Über Struktur und Aktivität der den H2O2-Zerfall katalysierenden Cu2+-Komplexe. — VI. Differenzierung von nativer RNS und nativer DNS bzw. denaturierter DNS auf Grund der katalytischen Eigenschaften

Summary The catalysis of H₂O₂ decomposition by Cu²⁺-complexes of RNA and DNA has been investigated. It is shown that both complexes decompose H₂O₂, but only the Cu²⁺-RNA-system shows peroxidative activity too, e.g. only in this case the nucleotide bases are degraded. Thermal denaturation of DNA also leads to a Cu²⁺-complex with peroxidative activity, the latter being dependent on the degree of denaturation.

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V. Mitteilung:S. Petri, H. Sigel undH. Erlenmeyer, Helv. chim. Acta49, 1778 (1966).

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12. Mitteilung überMetallionen und H ₂ O ₂; 11. Mitteilung:H. Ch. Curtius, P. Anders, R. Zell, H. Sigel undH. Erlenmeyer, Helv. chim. Acta49, 2256 (1966).     

Regulation ofL-valine absorption by opioids interacting withμ-receptors in rabbit ileum

In intact tissue, [d-Ala²,MePhe⁴, Gly-ol⁵] enkephalin (10^–5 M;-ligand), diminsihed short-circuit current (I_sc) and increased water, Na⁺ and Cl^– net fluxes in vitro under open circuit conditions; it also inhibitedL-valine absorption andL-valine-dependent variations of short-circuit current (I_{sc, val}). Naloxone (10^–6 M) antagonized these effects. In the absence of the muscularis and myenteric plexus this enkephalin or morphine (-ligand) reduced I_sc and I_{sc, val}. These enkephalin effects occurred at different times. Different concentrations of enkephalin were tested for their effects on I_{sc, val}. [d-Ala²,d-Leu⁵] enkephalin (mainly a -ligand) significantly decreased I_sc but not I_{sc, val}. The reduction ofL-valine absorption does not depend on the effects on basal ion transport. Interaction of opioids with-receptors located in the submucosal plexus and/or in the epithelial cell accounts for this reduction. This enkephalin effect seems to be at least partially under the control of the myenteric plexus.     

Glucocorticoids suppress cystathionine gamma-lyase expression and H2S production in lipopolysaccharide-treated macrophages

Hydrogen sulfide (H₂S) plays an important role in inflammation. We showed that macrophages expressed the H₂S-forming enzyme cystathionine gamma-lyase (CSE) and produced H₂S. Lipopolysaccharide (LPS) stimulated the CSE expression and H₂S production rate. l-cysteine reduced LPS-induced nitric oxide (NO) production. CSE inhibitor blocked the inhibitory effect of l-cysteine. CSE knockdown increased, whereas CSE overexpression decreased LPS-induced NO production. Dexamethasone suppressed LPS-induced CSE expression and the H₂S production rate as well as NO production. l-arginine increased, whereas N^G-nitro-l-arginine methyl ester (l-NAME) decreased LPS-induced CSE expression and H₂S production. Dexamethasone plus l-NAME significantly decreased LPS-induced CSE expression and H₂S production compared to l-NAME. Our results suggest that macrophages are one of the H₂S producing sources. H₂S might exert anti-inflammatory effects by inhibiting NO production. Dexamethasone may directly inhibit CSE expression and H₂S production, besides the NO-dependent way. Inhibition of H₂S and NO production may be a mechanism by which glucocorticoids coordinate the balance between pro- and anti-inflammatory mediators during inflammation.     

Antagonism of prostaglandin-induced cyclic AMP accumulation in the rat anterior pituitary in vitro by somatostatin analogues

Summary The PGE₂-induced cyclic AMP accumulation in the rat anterior pituitary in vitro is inhibited by [desamino¹]-, [desamino¹] [descarboxy¹⁴] and [d-Lys⁴]-somatostatin similarly to somatostatin, while the [descarboxy¹⁴]-somatostatin exhibits reduced activity; [d-Lys⁹]-somatostatin is ineffective at a higher concentration.The authors acknowledge the technical assistance ofG. Alexander. F. Bellini, D. Mangerel andJ. Rochon and thank Dr.G. Schilling and his associates for the analytical data.     

