Zur Stereochemie der Propandioldehydrase-Reaktion

Summary Propanedioldehydrase is shown to convert both (+)-(S)-2-²H-propanediol,3, and (–)-(R)-1-²H₂-propanediol,5, to specimens of deuterated propion-aldehyde, for which the (S)-configuration has been established. Thus, in the propanedioldehydrase reaction migration of hydrogen atoms from C–1 to C–2 always occurs with inversion of configuration.     

Furan fatty acid steryl esters from the marine spongeDictyonella incisa which show inflammatory activity

Summary Three new furan fatty acids, (9Z, 19Z)-3, 6-epoxyhexacosa-3,5,19-tetraenoic acid (1a), (8Z, 11Z, 14Z, 17Z)-3, 6-epoxyeicosa-3,5,8,11,14,17-hexaenoic acid (2a), and (8Z, 11Z, 14Z, 17E)-3, 6-epoxyeicosa-3,5,8,11,14,17-hexaenoic acid (3a), and a new polyunsaturated fatty acid (5Z, 8Z, 11Z, 14Z, 17E)-eicosa-5,8,11,14,17-pentaenoic acid (6a), present in the spongeDictyonella incisa as the respective steryl esters, have been isolated as methyl esters and their structures have been determined by spectral and chemical analysis. The furan fatty acid esters have shown a high inflammatory activity, which suggests their potential role as feeding deterrents.     

On the synthesis of serine and homoserine samples asymmetrically labelled with tritium and deuterium in the hydroxymethylene group

Summary (1 R) [1-³H,²H₁] 3-Phenylpropanol, the key intermediate in the synthesis of (4 R) [4-³H,²H₁] D, L-homoserine and of the (4 S)-isomer, is obtained from (1 S) [1-²H₁] 3-phenylpropanol and (1 RS) [1-³H] ethanol upon incubation with yeast alcohol dehydrogenase and NAD⁺; under similar conditions 2-phenylethanol undergoes very small exchange with [1-²H₂] ethanol.     

Force generation in glycerinated insect-flight muscles without ATP

Zusammenfassung Durch Zugabe und durch Auswaschen von Mg-Pyrophosphat (0,5 mM) oder Mg-Tripoly-Phosphat (1 mM) konnten (in Abwesenheit von ATP) in glyzerinextrahierten Fasern von fibrillären Insektenmuskeln (Lethocerus maximus) reversible Kontraktionszyklen und Änderungen des Dehnungswiderstandes bewirkt werden.

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Supported by Grant No. Ru 154/b of the Deutsche Forschungsgemeinschaft. The excellent technical assistance of Mrs.Helgard Jung is gratefully acknowledged.     

Rassenspezifisches Verhalten gegen einen Raubfeind

Summary German Pied Flycatchers (Ficedula hypoleuca hypoleuca) show a mobbing response to the Redbacked Shrike (Lanius collurio) as well as to owls. Spanish Pied Flycatchers (Ficedula hypoleuca iberiae) mob only at the latter. This correlates well with the fact that only nominatehypoleuca occurs together with the shrike, but both subspecies share their habitats with owls.

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Mit Unterstützung durch die Deutsche Forschungsgemeinschaft.     

Alkyl substituents and the cyclisation of esters

Summary K(CdCl₃) has a structure of the E 2₄-type. In comparison with the isotype (NH₄) (CdCl₃) only two of the three lattice constants have noticeably different values. They area andb which show a contraction of about 2%, whereas the constantc is about the same for both salts.     

Juvenile hormone catabolism inManduca sexta: Homologue selectivity of catabolism and identification of a diol-phosphate conjugate as a major end product

We studied time-dependent metabolism of (10R)-[³H] juvenile hormone (JH) III and (10R, 11S)-[³H]JH I injected intoManduca sexta larvae; the hormones are metabolized to polar metabolites, expecially the JH acid-diol, and an unknown. Products were analyzed using a reversed-phase liquid chromatography assay. (10R)-JH III is metabolized much more rapidly than (10R, 11S)-[³H]JH I, whether injected seperately or as a mixture of hormones. The unknown metabolites of JH I and JH III were identified as phosphate conjugates of JH I and JH III diol by tandem mass spectral analysis of isolated samples. The phosphate conjugate of JH I diol is the principle end product of JH I metabolism.     

