Functional Specificity of Sex Pheromone Receptors in the Cotton Bollworm Helicoverpa armigera

Male moths can accurately perceive the sex pheromone emitted from conspecific females by their highly accurate and specific olfactory sensory system. Pheromone receptors are of special importance in moth pheromone reception because of their central role in chemosensory signal transduction processes that occur in olfactory receptor neurons in the male antennae. There are a number of pheromone receptor genes have been cloned, however, only a few have been functionally characterized. Here we cloned six full-length pheromone receptor genes from Helicoverpa armigera male antennae. Real-time PCR showing all genes exhibited male-biased expression in adult antennae. Functional analyses of the six pheromone receptor genes were then conducted in the heterologous expression system of Xenopus oocytes. HarmOR13 was found to be a specific receptor for the major sex pheromone component Z11-16:Ald. HarmOR6 was equally tuned to both of Z9-16: Ald and Z9-14: Ald. HarmOR16 was sensitively tuned to Z11-16: OH. HarmOR11, HarmOR14 and HarmOR15 failed to respond to the tested candidate pheromone compounds. Our experiments elucidated the functions of some pheromone receptor genes of H. armigera. These advances may provide remarkable evidence for intraspecific mating choice and speciation extension in moths at molecular level.     

Synthesis of (S,E)-1-Methyl-9-dodecenyl Acetate,the Sex Pheromone of the Hessian Fly,Mayetiola destructor

(S,E)-1-Methyl-9-dodecenyl acetate (1), the sex pheromone of the Hessian fly, was synthesized by starting from ethyl (S)-3-hydroxybutanoate (2).     

Purification, Identification, Concentration and Bioactivity of (Z)-7-Dodecen-1-yl Acetate: Sex Pheromone of the Female Asian Elephant, Elephas maximus

In their natural ecosystems, adult male and female Asian elephants,Elephas maximus, live separately. For several weeks prior toovulation, female elephants release a substance in their urinewhich elicits a high frequency of non-habituating chemosensoryresponses, especially flehmen responses, from male elephants.These responses occur prior to, and are an integral part of,mating. Using bioassay-guided fractionation, quantitativelydependent on these chemosensory responses, a specific sex pheromonewas isolated and purified by an alternating series of organicand/or aqueous extractions, column chromatography, gas chromatographyand high-performance liquid chromatography. Using primarily¹H-proton nuclear magnetic resonance (NMR) spectrometry andgas chromatography-mass spectrometry (GC-MS) of the urine-derivedpheromone and its dimethyl disulfide derivative, we determinedthe structure of the active compound to be (Z)-7-dodecen-1-ylacetate (Z7-12:Ac). Concentrations of Z7-12:Ac in the femaleurine increased from non-detectable during the luteal phaseto 0.48µg/ml (0.002 mM) early in the follicular phaseand to 33.0µg/ml (0.146 mM) just prior to ovulation. Bioassayswith commercially available authentic synthetic Z7-12:Ac, using10 Asian male elephants at several locations in the US, demonstratedquantitatively elevated chemosensory responses that were robustduring successive tests, and several mating-associated behaviors.Bioassays with Z7-12:Ac with adult male elephants dwelling inmore natural social situations in forest camps in Myanmar revealedsome differing contextual pre-mating behavioral components.The remarkable convergent evolution of this compound suggeststhat compounds identified in mammalian exudates that are alsopresent in pheromone blends of insects should be re-evaluatedas potential mammalian chemosignals. Chem. Senses 22: 417–437,1997.     

