Identification of Cuticular and Web Lipids of the Spider Argiope bruennichi

Abstract

Emerging evidence shows that the cuticular and silk lipids of spiders are structurally more diverse than those of insects, although only a relatively low number of species have been investigated so far. As in insects, such lipids might play a role as signals in various contexts. The wasp spider Argiope bruennichi has probably the best investigated chemical communication system within spiders, including the known structure of the female sex pheromone. Recently we showed that kin-recognition in A. bruennichi could be mediated through the cuticular compounds consisting of hydrocarbons and, to a much larger proportion, of wax esters. By use of mass spectrometry and various derivatization methods, these were identified as esters of 2,4-dimethylalkanoic acids and 1-alkanols of varying chain lengths, such as tetradecyl 2,4-dimethylheptadecanoate. A representative enantioselective synthesis of this compound was performed which proved the identifications and allowed us to postulate that the natural enantiomer likely has the (2R,4R)-configuration. Chemical profiles of the silk and cuticular lipids of females were similar, while male cuticular profiles differed from those of females. Major components of the male cuticular lipids were tridecyl 2,4-dimethyl-C17-19 alkanoates, whereas those of females were slightly longer, comprising tridecyl 2,4-dimethyl-C19-21 alkanoates. In addition, minor female-specific 4-methylalkyl esters were detected.