A reinvestigation of the chemistry of the Dufours gland of the formicine ant,Anoplolepis custodiens

The components of individual Dufours glands excised fromAnoplolepis custodiens workers were analysed by GC-MS. In addition to then-alkanes andn-alkenes previously reported² in these glands, primary alcohols (C₁₉-C₂₂), secondary alcohols (C₂₀-C₂₃), 2-ketones (C₂₀-C₂₃) and possibly carboxylate ethyl esters (C₁₉ and C₂₁) were identified as components of these glands. It seems possible that these high-boiling compounds are used by the workers in laying trails on the hot sandy surfaces of their characteristic habitat and in lining of the inner walls of nests, but no standard compounds have been available to us for any behavioral studies.     

Accumulation of phenylpropanoids in the rectal glands of males of the Oriental fruit fly,Dacus dorsalis

Summary Two phenylpropanoid compounds, 2-allyl-4,5-dimethoxyphenol(II) and coniferyl alcohol(III), were characterized from body tissue of wild males of the Oriental fruit fly,Dacus dorsalis. These compounds accumulated in the rectal glands only when laboratory-reared males were fed with methyl eugenol. Compound II was released into the air during dusk, which coincides with the fly courtship period. Pheromonal and allomonal effects of the phenylpropanoids were examined.     

Relevance of chlorine-substituent for the antifungal activity of syringomycin and syringotoxin,metabolites of the phytopathogenic bacteriumPseudomonas syringae pv.syringae

Structural analogues of syringomycin and syringotoxin were produced by fermentation, characterized by FAB-MS and amino acid analysis and compared to the parent compounds in the antibiosis test againstRhodotorula pilimanae. The C-terminal residue was shown to be important for the activity.     

The male pheromone of the old house borerHylotrupes bajulus (L.) (Coleoptera: Cerambycidae): Identification and female response

We report here the identification of the long-range, male-produced sex pheromone of the Old house borerHylotrupes bajulus. Chemical analysis of hexane extracts obtained by surface extraction from dissected prothoracic glands and from headspace samples of the two sexes, revealed male-specific compounds: (3R)-3-hydroxy-2-hexanone, 2-hydroxy-3-hexanone, the diastereomeric diols (2R, 3R)-2,3-hexanediol and (2S, 3R)-2,3-hexanediol, 2,3-hexanedione, as well as 1-butanol.In wind tunnel bioassays we tested the influence of these male-specific compounds from the prothoracal glands on the behaviour of unmated and mated females. Specific behavioural sequences of the tested females (activity, running behaviour, searching, cleaning, flying, extension of ovipositor) were recorded. Unmated females were attracted by male beetles, headspace extracts of males, synthetic blends of the major pheromone compounds as well as by the components (3R)-3-hydroxy-2-hexanone, and the diastereomeric diols. Hexane, female beetles and 2,3-hexanedione did not attract unmated females. The reactions of mated females to male beetles and headspace samples did not differ significantly from those of the controls.The results of the bioassays show that the two-stage premating behaviour is initiated by emission of a long-range sex pheromone from the male prothoracal glands, which functions as an activator, attractant, and possibly aphrodisiac for unmated females.     

Influence on the trypsin activity by the side chain of arginine homologues

Summary The N--tosyl-p-nitroanilides of homoarginine and of the two shorter arginine homologues were synthesized. These compounds behave as specific, chromogenic substrates for trypsin.     

New tamjamine class alkaloids from the marine ascidianAtapozoa sp. and its nudibranch predators. Origin of the tambjamines inAtapozoa

Summary Two new tambjamine class alkaloids, possessing ichthyodeterrent properties, have been isolated from the organic extracts of the marine ascidianAtapozoa sp. and its nudibranch predators. The structure of the new metabolites were elucidated through interpretation of their physical and spectral data and by comparison with spectral data for related compounds. Microscopic examination ofAtapozoa considering the yellow color of the tambjamines suggested thatAtapozoa is capable of the de novo biosynthesis of these metabolites.     

