Biosynthesis of sex pheromone components and glycerolipid precursors from sodium [1-14C]acetate in redbanded leafroller moth

Sodium [1-¹⁴C]acetate in water-dimethyl sulfoxide (11) was applied topically to sex pheromone glands ofArgyrolaenia velutinana. Radiolabel was incorporated into the pheromone components (Z)-11-tetradecenyl acetate and (E)-11-tetradecenyl acetate, and also into triacylglycerols, diacylglycerols, ethanolamine phosphatides, and choline phosphatides. In the triacylglycerols, radiolabel appeared in (Z)-11-tetradecenoate, (E)-11-tetradecenoate, tetradecanoate, hexadecanoate, and octadecanoate. In the choline phosphatides, the same acyl moieties incorporated radiolabel but at lower levels. In the diacylglycerols and ethanolamine phosphatides, only the radiolabel in hexadecanoate and octadecanoate was above the limit of detection. At different times following application of sodium [1-¹⁴C]acetate, the relative proportions of labeled (Z)-11-tetradecenyl acetate and (E)-11-tetradecenyl acetate changed very little, but the relative proportions of labeled fatty acyl moieties in the triacylglycerols and choline phosphatides changed markedly. After 8 min, triacylglycerols had incorporated about equal amounts of radiolabel into (Z)-11-tetradecenoate, (E)-11-tetradecenoate, and tetradecanoate. As the incubation time was increased, triacylglycerols accumulated proportionately more radiolabeled (E)-11-tetradecenoate than (Z)-11-tetradecenoate, and accumulated proportionately less radiolabeled tetradecanoate. In the choline phosphatides, at all times of incubation the amount of radiolabel incorporated into (Z)-11-tetradecenoate was small but above the limit of detection, and the amounts of radiolabel in (E)-11-tetradecenoate and tetradecanoate were smaller and often below the limit of detection. In both the triacylglycerols and the choline phosphatides, the relative proportion of radiolabeled hexadecanoate decreased with time, and that of octadecanoate increased.     

Identification of new sex pheromone components inTrichoplusia ni,predicted from biosynthetic precursors

In addition to the previously identified components (Z)-7-dodecenyl acetate and dodecyl acetate, sex pheromone glands ofTrichoplusia ni release (Z)-5-dodecenyl acetate, 11-dodecenyl acetate, (Z)-7-tetradecenyl acetate, and (Z)-9-tetradecenyl acetate. Bioassays in a flight tunnel showed that a synthetic blend of these six compounds elicited complete flights to the source from 95% of the males tested and elicited hairpenciling responses at the end of the flights from 88% of the males tested. This blend was not significantly different from intact pheromone glands, which elicited complete flights to the source from 98% of the males tested and hairpenciling responses from 91% of the males tested. In contrast, the previously identified two-component blend elicited significantly fewer complete flights to the source (33%) and did not elicit hairpenciling responses from any of the males tested. The search for additional sex pheromone components was prompted by our previous identification of unusual fatty acyl moieties in the gland that seemed to be possible biosynthetic intermediates.     

Sex pheromone ofStenoma cecropia Meyrick (Lepidoptera: Elachistidae)

(Z,E)-9,11-tetradecadienal (Z9,E11–14: Ald; 11%), (Z,E)-9,11,13-tetradecatrienal (Z9,E11, 13–14: Ald; 67%), (Z,E)-9,11-tetradecadienyl acetate (Z9,E11–14: Ac, 5.5%), and (Z,E)-9,11,13-tetradecatrienyl acetate (Z9,E11,13–14: Ac; 16.5%) were identified in the extracts of female pheromone glands ofStenoma cecropia (Lepidoptera: Elachistidae). From electroantennograms and single sensillum recordings, receptors toZ9,E11,13–14:Ald andZ9,E11–14: Ald were found on male antenna. Behavioral data were obtained from olfactometric tests in the laboratory and field trapping experiments in Colombia. It appeared that a blend ofZ9,E11,13–14:Ald (83%) andZ9,E11–14:Ald (17%) was attractive to males. These aldehydes are assumed to be components of the sex pheromone ofS. cecropia, whereas the acetates found in gland extracts might be precursors of the pheromone.     

