Corpuscular diagnostics of a hollow-cathode discharge-III. The metal-ions-regime evolution

The variations in time of mass spectra of ions, extracted from the hollow-cathode discharge in the regime of the intensive sputtering of the cathode material were measured. The mass spectrum changes in time conspicuously. From the results of measurements a distinct anisotropy of ion beam is inferred. The discharge turns into a metal-ions regime.The helpful discussions with Dr. J. Musil are gratefully acknowledged.     

The small momentum transfer k L o C→K S 0 C regeneration at high energies

Results of the first elastic K _S ^o regeneration experiment on carbon, using magnetic spark chamber spectrometer, are presented in the beam momentum interval 10p50 GeV/c. The d ifferentia cross section d/dt is reconstructed in the range 0·0025–t0·02 (GeV/c)² and its slopeB is found to be momentum independent with an average valueB=(65±11) (GeV/c)^–2. The results are in agreement with the calculations using the coherent production model.     

Magnetic moments and the high field susceptibilities of MnFe2O4

An extended version of the noncollinear spin model bySawatzky et al. is developed to derive a dependence of the differential high field susceptibility on the degree of inversion of the ferrite MnFe₂O₄. Using the available data on the main molecular field coefficients it is shown that the present model imposes restrictions on values of. Determination of from the measurements of the field dependence of the saturated moments at low temperatures on samples with varying degrees of inversion reveals good quantitative agreement with the present model.     

Studies on bis(3,5-di-t-butyl-1,2-benzoquinone 1-oximato)manganese(II) and its mixed-ligand complexes

The synthesis, spectroscopy, and redox-reactivity towards PPh(3) of bis(3,5-di-t-butyl-1,2-benzoquinone 1-oximato)manganese(II), Mn(ox)(2), and its mixed-ligand complexes, Mn(ox)L(x) [L(x)=8-hydroxyquinolinato (L(1)), 2,2'-bipyridine (bpy) (L(2)), 1,10-Phenanthroline (phen) (L(3)) and N-(2-hydroxyphenyl)-3,5-di-t-butylsalicylaldiminato (L(4))] complexes, are presented. While some complexes exhibit solid-state ESR spectra they were ESR-silent in toluene or CHCl(3) at 300 K. The reduction of all ESR-silent complexes with an excess of PPh(3), independently from the nature of secondary L(x) ligands, results in the appearance of a six-line hyperfine coupling of 55Mn (I=5/2) (A(Mn)=95-100 G) and a seven-line radical signal, which was assigned to phosphiniminophenoxyl type radicals (g=2.0056-2.0075, A(P)=8. 5 G and A(N)=1.875 G).     

Bestimmung von C-Methylgruppen in organischen Sauerstoffverbindungen durch Oxydation mit Chromsäure unter optimalen Bedingungen. I

Zusammenfassung Eine Reihe sauerstoffhaltiger Modellsubstanzen, die Methylgruppen am primären, sekundären oder doppelt gebundenen Kohlenstoffatom enthalten, wurden mit einem Gemisch von 2 T. 5-n Chromsäure und 1 T. konz. Schwefelsäure 45 Minuten bei 130° C oxydiert. Die entstandene Essigsäure wurde mit Wasserdampf abdestilliert und alkalimetrisch titriert. Die angeführten Reaktionsbedingungen können als optimal angesehen werden, da sie die größte oxydative Wirkung haben, bei der jedoch Essigsäure nicht weiter oxydiert wird. Der Abbau des Kohlenstoffskeletts verläuft schneller und vollständiger als bei der Methode vonKuhn undRoth. Die Essigsäureausbeute lag zwischen 0,70 und 0,95 Mol Essigsäure je C-Methylgruppe und wurde in Abhängigkeit von der Struktur der untersuchten Stoffe diskutiert.

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Determination of C-methyl groups in organic oxygen compounds through oxidation with chromic acid under optimal conditions

Summary A number of oxygen-containing model substances, which contained methyl groups on primary, secondary or doubly bound carbon atoms, were oxidized with a mixture of 2 parts of 5N chromic acid and 1 part of conc. sulfuric acid for 45 minutes ar 130° C. The resulting acetic acid was distilled off with steam and titrated alkametrically. The cited reaction conditions may be regarded as optimal, because they exert the greatest oxidative action, which however the acetic acid is not further oxidized. The degradation of the carbon skeleton proceeds faster and more completely than in the method ofKuhn andRoth. The yield of acetic acid lay between 0.70 and 0.95 mol acetic acid per C-methyl group and was discussed with respect to the structure of the investigated material.

