis-6,7-epoxyicosa-3,9-diene, (A); (3R,4S,6S,7R,9Z)-3,4-6,7-diepoxyhenicos-9-ene, (C); and its 3S,4R,6S,7R isomer, (D); with amounts of 0.4, 5, and 8 ngt/female, respectively. Component B showed weak attractiveness to male moths in the field. The attractiveness was significantly enhanced by addition of component(s) C and/or D. No males were captured with either the antipode of component B or its mixtures with the minor components. In this field test, noctuid Hypocala rostrata males were also attracted with the synthetic P. nuda pheromone.     

Sex Pheromone of the Pine Sawfly, Gilpinia pallida: Chemical Identification, Synthesis, and Biological Activity

We present the identification of the sex pheromone in the pine sawfly, Gilpinia pallida, including analysis of the female pheromone content, male antennal response and attraction in the field, and synthesis of the most active pheromone component. Several 3,7-dimethyl-2-alkanols were identified from female whole-body extracts, including some compounds with a 2R configuration. This is the first observation of such compounds in a pine sawfly species. Antennae of male G. pallida responded strongly in electroantennograph (EAG) recordings to the (2S,3R,7R)-isomers of the propionates of 3,7-dimethyl-2-tridecanol, 3,7-dimethyl-2-tetradecanol, and 3,7-dimethyl-2-pentadecanol, as well as to the acetates of the tri- and pentadecanols (the acetate of the tetradecanol was not tested). The propionate of (2S,3R,7R)-3,7-dimethyl-2-tetradecanol caught more males in the field than the corresponding isomer of tri- or pentadecanol. We suggest that the (2S,3R,7R)-isomer of 3,7-dimethyl-2-tetradecanol is likely the main sex pheromone precursor in G. pallida, with a subsidiary role for the (2S,3R,7R)-isomer of the tridecanol. Preparation of highly pure (2R,3R,7R)- and (2S,3R,7R)-stereoisomers of 3,7-dimethyl-2-tetradecanol, including the biological active esters, was performed via chemoenzymatic methods and is described in detail.     

Enantiomeric composition of grandisol and grandisal produced byPissodes strobi andP. nemorensis and their electroantennogram response to pure enantiomers

Grandisol (cis-2-isopropenyl-1-methylcyclobutaneethanol) and its corresponding aldehyde, grandisal, were previously isolated and identified as aggregation pheromone components forPissodes strobi (Peck) andP. nemorensis Germar, but the enantiomeric ratios produced by these insects were not previously determined. We isolated grandisol and grandisal from males of bothP. strobi andP. nemorensis. The insect-produced grandisol was derivatized with trifluoroacetic anhydride, and the enantiomeric composition was determined by gas chromatography on an optically active cyclodextrin glass capillary column. The insect-produced grandisal was first reduced to grandisol before derivatization.P. nemorensis produced nearly 100% (1R,2S)-grandisol and nearly 100% (1S,2R)-grandisal.P. strobi produced 99% (1R,2S)-grandisol and approximately 60% (lR,2S)-grandisal. In electroantennogram (EAG) studies with liveP. nemorensis andP. strobi, no significant differences were found between the responses of males and females to racemic grandisol, racemic grandisal, or the 1R,2S and 1S,2R enantiomers of grandisol and grandisal, which is consistent with previous assertions that these compounds are aggregation pheromones. Although no studies to date withP. strobi have demonstrated a behavioral response to grandisol and grandisal,P. strobi antennae detected all enantiomers of grandisol and grandisal tested in EAG tests. The antennae of P.nemorensis responded significantly more to (1R,2S) grandisal than to (1S,2R)-grandisal, despite producing only (1S,2R)-grandisal.Coleoptera: Curculionidae.     

Sex Pheromone of Cabbage Aphid Brevicoryne brassicae: Identification and Field Trapping of Male Aphids and Parasitoids

The sex pheromone of the cabbage aphid, Brevicoryne brassicae, is shown by GC and GC-MS analysis of pheromone entrained from sexual females, and by electrophysiological studies on single cell preparations from male antennae, to comprise (4aS,7S,7aR)-nepetalactone. The compound proved to be attractive in a laboratory bioassay and release of the pheromone from glass vials placed above water traps in crops of autumn brassicaceous crops increased the catch of males of this species. The specialist parasitoid of B. brassicae, Diaeretiella rapae, and the more general aphid parasitoid Praon volucre were found in significantly larger numbers in pheromone traps as compared to the controls, under certain conditions.     

Sex attractant pheromone of damson-hop aphid Phorodon humuli (Homoptera,aphididae)

Behavioral studies using an olfactometer demonstrated that sexual females (oviparae) of the damson-hop aphid,Phorodon humuli, release a pheromone to which males respond. Volatiles produced by the oviparae were analyzed by coupled gas chromatography-single cell recording from the secondary rhinaria on the male antenna and showed the presence of one peak with major activity. Coupled gas chrornatography-mass spectrometry suggested a nepetalactol, which was shown to have the 4aR, 7S, 7aS stereochemistry by synthesis from the corresponding nepetalactone isolated from the labiate plantNepeta mussinii. Although the stereochemistry at carbon-1 is not yet established, a synthetic sample comprising ca. 70% 1S and 30% 1R attracted highly significant numbers of males to water traps placed within and adjacent to a hop garden. Initial studies also indicated attraction of males in both the olfactometer and in the field by volatiles from the primary host.