Nematidical activity of secondary and tertiary alkyl amides and amines.

Several C11 to C15 amides and amines that disrupt growth in certain insects showed high nematicidal activity in direct contact tests. Two amides and 9 amines killed Panagrellus at 5-10 ppm. Of these, 1 amide and 3 amines killed Meloidogyne larvae at 20 ppm.     

The sterols of the khapra beetle,Trogoderma granarium everts

Summary The khapra beetle,Trogoderma granarium Everts, does not dealkylate and convert dietary C₂₈- or C₂₉-phytostorols to C _2T sterols such as cholesterol. There is, however, an increase in the concentration of cholesterol and campesterol in its tissues relative to the dietary concentrations of these sterols, presumably as a result of selective uptake.We thank Dr S. R. Dutky of the Insect Physiology Laboratory, Agricultural Research, SEA, USDA, Beltsville, Maryland for providing GC-MS analyses.     

Action duCorynebacterium parvum sur les taux de lysozyme (muramidase) sérique

Summary An i.v. injection of 548 g of killedCorynebacterium parvum into C57B1 mice leads to significant changes in serum lysozyme (muramidase) levels. After an initial fall at 24 h, the activity of the enzyme increased progressively, reached a peak on the 9th day and returned to control range after the 15th day.     

The isolation,culture and organ differentiation from mesophyll protoplasts ofMollugo nudicaulis Lam., a C4 species

Summary Isolation and culture of mesophyll protoplasts fromMollugo nudicaulis, a C₄ species, is reported. Protoplasts developed into callus with root formation. However, no shoot was differentiated. This work was carried out as a part of our overall objective of inducing somatic fusion between the protoplasts of C₃ and C₄ species ofMollugo.     

Composition of epicuticular wax of rice,Oryza sativa

Summary The epicuticular wax of rice, varietyRibe, comprised n-alkanes, esters, aldehydes and free alcohols. The nalkanes contained 4 major chain lengths, C₂₇, C₂₉, C₃₁ and C₃₃. Triacontanal and dotriacontanal were the major aldehydes. Octacosanol comprised 89% of the free alcohols. The esters were mainly esters of C₁₆ to C₂₄ acids with C₂₂ to C₃₀ alcohols.This research was supported by the Consiglio Nazionale delle Ricerche, Rome.     

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.     

The C4-dicarboxylate transport system ofRhizobium meliloti and its role in nitrogen fixation during symbiosis with alfalfa (Medicago sativa)

TheRhizobium meliloti C₄-dicarboxylate transport (Dct) system is essential for an effective symbiosis with alfalfa plants. C₄-dicarboxylates are the major carbon source taken up by bacteroids. Genetic analysis of Dct^– mutant strains led to the isolation of thedct carrier genedctA and the regulatory genesdctB anddctD. The carrier genedctA is regulated in free-living cells by the alternative sigma factor RpoN and the two-component regulatory system DctB/D. In addition, DctA is involved in its own regulation, possibly by interacting with DctB. In bacteroids, besides the DctB/DctD system an additional symbiotic activator is thought to be involved indctA expression. Further regulation ofdctA in the free-living state is reflected by diauxic growth of rhizobia, with succinate being the preferred carbon source. The tight coupling of C₄-dicarboxylate transport and nitrogen fixation is revealed by a reduced level of C₄-dicarboxylate transport in nitrogenase negative bacteroids.     

Prostaglandin (15S)-PGA2 derivatives in the gorgonianPlexaura homomalla (Esper), formakükenthali Moser