Synthesis of the Deuterated Sex Pheromone Components of the Grape Borer,Xylotrechus pyrrhoderus

Adult males of the grape borer, Xylotrechus pyrrhoderus, secrete (S)-2-hydroxy-3-octanone [(S)-1] and (2S,3S)-2,3-octanediol [(2S,3S)-2] from their nota of prothoraces as sex pheromone components. Their structural similarity suggests that one of them is the biosynthetic precursor of the other component. In order to confirm the biochemical conversion, deuterated derivatives of both components were synthesized by starting from a Wittig reaction between hexanal and an ylide derived from D₅-iodoethane and ending with enantiomeric resolution by chiral HPLC. The molecular ions of 1 and 2 could scarcely be detected by using a GC-MS analysis, and the labeled compounds showed similar mass spectra to the unlabeled pheromone components. However, several fragment ions, including four deuterium atoms, were observed in the mass spectra of their acetate derivatives, indicating that the conversion could be confirmed by examining a compound with the diagnostic ions after acetylation of the volatiles collected from insects treated with the labeled precursors.     

Syntheses and NMR Analyses of Eight Geometrical Isomers of 10,12,14-Hexadecatrienyl Acetate,Sex Pheromone Candidates of the Mulberry Pyralid

Eight geometrical isomers of 10,12,14-hexadecatrienyl acetate, female sex pheromone candidates of the mulberry pyralid (Glyphodes pyloalis Walker), were synthesized by six routes. Each route consisted of reactions by which two of three double bonds were introduced stereospecifically and another rather nonspecifically, giving mainly two geometrical isomers, which were analyzed by 2D-NMR after separating by reversed-phase HPLC or by a reaction with tetracyanoethylene. The signals of the olefinic protons and carbons of each geometrical isomer were assigned by COSY spectra and by C-H COSY spectra, respectively, in addition to the signals of the allylic protons and carbons, and its chemical structure was revealed by the values of their chemical shifts and coupling constants. Furthermore, a new empirical rule concerning the chemical shift changes of these carbons by converting the configuration of the conjugated triene system is suggested.     

Synthesis of (S,E)-1-Methyl-9-dodecenyl Acetate,the Sex Pheromone of the Hessian Fly,Mayetiola destructor,by Lipase-catalyzed Enantioselective Hydrolysis

(S,E)-1-Methyl-9-dodecenyl acetate [(S)-8], the sex pheromone of the hessian fly, Mayetiola destructor, was synthesized in a highly enantiomerically pure form by Pseudomonas cepacia lipase-catalyzed hydrolysis.     

Zeolite-catalyzed Helferich-type glycosylation of long-chain alcohols. Synthesis of acetylated alkyl 1,2-trans glycopyranosides and alkyl 1,2-cis C2-hydroxy-glycopyranosides

Zeolite-catalyzed glycosylation of long-chain alcohols, using the inexpensive and readily available peracetylated beta-D-gluco- and galactopyranoses as glycosyl donors under solvent free conditions, has been explored for the first time. Among the various forms (H-, Na-, Fe- and Zn) of beta zeolite examined as catalysts in the reaction of 1,2,3,4,6-penta-O-acetyl-beta-D-galactopyranose with cetyl alcohol, Fe-beta zeolite gave the maximum yield of 63% of cetyl 2,3,4,6-tetra-O-acetyl-beta-D-galactopyranoside and cetyl 3,4,6-tri-O-acetyl-alpha-D-galactopyranoside. Fe-beta Zeolite-catalyzed glycosylation was found to be general affording the title compounds in each case in a moderate yield, but with a good stereoselectivity. The yield of synthetically valuable acetylated long-chain alkyl 1,2-cis C2-hydroxy-glycopyranosides obtained in the present single-step procedure is considerably higher than that of the previously reported multi-step method employing the Stork silicon tether approach.     

