A lure composed of (Z)-11-hexadecenal, (Z)-11-hexadecenyl acetate, and (Z)-11-hexadecen-1-ol at a ratio of 5 : 5 : 1 at a dose of 0.01 mg was optimal for the attraction of the Vietnamese strain of the diamondback moth (DBM). The combination of the sex pheromone with a plant volatile, allyl isothiocyanate, significantly increased the attraction of the pheromone trap. Females were also attracted, but they were only about 2% of all moths captured. In plots with 120-130 traps per ha, mass trapping with the combined lures reduced the DBM larval densities in cabbage fields as effectively as the spraying of insecticides 6 to 8 times. The weekly trap catches indicated that DBM adult densities in the mass-trapping fields were low until 28 days after transplantation, and then were kept to a modest increase until day 49. This field study also shows that the trap catches were well correlated with the DBM larval densities.

BACKGROUND The tea black tussock moth Dasychira baibarana Matsumura is a devastating pest in tea plantations that causes substantial economic losses. Presently, there is no effective method to control this pest other than pesticide application. The identified sex pheromone of D. baibarana could be used for detecting and monitoring this pest. RESULTS Gas chromatography-electroantennogram detection showed that D. baibarana male moth antennae responded strongly to three components in the female sex pheromone gland, which were identified as: (3Z,6Z)-cis-9,10-epoxyhenicosa-3,6-diene (Z3,Z6,epo9-21:H) (I), (3Z,6Z,11E)-cis-9,10-epoxyhenicosa-3,6,11-triene (Z3,Z6,epo9,E11-21:H) (II) and (3Z,6Z)-henicosa-3,6-dien-11-one (Z3,Z6-21:11-one) (III). Dasychira baibarana uses a unique composition of an epoxydiene, epoxytriene, and dienone with the same 3,6-dienyl motif as its sex pheromone. The epoxytriene and dienone were not previously characterized as insect pheromone components. Electroantennogram analysis showed that each synthetic compound strongly stimulated male antennae, and compounds II and III elicited stronger responses than compound I. A wind tunnel bioassay and field trapping experiments proved that, ternary blends of compounds I-III attracted D. baibarana. Efficient attraction was achieved with a rubber septum baited with 500 mu g of a mixture of compounds I-III at the ratio 25:20:55. CONCLUSION The three identified compounds elicited an electroantennogram response in D. baibarana male moth antennae, and a mixture of the three components at the ratio 25:20:55 attracted D. baibarana male moths in a wind tunnel assay and field trapping experiments. This blend could be used for integrated management of D. baibarana in tea plantations. (c) 2022 Society of Chemical Industry.

Hawk moths are classified into the subfamilies Sphinginae, Macroglossinae and Smerinthinae. The sex pheromones of hawk moths have been intensively investigated recently. However, these reports were mainly on Sphinginae and Macroglossinae and there are only a few reports on Smerinthinae. Here, we identified sex pheromone components from the Smerinthinae, Smerinthus tokyonis Matsumura (Lepidoptera: Sphingidae). Observation of female calling behavior showed that the behavior started immediately after the photo-phase started. Gas chromatography (GC) coupled with electroantennography detection analysis indicated that male antenna responded to three components in the pheromone gland extract. GC–MS and GC analyses demonstrated that the three components were (10Z,12E)–, (10E,12Z)–, and (10Z,12Z)–hexadecadienyl acetates in a 6:7:87 ratio. We subsequently performed behavioral assays in cages. We observed the orientation and contact behavior of males in response to different odor sources, including a solvent control, calling female, pheromone gland extract, and synthetic blend. Males did not respond to the solvent control, but did respond to the other sources. Since males responded more to the calling female than to the synthetic blend, additional cues seem to be required for complete mating behavior. Nevertheless, the pheromone components determined in this first study of a Smerinthinae species are important chemicals in mating communication.