Redundant and unique roles of coronin proteins in <Emphasis Type="Italic">Dictyostelium</Emphasis>

Dictyostelium discoideum harbors a short (CRN12) and a long coronin (CRN7) composed of one and two beta-propellers, respectively. They are primarily present in the cell cortex and cells lacking CRN12 (corA ⁻) or CRN7 (corB ⁻) have defects in actin driven processes. We compared the characteristics of a mutant cell line (corA ⁻ /corB ⁻) lacking CRN12 and CRN7 with the single mutants focusing on cytokinesis, phagocytosis, chemotaxis and development. Cytokinesis, uptake of small particles, and developmental defects were not enhanced in the corA ⁻ /corB ⁻ strain as compared to the single mutants, whereas motility and phagocytosis of yeast particles were more severely impaired. It appears that although both proteins affect the same processes they do not act in a redundant manner. Rather, they often act antagonistically, which is in accordance with their proposed roles in the actin cytoskeleton where CRN12 acts in actin disassembly whereas CRN7 stabilizes actin filaments and protects them from disassembly.     

Research Articles¶Naturally occurring 2′-O-methylpurine nucleosides with hypotensive properties

2′-O-Methylinosine (1) has been isolated for the first time and shown to be an intrinsic hypotensive principle. Its probable in vivo precursor, 2′-O-methyladenosine (3), showed stronger and even orally potent hypotensive activity. Resistance of the methyladenosine (3) against adenosine deaminase is thought to contribute to its long-lasting activity. The effect of both nucleosides (1 and 3) was not accompanied with any significant change in heart rate, which is often observed with adenosine. Received 2 October 1997; accepted 28 October 1997     

Die Synthese des Novobiocins

Summary The synthesis of the antibiotic novobiocin is described. First the essential carbohydrate, the 3-O-carbamoylnoviose was synthesized fromd-glucose. A number of steps (1–6) led to the 3,5,6-tri-O-benzyl-2-O-methyl-d-galactono--lactone (6) which is characterized by the correct array of carbon atoms inherent to the noviose. Further transformations (7–15) finally yielded the carbohydrate. The problem of glycosidation is discussed in some detail. Glycosidation of a suitable aglycon precursor (18) with 2,3-O-carbonyl--noviosyl-chloride (22) proved possible and led to the isolation of an-glycoside (23) which was further transformed (24–28) into novobiocin.

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Chemische Forschungsabteilung der F. Hoffmann-La Roche & Co. AG, Basel.

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Vortrag Dr.B. P. Vaterlaus, gehalten an der Gordon Research Conference on Steroids and other Natural Products, 16.–20. Juli 1962, New Hampton, N.H., USA, und vor der Basler Chemischen Gesellschaft, 8. November 1962. Im Auszug:H. Spiegelberg,Synthèse du 3-O-carbamoylnoviose, sucre de la novobiocine, Symposium international de chimie organique, Bruxelles, 15. Juni 1962;J. Kiss,The Synthesis of Noviose and Allied Compounds, Birkbeck College (Univ. London), 23. Oktober 1962. Der vorliegende Aufsatz ist Gegenstand von Detailpublikationen in den Helv. chim. Acta, in Vorbereitung (1963).     

The cell cycle of an established line ofDrosophila melanogaster cells in vitro

Riassunto La durata media delle fasi del ciclo cellulare (G₁, S e G₂) e del tempo di generazione totale (G _T ) in una linea stabilizzata di cellule diDrosophila melanogaster risulta essere rispettivamente di 1.8, 10.0, 7.2 e 18.8 ore.     

On the usefulness of macroeconomic forecasts as inputs to forecasting models

A forecasting model for y_t based on its relationship to exogenous variables (e.g. x?_t) must use x?_t, the forecast of x?_t. An example is given where commercially available x?_t's are sufficiently inaccurate that a univariate model for y_t appears preferable. For a variety of types of models inclusion of an exogenous variable x?_t is shown to worsen the y_t forecasts whenever x?_t must itself be forecast by x?_t and MSE (x?_t) > Var (x?_t). Tests with forecasts from a variety of sources indicate that, with a few notable exceptions, MSE (x?_t) > Var (x?_t) is common for macroeconomic forecasts more than a quarter or two ahead. Thus, either:

• (a) available medium range forecasts for many macroeconomic variables (e.g. the GNP growth rate) are not an improvement over the sample mean (so that such variables are not useful explanatory variables in forecasting models), and/or
• (b) the suboptimization involved in directly replacing x?_t by x?_t is a luxury that we cannot afford.

     

ZNS-aktive Phenylpropylamine vonCatha edulis FORSK. (Celastraceae) kenyanischer Herkunft

Summary The phenylpropylamine fraction ofCatha edulis FORSK. grown in Kenya has been investigated. The major components have been found to be (S)-(–)--aminopropiophenone (1), (+)-norpseudoephedrine (2) and(–)-norephedrine (3). Quantitative ratios of1, 2, 3 in tissues of different age are discussed.