Sensory and behavioral effects of gossyplure alcohol on sex pheromone response of male pink bollworm moths,Pectinophora gossypiella

(Z,Z)- and (Z,E)-7,11-hexadecadienol, reported to be pheromone precursors, interfere with the normal sequence of behavioral response of malePectinophora gossypiella to sex pheromone. The magnitude of the interference can be diminished with higher release rates of the sex pheromone. (Z,Z)-7,11-Hexadecadienol is more effective than itsZ,E isomer in eliciting the reduction in the behavioral response. Electroantennographic evidence suggests that each alcohol may be interfering more with receptor sites for the conformationally similar pheromone acetate than with receptor sites for the other pheromone isomer. Defining behavioral and physiological effects of pheromone analogs such as the alcohols of gossyplure may help to determine their potential for behavioral manipulations.     

Identification Of Sex Pheromone Components Of The Painted Apple Moth: A Tussock Moth With A Thermally Labile Pheromone Component

The sex pheromone of the painted apple moth, Teia anartoides (Lymantriidae) was investigated using GC-EAD and GC-MS analysis, derivatization, TLC analysis, and field cage and field trapping bioassays. The major sex pheromone components were identified as (6Z,9Z)-henicosa-6,9-dien-11-one and (6Z,9Z)-henicosa-6,9-diene. Other minor components of pheromone gland extracts included (6Z)-9R,10S-epoxyeicos-6-ene, (6Z)-9R,10S-epoxyhenicos-6-ene, (6Z,9Z)-henicosa-6,9-dien-11-ol, (6Z)-henicos-6-en-11-one, and (6Z, 8E)-henicosa-6,8-dien-11-one, but the roles of these minor components remain equivocal. In field cage and field experiments, a blend of all seven identified components [(6Z,9Z)-henicosa-6,9-dien-11-one (relative amount 100), (6Z,9Z)-henicosa-6,9-diene (100), (6Z)-9R,10S-epoxyeicos-6-ene (5), (6Z)-9R,10S-epoxyhenicos-6-ene (10), (6Z,9Z)-henicosa-6,9-dien-11-ol (5), (6Z)-henicos-6-en-11-one (1), and (6Z,8E)-henicosa-6,8-dien-11-one (25)] was as attractive to males as calling females, but tests with blends of the major component(s) with subsets of the minor components did not produce consistent results that unequivocally showed the various minor components to be critical components of the active blend. (6Z,9Z)-henicosa-6,9-dien-11-one is thermally labile and rearranges to (6Z,8E)-henicosa-6,8-dien-11-one and other products at ambient temperature, rendering the synthetic pheromone lure inactive after two days of field exposure.     

Mint root borer,Fumibotys fumalis (Guenee): Identification and field tests of female sex pheromone gland components

Compounds identified in sex pheromone gland extracts of femaleFumibotys fumalis (Guenee) consisted of (E,E)-10,12-tetradecadienyi acetate, (Z)-11-tetradecenyl acetate, (E)-11-tetradecenyl acetate, and (Z)-9-tetradecenyl acetate in a ratio of 100:18: 8:4, respectively. The compounds were identified by electroantennographic, gas Chromatographic, mass spectrometric, and chemical derivatization procedures. In mint fields synthetic components in gray elastomeric septa at ratios found in the sex pheromone gland and at doses of 3 or 10 mg of the diene produced trap catch comparable to traps baited with three females.Lepidoptera: Pyralidae     

Sex pheromone of tomato fruit borer, Neoleucinodes elegantalis

Five candidate pheromone components were identified by analyzing pheromone gland extracts by gas chromatography (GC), coupled GC-electroantennographic detection (EAD), and coupled GC-mass spectrometry (MS): (E)-11-hexadecenol(E11–16 : OH), (Z)-11-hexadecenol (Z11–16 : OH),(E)-11-hexadecenal, (E)-11-hexadecenyl acetate, and (Z)-3,(Z)-6,(Z)-9-tricosatriene (Z3,Z6,Z9–23 : Hy). In electroantennogram (EAG) recordings, synthetic E11–16 : OH elicited stronger antennal responses at low doses than other candidate pheromone components. Field tests demonstrated that synthetic E11–16 : OH as a trap bait was effective in attracting males, whereas addition of Z11–16 : OH inhibited the males' response. Z3,Z6,Z9–23 : Hy strongly enhanced attractiveness of E11–16 : OH, but was not attractive by itself. A pheromone blend with synergistic behavioral activity of an alcohol (E11–16 : OH) and hydrocarbon (Z3,Z6,Z9–23 : Hy) component is most unusual in the Lepidoptera. The synthetic two-component pheromone is approximately 60 times more attractive than the female-produced blend and might facilitate the control of this pest.     

