The study of trail laying, recruitment of workers and trail-following by worker ants comprises a co-operative study of entomologists and chemists that has resulted in the identification of the chemical nature of such pheromones in many species of five subfamilies of ants. These pheromones may comprise a single compound or, in one exceptional case, a blend of as many as 14 compounds, they may come from a single gland, or in some cases, a combination of two glands. They may be peculiar to a single species or may be shared by a number of species. They exist in the glandular secretion in nanogram to picogram quantities and are detected by workers in minute amounts on a trail. The present state of knowledge of these pheromones and their chemical structures is reviewed. Suitable bioassays and odour perception are discussed and the stereobiology of a few examples is considered.

https://onlinelibrary.wiley.com/doi/pdf/10.1111/j.1365-3032.2008.00658.x

Trail pheromones of ants.

Adults of forty-five aposematic insect species from four orders, and/or, in eight cases, their early stages, were examined for the presence of 2-methoxy-3-alkylpyrazines by coupled gas chromatography/mass spectrometry. The survey also included eight cryptic and related species and six unrelated mimics, twelve selected hostplants of those herbivores that had proved positive for such pyrazines, and nine well known toxic plants. Positive results were as follows: aposematic adult species, 26 (58 %); obscurely coloured species, 1 (12.5%); mimics, 2 (33%); host-plants, 5 (42%); well-known toxic plants, 4 (44%). Among the taxonomic groups, these pyrazines were found in the lepidopteran families and subfamilies Papilionidae, Danainae, Heliconiinae, Acraeinae, Zygaenidae and Arctiidae, and among the Coleoptera, in the Lycidae, Cantharidae, Endomychidae, Coccinellidae, Oedemeridae and Meloidae. Single cases of the occurrence of these pyrazines were also detected in the Hemiptera (Cercopidae) and Orthoptera (Pyrgomorphidae). Mimics were found with and without the pyrazines. Among the plants they were detected in Aristolochiaceae, Asclepiadaceae, Asteraceae, Papaveraceae, Passifloraceae, Solanaceae and Urticaceae. Some aposematic and phytophagous insects apparently sequester pyrazines from their hostplants whereas others, particularly the predatory species, manufacture these substancesde novo. Alerting signals in general are discussed.

Methylalkylpyrazines in aposematic insects, their hostplants and mimics.

Recently it has been shown that pyrazines are associated with many aposematic, chemically defended insects. We have demonstrated that naive hatchling chicks, when offered drinking water to which 2-methoxy-3-isobutylpyrazine is added, develop a neophobic ‘alerting’ reaction. The birds are not only capable of forming a conditioned aversion to the pyrazine when it is paired with quinine sulphate but they can also detect it from a distance probably by olfaction. This suggests that birds, a major group of insect predators, can interpret pyrazines as alerting or warning signals. The relationship of pyrazines with other alerting signals, and their evocative qualities are discussed.

The biological roles of pyrazines: evidence for a warning odour function

Pyrazine Biosynthesis in Corynebacterium glutamicum

2-Methoxy-3-alkylpyrazines have been identified as odour components in Danaus plexippus, Zygaena lonicerae and an Australian Amata species, by means of coupled gas chromatography/mass spectrometry, with selected ion monitoring. Wide variability in pyrazine content was observed with D. plexippus and this was correlated with similar variability in the larval food-plants, Asclepias spp., which are presumed to be the odour sources for this butterfly. The importance of pyrazines in the biology of aposematic insects and their role as ingredients of a generalized warning system are discussed.

Pyrazines as warning odour components in the Monarch butterfly, Danaus plexippus, and in moths of the genera Zygaena and Amata (Lepidoptera)

The major component of the trail pheromone of the South American leaf-cutting ant,Atta sexdens rubropilosa Forel, is 3-ethyl-2,5-dimethylpyrazine (II). Methyl and ethyl phenylacetate and methyl 4-methylpyrrole-2-carboxylate (I), which is the major component of the trail pheromone ofA. texana (Buckley) andA. cephalotes (L.), were also identified and may be minor components. The pheromone is stored in the poison gland.Atta sexdens sexdens (L.) also responds strongly to the pyrazine, which in large amounts evokes a weak response fromA. texana, A. cephalotes, andAcromyrmex octospinosus (Reich). Foraging workers ofAtta sexdens rubropilosa did not preferentially pick up baits impregnated with the pyrazine. The pyrazine was puffed into the nests ofA. cephalotes, and a particular response called “milling” was noted.

The major component of the trail pheromone of the leaf-cutting ant,Atta sexdens rubropilosa forel

Females of the dermestid beetle,Trogoderma variabile Ballion, exhibit a diel pattern of calling behavior. A potent sexual excitant and attractant for the male beetles can be collected on Porapak Q during aeration of female beetles, but cannot be detected in extracts of macerated females. The attractant has been identified as (Z)-14-methyl-8-hexadecenal. Of the five additional compounds previously identified as attractants in otherTrogoderma species, only two were found; (Z)-14-methyl-8-hexadecen-1-ol is present in extracts of macerated female beetles, but not in extracts of Porapak Q, and γ-caprolactone is present in extracts of Porapak Q. Three collection procedures were necessary to ensure that all the pheromone components had been isolated. Synthetic (Z)-14-methyl-8-hexadecenal elicits attraction and sexual arousal inT. Variabile males.

John H. Cross

Papers

The major component of the trail pheromone of the leaf-cutting ant,Atta sexdens rubropilosa forel

Sex pheromone components and calling behavior of the female dermestid beetle, Trogoderma variabile Ballion (Coleoptera: Dermestidae).