Aggregation pheromone characterization and comparison inDrosophila ananassae andDrosophila bipectinata

(Z)-11-Octadecenyl acetate (Z11–18Ac) and (Z)-11-eicosenyl acetate (Z11–20Ac) were identified as the aggregation pheromones ofDrosophila ananassae, andZ11–20Ac was identified as the aggregation pheromone ofDrosophila bipectinata. Z11–18Ac andZ11–20Ac were not attractive alone; however, in combination with fermenting food odors, the acetates attracted flies of both sexes in a wind-tunnel olfactometer. The pheromones were present in the ejaculatory bulb of sexually mature male flies and transferred to the female during mating. MaleD. bipectinata released little if anyZ11–20Ac to the food; however, recently mated females releasedZ11–20Ac to the surrounding surfaces in just a few hours after mating.D. ananassae males, on the other hand, appeared to release moreZ11–18Ac andZ11–20Ac to the surroundings than mated females. AlthoughD. bipectinata males had noZ11–18Ac, flies were as attracted toZ11–18Ac as to an equal quantity ofZ11–20Ac.D. ananassae were attracted toZ11–18Ac but not toZ11–16Ac orZ11–20Ac. However,Z11–20Ac in combination withZ11–18Ac was significantly more attractive thanZ11–18Ac alone.     

Intraspecific variation and interspecific differences in sex pheromones of sibling species inCtenopseustis obliquana complex

The specific status ofCtenopseustis obliquana pheromone-types I, II, and III has been more fully examined. Females of types I and III produce a mixture of (Z)-8- and (Z)-5-tetradecenyl acetates (Z8-14:Ac, Z5-14: Ac). The previously reported different ratios of these two components in females of the two types (type I=8020, III=9010) have been reinvestigated. The median ratios of each type differed significantly, although there was some overlap in the ranges of these ratios. A field cage trial showed that males of type III are attracted to females of type I, so the observed differences may be ascribed to intraspecific variation. In contrast to females of types I or III, females of type II produce Z5-14Ac but no Z8-14Ac. The electroantennogram (EAG) profile of antennae of type II males shows a maximum response to Z5-14Ac, while the EAG profiles of types I and III show a strong response to Z8-14Ac. In wind tunnel tests using mixtures of these two compounds, type II males prefer blends consisting of all or mostly Z5-14: Ac, while type I males showed a preference to a mix of 70% Z8-14Ac plus 30% Z5-14Ac. We found that type I males are attracted to type I females when offered a choice between type I and type II females in a field cage test and that type II males similarly prefer type II females. Males of types I and II have specialist cells for Z8-14Ac and Z5-14Ac but differ with respect to relative densities of these cells and to further cell types responsive to other alkenyl acetates. Type IIC. obliquana is considered therefore a sibling species of types I and III. In addition, the amount of Z5-14Ac produced by type II females varied geographically. Females from the North Island produced significantly less (median=1.2 ng) Z5-14Ac than females from the South Island (median=2.2 ng). Type II populations in the North Island morphologically resembled sympatric type I, rather than type II from the South Island and are designated as type II (North Island). Type II (North Island) populations have so far been found only at Rukuhia (near Hamilton) and from Kerikeri. In contrast, type II populations are sympatric with type III populations over much of the South Island. In a field cage trial, males of types II and II (North Island) were attracted to females of both II and II (North Island). We tentatively ascribe the differences between type II and type II (North Island) to intraspecific variation.     