Incorporation of [14C] amino acids into liver S-RNA of chick. Effect of orotic acid and vitamin B12

Riassunto La somministrazione dietetica di vitamina B₁₂ e di acido orotico determina un aumento della incorporazione dellal-serina C¹⁴ nello RNA solubile del fegato di pulcino carente di B₁₂, mentre non è in grado di influenzare quella dellal-leucina¹⁴C e dellal-metionina¹⁴C.     

Radical yields in X-irradiated aqueous solutions

Résumé La valeur deGh+Goh peut être obtenue en utilisant des solutions aqueuses de certains composés organiques contenant Cu²⁺ et/ou Fe³⁺. Les ions métalliques sont réduits par H et par les radicaux produits par l'oxydation des composés organiques par OH. A concentration convenable des réactifs, on a;G _Fe ²⁺ =G _H+G _OH.     

Obtention d'un dérivé du sclaréol à partir de l'ambréine

Summary One of the products of the chromic acid oxidation of the animal triterpene ambreine (V) has been identified with the lactone C₁₆H₂₆O₂ (III) whichRuzicka and coll. had isolated by oxidation of the plant diterpene sclareol (II). This identification confirms recent findings of the authors and ofRuzicka, Dürst andJeger and shows that the hydroxyle of ambreine (V) is at the same place as the hydroxyle of sclareol which is attached to the perhydronaphtalene ring.

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4^me communication sur les constituants de l'ambre gris     

Zur Biogenese des Xanthocillins,II1: Die Herkunft des Stickstoffs der Isonitril-Gruppen

Summary The incorporation of tyrosine-2-¹⁴C-¹⁵N into xanthocillin X (I) byPenicillium notatum Westling has been investigated showing that nitrogen of the isocyano groups originates from tyrosine, which is incorporated as C₆-C₂-N-unit.

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1. Mitteilung:H. Achenbach undH. Grisebach, Z. Naturforsch.20b, 137 (1965).     

Sur l'action de l'acide 2,4-dichlorophénoxyacétique sur la croissance des racines deZea mays et dePisum cultivéesin vitro

Summary (1) A response ofZea mays andPisum roots cultured aseptically to 2,4-dichlorophenoxyacetic acid has been observed.Depending on the concentrationZea mays shows an increase of the growth rate (optimal concentration 10^–11 mol) which turns over to an inhibition (above 10^–7 mol). The curve is similar to that obtained by 3-indoleacetic acid, which proves the phytohormonal character of 2,4-D.(2) ThePisum root is more sensitive than theZea mays root. A concentration of 10^–7 molinhibitsPisum in a high degree, whileZea mays is no more inhibited, thus demonstrating the selective herbicidal action of 2,4-D against isolated roots of Dicotyledons culturedin vitro.     

Die Einlagerung von radioaktivem Schwefel in die Flügel von Acrididen nach Applikation von35S-Natriumsulfat-und35S-l-Cystinlösungen

Summary Psophus stridulus L. andOedipoda coerulescens L. were fed or injected with solutions of Na ₂ ³⁵ SO₄ and³⁵S-l-cystine. The radioactive radiation pattern of the wings was found to depend on the time of application. Differences in radiation intensity were found to correspond to the red, blue and dark areas.     

Dissociation-constants of metal-ion-complexes with alkaline phosphatase from pig kidney

Summary Using metal-ion buffers it was possible to remove Zn²⁺, Mg²⁺ and Mn²⁺ ions of pig kidney alkaline phosphatase reversibly. The dissociation constants obtained are K_EMg:4·10^–7 M, K_EMn:4·10^–8 M and K_EZn:8·10^–13 M (22°C, pH:9.6, :0.07).Acknowledgement: The authors thank Dr.H. U. Wolf for helpful suggestions and valuable discussion and MissH. Köth for technical assistance.     

