Microdynamics of solid anilinium chloride

Intraionic C₃ reorientation of the anilinium NH⁺₃ group was evidenced by measurements of the temperature dependence of the proton spin—lattice relaxation time, by rotating frame experiments and cw NMR data. Analysis of the results yielded a rotor hindering potential E = 33.6 kJ/mole and τ_o = 4 × 10⁻¹³ s.     

Analysis of aerosols at the bosporus bridge of Istanbul

Air samples collected at the second Bosporus bridge of Istanbul which carries a heavy traffic load between Asia and Europe, were analyzed for 22 elements by the INAA method. Pb, Cd and Fe concentrations in the samples were determined by AAS. Iron concentrations were used as a cross check between the two methods. In order to define the enrichment factors for the elements in the bridge area, a sample collected from our university campus which can be considered as a rural site, was also analyzed. Differences were observed especially for Br, Al, Mg, Ti, Cu and Na between the two sites. Based on the results of the samples from the bridge, we got a value of 0.58(16) for the Br/Pb-ratio.     

Freie Elektronenpaare in lokalisierten CNDO/2-Wellenfunktionen der Stickstoffverbindungen

The method for constructing hybrid orbitals described earlier is now used for the analysis of CNDO/2 wave functions of molecules containing nitrogen atoms in order to get information on the type of hybridization of nitrogen lone pair orbitals in various compounds.     

On the construction of least favourable pairs of distributions

Summary Convex programming techniques were used by Witting and Krafft in [4] in order to reduce a testing problem for composite hypotheses to one for simple hypotheses. This is realized in terms of least favourable pairs of distributions, which represent the solution of the dual of a suitable program. Without further assumptions on the hypotheses, however, the results, derived that way (cf. Baumann [1], Österreicher [6] and Kusolitsch and Österreicher [5]), are of less practical impact. This is due to the fact that in this case the least favourable pairs depend on the level of the testing problem. Conditions avoiding this, were given by Huber and Strassen in [3]. These conditions make use of 2-alternating capacities in the sense of Choquet. The present paper offers a rather general principle of constructing the least favourable distribution in the case, when one of the two hypotheses is simple. This method works also for the local variation model and the Prohorov neighbourhood model in the case of monotone likelyhood ratio. For simple cases—subsuming the gross error model and the total variation model, for which the solution was given by Huber in [2]—a least favourable pair is obtained by using the mentioned technique of construction two times successively.     

Mechanism of hydrogenolysis and isomerization of oxacyloalkanes on metals, V. Selectivities of metal catalysts in ring-opening reactions of oxiranes

The deoxygenation of methyloxirane to propene and its isomerization to oxo compounds on a Ni/SiO₂ catalyst were studied in a pulse microreactor, in the presence of H₂ as carrier gas, at 473 K. It was found that the deoxigenation leads to the creation of new types of active centers (Lewis acid site-basic site), which cause a change in the direction of ring opening. The differences in regioselectivity observed between Ni and Cu, and Pt and Pd, can be explained by the different affinities of the metals for oxygen. This finding can be generalized to other oxygen-containing compounds.

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=qa Ni/SiO₂ 473 . , - - , . Ni Cu, Pt Pd . .

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Part IV: J. Catal. (to be published)     

Temperature effects in the oxidation of aliphatic ketones by solutions of thallic sulfate

The oxidation of aliphatic ketones by thallium(III) sulfate in aqueous medium has been studied from the point of view of the temperature effect and the enthalpy-entropy relationship. It has been found that the isokinetic relationship is fulfilled in this case.

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(III) - . , .