Summary The lipid fraction, 17%, of air-driedPlexaura homomalla formakükenthali, collected in the Caribbean at Puerto Rico, yielded 50% of its weight as the mammalian prostaglandin (15S)-PGA₂ methyl ester. The freeze-dried gorgonian yielded (15S)-PGA₂ largely as the acetate of the methyl ester. (15S)-PGA₂ was also obtained from material collected at St. Croix and at South Caicos. Field observations indicate thatPlexaura kükenthali may be a species separate fromPlexaura homomalla and that it is abundant on some shallow water reefs in the Caribbean. Prostaglandins could not be detected in the lipid fraction of eggs isolated fromPlexaura homomalla (Esper) formahomomalla.Acknowledgments. We gratefully acknowledge support from the Office of Sea Grant, NOAA, Department of Commerce (Grant 047-158-44067), and the use of facilities at the Isla Mayagues Marine Laboratory of the University of Puerto Rico, Mayaguez, the West Indies Laboratory of Fairleigh Dickinson University at St. Croix, U.S.V.I., and the Marine-Biologisch Instituut at Curacao. Special thanks to Dr. F.M. Bayer, Curator, Department of Zoology, National Museum of Natural History-Smithsonian Institution for checking identity of gorgonians used in this study.     

Synthesis and metabolism of vertebrate-type steroids by tissues of insects: A critical evaluation

Summary This review covers the synthesis and the metabolism of vertebrate-type steroids (progesterone, testosterone, estradiol, corticosteroids) by insect tissues and discusses the significance of the reactions for insect physiology. Biosynthesis of vertebrate-type steroids from cholesterol hitherto has been demonstrated in only two insect species, i.e. the water beetleAcilius sulcatus (Coleoptera) and the tobacco hornwormManduca sexta (Lepidoptera). InAcilius, steroid synthesis is associated with exosecretion (chemical defense). Nothing, however, is known about a physiological role of the C₂₁ steroid conjugate present in ovaries and eggs ofManduca. No synthesis of vertebrate-type steroids was observed in any other insect investigated to date. Most metabolic conversions of steroids by insects concerned oxidoreduction of oxygen groups (hydroxysteroid dehydrogenase activity) and (polar and apolar) conjugate formation. All important enzymatic steps involved in synthesis and catabolism, as known from studies with tissues of vertebrates, were not, or hardly observed. The conclusion is drawn that typical vertebrate-type (C₂₁, C₁₉ and C₁₈) steroids probably do not act as physiologically active substances in insects.     

Nest cell lining of the solitary beeHylaeus bisinuatus (Hymenoptera: Colletidae)

The nest cell lining ofHylaeus bisinuatus (Hymenoptera: Colletidae) was shown by high-resolution solidstate [¹³C]NMR to be composed of lipid polymer and protein. The lipid polymer was shown by reduction and subsequent GC/MS analysis to be comprised of -hydroxy fatty acids (C₂₀, C₂₂, C₂₄ and C₂₆) and fatty alcohols (C₁₆ to C₃₀). The protein portion of the lining had a silk-like amino acid composition.     

Alkaloid biosynthesis

Zusammenfassung Es wird eine neue Theorie der Alkaloidbiosynthese vorgeschlagen, die alle Alkaloidtypen vereinigt. Die Grundidee dieser Theorie beruht auf der Überlegung, dass die Alkaloide eher mit Kohlehydraten als mit Aminosäuren genetisch verwandt sind. Alle Strukturtypen der Alkaloide sind hypothetisch teilbar in C₄, C₆-C₁, C₆-C₂ und C₆-C₃-Fragmente, und können daher in Beziehung zum Davis-Sprinson-Schema, welches die Biosynthese aromatischer Naturstoffe behandelt, gebracht werden.

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From a lecture, entitledAlkaloid Biosynthesis, presented on October 8, 1958, as one of a series of ten lectures onRecent Advances in the Chemistry of Natural Products sponsored by the New York Section of the American Chemical Society during fall of 1958.     

Vincanorin und Vincarein,zwei neue Alkaloide ausVinca minor L.

Summary The isolation of two new alkaloids fromVinca minor L. (Apocynaceae) is described. Vincarein, C₂₁H₂₄N₂O₄, and Vincanorin, C₁₉H₂₂N₂O, both probably belong to the group of indol alkaloids.     

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.     

