title: Identification and Synthesis of Branched Wax-type Esters, Novel Surface Lipids from the Spider Argyrodes elevatus (Araneae: Theridiidae).
abstract: The analysis of cuticular extracts from the kleptoparasitic spider Argyrodes elevatus revealed the presence of unusual esters, new for arthropods. These novel compounds proved to be methyl-branched long-chain fatty acid esters with methyl branches located either close or remote from the internally located ester group. The GC/MS analysis of the prosoma lipid blend from the male cuticle contained one major component, undecyl 2-methyltridecanoate (1). In contrast, four major wax-type esters, 2-methylundecyl 2,8-dimethylundecanoate (2), 2,8-dimethylundecyl 2,8-dimethylundecanoate (3), heptadecyl 4-methylheptanoate (4), and 14-methylheptadecyl 4-methylheptanoate (5), were identified in the lipid blend of female prosomata. Structure assignments were based on mass spectra, gas chromatographic retention indices, and microderivatization. Unambiguous proof of postulated structures was ensured by an independent synthesis of all five esters. Preferentially, odd-numbered carbon chains pointed to a distinct biosynthetic pathway, different from that of common fatty acids, because one or two C3starter units are incorporated during the biosynthesis of all acid and alcohol building blocks present in the five esters. The striking sexual dimorphism together with the unique biosynthesis points to a function of the esters in chemical communication of the spiders, although no behavioral data are currently available to test this assumption.
authors.affiliation: Institute of Organic Chemistry, Technische Universität Braunschweig, Hagenring 30, DE-38106, Braunschweig.
authors.forename: Satya Prabhakar
authors.initials: SP
authors.lastname: Chinta
authors.affiliation: Institute of Organic Chemistry, Technische Universität Braunschweig, Hagenring 30, DE-38106, Braunschweig.
authors.forename: Stephan
authors.initials: S
authors.lastname: Goller
authors.affiliation: General and Systematic Zoology, University of Greifswald, Anklamer Str. 20, DE-17489, Greifswald. gabriele.uhl@uni-greifswald.de.
authors.forename: Gabriele
authors.initials: G
authors.lastname: Uhl
authors.affiliation: Institute of Organic Chemistry, Technische Universität Braunschweig, Hagenring 30, DE-38106, Braunschweig. stefan.schulz@tu-bs.de.
authors.forename: Stefan
authors.initials: S
authors.lastname: Schulz
mesh_terms: D000818:Animals; D004952:Esters / Q000032:analysis* / Q000737:chemistry / Q000378:metabolism*; D005260:Female; D008055:Lipids / Q000032:analysis* / Q000096:biosynthesis* / Q000737:chemistry; D008297:Male; D015394:Molecular Structure; D013112:Spiders / Q000737:chemistry*; D013499:Surface Properties; D014885:Waxes / Q000737:chemistry*
chemical_list: D004952:Esters; D008055:Lipids; D014885:Waxes
keywords: Chemical communication; Cuticular lipids; Methyl-branched esters; Microderivatization; Pheromones; Sexual dimorphism