Identification of sex pheromones of two sibling species in dingy cutworm complex,Feltia jaculifera (GN.) (Lepidoptera: Noctuidae)

The sex pheromone components of the two sibling species of the dingy cutworm that occur on the prairies of western Canada were identified in abdomen-tip extracts from calling female moths. Three monounsaturated acetates, (Z)-7-dodecenyl acetate, (Z)-9-tetradecenyl acetate, and (Z)-11-hexadecenyl acetate, are common to both species in ratios of 100133 for species A and 0.30.5100 for species B. The most effective synthetic blends for the attraction of male moths in the field consisted of these three components in ratios of 1010 at 8.8g/lure for species A and 112000 at 500g/lure for species B. The addition of Z5-12Ac to either blend reduced the catches and the addition of Z7-12OH orZ11-16OH to the three-component blend reduced the catches of species B males. The species are morphologically indistinguishable, but the identity of the males attracted to the synthetic blends could be confirmed by their antennal responses to a test blend of the three components using a GC-EAD system. Both synthetic attractant blends are competitive with females and will be useful for studying the distribution, biology, and relative abundances of the two species.Contribution no. 3879005 of the Lethbridge Research Station.     

Field response ofDendroctonus brevicomis toexo-brevicomin,frontalin, and myrcene released at two proportions and three levels

Racemicezo-brevicomin, racemic frontalin, and myrcene were released at two proportions (51400 and 111), each at three levels (1 ×, 10 ×, and 100 ×) in a ponderosa pine forest in central California. The 51400 mix was based on an estimate of the relative amounts released from a ponderosa pine under attack by the western pine beetle,Dendroctonus brevicomis. MoreD. brevicomis were trapped at a source of the three compounds released at 51400 than were trapped at a source released at 111, at all three levels, but this difference was statistically significant only at the 1 × and 10 × levels. Sex ratio of trapped beetles and distribution of catch at the source of attractant and 5 m away apparently did not differ between relative release rates.Coleoptera: Scolytidae.Trade names are mentioned solely for information. No endorsement by the U.S. Department of Agriculture is implied.     

Blackheaded fireworm: Laboratory and field studies of its sex pheromone

Electroantennogram (EAG) responses of maleRhopobota naevana (Hübner), the blackheaded fireworm, to all of the monoene straightchain 12- and 14-carbon alcohols and acetates implicated (Z)-11-tetradecenl-1-ol (Z11–14OH) and its acetate (Z11–14Ac) as sex pheromone components.Z11–14Ac produced the strongest EAG response of all compounds tested. Gas chromatography-mass spectrometry (GC-MS) analysis of extract of female sex pheromone glands (SPG) confirmed the presence ofZ11–14OH (125 pg/female) andZ11–14Ac (600 pg/female) (all other monoenes had different retention times). In field tests, traps baited withZ11–14OH alone captured males, but traps baited withZ11–14Ac alone did not. Traps baited with a combination ofZ11–14OH andZ11–14Ac in various ratios did not produce better trap catches thanZ11–14OH alone. (Z)-9-Dodecen-1-ol acetate (Z9–12Ac), reported by others to be a field attractant, did not produce trap catch in our tests, but in combination withZ11–14 OH (982 in septa corresponding to 95:5 in vapor,Z11–14OH toZ9–12AC) produced a sevenfold increase in catch overZ11–14OH alone. IfZ9–12AC had been present in extract of SPG at 2–5% ofZ11–14OH, it would not have been detected in our GC-MS experiment. Rhopobota naevana (Hübner) Lepidoptera: Tortricidae: Olethreutinae.     

Attraction ofCacoecimorpha pronubana male moths to synthetic sex pheromone blends in the wind tunnel

Attraction ofCacoecimorpha pronubana male moths to blends of four sex pheromone components was studied in the wind tunnel.Z11–14Ac alone did not elicit upwind flight, admixture of 10%Z11–14OH or more led to successful attraction of males to the source. Attractivity of these binary blends was further enhanced by addition ofE11–14Ac orZ9–14Ac; the optimum was a blend ofZ11–14Ac,Z11–14OH,E11–14Ac, andZ9–14Ac at the proportion of 1003033. In ternary and quaternary blends, the effect ofZ11–14OH andE11–14Ac was strongest at 30% and 3%, respectively. By contrast,Z9–14Ac increased behavioral responses over a wide range.     

Compounds modifying the activity of two sex attractants for males of the pea moth,Cydia nigricana (F.)