Oxygen equilibrium ofPriapulus hemerythrin

Summary The hemerythrin-containing coelomic fluid ofPriapulus caudatus shows a relatively low O₂ affinity (half-saturation O₂ tension P₅₀=8 mm at 10 °C) and a low O₂ capacity (near 1 vol.%). O₂ affinity is independent of pH but shows a large temperature sensitivity. A major role as a continuous O₂ transporter seems to be excluded.Acknowledgments. A major part of this work was carried out at the Kristineberg Marine Laboratory, Fiskebäckskil (Sweden) and in the Zoophysiology Department, Aarhus Universitet (Denmark).     

Über physiologische,durch einen Gehalt an verschiedenen Alkaloiden charakterisierte Rassen vonSedum acre L

Summary It is shown thatSedum acre L. collected near Darmstadt contains an alkaloid Sedridin C₈H₁₇ON, while in the literature a sample of the plant collected in Canada showed a content of Sedamin (C₁₄H₂₁ON) and Nicotine. The constitution of Sedridin has been proved and its biogenesis is discussed.     

Chemical defense in the three European species ofCrematogaster ants

The composition of the Dufour gland of the antC. scutellaris has been reinvestigated by gas chromatography/mass spectrometry. The major components of the gland are (2E,5E,12Z)-4-oxoheneicosa-2,5,12-trien-1-ol acetate (1a) its ¹⁴ and ¹⁶ double bond isomers (1b and1c), and the corresponding (Z,Z)-dienes5a and5b, all containing an acetylated C₂₁ chain. The previously proposed structures1d, 1e, and5c, which are based on an homologous acetylated C₂₃ chain, correspond to minor derivatives present in the gland. Traces of acetylated C₁₉ homologs, tentatively identified as1g-1i, have also been found. The Dufour gland contents of the two other EuropeanCrematogaster species have also been studied.C. auberti is very similar toC. scutellaris in producing mainly1a, 1b and1c, together with the same higher and lower homologs, but it lacks the dienic derivatives5, whereasC. sordidula contains essentially the acetylated C₁₉ compounds1g, 1h, and1i, accompanied by acetylated C₁₇ homologs.     

Das Prinzip der Äthylogie in der organischen Chemie

Summary The concept of ethylogy is introduced to correlate reactions of compounds of the typea-C-X and those of their ethyloguesa-C-C-C-X,a being a group capable of electron donation andX an electron-accepting leaving group.Besides normal substitution and elimination ofX ina-C -C -C -X, the latter type of compound may undergo cleavage of the C -C bond. This fragmentation produces an olefin in addition to the products also derivable from the simpler compounda-C-X. A number of such fragmentation reactions are reviewed.In the case of-halo amines, there are indications that, depending on structure and stereochemistry, fragmentation can occur by a one-step or two-step process. It is considered likely that the duality and merging of mechanism encountered in simple systemsa-C-X will also prevail in the fragmentation of their ethylogues.     

Zur Biosynthese der C9–10-Einheit der Indolalkaloide

Summary After administration of various C₂-compounds as well as leucine-2-¹⁴C toCatharanthus roseus shoots and glycine-2-¹⁴C toStrychnos nux vomica plants no specific incorporation into the non-tryptophan C_9–10 moiety of indole alkaloids was observed. The results indicate that glycine-2-¹⁴C is transformed into serine and is incorporated via tryptophan into strychnine.     

Photochemical transformations of 6-Amino-penicillanic acid and phenoxymethylpenicillin

Zusammenfassung Bei der Bestrahlung von 6-Aminopenicillansäure mit UV-Licht entstehen Aminomethylpenicillin (Id), N-Formylpenicillamin (II) und ein Stoff der Summenformel C₅H₉NS, der vermutlich Struktur III besitzt. Phenoxymethylpenicillin wird bei der UV-Bestrahlung in ein Gemisch vonp- undo-Hydroxybenzylpenicillin umgewandelt.     

Rauwolfia alkaloids,XVI. Deserpidine,a new alkaloid fromRauwolfia canescens

Zusammenfassung AusRauwolfia canescens wurde Deserpidin, C₃₂H₃₈O₈N₂, isoliert und eine Konstitutionsformel für dieses neue Alkaloid vorgeschlagen.

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Communication XV,C. F. Huebner et al., J.A.C.S. (in press).

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From lecture given at Columbia University, New York, January 12th, 1955.