Interaction ofRhizobium loti strain and host on the biosynthesis of unusual amino acids in leguminous plants

Summary The effect of differentRhizobium loti strains on the biosynthesis of 2,3-diamino-butanoic acid and 2,4-diamino-3-methyl-butanoic acid in root nodules ofLotus tenuis, Anthyllis vulneraria andLupinus densiflorus has been investigated. Results suggest that biosynthesis isRhizobium strain dependent, that the bacteroid is the site of synthesis of the compounds and that their biosynthesis is confined to the symbiosis.     

Screening of newly synthesized non-alkylating sterilant compounds against the adultChrotogonus trachypterus Blanch. (Orthoptera: Acrididae)

Summary Out of the 9 new non-alkylating compounds screened againstC. trachypterus, the compounds 62206, 24220 and 51160 have been found most effective, 51007 and 50882 exhibit intermediate effectiveness, 61914 only slightly effective and 50994, 2406 and 51240 almost non-effective.This work was financed out of PL 480 USA funds.     

Enrichment of ligands with molecular dockings and subsequent characterization for human alcohol dehydrogenase 3

Alcohol dehydrogenase 3 (ADH3) has been assigned a role in nitric oxide homeostasis due to its function as an S-nitrosoglutathione reductase. As altered S-nitrosoglutathione levels are often associated with disease, compounds that modulate ADH3 activity might be of therapeutic interest. We performed a virtual screening with molecular dockings of more than 40,000 compounds into the active site of human ADH3. A novel knowledge-based scoring method was used to rank compounds, and several compounds that were not known to interact with ADH3 were tested in vitro. Two of these showed substrate activity (9-decen-1-ol and dodecyltetraglycol), where calculated binding scoring energies correlated well with the logarithm of the k _cat/K _m values for the substrates. Two compounds showed inhibition capacity (deoxycholic acid and doxorubicin), and with these data three different lines for specific inhibitors for ADH3 are suggested: fatty acids, glutathione analogs, and cholic acids.     

Arylpyridyl-thiosemicarbazones: A new class of anti-juvenile hormones active against Lepidoptera

Summary A new class of anti-juvenile hormone agents is described. Active anti-juvenile hormone compounds were either diazine thiosemicarbazones or aryl substituted pyridyl thiosemicarbazones, synthesized from substituted benzaldehydes. While many analogs in these classes showed feeding and growth inhibition in a variety of insects, a select group caused formation of precocious pupal characteristics inAgrotis ipsilon (black cutworm) andHeliothis virescens (tobacco budworm) and black cuticle and precocious pupae inManduca sexta (tobacco hornworm). They were active only by diet incorporation. The symptoms of precocious development could be reversed by co-administration of a juvenoid. One of the active compounds was shown to inhibit juvenile hormone biosynthesis in vitro by corpora allata of the cockroachDiploptera punctata. However, none of the compounds were active inhibitors of purified chicken liver prenyl transferase.     

Study of the metabolites ofPhyllosticta maydis. I. Isolation and partial identification

Summary Various metabolites of the fungusPhyllosticta maydis have been isolated, particularly mevalonolactone. The most interesting of these compounds, which is highly toxic to corn seeds (Zea mays), and which is probably a complex polyol, is the subject of the present report.Acknowledgment. The authors are indebted to Professor T. Gäumann for his cooperation and Dr J.C. Tabet who performed the measurements of mass-spectrometry.     

Chemical defence in the larvae of the leaf beetleGonioctena viminalis L. (Coleoptera: Chrysomelidae)

Summary The leaf beetle larva ofGonioctena (Phytodecta) viminalis L. has been shown to produce five volatile constituents within its paired abdominal defensive gland reservoirs. It is the first time that these compounds have been reported to occur in coleopteran defensive glands (linalool, phenylethanol) and Chrysomelidae larvae (6-methyl-5-hepten-2-one, 6-methyl-5-hepten-2-ol, 2-hexenal). In addition to the gross morphology of theGonioctena gland and its discharge behavior, the natural products found are discussed in terms of chemotaxonomy.     