Hellula undalis is a harmful insect pest of green mustard in the Mekong Delta of Vietnam. In order to establish a tool for a sustainable pest control program, the sex pheromone of H. undalis inhabiting the Mekong Delta was examined. GC-EAD and GC-MS analyses of pheromone gland extracts from the virgin females elucidated three new components, (Z)-11-tetradecenyl acetate (Z11-14:OAc), (Z)-11-hexadecenal (Z11-16:Ald), and (11E,13E)-11,13-hexadecadien-1-ol, in addition to the known pheromone component (11E,13E)-11,13-hexadecadienal (E11,E13-16:Ald). Double bond positions of the two monoenyl components were determined by GC-MS analysis of the pheromone extract treated with dimethyl disulfide. On the other hand, GC-MS analysis of the female body extract detected the unsaturated hydrocarbon (3Z,6Z,9Z)-3,6,9-tricosatriene (Z3,Z6,Z9-23:H). Field examinations of their synthetic compounds indicated the significant role of E11,E13-16:Ald as a major component and a clear synergistic effect of the two monoenyl compounds as a minor component. Although the 3:3:7 mixture of Z11-14:OAc, E11-16:Ald, and E11,E13-16:Ald captured the largest number of males among the tested mixtures, the activity was still quite a bit lower than that of virgin females. However, the 3:3:7:1 mixture, which was prepared by adding a small amount of Z3,Z6,Z9-23:H to the 3:3:7 ternary lure, succeeded in attracting males more powerfully than the females did. This strong synergistic effect was not observed when the triene was added to unmixed E11,E13-16:Ald, indicating important roles of not only the triene but also the two monoenyl compounds as natural pheromone components.

Why workers forfeit direct reproduction is a crucial question in eusocial evolution. Worker reproduction provides an excellent opportunity to understand the mechanism of kin conflict resolution between the queen and workers. We evaluated behavioral and physiological differences among females in the paper wasp Polistes chinensis antennalis to examine why some workers reproduce under queenright conditions. Reproductive workers were old and foraged less early in the season; their cuticular hydrocarbon (CHC) profiles overlapped with those of queens but were significantly different. The distinct CHC profile of the eggs of the queen likely represented a cue for policing against those by workers. Juvenile hormone (JH) and dopamine seemed to be associated with gonadotropic function, and the JH level of reproductive workers was similar to that of the queen. The high JH level of reproductive workers likely facilitated their reproduction even under queenright conditions. Gene expression levels of the queen and reproductive workers differed only in vitellogenin. These results suggest that worker reproduction is facilitated by an increase in JH level; however, CHC is not a fertility-linked signal, but a queen-linked signal; consequently, reproductive workers without a queen-linked signal might be allowed to stay within the colony.

Since the first identification of bombykol, sex pheromones of about 700 moth species have been elucidated. Additionally, field evaluations of synthetic pheromones and their related compounds have revealed the male attraction of another 1,300 species. These pheromones and attractants are listed on the web-sites, "Pheromone Database, Part I." Pheromone components are classified according to their chemical structures into two major groups (Types I and II) and miscellaneous. Based on our previous review published in 2004, studies reported during the last two decades are highlighted here to provide information on the structure characteristics of newly identified pheromones, current techniques for structure determination, new enantioselective syntheses of methyl-branched pheromones, and the progress of biosynthetic research. Besides the moth sex pheromones, various pheromones and allomones from many arthropod species have been uncovered. These semiochemicals are being collected in the "Pheromone Database, Part II." The chemical diversity provides a wonderland for natural product chemists.

Female sex pheromone of a clearwing moth Nokona feralis (Leech) (Lepidoptera: Sesiidae), a pest of kiwifruit, was identified to be a 7:3 mixture of (3E,13Z)-3,13-octadecadienyl acetate (E3,Z13-18:OAc) and (3E,13Z)-3,13-octadecadien-1-ol (E3,Z13-18:OH) by GC-EAD and GC/MS analyses. Males were attracted to wide-range mixtures of E3,Z13-18:OAc and E3,Z13-18:OH, and a 7:3 mixture of those two compounds strongly attracted the males in the field.