(E)-10-Dodecen-1-yl acetate (E10–12Ac) and (E,E)-8,10-dodecadien-1-ylacetate (E,E8,10–12Ac) are sex attractants for males of the pea moth,Cydia nigricana (F.). Thirty-two structurally related compounds with chain lengths of 9–14 carbon atoms were exposed withE10–12Ac orE,E8,10–12Ac in traps in the field to investigate their influence on the activity of the attractants. Only alchols and acetates unsaturated at C-8, -9, or -10 greatly influenced moth captures. (Z) and (E)-8-dodecen-1-ol were weak synergists forE10–12Ac but no synergists forE,E8,10–12Ac were found. (Z) and (E)-8-dodecen-1-yl acetate and (E,E)-8,10-dodecadien-1-ol inhibited bothE10–12Ac andE,E8,10–12Ac while (E)-10-dodecen-1-ol, 10-dodecyn-1-ol, (Z) and (E)-9-dodecen-1-yl acetate, (Z)-10-dodecen-1-yl acetate, and undecyl acetate inhibited only the former attractant.     

Sex pheromone of the armyworm,Pseudaletia unipuncta (Haworth) (Lepidoptera: Noctuidae)

(Z)-11-Hexadecen-1-ol acetate (Z11–16Ac) free of theE isomer (<1%), hexadecan-1-ol acetate (16 Ac), and a hexadecen-1-ol [the (Z)-11 isomer based on the retention time on a Carbowax capillary column] were identified in extracts of the sex pheromone glands of adult virgin female armyworms,Pseudaletia unipuncta. Also, gas Chromatographic retention times on polar and nonpolar columns indicated the possible presence of (Z)-9-hexadecen-1-ol acetate (Z9–16Ac). The ratioZ11–16Ac/16Ac/Z11–16OH/Z9–16Ac was 10.150.130.02. Infield testsZ11–16 Ac was attractive alone, and the addition ofZ9–16Ac,Zll–16 OH, or 16 Ac singly or in combination in ratios found in the gland did not increase trap capture.Mention of a proprietary product does not constitute an endorsement of this product by the USDA.     

Effects of dodecyl acetate andZ-10-tridecenyl acetate on attraction ofEupoecilia ambiguella males to the main sex pheromone component,Z-9-Dodecenyl acetate

Attraction ofE. ambiguella males toZ-9-dodecenyl acetate (Z9-12Ac), alone and in combination with dodecyl acetate (12Ac) orZ-10-tridecenyl acetate (Z10-13Ac) was tested in both wind-tunnel and field experiments. In the laboratory, response toZ9-12Ac reached a distinct dosage optimum at which attraction was nearly as good as to live females. Addition of 12Ac, a minor component of female glands and effluvia, had no effect at low doses ofZ9-12Ac and only marginally improved attraction at the optimum. However, inclusion of 12Ac with an overdose ofZ9-12 Ac fully restored activity. In the field,Z9-12Ac alone was not very attractive at any dose; catches markedly increased by adding 12Ac and climbed with increasing dose of each compound up to 10 mg. Optimum ratio ofZ9-12Ac to 12Ac was 11 to 15. Another compound,Z10-13Ac, had the same effect as 12Ac in the laboratory and the field but was effective at a lower dose. In the field, inclusion of the synergist permits use of high cap loads to attract more males, perhaps from greater distances.     

Sex pheromone ofEupoecilia ambiguella female: Analysis and male response to ternary blend