Sex pheromones and reproductive isolation in four european small ermine moths

Reproductive isolation among four sympatric small ermine moths (Yponomeuta) is analyzed in terms of niches in the sexual communication channel. Potential pheromone components were identified from pheromone gland secretions ofY. evonymellus,Y. cagnagellus,Y. padelius, andY. vigintipunctatus by gas chromatography with flame ionization and electroantennographic detection and tested for behavioral activity in the field. The species were found to share (Z)-11-tetradecenyl acetate (Z11-14: OAc) in combination with varying proportions of theE isomer as primary sex pheromone components.Y. cagnagellus differs from the rest of the species by having only a small amount (1.5%) ofE isomer relative toZ isomer in its pheromone. The closely relatedY. padelius has a three-component pheromone including large amounts (ca. 400%) of (Z)-11-hexadecenyl acetate (Z11–16:OAc) in addition toZ11–14: OAc (100%) andE11–14: OAc (34%).Z11–16: OAc appears to reduce trap catches ofY. evonymellus andY. vigintipunctatus when added to the pheromone. Although these species are the two most distantly related European small ermine moths, they seem to share the same sex pheromone, i.e.,Z11–14OAc (+20%E) and (Z)-11-tetradecenol. Our interpretation is that this might have been the sex pheromone of the ancestor of today'sYponomeuta species.1 Lepidoptera: Yponomeutidae Latr.     

Identification of Sex Pheromone of Adzuki Bean Borer,Ostrinia scapulalis

By means of gas chromatography with electroantennographic detection (GC-EAD), gas chromatography–mass spectrometry (GC-MS), and a series of bioassays, (Z)-11-tetradecenyl acetate (Z11–14:OAc) and (E)-11-tetradecenyl acetate (E11–14:OAc) at a ratio of 100:3 were identified as the female sex pheromone of the adzuki bean borer,Ostrinia scapulalis. The average amounts ofZ11–14: OAc andE11–14:OAc in a single sex pheromone gland were 6.6 ± 2.4 ng and 0.2 ± 0.1 ng, respectively. In a wind-tunnel bioassay, the binary blend ofZ11- andE11–14:OAc elicited almost the same male behavioral responses as did virgin females and sex pheromone gland extract. In field trapping experiments, rubber septa impregnated with the binary blend (50 g/septum) attracted more males than virgin females. The sex pheromone ofO. scapulalis thus turned out to be similar to that of theZ-type European corn borer,O. nubilalis, in both components and their ratio.     

Identification of volatile sex pheromone components released by the southern armyworm,Spodoptera eridania (Cramer)

Analysis of sex pheromone gland extracts and volatile pheromone components collected from the calling female southern armyworm,Spodoptera eridania (Cramer), by high-resolution capillary gas chromatography and mass spectroscopy indicated that a number of 14-carbon mono- and diunsaturated acetates and a monounsaturated 16-carbon acetate were produced. Gland extracts also indicated the presence of (Z)-9-tetradecen-1-ol. However, this compound was not found in collections of volatiles. Field trapping studies indicated that the volatile blend composed of (Z)-9-tetradecen-1-ol acetate (60%), (Z)-9-(E)-12-tetradecadien-1-ol acetate (17%), (Z)-9-(Z)-12-tetradecadien-1-ol acetate (15%), (Z)-9-(E)-11-tetradecadien-1-ol acetate (5%), and (Z)-11-hexadecen-1-ol acetate (3 %) was an effective trap bait for males of this species. The addition of (Z)-9-tetradecen-1-ol to the acetate blends tested resulted in the capture of beet armyworm,S. exigua (Hubner), males which provides further evidence that the alcohol is a pheromone component of this species.     

New Pheromone Components of the Grapevine Moth <Emphasis Type="Italic">Lobesia botrana</Emphasis>

Analysis of extracts of sex pheromone glands of grapevine moth females Lobesia botrana showed three previously unidentified compounds, (E)-7-dodecenyl acetate and the (E,E)- and (Z,E)-isomers of 7,9,11-dodecatrienyl acetate. This is the first account of a triply unsaturated pheromone component in a tortricid moth. The monoenic acetate (E)-7-dodecenyl acetate and the trienic acetate (7Z,9E,11)-dodecatrienyl acetate significantly enhanced responses of males to the main pheromone compound, (7E,9Z)-7,9-dodecadienyl acetate, in the wind tunnel. The identification of sex pheromone synergists in L. botrana may be of practical importance for the development of integrated pest management systems. Electronic supplementary material Supplementary material to this paper is available in electronic form at and accessible for authorised users.     