Leucinodes orbonalis is one of the most damaging insect pests affecting eggplant in the Mekong Delta of Vietnam. While (E)-11-hexadecenyl acetate (E11–16:OAc) and its alcohol, (E)-11-hexadecenol (E11–16:OH), have been identified as major and minor sex pheromone components, respectively, few males were attracted to a blend of these compounds in Vietnamese fields. In order to utilize synthetic pheromone of L. orbonalis as a tool for sustainable pest management programs, we reexamined the pheromone of this species in order to search for other minor components. Gas chromatography-electroantennogram detection and gas chromatography/mass spectrometry analyses of abdominal tip extract revealed the presence of two electroantennogram-active compounds, E11–16:OAc and (3Z,6Z,9Z)-3,6,9-tricosatriene (Z3,Z6,Z9–23:H) in a ratio of 100:2. An extract of the abdomen and thorax showed an additional electroantennogram-active component, (3Z,6Z,9Z)-3,6,9-docosatriene (Z3,Z6,Z9–22:H), with the three compounds (E11–16:OAc, Z3,Z6,Z9–23:H and Z3,Z6,Z9–22:H) being present in a ratio of 100:45:1, indicating that the trienes were mainly present on the cuticular surface. In the field, traps baited with E11–16:OAc and the C23 triene, in a mix of 10:1, caught more male moths than traps baited with the acetate alone. A field evaluation of other polyunsaturated hydrocarbons showed that the C22 triene found in body extract also increased catches when added to the acetate, but no other hydrocarbons did. In contrast, to other studies with this moth, the addition of E11–16:OH to E11–16:OAc plus the C22 or C23 triene, resulted in decreased trap catches.

The lilac pyralid, Palpita nigropunctalis Bremer (Lepidoptera: Crambidae), is a common pest of Oleaceae plants. A crude extract of the female sex pheromone glands was examined by gas chromatography-electroantennogram detection (GC-EAD) and GC coupled to a mass spectrometer (GC/MS). The GC-EAD analysis revealed three EAG-active components (I-III) in a ratio of 1:0.2:0.01 (I: H: III). GC/MS analysis successfully recorded the mass spectra of I and II. For I, ions at m/z 238 (M+) and 220 ([M-18](+)) indicated the structure of a monoenyl aldehyde with a 16-carbon chain. For II, M+ was not detected, but ions at m/z 222 ([M-60](+)) and 61 ([AcOH +1](+)) suggested that II was a monoenyl acetate with a 16-carbon chain. Further GC/MS analysis of the extract treated with dimethyl disulfide revealed that the double bonds in both I and II are located at the same position of 11th-carbon. In addition, the pheromone extract was examined by GC/Fourier transform-infrared spectro-photometer (GC/FT-IR). An IR spectrum of I showed characteristic absorption at 1716 and 966 cm(-1), indicating a formyl group and E configuration of the double bond, respectively. In the case of II, absorption at 1745 and 968 cm(-1) indicated an ester carbonyl and E configuration, respectively. Taken together and by comparison with authentic standards, I and II were confirmed as (E)-11-hexadecenal and (E)-11-hexadecenyl acetate, respectively; while III was speculated as (E)-11-hexadecen-1-ol. The synthetic I, II and III all coincided well with those of the natural components in chemical data, and elicited strong electroantennographic activity in male P. nigropunctalis.