     

Analytische Aspekte der Oxydation organischer Stickstoffverbindungen mit Chromsäure. II

Zusammenfassung Eine Halbmikromethode zur Bestimmung der an Kohlenstoff oder Sauerstoff gebundenen Nitro- und Nitrosogruppen in organischen Verbindungen wurde ausgearbeitet. Die Methode beruht auf dem oxydativen Aufschluß der Substanz mit einem Chromsäure—Schwefelsäure-Gemisch, wobei die Nitro- und Nitrosogruppen quantitativ in Salpetersäure übergehen. Diese wird mit Devarda-Legierung in alkalischem Medium zu Ammoniak reduziert, das dann im Stickstoffstrom abdestilliert und acidimetrisch titriert wird.

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Summary A semimicro method for determining nitro- and nitroso groups attached to carbon or oxygen in organic compounds has been worked out. The method is based on the oxidative decomposition of the sample with a chromic acid-sulfuric acid mixture, the nitro and the nitroso groups being quantitatively transformed into nitric acid. The latter is reduced to ammonia by means of Devarda alloy in alkaline medium, and is then distilled off in a stream of nitrogen and titrated with a standard acid solution.

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Résumé On a mis au point une méthode à l'échelle semimicro pour le dosage dans les substances organiques de groupes nitro et nitroso liés au carbone ou à l'oxygène. La méthode repose sur l'attaque oxydante de la substance par un mélange acide chromique-acide sulfurique, ce qui transforme quantitativement les groupes nitro et nitroso en acide nitrique. Au moyen de l'alliage de Devarda en milieu alcalin, on réduit celui-ci en ammoniac que l'on chasse par distillation dans un courant d'azote et que l'on titre par acidimétrie.

     

Glycoprotein synthesis as a function of epithelial cell arrangement: biosynthesis and release of glycoproteins by human breast and prostate cells in organ culture.

We demonstrate that a technique is available to investigate glycoprotein synthesis in organ cultures of human breast and prostate surgical specimens where the 3-dimensional epithelial cell arrangement remains intact. Malignant breast and prostate epithelium maintained their capacity to synthesize glycoproteins for at least 3 days as followed by the incorporation of [3H]glucosamine into macromolecules. Over 70% of incorporation was by malignant cells as judged by autoradiography. Labeled glycoproteins were released into glandular lumina and consequently into the culture fluid. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis revealed predominantly one group of macrmolecules released with an apparent molecular weight of 48,000 +/- 6,000 daltons. This glycoprotein was found in all of the breast specimens studied, which included 1 medullary, 1 infiltrating lobular, and 8 infiltrating duct carcinomas. The pattern was independent of the availability of estrogen receptors. A similar glycoprotein was also observed in the culture media from a Grade I and a Grade II well-differentiated infiltrating prostate carcinoma. Incorporation was below the level of detection in 4 of 6 cases of benign prostatic hyperplasia. A more complex pattern of labeled glycoproteins was found in the media of a Grade II and a Grade III poorly-differentiated prostate carcinoma. The established human mammary carcinoma cell line MCF-7 synthesized and released a similar 48,000 molecular weight glycoprotein but additional components with larger molecular weights were also released. An intriguing interpretation that 3-dimensional tissue integrity restricts some glycoprotein synthesis is discussed. Cells grown in 2-dimensional monolayers could escape from such a topographic restriction and express additional families of glycoproteins.     

Transfer reaction of the polystyrene radical with electron-acceptor molecules of tetrachlorophthalanhydride

The transfer constants (C_s) of the polystyrene radical with some derivatives of phthalic acid have been determined. Among the agents used, tetrachlorophthalanhydride (TCPA) differs distinctly from other compounds by its value of C_s 3·1 × 10^?3 for thermal and 3·4 × 10^?3 for initiated polymerization of styrene. The values of C_s for phthalanhydride, dimethyl phthalate, and tetrachlorodimethyl phthalate are lower by two decimal orders. The considerable decrease in the degree of polymerization of styrene prepared in the presence of TCPA is mainly attributed to the increased reactivity of chlorine atoms in TCPA induced by the acceptor effect of anhydride ring. Participation of a TCPA-styrene complex in transfer reaction has been assumed but not proved.