Sex gland extracts and washes ofEupoecilia ambiguella contain 10–20 ng/female of the primary sex pheromone componentZ-9-dodecenyl acetate (Z9–12Ac), accompanied by a number of related compounds. These areE-9-dodecenyl acetate (E9–12Ac),Z-9-dodecen-1-ol (Z9–12OH), saturated acetates of 12, 16, 18, and 20 carbons, and traces of a doubly unsaturated acetate, tentatively identified as a 9,11-dodecadienyl acetate. Octadecyl acetate predominates among the pheromone-related components, making up 1–2, occasionally 20–30 times the amount ofZ9–12Ac. The same compounds were also found in field-collected females and in effluvia.Z-9-Undecenyl acetate, which is a male attractant on its own, was also found in a sample of female effluvia. A hierarchy is observed in the ethological function of the pheromone components.Z9–12Ac is an attractant forE. ambiguella males. Dodecyl acetate (12Ac) is not attractive on its own but augments male catch when added to the main attractant. Addition of 18Ac augments attraction only when bothZ9–12Ac and 12Ac are present. Windtunnel tests demonstrate that 18Ac also raises the disorientation threshold, as previously shown for 12Ac. Other compounds, with the possible exception of additional saturated acetates, had either no effect on trap catch or, in the case ofE9–12Ac,Z9–12OH, andE-9,11-dodecadienyl acetate, were inhibitory above a certain level. A blend of roughly equal parts ofZ9–12Ac, 12Ac, and 18Ac provides the best attractant blend forE. ambiguella known to date.     

Sex pheromone ofGrapholita funebrana occurrence ofZ-8- andZ-10-Tetradecenyl acetate as secondary components

Z-8-Dodecenyl acetate (Z8–12Ac),E-8-dodecenyl acetate (E8–12Ac),Z-8-tetradecenyl acetate (Z8–14Ac),Z-10-tetradecenyl acetate (Z10–14Ac), andZ-8-dodecen-1-ol (Z8–12OH) were identified in the proportions 10013052 in female sex gland extracts ofGrapholita funebrana, accompanied by saturated acetates from 12 to 20 carbons with tetradecyl acetate predominating.Z10–14Ac has not previously been described as a lepidopteran sex pheromone component. Best attraction of males is obtained withZ8–12Ac in the presence of a higher proportion ofE8–12Ac than in the female. Inclusion of the 14-carbon acetates did not augmentG. funebrana catches but inhibitedG. molesta. On the other hand, addition ofZ8–12OH at the level optimal forG. molesta reduced attraction ofG. funebrana.     

Components of female sex pheromone of cocoa pod borer moth,Conopomorpha cramerella

The cocoa pod borer,Conopomorpha cramerella (Snellen) (Lepidoptera: Gracillariidae), is the most serious pest of cocoa in Southeast Asia. Analyses of ovipositor washings and entrained volatiles from virgin female moths by gas chromatography (GC) linked to electroantennography (EAG), and comparison of EAG responses from the male moth to synthetic compounds indicated the presence of theE,Z,Z andE,E,Z isomers of 4,6,10-hexadecatrienyl acetate and the corresponding alcohols, and of hexadecyl alcohol. Amounts of pheromone produced were less than 0.1 ng/female, and no peaks for the unsaturated components were observed on GC analysis. Extensive field testing of synthetic mixtures in Sabah, East Malaysia, showed that traps baited with a polyethylene vial impregnated with 1.2 mg of a mixture of the above five components in 40604610 ratio caught more maleC. cramerella moths than traps baited with a virgin female moth.     

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.     

Trail-following responses of the Argentine ant,Iridomyrmex humilis (Mayr), to a synthetic trail pheromone component and analogs

Behavioral evidence indicates that (Z)-9-hexadecenal (Z9-16ALD) is a trail pheromone component ofIridomyrmex humilis, and that the true trail pheromone may be multicomponent. Trail-following responses ofI. humilis workers to several concentrations of syntheticZ9-16ALD, a constituent of the Pavan's gland, were found to be comparable to responses to gaster extract trails containing ca. 100 times lessZ9-16ALD. Of the five aldehyde analogs tested, only (Z)-7-hexadecenal (Z7-16ALD) elicited significant trail-following. However, following responses to severalZ9-16ALD-Z7-16ALD combinations were lower than responses toZ9-16ALD alone. Trails on filter paper of biologically relevant concentrations ofZ9-16ALD lose activity within 2 hr in the laboratory. The release rate ofZ9-16ALD measured from filter paper trails was 0.25 ± 0.10 pg/cm-sec. This was used to estimate the trail-following threshold for this compound of Argentine ant workers.     