Lepidopteran larvae damage to the branches of cultivated kiwifruit is a serious problem in the southwest part of Ehime Prefecture, Japan. We reared these larvae using seedlings of kiwifruit, and found that this species was a clearwing moth, Nokona feralis (Leech). After emergence, the 1st instar larvae bored into the current shoots from the base of the petiole, and almost all of the leaves near the positions where the larvae bored were withered. Larvae moved to 30-40 mm diameter branches and bored into them, and expelled a large amount of frass from the site the larvae attacked. The puparia were observed mainly on 20-50 mm diameter branches. One to five eggs were laid, mainly on the petiole base. Ovipositions by females were observed until the middle of October. Eggs overwintered and then larvae hatched the next April. The hatching rate was 30.4% and 39.2% of eggs were attacked by a parasitoid wasp. Males were captured by pheromone traps from early September to the middle of October, and a peak of male capture was observed from late September to early October. Of 28 pheromone traps placed across Ehime Prefecture, only 4 traps in the southwest region (Ainan Town, Uwajima City, and Yawatahama City) captured males. To suppress larval attack, some insecticides were carried out in the season of larval hatch. Cypermethrin, methidathion (DMTP), and cartap effectively prevented the larval attack to kiwifruit.

Fifteen subspecies of the wood tiger moth, Arctia plantaginis (Lepidoptera: Erebidae: Arctiinae), have been recorded in the Northern Hemisphere. An analysis of crude pheromone extracts by GC equipped with an electroantennographic (EAG) detector showed four EAG-active components (Comps. I–IV) that were commonly involved in the pheromone glands of two subspecies inhabiting Japan and Finland. Comp. I is a major component (>75%) and the others are minor components (3% - 15%). Their mass spectra, measured by GC/MS, revealed the chemical structures of C21 unsaturated hydrocarbons as follows: 3,6,9-triene for Comp. I, 4,6,9-triene for Comp. II, 1,3,6,9-tetraene for Comp. III, and 2,4,6,9-tetraene for Comp. IV. Comps. I and III are known Type II pheromone compounds, and their retention times coincide with those of the authentic standards with all Z configurations. As a next step, the extract was analyzed by GC/FT-IR to determine the configuration of Comps. II and IV. Their IR spectra showed two characteristic C-H bending absorptions around 990 and 945 cm-1 due to the conjugated dienyl moieties; thus, Z and E configurations were assigned to the double bonds at the 2- and 4-positions, respectively. Their Z double bonds at the 6- and 9-positions are indicated by no absorptions around 970 cm-1, due to the isolated double bonds with E configurations. Finally, the structures of Comps. II and IV were confirmed by synthesis using a double Wittig reaction. The synthetic (4E,6Z,9Z)-4,6,9-triene and (2Z,4E,6Z,9Z)-2,4,6,9-tetraene showed strong EAG activity, and their chemical data coincided well with those of the natural Comps. II and IV, indicating the correctness of the structure determination by GC/FT-IR analysis and its usefulness for Type II pheromone compounds.

The sex pheromone of the hibiscus flower borer Rehimena surusalis (Walker) 19 (Lepidoptera: Crambidae) was analyzed by gas chromatography with electroantennographic 20 detection (GC-EAD) and GC-mass spectrometry (GC-MS). Three EAD-active components 21 were found in crude pheromone gland extracts of calling females. GC-MS and GC analyses 22 using synthetic chemicals and derivatization of the extracts identified three components as 23 (10E,12Z)-hexadeca-10,12-dienal (E10,Z12-16:Ald,), (10E,12E)-hexadeca-10,12-dienyl 24 acetate (E10,Z12-16:OAc) and (3Z,6Z,9Z)-tricosa-3,6,9-triene (Z3,Z6,Z9-23:HC). In field 25 tests, male moths were remarkably attracted to a ternary blend of E10,Z12-16:Ald, E10,Z1226 16:OAc and Z3,Z6,Z9-23:HC at a ratio of 1:5:14, but single and binary blend of either 27 compound showed only weak or no attraction activity. 28