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ZNS-aktive Phenylpropylamine vonCatha edulis FORSK. (Celastraceae) kenyanischer Herkunft

     

Observations on two types of protein granules in primate and avian parathyroid cells

Zusammenfassung In Parenchymzellen der Epithelkörperchen von Affen (Macaca cyclopis) und Wachteln (Coturnix coturnix japonica) lassen sich zwei Typen von Proteingranula histochemisch unterscheiden. Die cytophysiologische Wertung dieser Granula wurde diskutiert.     

Zonaroic acid from the brown seaweedDictyopteris undulata (=zonarioides)

Summary A sesquiterpene-substituted 4-hydroxybenzoic acid, zonaroic acid (5), is described from the brown seaweedDictyopteris undulata (=zonarioides). The absolute stereochemistry in the zonarol (1)-chromazonarol (2) and zonaroic acid (5) series has also been defined. The occurrence of5 along with zonarol (1), the corresponding sesquiterpene-substituted hydroquinone, suggests that 4-hydroxybenzoic acid is the ring precursor as in ubiquinone biogenesis.     

Antimutagenic unusual amino acids from plants

Summary Five unusual amino acids were identified as antimutagens against spontaneous mutation ofSalmonella typhimurium TA100: L-azetidine-2-carboxylic acid (1) from Liliaceae plants, -(methylenecyclopropyl)glycine (2) fromLitchi chinensis seeds, and 2-amino-4-methylhex-5-ynoic acid (3), hypoglycin A (4), and (2S, 4R)-2-amino-4-hydroxyhept-6-ynoic acid (5) fromEuphoria longana seeds. The absolute stereochemistry of5 was determined by its chiral synthesis from L-allylglycine, proving that5 is the C-4 epimer of the amino acid previously isolated from dried longan seeds.This work was partly supported by a Grant-in-Aid form the Ministry of Education, Science, and Culture, Japan, No. 57740283 (to HK).     

Defensive secretions of Nematinae larvae (Symphyta - Tenthredinidae)

Summary The composition of the defensive secretion of larvae of 8 Nematinae species is reported. 7 derivatives have been identified: benzaldehyde, (E)-2-hexenol, (E)-2-hexenal, (E)-4-oxo-2-hexenal, geranial, neral andcis, trans-dolichodial.Maître de recherches du Fonds National de la Recherche Scientifique.We gratefully acknowledge the Fonds National de la Recherche Scientifique for financial support. We express our sincere thanks to Professor B. Zwanenburg and Dr J. M. J. Verlaak for helpful suggestions.     

Total synthesis of oestrogenic hormones

Zusammenfassung Die Totalsynthesen von (±)-Östron, (±)-d-homo-Equilenin-methyläther und (±)-iso-Equilenin werden beschrieben.

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Acknowledgments. We thank the Department of Scientific and Industrial Research for the award of maintenance grants.     

Pheromone components of the female elephant hawk-moth,Deilephila elpenor,and the silver-striped hawk-moth,Hippotion celerio

By means of gas chromatographic and mass spectroscopic methods, and combined GC-electroantennogram and electrosensillogram techniques, (E)-11-hexadecenal and (10E, 12E)-10,12-hexadecadienal [(E,E)-bombykal is also the main constituent of the pheromone of the silver-striped hawk-mothHippotion celerio. The biological activity of the substances was demonstrated with electroantennogram and single cell recording, and the physiological efficacy of the different hexadecadienal isomers compared.Pheromones, 79; as Pheromones, 78 is taken: Wu, Cai-Hong, and Bestmann, H. J., Chinese Science Bulletin34 (1989) 1475; pheromones, 77: Attygalle, A. B., Steghaus0Kovac, S., Ahmed, V. U., Maschwitz, U., Vostrowsky, Ol, and Bestmann, H. J., Naturwissen-schaften78 (1991) 90.     

The effect of perchlorate ion and some pharmacological agents on the sensitivity of the frog (Rana pipiens) rectus abdominis to acetylcholine

Zusammenfassung Die Reaktion des mit Eserin vorbehandelten musculus rectus abdominis des Frosches auf Acetylcholin liess sich durch Oxotremorin (2.0·10^–5 M), Arecolin (2.0·10^–5M), Aceclidin (1.0·10^–4 M) und Carbachol (2.0·10^–7 M) verstärken, während Atropin (1.0·10^–5 M) hemmend wirkte. Perchlorationen in Konzentrationen über 2 · 10^–4 M sensibilisierten den Froschmuskel erheblich und reduzierten die Grenzdosis, bei der eine Potenzierung durch Substanzen mit muskarinähnlicher Wirkung beobachtet wird. Alle beschriebenen Reaktionen liessen sich durch Gehirnextrakte verstärken, in denen zuvor Acetylcholin durch Kochen in alkalischer Lösung zerstört worden war.

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This work was supported by NIH Grants No. NB 03007 and No. 5-F1-GM-22,905.