Insect cuticular hydrocarbons (CHCs) were probed by matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry with a lithium 2,5-dihydroxybenzoate matrix. CHC profiles were obtained for 12 species of diverse insect taxa (termites, ants, a cockroach, and a flesh fly). MALDI spectra revealed the presence of high molecular weight CHCs on the insect cuticle. Hydrocarbons with more than 70 carbon atoms, both saturated and unsaturated, were detected. When compared with gas chromatography/mass spectrometry (GC/MS), MALDI-TOF covered a wider range of CHCs and enabled CHCs of considerably higher molecular weight to be detected. Good congruity between GC/MS and MALDI-TOF was observed in the overlapping region of molecular weights. Moreover, a number of previously undiscovered hydrocarbons were detected in the high mass range beyond the analytical capabilities of current GC/MS instruments. MALDI was shown to hold potential to become an alternative analytical method for insect CHC analyses. The ability of MALDI to discriminate among species varying in the degree of their relatedness was found to be similar to GC/MS. However, neither MALDI-MS nor GC/MS data were able to describe the phylogenetic relationships.

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A female-produced sex pheromone of Stylops muelleri was identified as an unusually branched saturated aldehyde (9R)-3,5-syn-3,5,9-trimethyldodecanal. We named it stylopsal. Its structure was established by using mass spectrometry, infrared spectroscopy, and organic synthesis of candidate compounds. The synthetic standard of (9R)-3,5-syn-3,5,9-trimethyldodecanal gave identical chromatographic and mass spectrometric data as the natural pheromone and also was active in electroantennographic and behavioral assays. The female fat body lipids contained the corresponding fatty acid, indicating a possible link between lipid metabolism and the pheromone biosynthesis.

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Male wing gland secretion and volatiles emanating from calling males were investigated in the bumble bee wax moth, Aphomia. sociella, using comprehensive two-dimensional gas chromatography-mass spectrometry (GCxGC-TOF-MS), gas chromatography-infrared spectroscopy (GC-FTIR), enantioselective gas chromatography, electroantennography (EAG), gas chromatography with electroantennographic detection (GC-EAD), and NMR. GC-EAD analysis of the male wing gland secretion revealed seven active areas, corresponding to 1-hexanol (1), 2-phenylethanol (2), [(R),(Z)]-nona-2,6-dien-4-olide (3), [(S),(Z)]-nona-6-en-4-olide (4), mellein (5), phytone (6), and a mixture of C(18) fatty acids (7). Solid-phase microextraction (SPME) confirmed the presence of 2-phenylethanol, nona-2,6-dien-4-olide, nona-6-en-4-olide, mellein, and phytone in volatiles emanating from a calling male. Though the abundance of these compounds slightly differed in SPME and gland secretion analysis, nona-2,6-dien-4-olide and mellein dominated in both samples, followed by 2-phenylethanol, nona-6-en-4-olide, and phytone. The strong antennal responses elicited by components of the secretion suggest that one or more of these compounds constitute the sex pheromone. Both sexes perceived male wing gland secretion, with females being significantly more sensitive compared to males.

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The asymmetric total synthesis of the diastereomers of stylopsal establishes the absolute configuration of the first reported sex pheromone of the twisted-wing parasite Stylops muelleri as (3R,5R,9R)-trimethyldodecanal. The key steps for the diastereo- and enantiodivergent introduction of the methyl groups are two different types of asymmetric conjugate addition reactions of organocopper reagents to α,β-unsaturated esters, whereas the dodecanal skeleton is assembled by Wittig reactions. The structure of the natural product was confirmed by chiral gas chromatography (GC) techniques, GC/MS and GC/electroantennography (EAD) as well as field tests. An investigation into the biosynthesis of the pheromone revealed that it is likely to be produced by decarboxylation of a 4,6,10-trimethyltridecanoic acid derivative, which was found in substantial amounts in the fat body of the female, but not in the host bee Andrena vaga. This triple-branched fatty acid precursor thus seems to be biosynthesized de novo through a polyketide pathway with two consecutive propionate-propionate-acetate assemblies to form the complete skeleton. The simplified, motionless and fully host-dependent female exploits a remarkable strategy to maximize its reproductive success by employing a relatively complex and potent sex pheromone.

Prey-specialised predators have evolved specific cognitive adaptations that increase their prey searching efficiency. In particular, when the prey is social, selection probably favours the use of prey intraspecific chemical signals by predatory arthropods. Using a specialised ant-eating zodariid spider, Zodarion rubidum, which is known to prey on several ant species and possesses capture and venom adaptations more effective on Formicinae ants, we tested its ability to recognise chemical cues produced by several ant species. Using an olfactometer, we tested the response of Z. rubidum towards air with chemical cues from six different ant species: Camponotus ligniperda, Lasius platythorax and Formica rufibarbis (all Formicinae); and Messor structor, Myrmica scabrinodis and Tetramorium caespitum (all Myrmicinae). Z. rubidum was attracted to air carrying chemical cues only from F. rufibarbis and L. platythorax. Then, we identified that the spiders were attracted to airborne cues coming from the F. rufibarbis gaster and Dufour's gland, in particular. Finally, we found that among several synthetic blends, the decyl acetate and undecane mixture produced significant attraction of spiders. These chemicals are produced only by three Formicine genera. Furthermore, we investigated the role of these chemical cues in the communication of F. rufibarbis and found that this blend reduces their movement. This study demonstrates the chemical cognitive capacity of Z. rubidum to locate its ant prey using chemical signals produced by the ants. The innate capacity of Z. rubidum to olfactory detect different ant species is narrow, as it includes only two ant genera, confirming trophic specialisation at lower than subfamily level. The olfactory cue detected by Zodarion spiders is probably a component of the recruitment or trail pheromone.