Recent work has suggested that hawk moths share pheromone components but are sexually separated by qualitative and quantitative differences in their pheromone blends. During field assays on the sex pheromones of other species, a diurnal hawk moth, Neogurelca himachala sangaica (Lepidoptera: Sphingidae), was frequently captured, but the composition of the sex pheromone of this species was not known. Analysis of hexane extracts of the pheromone glands of calling female by gas chromatography (GC) using an electroantennographic detector (EAD) revealed two components that elicited EAD responses from male moth antennae. These components were identified by their mass spectra and retention indices on two GC columns as (10E,12Z)-10,12-hexadecadienal (E10,Z12–16:Ald) and a trace of its (10E,12E)-isomer (E10,E12–16:Ald) in 98:2 ratio. In field experiments, E10,Z12–16:Ald alone attracted male moths, and addition of E10,E12–16:Ald significantly reduced the attractiveness, even at the naturally-occurring ratio. Analysis of the data using a generalized linear mixed model showed that E10,Z12–16:Ald positively contributed to attractiveness, whereas E10,E12–16:Ald did so negatively, and it was concluded that the sex pheromone of N. himachala sangaica consists solely of E10,Z12–16:Ald, bombykal. The negative effect of E10,E12–16:Ald on attractiveness could promote the species-specificity of this single-component pheromone system.

While 11 species in the family Saturniidae are found in Japan, no sex pheromones of the native species had been investigated previously. We collected larvae of Rhodinia fugax in Nagano and Tottori Prefecture, and of Loepa sakaei in Okinawa Prefecture, and extracted sex pheromones of these two species from virgin female moths. In gas chromatography-electroantennogram detection (GC-EAD) analyses, male antennae of each species responded to one component in the respective pheromone extracts of conspecific females. Chemical analyses of the extracts by GC/mass spectrometry revealed that the EAD-active compounds of R. fugax and L. sakaei were a hexadecadienal and a tetradecadienyl acetate, respectively. The two species belong to the subfamily Saturniinae, and the mass spectra of both were similar to that of the 6,11-hexadecadienyl acetate identified from Antheraea polyphemus, classified in the same subfamily, suggesting the same 6,11-dienyl structure for the C16 aldehyde and a 4,9-dienyl structure for the C14 acetate. Based on this assumption, four geometrical isomers of each dienyl compound were stereoselectively synthesized via acetylene intermediates, compared to the natural products, and tested in the field. Male catches confirmed the pheromone structures of the two Japanese saturniid species as (6E,11Z)-6,11-hexadecadienal for R. fugax and (4E,9Z)-4,9-tetradecadienyl acetate for L. sakaei. The compounds have a characteristic 1,6-dienyl motif common to the pheromones of Saturniinae species.

The sex pheromone of the hibiscus flower borer Rehimena surusalis (Walker) (Lepidoptera: Crambidae) was analyzed by gas chromatography with electroantennographic detection (GC-EAD) and GC-mass spectrometry (GC/MS). Three EAD-active components were found in crude pheromone gland extracts of calling females. GC/MS and GC analyses using synthetic chemicals and derivatization of the extracts identified three components as (10E,12Z)-hexadeca-10,12-dienal (E10,Z12-16:Ald,), (10E,12E)-hexadeca-10,12-dienyl acetate (E10,Z12-16:OAc), and (3Z,6Z,9Z)-tricosa-3,6,9-triene (Z3,Z6,Z9-23:HC). In field tests, male moths were strongly attracted to a ternary blend of E10,Z12-16:Ald, E10,Z12-16:OAc, and Z3,Z6,Z9-23:HC at a ratio of 1:5:14, but single and binary blends showed only weak or no attraction.

Insect pheromones are some of the most interesting natural products because they are utilized for interspecific communication between various insects, such as beetles, moths, ants, and cockroaches. A large number of compounds of many kinds have been identified as pheromone components, reflecting the diversity of insect species. While this review deals only with chiral methyl-branched pheromones, the chemical structures of more than one hundred non-terpene compounds have been determined by applying excellent analytical techniques. Furthermore, their stereoselective syntheses have been achieved by employing trustworthy chiral sources and ingenious enantioselective reactions. The information has been reviewed here not only to make them available for new research but also to understand the characteristic chemical structures of the chiral pheromones. Since biosynthetic studies are still limited, it might be meaningful to examine whether the structures, particularly the positions and configurations of the branched methyl groups, are correlated with the taxonomy of the pheromone producers and also with the function of the pheromones in communication systems.

