Palladium-tetraphosphine complex: an efficient catalyst for the coupling of aryl halides with alkynes

The cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)-cyclopentane-[PdCl(eta3-C3H5)]2 system catalyses the coupling of aryl halides with alkynes with very high ratios of substrates-catalyst in good yields; a turnover number of 2600000 can be obtained for the reaction of 4-trifluoromethylbromobenzene with phenylacetylene in the presence of this catalyst.     

Lanthanum-based perovskites obtained in molten nitrates or nitrites

Lanthanum-based perovskites, LaMO₃ (where M = Mn, Fe, Co, Ni), have been synthesised from lanthanum precursors and corresponding 3d transition metal salts in molten alkali metal nitrates or nitrites. The reactivity of eight precursors in three molten salts of different basicity was analysed. Single phase orthorhombic LaMnO_3.11, and orthorhombic LaFeO₃ have been obtained in molten NaNO₂ at 723 K, for 2 h. LaCoO₃ is also formed in molten nitrite, but an increase of basicity, by adding Na₂O₂, was necessary to obtain LaNiO₃. The reaction systems were investigated by thermal analysis. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and specific surface area measurements (BET method) were used to characterise the synthesised nanopowders.     

Significance of oligomerization reactions in the transesterification of dimethyl terephthalate with ethylene glycol

Experimental investigations dealing with and mathematical models proposed for the kinetics of the transesterification of dimethyl terephthalate with ethylene glycol were critically reviewed. The models were found to be inadequate, while the investigations were found to be entirely lacking in information about the significance of oligomerization reactions. The significance of these reactions was deduced to be negligible by carrying out an analysis of the kinetics of possible ester interchange and transesterification reactions by use of data on methanol reported in the reviewed literature. This analysis was made possible by the application of numerical quadrature routines in testing the assumed models by the integral method.     

Advanced approaches for the characterization of a de novo designed antiparallel coiled coil peptide

We report here an advanced approach for the characterization of the folding pattern of a de novo designed antiparallel coiled coil peptide by high-resolution methods. Incorporation of two fluorescence labels at the C- and N-terminus of the peptide chain as well as modification of two hydrophobic core positions by Phe/[15N,13C]Leu enable the study of the folding characteristics and of distinct amino acid side chain interactions by fluorescence resonance energy transfer (FRET) and NMR spectroscopy. Results of both experiments reveal the antiparallel alignment of the helices and thus prove the design concept. This finding is also supported by molecular dynamics simulations. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) in combination with NMR experiments was used for verification of the oligomerization equilibria of the coiled coil peptide.     

Die Bestimmung des Gresamtschwefels in Viscose

Zusammenfassung Die Bestimmung des Gesamtschwefels in Viscose wurde untersucht. Es wurde gezeigt, da\ die gravimetrische Bestimmung, wobei mit Wasserstoffperoxyd oxydiert wird, nicht als Bezugsmethode betrachtet werden darf. Eine neue Bezugsmethode wird vorgeschlagen, wobei die Viscose durch Erhitzen mit einem Gemisch von SalzsÄure, JodwasserstoffsÄure und unterphosphoriger SÄure zersetzt wird.Mittels der Behandlung mit diesem reduzierenden SÄuregemisch werden die in der Viscose vorhandenen Schwefelverbindungen quantitativ in Schwefelwasserstoff und Schwefelkohlenstoff übergeführt.Der Autor wünscht der Direktion der N.V. Onderzoekingsinstituut Research zu danken für die Genehmigung, diese Arbeit zu veröffentlichen.     

Hydrogen-bonding contributions to the lattice energy of salts for second harmonic generation

The lattice energies of a series of organic dihydrogenphosphate salts capable of second harmonic generation (SHG) have been calculated. These calculations, coupled with empirical data, indicate that a minimum of 20–25% of the lattice energy arises from hydrogen-bond interactions. Hydrogen bonding is shown to be a strong enough force to have a profound effect on the overall packing and crystal geometry of such ionic materials, and is thus an important factor to consider for crystal engineering.     

Energy levels of paramagnetic ions: Algebra. III. The case of dN ions in cubical symmetry

The formalism developed in the first two papers of this series is applied to the investigation of a new weak-field model. This crystal-field model lies on the use of a symmetry-adapted weak-field basis and an effective Hamiltonian involving in a symmetrical way both spin- and orbit-dependent contributions. Some general properties of this Hamiltonian are studied and complete calculation of its matrix elements is conducted in a symmetry-adapted weak-field basis in the case of an arbitrary configuration nl^N in any symmetry. The case of a configuration nd^N in octahedral symmetry is fully explored. In this case, the proposed weak-field model is restricted to a 12-parameter model which accounts for isotropic and anisotropic Coulomb interactions, isotropic and anisotropic spin-orbit interactions, and crystal-field interactions. A comparison between this 12-parameter weak-field model and the 14-parameter strong-field model is established. Equivalence between the latter two models requires two constraint relations to be satisfied for some strong-field parameters. These two relations are examined with various viewpoints.     

A modification of the heteropoly blue method for the microgram determination of arsenic in biological materials

Summary A sensitive method has been developed for analysis of trace amounts of arsenic in biological materials using the heteropoly blue method. The method employs a closed apparatus and a nitrogen atmosphere, and allows the detection of arsenic in ppm concentration using samples of 100 mg.

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Zusammenfassung Eine empfindliche Methode zur Bestimmung von Arsenspuren in biologischem Material im Wege der Molybdänblaumethode wurde ausgearbeitet. Man arbeitet dabei in einer geschlossenen Apparatur in Stickstoffatmosphäre und kann so in 100-mg-Proben Arsenkonzentrationen in der Größenordnung von ppm bestimmen.

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Presented at the 6th Annual Northeast Regional Meeting of the American Chemical Society, Burlington, Vermont, August 19, 1974.