Sex pheromone of aPlanotortrix excessana sibling species and reinvestigation of related species

The sex pheromone of aPlanotortrix excessana sibling species was investigated. Females were found to produce eight potential pheromone components: dodecyl acetate, tetradecyl acetate (14OAc). (Z)-5-tetradecenyl acetate (Z5-14OAc), (Z)-7-tetradecenyl acetate (Z7-14OAc), (Z)-9-tetradecenyl acetate, hexadecyl acetate, (Z)-7-hexadecenyl acetate, and (Z)-9-hexadecenyl acetate. When these compounds were bioassayed using field-trapping and wind-tunnel techniques, only 14OAc,Z5-14OAc, andZ7-14OAc were found to be behaviorally active. The sex pheromone glands of females of other species including,Planotortrix MBS,Planotortrix M,P. notophaea, Ctenopseustis servana, and aC. obliquana sibling species, were also found to containZ5-14OAc orZ7-14OAc, singly or in combination. In the case ofPlanotortrix M, the addition ofZ7-14OAc to the previously identified sex pheromone blend ofZ5-14OAc and 14OAc was found to increase trap captures of male moths of this species. Thus in these New Zealand species (and in some Australian species),Z5-14OAc andZ7-14OAc appear to be utilized in combination in pheromonal communication just as (Z)-11-tetradecenyl acetate and (E)-11-tetradecenyl acetate are used by many species of Holarctic Tortricidae in the tribe Archipini.Lepidoptera: Tortricidae: Tortricinae.     

Apple ermine moth,Yponomeuta malinellus Zeller Two components of female sex pheromone gland highly effective in field trapping tests

When electroantennographic responses of maleYponomeuta malinellus Zeller to model compounds were determined at dosages of 0.3–30 ng, the strongest responses were obtained from (Z)-9-dodecen-1-ol acetate (Z9–12Ac). Also, strong responses were obtained from (Z)-11-tetradecenal (Z11–14A1) and (Z)-11-tetradecen-1-ol (Zl1–14OH). At a dosage of 0.3 ng,Z11–14A1 produced a stronger response thanZ11–14OH, while at a dosage of 30 ng,Z11–14OH andZ11–14A1 produced equal responses. Gas chromatographic and mass spectral analysis of extracts of female sex pheromone glands showed the presence ofZ9–12Ac, tetradecan-1-ol (14OH), (E)-11-tetradecen-1-ol (E11–14OH),Z11–14OH, hexadecan-1-ol, and hexadecan-1-ol acetate in a ratio of 0.62003710014035. In field tests,Z9–12Ac andZ11–14OH together were required for trap catch, and addition ofZ11–14A1,E11–14OH, 14OH, or (Z)-11-tetradecen-1-ol acetate did not increase catch. Ratios in rubber septa of 0.599.5 to 1.598.5 (Z9–12 Ac/Z11–14OH) captured the most males and captures were statistically equivalent for dosages of 10–1000 g/rubber septum. Traps baited with the synthetic lure produced better catches than those baited with females.Lepidoptera: Yponomeutidae.     

Behavioral responses of maleArgyrotaenia velutinana (Lepidoptera: Tortricidae) to components of its sex pheromone