Amperometric studies on chromium (III) and iron (III) hydroxocyanotungstates (IV)

Zusammenfassung Die Zusammensetzung von in wässeriger Lösung gebildeten Ionenpaaren des Anions [W(CN)₄(OH)₄]^4- mit Cr³⁺ bzw. Fe³⁺ wird amperometrisch ermittelt.

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Acknowledgment. The authors are grateful to Dr.S. M. F. Rahman for providing necessary facilities and C.S.I.R. (India) for awarding a Junior Fellowship to one of them (K. U.).     

Der Einfluss von 2-Deoxy-D-glucose auf die Substratoxydation in Ascites-Tumorzellen

Summary The effect of the glycolytic inhibitor 2-deoxy-D-glucose on the oxidation of¹⁴C-labelled substrates of the tricarboxylic acid cycle was investigated in ascites carcinoma cells of the mouse. In the presence of high concentrations of glucose, deoxyglucose stimulates the oxidation of pyruvate C-2 and C-3 to CO₂, but not the oxidation of succinate C-1,4 to CO₂. While deoxyglucose causes, in the absence of glucose, an inhibition of the oxidation of exogenous palmitate C-1 to CO₂, it causes, in the presence of glucose, a stimulation of the palmitate oxidation. There is a possible correlation between the effect of deoxyglucose on the intracellular ATP metabolism and the effect of deoxyglucose on the palmitate oxidation.     

Isomériecis-trans des ménaquinones et oxydations phosphorylantes dans les extraits deMycobacterium phlei

Summary Incubation ofM. phlei washed cells with [¹⁴C³H₃]-l-methionine led to [2-¹⁴C³H₃] dihydromena-quinone-9 with an isotope ratio identical to that of methionine. Chromatography of the doubly labelled quinone indicated, despite a pronounced isotope effect, that bothcis andtrans isomers had the same isotope ratio. This result eliminates any possibility of hydrogen exchange in the 2-methyl group of menaquinones during oxydative phosphorylation, even in thecis isomer. Furthermore, it is confirmed that this compound is certainly formed from natural or synthetic menaquinones during isolation or incubation periods by the effect of daylight irradiation.     

Zur Kenntnis des Muscarins

Summary The alkaloid muscarin was isolated from fly agaric. The analyses of crystallized salts (chloride, tetra-chloroaurate,Reinecke's salt) led to C₉H₂₀O₂N⁺ as the simplest formula. The presence of aldehyde and tri-methyl-ammonium groups, which had been assumed hitherto, could not be proved. The quaternary nature of the nitrogen atom was shown. Pharmacological tests on frog heart, rabbit gut and cats show the purely peripheral parasympathomimetic effect of the smallest doses.     

The photosynthetic energy conversion process in isolated chloroplasts

Zusammenfassung Dieser kurze Überblick über das Gebiet der Photosynthese in isolierten Chloroplasten wäre unvollständig, würde nicht die Abhängigkeit des erzielten Fortschrittes von mindestens zwei «verbesserten analytischen Methoden» betont, welcheEmil Fischers ¹ 60 Jahre zurückliegende Prophezeiung erfüllen. Zur Entdeckung der Photophosphorylierung und der Kohlenhydratsynthese durch isolierte Chloroplasten war die Einführung der Isotopen-Technik in die Biologie durchvon Hevesy ¹⁰⁷ und die Entwicklung der Papierchromatographie durchMartin undSynge ¹⁰⁸ von besonderer Bedeutung.Untersuchungen an isolierten Chloroplasten führten zu einer Auffassung der Photosynthese, die sich von der herkömmlichen Ansicht — als eines CO₂-Assimilationsprozesses — unterscheidet: Die Photosynthese scheint im wesentlichen ein Prozess zur Umwandlung der Strahlungsenergie des Sonnenlichtes in chemische Energie zu sein. Diese Umwandlung steht in engerer Beziehung zur Phosphorassimilation und zur Reduktion des Eisenproteids Ferredoxin als zur Kohlensäureassimilation. Die ersten, chemisch definierten Produkte dieser Energieumwandlungsreaktion in der Photosynthese erwiesen sich nicht als Zwischenprodukte der Kohlenstoffassimilation, sondern als ATP und reduziertes Ferredoxin.