Engineered Repressible Lethality for Controlling the Pink Bollworm, a Lepidopteran Pest of Cotton

The sterile insect technique (SIT) is an environmentally friendly method of pest control in which insects are mass-produced, irradiated and released to mate with wild counterparts. SIT has been used to control major pest insects including the pink bollworm (Pectinophora gossypiella Saunders), a global pest of cotton. Transgenic technology has the potential to overcome disadvantages associated with the SIT, such as the damaging effects of radiation on released insects. A method called RIDL (Release of Insects carrying a Dominant Lethal) is designed to circumvent the need to irradiate insects before release. Premature death of insects’ progeny can be engineered to provide an equivalent to sterilisation. Moreover, this trait can be suppressed by the provision of a dietary antidote. In the pink bollworm, we generated transformed strains using different DNA constructs, which showed moderate-to-100% engineered mortality. In permissive conditions, this effect was largely suppressed. Survival data on cotton in field cages indicated that field conditions increase the lethal effect. One strain, called OX3402C, showed highly penetrant and highly repressible lethality, and was tested on host plants where its larvae caused minimal damage before death. These results highlight a potentially valuable insecticide-free tool against pink bollworm, and indicate its potential for development in other lepidopteran pests.     

The Structure,Stability and Pheromone Binding of the Male Mouse Protein Sex Pheromone Darcin

Mouse urine contains highly polymorphic major urinary proteins that have multiple functions in scent communication through their abilities to bind, transport and release hydrophobic volatile pheromones. The mouse genome encodes for about 20 of these proteins and are classified, based on amino acid sequence similarity and tissue expression patterns, as either central or peripheral major urinary proteins. Darcin is a male specific peripheral major urinary protein and is distinctive in its role in inherent female attraction. A comparison of the structure and biophysical properties of darcin with MUP11, which belongs to the central class, highlights similarity in the overall structure between the two proteins. The thermodynamic stability, however, differs between the two proteins, with darcin being much more stable. Furthermore, the affinity of a small pheromone mimetic is higher for darcin, although darcin is more discriminatory, being unable to bind bulkier ligands. These attributes are due to the hydrophobic ligand binding cavity of darcin being smaller, caused by the presence of larger amino acid side chains. Thus, the physical and chemical characteristics of the binding cavity, together with its extreme stability, are consistent with darcin being able to exert its function after release into the environment.     

Synthesis of (R,Z)-7, 15-Hexadecadien-4-olide,the Sex Pheromone of the Yellowish Elongate Chafer (Heptophylla picea)

(R, Z)-7,15-Hexadecadien-4-olide, the sex pheromone of the yellowish elongate chafer (Heptophylla picea), was synthesized from l-malic acid in 15 steps. The synthetic pheromone was identical with the natural product in its MS, IR, GLC retention time, and biological activity.     

Application of a Sex Pheromone,Pheromone Analogs,and Verticillium lecanii for Management of Heterodera glycines

A mutant strain of the fungus Verticillium lecanii and selected bioregulators of Heterodera glycines were evaluated for their potential to reduce population densities of the nematode on soybean under greenhouse conditions. The bioregulators tested were the H. glycines sex pheromone vanillic acid and the pheromone analogs syringic acid, isovanillic acid, ferulic acid, 4-hydroxy-3-methoxybenzonitrile, and methyl vanillate. A V. lecanii-vanillic acid combination and a V. lecanii-syringic acid combination were also applied as treatments. Syringic acid, 4-hydroxy-3-methoxybenzonitrile, V. lecanii, V. lecanii-vanillic acid, and V. lecanii-syringic acid significantly reduced nematode population densities in the greenhouse tests. Results with vanillic acid, isovanillic acid, and ferulic acid treatments were variable. Methyl vanillate did not significantly reduce cyst nematode population densities in the greenhouse tests.     

A Facile Synthesis of 2-methyl-heptadecane,Sex Pheromone of Tiger Moths (Arctiidae)

The structure of 13- and 15-hydroxysolanascone-γ-glucopyranosides, sesquiterpenoid glycosides isolated from flue-cured tobacco leaves, were deduced from the spectral data and by means of the chemical conversion method.     

Simple Synthesis of the Major Sex Pheromone Components of Drosophila ananassae and D. pallidosa

The major sex pheromone components of Drosophila ananassae and D. pallidosa, (Z,Z)-5,25-hentriacontadiene and (Z,Z)-5,27-tritriacontadiene, respectively, were synthesized by using the Wittig olefination and sulfone coupling reactions as the C–C bond-forming steps.