Males of the redbanded leafroller,Argyrotaenia velutinana (Walker) (Lepidoptera: Tortricidae), were studied for their behavioral responses in laboratory olfactometers and in the field to the 3 components of the female-produced sex pheromone:cis-11-tetradecenyl acetate (c11–14Ac),trans-11-tetradecenyl acetate (t11–14Ac), and dodecyl acetate (12Ac). Dodecyl acetate, when evaporated with c11–14Ac (8%trans) in the field, modified the behavior of feral males nearby the chemical source, causing an increase in the frequency of landing and close approach to the pheromone dispenser. Apparently, an inflight behavioral modification concerning landing or not landing occurs within 60 cm of the source and is mediated by 12Ac. In laboratory olfactometers, c11–14Ac (8%trans) demonstrated a lower threshold for male activation than pure c11- and t11–14Ac and blends of the two isomers. Additionally, over a wide range of dosages, males responded with optimum wing-fanning response to c11–14Ac (8%trans) compared to pure c11–14Ac, c11–14:Ac (30%trans), and pure t11–14Ac, suggesting that thecistrans ratio rather than absolute amounts of either isomer, is a crucial factor in eliciting male response. When presented with c11–14Ac (8%trans) (11), dodecyl acetate caused a significant prolongation of wing-fanning over c11–14Ac (8%trans) alone and resulted in a greater percentage of males moving upwind to the source. Since the increase in wing-fanning and orientation occurred at higher concentrations of the 3-component mixture, the effect of 12Ac in the laboratory may reflect the close-range role of 12Ac in the field.     

Preparation of nanosize Pt clusters using ion exchange of Pt(NH3) 4 2+ inside mesoporous channel of MCM-41

Mesoporous molecular sieve MCM-41 with a Si/Al ratio of 35 was obtained by hydrothermal synthesis using a gel mixture with a molar composition of 6 SiO₂0.1 Al₂O₃1 hexadecyltrimethylammonium chloride 0.25 dodecyltrimethylammonium bromide 0.25 tetrapropylammonium bromide0.15 (NH₄)₂O1.5 Na₂O300 H₂O. The MCM-41 sample was calcined in O₂ flow at 813 K and subsequently ion exchanged with Ca²⁺. A small Pt cluster has been supported on the MCM-41 sample following a procedure using ion exchange of Pt(NH₃) ₄ ²⁺ . The Pt(NH₃) ₄ ²⁺ ion supported on MCM-41 has been activated in O₂ flow at 593 K and subsequently reduced with Fh flow at 573 K, in the same way used for the preparation of a Pt cluster entrapped inside the supercage of zeolite NaY. The resulting Pt cluster supported on the MCM-41 shows hydrogen chemisorption oftotal two H atoms per Pt at 296 K (based on the total amount of Pt) and high catalytic activity for hydrogenolysis of ethane. The chemical shift in¹²⁹Xe NMR spectroscopy of adsorbed xenon indicates that the Pt cluster is located inside the mesoporous molecular sieve.     

Selective vapor phase hydroformylation of ethylene over cluster-derived cobalt catalyst

Vapor phase hydroformylation of ethylene was studied with silica-supported metal catalysts. A cobalt metal catalyst derived from Co₂(CO)₈ gave propanal and its derivatives in as high selectivity of about 36% as Rh/SiO₂ catalyst under the reaction conditions of 1.1 MPa of a gas-mixture of ArCOC₂H₄H₂ = 1333 at 423–503 K. On the other hand, conventional cobalt catalysts derived from cobalt nitrate, chloride, or acetate, and other noble metal catalysts (Pd/SiO₂ and Ir/SiO₂) produced mainly ethane.     

Redundancy in a chemical signal: Behavioral responses of maleTrichoplusia ni to a 6-Component sex pheromone blend

The flight response of maleTrichoplusia ni was observed in a flight tunnel to a sex pheromone blend composed of six components:Z7–12Ac, 12Ac,Z5-12Ac, 11-12Ac,Z7-14Ac, and Z9-14Ac. The number of males reaching a 3000-g source of this blend was > 95%, equal to that observed to female glands and significantly greater than with the previously identified two-component blend (Z7-12Ac + 12Ac). In subtraction tests, all five-component blends, with the exception of the blend lacking the primary componentZ7-12Ac, and several four-component blends elicited similar peak levels of upwind flight, source contacts, and hairpencil displays to that observed with the six-component blend. We characterize the substitution of certain minor components for one another as a form of redundancy in the chemical signal and suggest that it contributes to response specificity and signal recognition in males. The results also support the concept that the full blend of components acts as a unit to influence male behavior at all phases of the response. Individual minor components were not responsible for eliciting specific behaviors in the sequence.