Stereoisomeric analysis of 6,10,14-trimethylpentadecan-2-ol and the corresponding ketone in wing extracts from African Bicyclus butterfly species.

Gas chromatography (GC) and mass spectrometry (MS) were used to determine the stereoisomeric compositions of 6,10,14-trimethylpentadecan-2-ol and 6,10,14-trimethylpentadecan-2-one in wing extracts from 17 Bicyclus butterfly species from different regions of Africa. All samples were purified using solid phase extraction (SPE). Since some species contained both alcohol and ketone, these were separated and the ketone was reduced to the alcohol before analysis as either (R)-trans-chrysanthemoyl or (S)-2-acetoxypropionyl esters. A novel asymmetric synthesis was developed for a reference mixture of (2R/S,6S,10R)-6,10,14-trimethylpentadecan-2-ol with known composition of the eight stereoisomers. The mixture then was used as the (R)-trans-chrysanthemoyl esters to correlate each of the eight gas chromatographic peaks to a specific stereoisomer of the extracted wing compounds. Seven butterfly species showed (2R,6R,10R)-configuration of the alcohol, four species contained minute amounts of alcohol too small to determine the stereochemistry, nine species showed (6R,10R)-configuration of the ketone, and one species contained minute amounts of ketone too small to determine the stereochemistry. No other stereoisomers of alcohol or ketone could be detected in the extracts, and the quantities of the compounds in the wing extracts varied from 5 to 900 ng per sample for each species.

Acquisition of species-specific perfume blends: influence of habitat-dependent compound availability on odour choices of male orchid bees (Euglossa spp.).

Male orchid bees (Euglossini, Apidae, Hymenoptera) expose species-specific blends of volatile chemicals (perfume bouquets) during their courtship display. The perfumes are acquired by collecting fragrant substances from environmental sources, which are then accumulated in specialised hind leg pouches. To balance the perfume composition, the males need to find and collect the required substances in specific relative amounts while facing seasonal, local or habitat-dependent differences in compound availability. Experience-dependent choice of odours, i.e. 'learned avoidance' of recently collected components, has been proposed as the mechanism that mediates the accumulation of the stereotypical compound ratios. In the present study, we used the presence of certain compounds in male hind leg pouches as proxy for the respective local compound availability, and investigated whether differences in content are correlated with differences in chemical choice assays. Our results suggest that volatile availability differs between localities (n = 16) as well as habitats (n = 2; coastal vs. inland) across the Yucatán peninsula, Mexico, for both studied species. Male Euglossa dilemma showed a pronounced preference for benzyl benzoate and eugenol at locations where those compounds were rare in hind leg extracts, as predicted by the learned avoidance model. No equivalent correlations were found for Euglossa viridissima. This is the first study to combine chemical analyses of perfumes with bioassays of odour choice. It strengthens the view that negative feedback from collected odours modifies future chemical choice and helps males to acquire specific perfume blends.

Sex pheromone of the pine sawfly Macrodiprion nemoralis (Hymenoptera:Diprionidae): identification of (2S,3R,7R,9S)-3,7, 9-trimethyl-2-tridecanol as the precursor for the active pheromone acetate.

The main component of the sex pheromone precursor in females of Macrodiprion nemoralis was identified as a threo-3,7, 9-trimethyl-2-tridecanol isomer, approximately 800 pg per female, by gas chromatography-mass spectrometry. Comparison of mass spectrometric ion chromatograms showed that the natural compound in the female extract has the same retention time and mass spectrum as one of the two synthetic threo peaks. The acetate of the synthetic 16-isomer mixture caught a large number of males in the field, confirming the structure of the active pheromone. Comparison of gas chromatograms of the natural female extract with the eight synthetic threo stereoisomers showed that the pheromone is the (2S,3R,7R, 9S)-stereoisomer of 3,7,9-trimethyl-2-tridecyl acetate.

Species-specific, two-component, volatile signals in two sympatric ant-lion species:Synclysis baetica andAcanthaclisis occitanica (Neuroptera, Myrmeleontidae).

The thoracic glands of males in two ant-lion speciesSynclysis baetica andAcanthaclisis occitanica, which occur sympatrically in Israel, were found to contain a volatile secretion with two-component blends of nerol oxide and (R,Z)-6-tridecen-2-ol (approx 1∶5) and nerol oxide and 10-homonerol oxide (approx. 1∶2), respectively. Chemical analyses were performed using gas chromatography-mass spectrometry, chiral gas chromatography, and ozonolysis, and the proposed structures were confirmed by synthesis. The species-specific, few-component volatile signals are thought to function as a reproductive isolation mechanism between the two sympatric species. Biochemical relationships between the nerol derivatives and between the unsaturated secondary alcohols are discussed.

Sex pheromone perception in male pine sawflies, Neodiprion sertifer (Hymenoptera; Diprionidae).

Electroantennographic and single sensillum recordings were performed on male pine sawfly, Neodiprion sertifer, antennae. Responses to the sex pheromone component (2S, 3S, 7S)- 3,7-dimethyl-2-pentadecenyl (diprionyl) acetate (SSS:OAc), to the behavioral inhibitor (2S, 3R, 7R)-diprionyl acetate (SRR:OAc), to the six other enantiomers of diprionyl acetate, and to the biosynthetic precursor diprionol were recorded. Responses to trans-perillenal, a monoterpene identified in female gland extracts and to (2S, 3S, 7S)-diprionyl propionate (SSS:OPr), a field attractant for N. sertifer and some related sawfly species were also recorded. EAG recordings demonstrated a high antennal sensitivity to SSS:OAc and to SSS:OPr. A somewhat lower response was elicited by SRR:OAc. Single sensillum recordings revealed 8-12 different cells firing in each sensillum, corresponding to the number of cells observed in earlier morphological investigations. Out of these cells all, except one, responded to SSS:OAc and to SSS:OPr. No differences in the response to the two components could be observed. The largest amplitude cell in each sensillum was specifically tuned to the behavioral antagonist, SRR:OAc. The pheromone perception system encountered in male pine sawflies thus differs clearly from that observed in moths.

Release rates for pine sawfly pheromones from two types of dispensers and phenology of Neodiprion sertifer.

Comparisons of release rates, duration in the field, and catch efficiency of polyethylene and cotton roll dispensers for the sex pheromones of sawflies (Hymenoptera: Diprionidae) were conducted. The release rates of the Neodiprion sertifer (Geoffr.) and Diprion pini (L.) sex pheromones, the acetates of pentadecanol and (2S,3S,7S)-3,7-dimethyl (2S,3R,7R)-3,7-dimethyl-2-tridecanol from polyethylene dispensers were measured at different temperatures in the laboratory. The release rates for the substances depended on both the temperature and initial load in the vials. The catch from cotton rolls baited with 100 micrograms of the acetate or propionate of 3,7-dimethyl-2-pentadecanol was compared to the catch from regularly renewed cotton rolls baited with 10 micrograms of the same acetate. The catch was higher for the 100-microgram cotton rolls for, at most, 45 days, and there was no significant differences in catch between the acetate and the propionate. The catch in traps baited with polyethylene or cotton roll dispensers loaded with the acetate of 3,7-dimethyl-2-pentadecanol was compared and showed that cotton roll traps mirrored the decreasing release of the substance rather than the actual flight activity. The length of the flight period of N. sertifer in Sweden, the Czech Republic, Italy, and Greece did not exceed 100 days in any of the countries. By adjusting the initial pheromone load of the polyethylene vials to the expected temperatures, it should be possible to get a constant and sufficiently high release rate during the entire flight period.