Intrapopulational changes in sex pheromone composition during scotophase in oriental tobacco budworm,Helicoverpa assulta (Guenée) (Lepidoptera: Noctuidae)

Solvent extracts of individual pheromone glands were prepared from femaleHelicoverpa assulta (Guenée) at 2-hr intervals throughout the scotophase. The amounts of female sex pheromone components, (Z)-9-hexadecenal, (Z)-11-hexadecenal, (Z)-9-hexadecenyl acetate, and (Z)-11-hexadecenyl acetate, in the extracts were determined by gas chromatographic analysis. Although females called from early scotophase (2 hr) until late scotophase (6 hr) the quantity of extracted pheromone remained high at 8 hr, the end of the scotophase. More than 70% of the pheromone gland extracts contained sex pheromone components regardless of whether the donor females had been called or resting. Pheromone components were absent from gland extracts prepared at the onset of the scotophase. The quantity of (Z)-9-hexadecenal and (Z)-11-hexadecenal increased rapidly to reach a maximum of approximately 260 and 30 ng/female, respectively, that was maintained for up to 8 hr, the duration of the scotophase. The quantity of (Z)-9-hexadecenyl acetate and (Z)-11-hexadecenyl acetate increased continuously during the scotophase to peak at 600 and 30 ng/female, respectively, 8 hr into the scotophase. At the end of scotophase the quantity of all pheromone components decreased significantly.     

Reinvestigation confirms action of Δ11-desaturases in spruce budworm moth sex pheromone biosynthesis

The biosynthesis of a large number of sex pheromone components of various moth species has been shown to start with common fatty acids and involve chain shortening by two carbons and introduction of a double bond at the 11–12 position. A recent report indicates that one of these common components, (E)-11-tetradecenyl acetate, is present in the eastern spruce budworm,Choristoneurafumiferana, but is not made by this pathway. Reinvestigation of this insect using in vivo and in vitro techniques indicates that the acetate indeed is made by a sequence of reactions similar to that used in other leafroller moths. In fact, evidence was found for the presence of several 11-desaturase systems in spruce budworm. One produced a large quantity of (Z)-11-hexadecanoic acid, and another produced (E)-11-tetradecanoic acid. It is not known if the small amount of (Z)-11-tetradecanoic acid is produced by either of those two systems or by a third system. A comparison with other species showed that cabbage looper moths have only the first system, redbanded leafroller moths use the last two systems, and European corn borer moths have all three.     

Chemistry and field evaluation of the sex pheromone of western spruce budworm,Choristoneura occidentalis,Freeman

Chemical analyses and field bioassays showed a mixture of 92% (E)- and 8% (Z)-11-tetradecenal to be the sex attractant pheromone of the western spruce budworm,Choristoneura occidentalis Freeman. Females were also found to emit small amounts of the corresponding acetates and alcohols, but these components were not active in the bioassay. In contrast, in whole female tip extracts, (E)-11-tetradecenyl acetate predominates, and aldehyde pheromone components are present in lesser quantities, suggesting that final biosynthesis of pheromone takes place just prior to or during emission. At release rates approximating that of the female (2–4 ng/hr), a 928EZ blend of the synthetic aldehydes was at least as attractive as live females. Addition of the corresponding acetates or alcohols up to 50% of the aldehyde content did not significantly enhance or inhibit attraction. No major differences were apparent in pheromone production of females from a laboratory stock or from field collections from diverse geographic locations ranging from Colorado to British Columbia.     

(3Z,6Z,9Z, 12Z, 15Z)-Pentacosapentaene, a key pheromone component of the fir coneworm moth, Dioryctria abietivorella

The sex pheromone of the fir coneworm moth consists of a blend of (3Z,6Z,9Z,12Z,15Z)-pentacosapentaene and (9Z,11E)-tetradecadienyl acetate. Analogous blends of polyunsaturated, long-chain hydrocarbons with much shorter chain aldehydes or alcohols recently have been discovered in three other moth species in the superfamily Pyraloidea. These combinations of components from two distinct structural classes may represent an important and widespread new pheromone blend motif within the Lepidoptera.     

(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.     

