title: Analysis of chemical profiles of insect adhesion secretions by gas chromatography-mass spectrometry.
abstract: This article reports on the chemical analysis of molecular profiles of tarsal secretions of the desert locust Schistocerca gregaria (Forsskål, 1775) by gas chromatography hyphenated with quadrupol mass spectrometry (GC-MS) as well as (1)H-nuclear magnetic resonance ((1)H NMR) spectroscopy. Special focus of this study was to elaborate on sampling methods which enable selective microscale extraction of insect secretions in a spatially controlled manner, in particular tarsal adhesive secretions and secretions located on cuticle surfaces at the tibia. Various solvent sampling procedures and contact solid-phase microextraction (SPME) methods were compared in terms of comprehensiveness and extraction efficiencies as measured by signal intensities in GC-MS. Solvent sampling with water as extraction solvent gave access to the elucidation of chemical profiles of polar compound classes such as amino acids and carbohydrates, but is extremely tedious. Contact SPME on the other hand can be regarded as a simplified and more elegant alternative, in particular for the lipophilic compound fraction. Many proteinogenic amino acids and ornithine as well as carbohydrate monomers arabinose, xylose, glucose, and galactose were detected in tarsal secretions after acid hydrolysis of aqueous extracts. Qualitatively similar but quantitatively significantly different molecular profiles were found for the lipid fraction which contained mainly n-alkanes and internally branched monomethyl-, dimethyl-, and trimethyl-alkanes in the C23-C49 range as well as long chain fatty acids and aldehydes. Especially, hydrocarbons with >C40 carbon numbers have previously been rarely reported for insect secretions. The results suggest that the investigated insect secretions are complex emulsions which allow the attachment of tarsi on various otherwise incompatible materials of smooth and rough surfaces. The solid consistence of the established alkanes at ambient temperatures might contribute to a semi-solid consistence of the adhesive, amalgamating partly opposing functions such as slip resistance, tarsal release, desiccation resistance, and mechanical compliance. The methods developed can be extended to other similar applications of studying compositions of insect secretions of other species.
authors.affiliation: Institute of Organic Chemistry, University of Tübingen, Auf der Morgenstelle 8, 72076 Tübingen, Germany.
authors.forename: Manuela
authors.initials: M
authors.lastname: Reitz
authors.affiliation: Institute of Pharmaceutical Sciences, University of Tübingen, Auf der Morgenstelle 8, 72076 Tübingen, Germany.
authors.forename: Heike
authors.initials: H
authors.lastname: Gerhardt
authors.affiliation: Institute of Evolution and Ecology, University of Tübingen, Auf der Morgenstelle 28, 72076 Tübingen, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Schmitt
authors.affiliation: Institute of Evolution and Ecology, University of Tübingen, Auf der Morgenstelle 28, 72076 Tübingen, Germany.
authors.forename: Oliver
authors.initials: O
authors.lastname: Betz
authors.affiliation: Institute of Organic Chemistry, University of Tübingen, Auf der Morgenstelle 8, 72076 Tübingen, Germany. Electronic address: klaus.albert@uni-tuebingen.de.
authors.forename: Klaus
authors.initials: K
authors.lastname: Albert
authors.affiliation: Institute of Pharmaceutical Sciences, University of Tübingen, Auf der Morgenstelle 8, 72076 Tübingen, Germany. Electronic address: michael.laemmerhofer@uni-tuebingen.de.
authors.forename: Michael
authors.initials: M
authors.lastname: Lämmerhofer
mesh_terms: D000818:Animals; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D006110:Grasshoppers / Q000378:metabolism*; D052617:Solid Phase Microextraction
keywords: Acrididae; Adhesion secretions; Amino acids; Carbohydrates; Contact solid-phase micro extraction (SPME); Gas chromatography–mass spectrometry (GC–MS); Hydrocarbons; Insect; Insect metabolites; Orthoptera