piperidines and stenusin

Beetles of the species Stenus comma live and hunt close to ponds and rivers, where they occasionally fall on the water surface. To escape this jeopardized state, the beetle developed a strategy relying on the excretion of a secretion containing the substances stenusine and norstenusine. They reduce surface tension and propel the bug to the saving river bank. These substances were synthesized and analyzed with respect to their equilibrium and dynamic adsorption properties at the air-water interface (pH 7, 23 ± 1 °C). The surface dilatational rheological characteristics in a frequency range from 2 to 500 Hz at molar bulk concentrations of 20.6 mmol L(-1) were studied using the oscillating bubble technique. Both alkaloids formed surface viscoelastic adsorption layers. The frequency dependence of the surface dilatational modulus E could successfully be described by the extended Lucassen-van den Tempel model accounting for a nonzero intrinsic surface viscosity κ. The findings confirmed a dual purpose of the spreading alkaloids in the escape mechanism of the Stenus beetle. Next to generating a surface pressure, a transition to surface viscoelastic behavior of the adsorbed layers was observed.

Topics: Adsorption; Air; Alkaloids; Animals; Coleoptera; Piperidines; Surface Tension; Viscosity; Water

Rove beetles of the genus Stenus produce and store bioactive alkaloids like stenusine (3), 3-(2-methylbut-1-enyl)pyridine (4), and cicindeloine (5) in their pygidial glands to protect themselves from predation and microorganismic infestation. The biosynthesis of stenusine (3), 3-(2-methylbut-1-enyl)pyridine (4), and cicindeloine (5) was previously investigated in Stenus bimaculatus, Stenus similis, and Stenus solutus, respectively. The piperideine alkaloid cicindeloine (5) occurs also as a major compound in the pygidial gland secretion of Stenus cicindeloides. The three metabolites follow the same biosynthetic pathway, where the N-heterocyclic ring is derived from L-lysine and the side chain from L-isoleucine. The different alkaloids are finally obtained by few modifications of shared precursor molecules, such as 2,3,4,5-tetrahydro-5-(2-methylbutylidene)pyridine (1). This piperideine alkaloid was synthesized and detected by GC/MS and GC at a chiral phase in the pygidial glands of Stenus similis, Stenus tarsalis, and Stenus cicindeloides.

Topics: Alkaloids; Animals; Coleoptera; Gas Chromatography-Mass Spectrometry; Piperidines

Rove beetles of the genus Stenus Latreille and the genus Dianous Leach possess pygidial glands containing a multifunctional secretion of piperidine and pyridine-derived alkaloids as well as several terpenes. One important character of this secretion is the spreading potential of its different compounds, stenusine, norstenusine, 3-(2-methyl-1-butenyl)pyridine, cicindeloine, α-pinene, 1,8-cineole and 6-methyl-5-heptene-2-one. The individual secretion composition enables the beetles to skim rapidly and far over the water surface, even when just a small amount of secretion is emitted. Ethological investigations of several Stenus species revealed that the skimming ability, skimming velocity and the skimming behaviour differ between the Stenus species. These differences can be linked to varied habitat claims and secretion saving mechanisms. By means of tensiometer measurements using the pendant drop method, the spreading pressure of all secretion constituents as well as some naturally identical beetle secretions on the water surface could be established. The compound 3-(2-methyl-1-butenyl)pyridine excelled stenusine believed to date to be mainly responsible for skimming relating to its surface activity. The naturally identical secretions are not subject to synergistic effects of the single compounds concerning the spreading potential. Furthermore, evolutionary aspects of the Steninae's pygidial gland secretion are discussed.

Topics: Alkaloids; Animals; Behavior, Animal; Coleoptera; Piperidines; Species Specificity

Most rove beetles of the genus Stenus protect themselves against microorganisms and predators such as ants and spiders by producing the alkaloid stenusine (1) in their pygidial glands. The biosynthesis of 1 was previously investigated in S. bimaculatus, where L-lysine forms the piperidine ring, L-isoleucine the side chain, and acetate the N-ethyl group. In addition to 1, S. similis keeps the pyridine alkaloid (Z)-3-(2-methyl-1-butenyl)pyridine (2) in its pygidial glands. Feeding S. similis beetles with [D,15N]-labeled amino acids followed by GC/MS analysis showed that L-Lys yields the pyridine ring and L-Ile the 2-methyl-1-butenyl side chain. Thus the alkaloids 1 and 2 probably share two precursor molecules in their biosynthesis.

Topics: Alkaloids; Animals; Coleoptera; Gas Chromatography-Mass Spectrometry; Germany; Isoleucine; Lysine; Molecular Structure; Piperidines; Pyridines; Stereoisomerism

Stenusine is well known as the alkaloid, discharged by the rove beetle, genus Stenus Latreille (Coleoptera, Staphylinidae). The Stenus beetles employ the alkaloid as an escape mechanism when on water surfaces. In the case of danger, they lower their abdomen and emit stenusine from their pygidial glands. Stenusine shows a low surface tension and therefore a high spreading pressure; these properties propel the beetle quickly over the water. Many Steninae do not live in habitats with open waters, but in detritus, leaf litter, mosses, etc. This raises the possibility that stenusine might also have another function, e.g., as antibiotic or fungicide. Stenus beetles show an intense grooming behaviour. With gas chromatography-mass spectrometry analyses we could prove that they cover themselves with their secretion. To tests its antimicrobial properties we conducted agar diffusion tests with stenusine and norstenusine, another substance that is abundant in most Stenus species. Both compounds have an antimicrobial effect on entomopathogenic bacteria and fungi. Stenusine not only allows for an extraordinary method of locomotion on water surfaces, it also protects the Steninae from being infested with microorganisms.

Topics: Alkaloids; Animals; Anti-Infective Agents; Coleoptera; Hydrogen-Ion Concentration; Models, Molecular; Piperidines

The rove beetles of the genus Stenus Latreille synthesize the alkaloid stenusine in their pygidial glands, which are located in the last three segments of their abdomen. It is proposed that stenusine is derived from the two amino acids, L-lysine and L-isoleucine. Feeding S. bimaculatus beetles with deuterium-labeled amino acids and using GC/MS analysis showed that L-lysine forms the piperidine ring of the stenusine molecule. The side chain originates from L-isoleucine and the N-ethyl group from acetate.

Topics: Alkaloids; Animals; Coleoptera; Drosophila melanogaster; Gas Chromatography-Mass Spectrometry; Isoleucine; Lysine; Molecular Structure; Piperidines

Most species of the rove beetle genus Stenus employ the spreading alkaloid stenusine as an escape mechanism on water surfaces. In the case of danger, they emit stenusine from their pygidial glands, and it propels them over the water very quickly. Stenusine is a chiral molecule with four stereoisomers: (2'R,3R)-, (2'S,3R)-, (2'S,3S)-, and (2'R,3S)-stenusine. The percentile ratio of these four isomers is only known for the most common species of the genus: Stenus comma. With the intention of determining the stereoisomer ratios of five additional species from the two subgenera, Stenus and Hypostenus, we used GC/mass spectrometry measurements with a chiral phase. The results showed that the ratio differs among the genus. These findings can be a basis for chemotaxonomy. It is also possible that the biological function of stenusine, e.g., as antibiotic or fungicide, varies with changing stereoisomer composition.

Topics: Alkaloids; Animals; Coleoptera; Ecosystem; Piperidines; Species Specificity; Stereoisomerism