The sex pheromone of Herpetogramma submarginale (Swinhoe) was studied by gas chromatography (GC) with electroantennographic detection and GC coupled with mass spectrometry. Two pheromone candidates detected in the gland extracts of females were identified as (Z)-13-hexadecenyl acetate (Z13-16:OAc) and (E)-13-hexadecenyl acetate (E13-16:OAc) in a ratio of 87:13 by mass spectral analysis of the natural pheromone components and their dimethyldisulfide adducts. In field tests, Z13-16:OAc alone attracted H. submarginale males and caught significantly more males than live virgin females. Addition of E13-16:OAc did not enhance the attractiveness of Z13-16:OAc. Derivatives of Z13-16:OAc also were tested as potential pheromone components. Addition of (Z)-13-hexadecen-1-ol significantly reduced the number of males captured, and (Z)-13-hexadecenal had no effect on the attractiveness of the lure. These results suggest that the female-produced sex pheromone of H. submarginale is Z13-16:OAc. This hexadecenyl acetate is a novel moth sex pheromone component.

Sex pheromones of nocturnal hawk moths have been identified previously, but not those of diurnal hawk moths. Here, we report laboratory analyses and field testing of the sex pheromone of the diurnal hawk moth, Hemaris affinis (Bremer 1861) (Lepidoptera: Sphingidae). Sex pheromone glands were removed and extracted in hexane during peak calling activity of virgin female moths. Analysis of gland extracts by gas chromatography (GC) with electroantennographic detection revealed three components that elicited responses from male moth antennae. These components were identified, based on their mass spectra and retention indices on two GC columns, as ( Z )-11-hexadecenal and (10 E , 12 Z )- and (10 E ,12 E )-10,12-hexadecadienals with a ratio of 45:20:35. In a field experiment, traps baited with the three-component synthetic blend, but none of the single- or two-component blends, caught male moths. All three pheromone components have been identified previously in pheromones of other Lepidoptera, including Sphingid moths, and thus the ternary blend is probably responsible for the species specificity of the pheromone of this moth.

The sweet potato vine borer moth, Omphisa anastomosalis (Pyraloidea: Crambidae), is a serious pest in tropical and subtropical Asia-Pacific regions. In previous work using a population from Okinawa, Japan, (10E,14E)-10,14-hexadecadienal (E10,E14-16:Ald) was identified as the major pheromone component, with hexadecanal, (E)-10-hexadecenal, and (E)-14-hexadecenal as minor components. However, traps baited with the synthetic compounds were less effective at attracting males in the field than those baited with virgin females. While Pyraloidea females usually produce only Type I pheromone components (unsaturated fatty alcohols and their derivatives), the pheromones of some Pyraloidea species have been shown to involve a combination of both Type I and Type II components (unsaturated hydrocarbons and their epoxides). We examined an extract of the pheromone glands of female O. anastomosalis from Vietnam by gas chromatography coupled to mass spectrometry and detected (3Z,6Z,9Z)-3,6,9-tricosatriene (Z3,Z6,Z9-23:H) in addition to the compounds identified previously. All four isomers of 10,14–16:Ald were synthesized. A mixture of synthetic E10,E14-16:Ald and Z3,Z6,Z9-23:H in a ratio of 1:0.2–1:2 was attractive to male moths in Vietnam, indicating the strong synergistic effect of the Type II compound. Addition of the other minor pheromone components to the binary blend did not increase the number of male moths captured. Combinations of Z3,Z6,Z9-23:H with the other three geometrical isomers of E10,E14-16:Ald attracted no males, further substantiating the 10E,14E configuration of the natural diene component. E10,E14-16:Ald mixed with other polyunsaturated hydrocarbons showed that mixtures that included a C21 triene, a C22 triene, or a C23 pentaene attracted as many males as did the mixture with Z3,Z6,Z9-23:H. The identification of a highly attractive sex pheromone will help in developing efficient strategies for monitoring and control of O. anastomosalis populations in sweet potato fields.