Pheromone gland components of some australian tortricids in relation to their taxonomy

A survey has been carried out to identify the major sex pheromone gland components in 30 species of Australian tortricid moths. While more than half the species examined have (Z)-11-, (E)-11-, and/or (Z)-9-tetrade-cenyl acetates as the principal components, these compounds were not detected in some plesiomorphic taxa where combinations of (Z)-5 and (Z)-7 or (Z)-8 and (Z)-10 isomers are present. The results are discussed in relation to tortricid classification and current theories on pheromone evolution.     

Isolation, Identification, Synthesis, and Field Evaluation of the Sex Pheromone of the Brazilian Population of Spodoptera frugiperda

Several studies have shown intraspecific geographical variation in the composition of sex pheromones. Pheromone lures from North America and Europe were not effective against the fall armyworm Spodoptera frugiperda (Smith, 1797) (Lepidoptera: Noctuidae) in Brazil, so we examined the composition of the sex pheromone produced by females from Brazilian populations. Virgin female gland extracts contained (Z)-7-dodecenyl acetate (Z7-12:Ac), (E)-7-dodecenyl acetate (E7-12:Ac), dodecyl acetate, (Z)-9-dodecenyl acetate, (Z)-9-tetradecenyl acetate (Z9-14:Ac), (Z)-10-tetradecenyl acetate, tetradecyl acetate/(Z)-11-tetradecenyl acetate (Z11-16:Ac), and (Z)-11-hexadecenyl acetate. The relative proportions of each acetate were 0.8:1.2:0.6:traces:82.8:0.3:1.5:12.9, respectively. This is the first time that E7-12:Ac has been reported from the pheromone gland of S. frugiperda. Only three compounds, Z9-14:Ac, Z7-12:Ac, and E7-12:Ac, elicited antennal responses, and there were no differences in catch between traps baited with either Z7-12:Ac + Z9-14:Ac or Z7-12:Ac + Z9-14:Ac + Z11-16:Ac blends. However, the Z7-12:Ac + Z9-14:Ac + E7-12:Ac blend was significantly better than Z7-12:Ac + Z9-14:Ac, indicating that E7-12:Ac is an active component in the sex pheromone of the Brazilian populations of S. frugiperda.     

Support for (Z)-11-Hexadecanal as a Pheromone Antagonist in Ostrinia nubilalis: Flight Tunnel and Single Sensillum Studies with a New York Population

The flight-tunnel response of male Z-strain European corn borer moths (ECB), Ostrinia nubilalis, from a population in New York State (USA), was significantly antagonized by addition of 1% (Z)-11-hexadecanal (Z11-16:Ald) to their sex pheromone (a 97:3 mix of (Z)- and (E)-11-tetradecenyl acetate [Z/E11-14:OAc]). The level of antagonism was equivalent to that observed for the previously identified ECB antagonist, (Z)-9-tetradecenyl acetate (Z9-14:OAc), and supports a recent report showing that Z11-16:Ald, a minor pheromone component of the Noctuid moth, Sesamia nonagrioides, caused antagonism of ECB pheromone communication in sympatric populations in the Iberian Peninsula. Single-sensillum recordings from ECB antennae, which included cross-adaptation experiments, showed that the same olfactory receptor neuron processing Z9-14:OAc inputs was responsible for detecting Z11-16:Ald, and that this neuron was not responsive to two other aldehydes, (Z)-9-tetradecanal (Z9-14:Ald) and (Z)-9-hexadecanal (Z9-16:Ald), found in other moth sex pheromones. Our results show that the antagonism is not confined to one geographic region, is specific for Z11-16:Ald, and that antagonist pathways might have the potential for processing a number of structurally similar compounds.     

Novel sex pheromone components from the fall cankerworm moth,Alsophila pometaria

A sex pheromone extract from fall cankerworm moths,Alsophila pometaria, attracted conspecific males in field tests. Four EAG-active components were isolated from the extract and identified by GC-MS, highfield PMR spectroscopy, and microchemical techniques asn-nonadecane (I), (Z,Z,Z)-3,6,9-nonadecatriene (II), (Z,Z,Z,E)-3,6,9,11-nonadecatetraene (III), and (Z,Z,Z,Z)-3,6,9,11-nonadecatetrane (IV). Studies of the behavioral responses of male moths in a flight tunnel to the isolated components showed II, III, and IV were the major components of the sex pheromone. No sex pheromone behavioral responses were observed for I.Lepidoptera: Geometridae.issued as NRCC No. 22964.