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Methanol dehydrogenase (MDH, EC 1.1.99.8) was first described in 1964 by Anthony and Zatman (Anthony and Zatman 1964, 1965, 1967a,b). Since that time a large number of MDH’s have been found with similar properties (Anthony 1986) including the dimeric MDH from Hyphomicrobium X (Duine et al. 1978). Methanol dehydrogenases are dye-linked enzymes, efficient electron transfer occurring exclusively to cationic electron acceptors at relatively high pH values (> 9). Enzymatic activity requires the presence of ammonia and sometimes higher amines as activators. Like many other quinoproteins, MDH’s are characterized by a broad substrate specificity, besides methanol a wide range of primary alcohols is oxidized and some enzymes also oxidize secondary alcohols. Formaldehyde, and sometimes acetaldehyde, is also a substrate. Modulation of the substrate specificity by a modifier protein has been observed in several organisms (Bolbot and Anthony, 1980) and it has been suggested that this protein functions as a regulator of formaldehyde oxidation.

Two sex pheromones, periplanone A and periplanone B were isolated from the American cockroach Periplaneta americana. The technique is described for collecting periplanone B from the alimentary tracts of virgin females. Periplanone A was extracted from the excreta of the insects. Mass spectral analysis of the pheromones and related compounds were performed and the results are reported here. Evidence is presented suggesting that periplanone A is in fact a degradation product of periplanone B. A reaction scheme is considered for the pathway: periplanone B periplanone A (stable, but inactive) PA 22–VII.

The sex pheromone of the potato tuberworm moth, Phthorimaea operculella (Zell.) has been identified as a mixture of trans-4, cis-7-tridecadienyl acetate and trans-4, cis-1, cis-10 tridecatrienyl acetate. The identifications have been carried out by means of electroantennography, mass, infrared and n.m.r. spectroscopy. The identifications have been confirmed by synthesis. Both compounds occur in the insects in about equal amounts. The individual compounds are attractive to male moths in pheromone traps. The triolefinic ester was found to be much more attractive than the diolefinic ester. However, mixtures of both compounds in the ranges of 4:1 tot 1:4 are much more attractive than the individual compounds or traps baited with two virgin female moths. ZUSAMMENFASSUNG SEXUALPHEROMONE DER KARTOFFELMOTTE, PHTHORIMAEA OPERCULELLA. ISOLIE-RUNG, IDENTIFIKATION UND FREILANDBEWERTUNG Das Sexualpheromon von Phthorimaea operculella (Gelechiidae) wurde identifiziert als ein Gemisch von trans-4, cis-7-Tridecadienylacetat und trans-4, cis-1, cis-10-Tridecatrienylacetat. Die beiden Identifizierungen wurden durchgefuhrt mit Hilfe von Elektroantennografie, Massenspektroskopie, Ultrarotspektroskopie und Kernspinnresonanzspektroskopie. Die beiden Identifizierungen wurden durch Synthese bestatigt. Die Pheromonkomponenten wurden in etwa gleiche Mengen von den Faltern isoliert. Beide Substanzen erwiesen sich sowohl in naturlicher wie in synthetischer Form als aktiv in der Elektroantennografie sowie im biologischen Test und in Sexfallen. Ein Mischungsverhaltnis der beiden Komponenten von 4: 1 bis 1: 4 weist eine viel hohere Lockstoffwirkung auf als die beiden Einzelkomponenten oder als zwei lebende Weibchen. Ein Isomer des naturlichen Tridecatrienylacetat, namlich cis-4, trans-7, cis-10-Tridecatrienyl-acetate, war nur schwach aktiv in den verschiedenen Testen. In Sexfallen wurde die Aktivitat dieses Isomers durch Zusatz von trans-4, cis-7-Tridecadienylacetat nicht erhoht.

Two independently biologically active compounds, periplanone A and periplanone B can be isolated from fecal material of the American cockroach,Periplaneta americana. In fecal material these occur in a ratio of 1 ∶ 10 while, in intestinal tracts only periplanone B has been found. The latter has been identified as (1Z,5E)-1,10(14)-diepoxy-4(15),5-germacradien-9-one; the identification was confirmed by synthesis. Only the CD (-) enantiomer (1R,2R,5E,7S,10R) exhibited activity. The lower threshold of activity of both natural and synthetic CD (-) pheromone, is 10(-6)-10(-7) μg. Periplanone A has been identified (apart from its stereochemical configuration) as 7-methylene-4-isopropyl-12-oxa-tricyclo[4.4.2.0(1,5)]-9-dodecen-2-one). The structure of this rather unstable compound could be deduced by comparing its NMR, UV, IR, and mass spectra with the NMR and mass spectra of its rearrangement product. Both structures still require confirmation by synthesis, but their spectral data are in complete agreement with the proposed structures. The presence of only periplanone B in the gut and the presence of both periplanone A and periplanone B in the feces suggests that periplanone B is a genuine sex pheromone, whereas peri-planone A might be a biologically active transformation product, which in turn can isomerize into a more stable, but inactive compound.

Two sex pheromones, periplanone A and periplanone B were isolated from the American cockroach Periplaneta americana. The technique is described for collecting periplanone B from the alimentary tracts of virgin females. Periplanone A was extracted from the excreta of the insects. Mass spectral analysis of the pheromones and related compounds were performed and the results are reported here. Evidence is presented suggesting that periplanone A is in fact a degradation product of periplanone B. A reaction scheme is considered for the pathway: periplanone B periplanone A (stable, but inactive) PA 22–VII.

Das aus Arbeiterinnen der Ameise Monomorium pharaonis L. isolierte 5-Methyl-3-butyl-octahydroindolizin (I), eine bisher unbekannte Verbinart aus.

Aus Arbeiterinnen der AmeiseMonomorium pharaonis (L.) wurde 5-Methyl-3-butyl-octahydroindolizin isoliert. Dieses Pheromon ubt eine starke Lockstoffwirkung auf die Arbeiterinnen dieser Ameisenart aus. Die Struktur wurde durch Spektral-analyse und Synthese aufgeklart. Unseres Wissens ist dies das erste Pheromon aus Insekten mit dem Indolizingerust.