The postpharyngeal glands and the cuticle of Formicidae contain the same characteristic hydrocarbons

Summary Comparison of the contents of the postpharyngeal gland and cuticular hydrocarbons of five species of ant have shown them to contain the same compounds and to be characteristic of the species. For four species (Formica selysi, Camponotus lateralis, Camponotus vagus andManica rubida), quantitative similarity was very close, but more divergent in the fifth (Myrmica rubra). Glands and cuticle ofM. rubra queens were shown to be closely similar to those of workers, except the glands of queens are larger, but the cuticle of larvae was different from that of adult cuticle and postpharyngeal glands.     

Secondary metabolites of the chemically rich ascoglossanCyerce nigricans

Summary Two new metabolites of an apparent propionate origin have been isolated from the organic extract of the ascoglossan molluscCyerce nigricans. The proposed structures for the new natural products are based on interpretation of their physical and spectral properties. The new compounds isolated lacked the potent ichthyodeterrent properties of the whole animal extract suggesting that other molecules are involved in the defense of this shell-less mollusc.     

Mushroom toxins of the genusCortinarius

Summary 3 major components of the toxic fungusCortinarius speciosissimus have been isolated and their structures determined as cyclic polypeptides. 2 of these compounds have been shown in laboratory animals to cause nephrotoxicity characteristic of Cortinarius mushroom poisoning.The work was carried out with support from the Scottish Home and Health Department grant No. K/MRS/50/C350 and the Science and Engineering Research Council.     

Biological properties of alkaloids. Influence of quinolizidine alkaloids and gramine on the germination and development of powdery mildew,Erysiphe graminis f.sp.hordei

Summary The quinolizidine alkaloids sparteine, lupanine and 13-tigloyl-oxylupanine and the indole alkaloid gramine inhibited the germination of conidia ofErysiphe graminis f.sp.hordei Marchal and also the further development to appressoria. Half-maximal inhibitory concentrations of these alkaloids were 1–5 mmol/l. This result provides further evidence for a role of alkaloids as chemical defense compounds in plants.     

Biosynthesis of roquefortine and 3,12-dihydroroquefortine by the culturePenicillium farinosum

Summary A new culturePenicillium farinosum synthesizing roquefortine and 3, 12-dihydroroquefortine was found. UnlikeP. roqueforti, a known producer of these compounds, the culture under study does not synthesize clavine alkaloids. The maximal roquefortine content was observed in the late logarithmic and early stationary growth phases while the maximal 3, 12-dihydroroquefortine content was obtained in the beginning of the stationary phase.Thanks are due to Drs V. M. Adanin and M. Yu. Nefedova for mass- and IR-spectra.     

A simple method for in vivo testing of glandular enzymatic activity on potential precursors of larval defensive compounds inPhratora species (Coleoptera: Chrysomelinae)

The presence of glandular -glucosidase and oxidase-specific activities, and the possible role of phenolglucosides and related compounds as precursors for larval defensive compounds, were directly demonstrated by introducing salicin, saligenin and helicin into the defensive glands ofPhratora species.Ph. tibialis andPh. laticollis that normally secrete endogenously-produced iridoid monoterpenes and do not use phenolglucosides from their food sources as precursors, were able to produce salicyladehyde from helicin when the latter was introduced into the defensive glands.     

Metabolism of endosulfan in the Indian honey bee

Summary Metabolism of topical endosulfan in the Indian honey bee,Apis cerana indica F., was studied. The two endosulfan isomers were found to be interconvertible in bees. The products of metabolism were endosulfan sulfate, diol, ether, hydroxyether, lactone and two unknown compounds. Endosulfan diol, hydroxyether and lactone were found to be conjugated in excreta of the treated bees.Acknowledgment. Authors are grateful to the department of Horticulture and Food Technology for providing gas chromatography facilities.     

Glycerol monoethers in the scent gland secretions of the western diamondback rattlesnake (Crotalus atrox; Serpentes,Crotalinae)

Summary 1-O-Monoalkylglycerols with C₁₂ to C₂₀ chains were identified in the scent, gland secretions of the western diamondback rattlesnake (Crotalus atrox). This is the first documentation of these compounds in the skin secretions of a reptile.