Defense compounds deterrents

Not surprisingly, although the evolution of sequestered microbial toxins appears to be rather widespread in marine environments, sequestration of defensive alkaloids in the apparent absence of microorganisms may generally characterize the chemical defenses of terrestrial animals. Careful searches for possible microbial syntheses of defensive compounds (allomones) have not been generally implemented, but recent studies in a few laboratories raise the possibility that microbial endosymbionts may be of major importance in the biogenesis of selected insect deterrents. 

Defensive Compounds. Larvae of the weevil Oxyops vitiosa produce a shiny orange secretion that covers their integument and probably acts as deterrent against ants [420]. The composition of the secretion resembles the terpenoid pattern of the host foliage (Melaleuca quinquenervia) from where it is sequestered (concentration about twice that of the host foliage). It contains the sesquiterpene (+)-viridoflorol 230 (Scheme 25), the monoterpene hydrocarbons a-pinene 45, P-pinene 46, limonene 171, a-terpinene 231, and y-terpinene 232 as well as the oxygenated monoterpenesl,8-cineole 58, a-terpineol 233, and terpinen-4-ol 234. 

Monarch butterflies t.g., Danaus plexipus) combine two sets of natural compounds. Larvae feed on plants rich in cardiac glycosides and use them as chemical defense compounds. Adult butterflies visit plants with PAs, where they collect PAs that are converted to pheromones or transferred to their eggs 4,17,31,33,361,515). A similar PA utilization scheme was observed with larvae of the moth Utetheisa ornatrix 367,516), where the compounds were shown to be deterrent for spiders and birds 225, 525). The chrysomelid beetle Oreina feeds on PA-containing plants, such as Adenostyles, and stores the dieUuy PAs in the defense fluid 463,524). 

One example for a chemically defended zooplankton species is the Antarctic pteropod Clione antarctica. This shell-less pelagic mollusk offers a potentially rich source of nutrients to planktivorous predators. Nonetheless fish do not prey on this organism, due to its efficient chemical defense. In a bioassay-guided structure elucidation, pteroenone 37 could be isolated and characterized as the main defensive principle of C. antarctica [82,83]. If embedded in alginate, this compound is a feeding-deterrent in nanomolar concentrations. This unusual metabolite is likely to be produced by C. antarctica itself and not accumulated from its food, since its major food sources did not contain any detectable quantities of 37. 

Predators ignore sea hares because, like other mollusks without shells, they have chemicals that afford them the protection once given by a shell. (We saw earlier that a compound from a tropical sea hare is now a promising anticancer drug.) Many sea hares have an acrid or fetid odor that is distinctly unpleasant to humans. Their egg masses and their skin must be distasteful, because one exploratory bite is enough to convince a would-be assailant to look elsewhere for food. For some species, the deterrents responsible for these properties may come directly from their seaweed diet, but other species seem to synthesize these defenses for themselves. The evidence is mixed and confusing. 

Only a few compounds or mixtures of compounds have been shown beyond doubt to be mammalian pheromones. This is the main reason why the subject matter of this chapter is not restricted to pheromones and why exocrine secretions and other mammalian excretions in general will be discussed as possible sources of pheromones, even though their role in the chemical communication of the species under discussion has not yet been established. Feeding deterrents are not discussed. In general defensive secretions are also not discussed, but the anal sac secretions of the mustelids are included, because it is possible that these secretions could also fulfill a semiochemical role, in addition to being used for defense. 

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