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Based, in part, on a paper presented at the Advanced Study Institute on the Biochemistry of the Chloroplasts, Aberystwyth, Wales, U.K., August 26, 1965. — The research work from the author's laboratory reported herein has been aided by grants from the National Institutes of Health, Office of Naval Research and the Charles F. Kettering Foundation.     

Inhibition of tyrosine degradation in vivo by the dopa decarboxylase blocking agent NSD-1034

Zusammenfassung Der Stoffwechsel von H ₃ ² -3, 5-l-Tyrosin wurde in mit NSD-1034 (100 mg/kg) vorbehandelten Versuchstieren (Hähnchen, katzen) untersucht. Als Folge des durch NSD-1034 stark gehemmten Abbaus entstanden während der Versuchszeit (ca. 20 min) nahezu kein Tritiumwasser und keine aromatischen Abbauprodukte. Auch die sonst zu beobachtenden radioaktiven Metabolite des H³-Tyrosins (Glutamin- und Asparaginsäure, Dopamin und Noradrenalin) waren nicht nachweisbar. Ausserdem war der Gehalt an H³-Tyrosin in Organen behandelter Tiere höher als in Kontrollen.     

Über Peptidsynthesen,XLIV. Synthese von Ser4-Glu(NH2)8-Oxytocin (Glumitocin)

Summary Ser⁴-Glu(NH₂)⁸-Oxytocin has been synthesized. The identity of the synthetic compound with the neurohypophysal hormone (Glumitocin) recently isolated from species of cartilaginous is demonstrated.

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Über Peptidsynthesen XLIII. Mitteilung,E. Klieger, Experientia23, 620 (1967).     

Development of the eggs ofPhallusia mammillata in sea-water devoid of sulphate ions

Riassunto Viene studiato lo sviluppo diPhallusia mammillata in acqua di mare priva di ioni SO ₄ ⁼ . Le anomalie riscontrate a carico della larva riguardano principalmente il sistema muscolare della coda. Viene discusso il probabile ruolo esplicato dagli ioni SO ₄ ⁼ nel corso dello sviluppo.

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We are very much obliged to the Director, Dr.Peter Dohrn and to the staff of the Stazione for effective support and help in our work.     

Formation of 4-ketocyclophosphamide by the oxidation of cyclophosphamide with KMnO4

Zusammenfassung Oxydation des (³²P) Cyclophosphamides durch KMnO₄ in Wasser oder Aceton führt zu 4-Ketocyclophosphamid und einem N-dechloroäthylierten Derivat des Cyclophosphamides, beides bekannte Metaboliten der Droge. Die Auftrennung der Produkte gelingt durch Dünnschichtchromatographie und die Richtigkeit der Strukturen wurde durch Massenspectrometrie nachgewiesen.

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Acknowledgments. This investigation was supported by grants to the Chester Beatty Research Institute (Institute of Cancer Research: Royal Cancer Hospital) from the Medical Research Council and Cancer Research Campaign. The A.E.I. MS-12 mass spectrometer was purchased on a special grant No. G969/189/C from the Medical Research Council. The work was carried out partly during the tenure of a Ludwig Fellowship awarded by Cancer Research Institute. The interest of ProfessorA. B. Foster and Dr.T. A. Connors in this work, and the skilled technical assistance of Mr.M. H. Baker, are gratefully acknowledged.