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In dieser Mitteilung ist der erste Teil der Dissertationsarbeit von Frau Dipl.-Ing.B. Voláková inbegriffen.     

Extraction of Am(III) in the presence of lanthanides and yttrium by benzyldimethyldodecylammonium nitrate from acidic nitrate solutions

We have investigated the effect of coextraction of lanthanides and yttrium on the distribution coefficients D_Am in the extraction of americium by benzyldimethyldodecylammonium nitrate (BDMLNNO₃) from nitrate solutions. In the coextraction of lanthanides, the extraction of Am(NO₃)₃ is suppressed, which is markedly manifested in the extraction of light lanthanides (La, Ce, Pr); of the series of lanthanides their extraction is the highest. The effect of nitric acid and the possibility of separation of lanthanides and americium by the application of three-stage multiple extraction is discussed.     

Simultaneous determination of neodymium, erbium and holmium in rare earth mixtures with 2-phenyltrifluoroacetone and octylphenol poly(ethyleneglycol) ether by third-derivative spectrophotometry

The complexes of the rare earth metals with 2-phenyltrifluoroacetone in the presence of TX-100 are reported. The characteristic absorbances of neodymium, holmium and erbium complexes can be increased by factors of 8.5, 31 and 15 respectively, compared to those of the cholrides. The third-derivative spectra have been used to eliminate the interference of cerium, and the sensitivities are increased again by factors of 7.4, 5.5 and 6.5. A method for the direct determination of neodymium, erbium and holmium in rare earth mixtures is proposed.     

Distribution of fallout radionuclides through soil surface layer

The distribution of¹³⁷Cs through soil layers has been investigated by field sampling. The investigation deals with¹³⁷Cs concentration found after the Chernobyl accident. The relationship between important soil characteristics, total precipitation and cesium distribution are analyzed. Cesium is strongly sorbed in the top soil layer and its migration downward is limited. Measurements performed over a 3-year period revealed that approximately 20–38 per cent of total¹³⁷Cs is located in the upper soil layer.     

Preparation and stereoselectivity of 1,3-dipolar cycloaddition ofD-glucose-derived nitrones to N-arylmaleimides

Summary Nitrones2 derived fromD-glucose oxime and benzaldehydes without employing any protection of hydroxyl group were isolated in pure state. The 1,3-dipolar cycloaddition of2 to N-arylmaleimides gave predominantly theanti isoxazolidines3 and was rationalized byZ/E isomerization of N-glycosylnitrones2. The structure and steric configuration of the products have been assigned on the basis of¹H- and¹³C-NMR spectroscopy. AM1 calculations of the nitrones and MM2 calculations of the adducts were performed.

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Darstellung und Stereoselektivität der 1,3-dipolaren Cycloaddition vonD-Glucose-abgeleiteten Nitronen an N-Arylmaleimiden

Zusammenfassung Die Nitrone2 wurden ausD-Glucoseoxim und Benzaldehyden ohne Schutz von Hydroxylgruppen in reinem Zustand erhalten. Die 1,3-dipolare Cycloaddition von2 an N-Arylmaleimiden ergab bevorzugt dieanti-Isoxazolidine3; dies wurde über eineZ/E-Isomerisierung der N-Glycosylnitrone2 rationalisiert. Struktur und Stereochemie wurden auf Basis von¹H- und¹³C-NMR-Spektroskopie ermittelt. Außerdem wurden AM1-Berechnungen an den Nitronen und MM2-Rechnungen an den Addukten ausgeführt.

     

Synthesis and Conformational Analysis of the Multidrug Resistance-Reversing Agent Hapalosin and Its Non-N-methyl Analog

Hapalosin was initially synthesized by macrolactonization, and a second synthesis was achieved by cycloamidation. In both syntheses, three of the five stereocenters in hapalosin were established by two Brown allylboration reactions. The synthesis of the non-N-Me analog of hapalosin involved chelation-controlled reduction of a gamma-amino-beta-keto ester and cycloamidation. In CDCl(3) at 25 degrees C, synthetic hapalosin exists as a 2.3:1 mixture of conformers, while its non-N-Me analog exists only as a single conformer. (1)H,(1)H-NOESY and computation reveal that the configuration of the amide bond is responsible for the conformations of the two compounds. The major conformer of hapalosin is found to be an s-cis amide, the minor conformer an s-trans amide, and the non-N-Me analog an s-trans amide. Applying distance constraints to protons that exhibit NOESY correlations, computation shows that the major conformer of hapalosin and the non-N-Me analog have very different conformations. By contrast, the minor conformer of hapalosin and the non-N-Me analog have very similar conformations.