Dipolar 31P NMR spectroscopy of crystalline inorganic phosphorus compounds.

The ability of the 90 degrees-t1-180 degrees pulse sequence to produce accurate dipole-dipole coupling information in solids is investigated. To this end, the experimental 31P spin echo decays are measured for eighteen crystalline phosphides and phosphorus chalcogenides and compared with simulations, based on the known internuclear distances in these compounds. The experimental results are generally found accurate in compounds where the dominant contribution to the dipole-dipole coupling arises from nuclei in structurally inequivalent sites with large chemical shift anisotropies. For this situation, the quantum mechanical "flip-flop" term in the dipolar Hamiltonian is suppressed and the dipole-dipole coupling is entirely heteronuclear in character. All of those compounds that do not obey this condition show accelerated spin echo decays due to a fractional contribution of the flip-flop term and possibly incomplete refocusing of chemical shift terms on the time scale of the experiment. The results confirm on an empirical basis that the spin echo NMR technique can provide accurate dipole-dipole coupling information (and thus distance distributions) in disordered solids and glasses.     

Influence of development distance on resolution in thin-layer chromatography

Theoretical equations are given to relate resolution with development distance. Comparative experiments undertaken with quaternary ammonium compounds as test substances and using a selection of basic drugs are presented. As expected, resolution decreases with shorter development distance. However, this effect is less pronounced for compounds with small R_f values and when the spot size at the starting point is kept small. It was also shown that, for correctly assessing resolution in relation to development distance, the amounts of material spotted have to be decreased for shorter development distances.     

Scanning electron microscopic studies on different habits of gel grown doped manganese carbonate crystals

The effect of impurities on the growth of manganese carbonate crystals has been studied. Stereophotogrammetric analysis showed that all crystal faces have the same Miller indices and the peanut-shaped forms are twins with twin axis 0001.     

Total and Semi‐Syntheses of Antimicrobial Thuggacin Derivatives

The total and semi‐synthesis of 13 new macrolactones derived from thuggacin, which is a secondary metabolite from the myxobacterium Sorangium cellulosum, are reported. The thuggacins have attracted much attention due to their strong antibacterial activity, particularly towards Mycobacterium tuberculosis. This study focuses on 1) thuggacin derivatives that cannot equilibrate by transacylation between the three natural thuggacins A–C, 2) the roles of the thiazole ring, and 3) the hexyl side chain at C2. Semi‐synthetic O‐methylation at C17 suppressed the transacylations without a substantial loss of antibacterial activity. Exchanging the C17–C25 side chain for simplified hydrophobic chains led to complete loss of antibacterial activity. Exchange of the thiazole by an oxazole ring or removal of the hexyl side chain at C2 had no substantial effect on the biological properties.     

Phase-field approach to fracture for finite-deformation contact problems

The present contribution deals with a variationally consistent Mortar contact algorithm applied to a phase-field fracture approach for finite deformations, see [4]. A phase-field approach to fracture allows for the numerical simulation of complex fracture patterns for three dimensional problems, extended recently to finite deformations (see [2] for more details). In a nutshell, the phase-field approach relies on a regularization of the sharp (fracture-) interface. In order to improve the accuracy, a fourth-order Cahn-Hilliard phase-field equation is considered, requiring global C¹ continuity (see [1]), which will be dealt with using an isogeometrical analysis (IGA) framework. Additionally, a newly developed hierarchical refinement scheme is applied to resolve for local physical phenomena e.g. the contact zone (see [3] for more details). The Mortar method is a modern and very accurate numerical method to implement contact boundaries. This approach can be extended in a straightforward manner to transient phase-field fracture problems. The performance of the proposed methods will be examined in a representative numerical example. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A General and Highly Selective Palladium‐Catalyzed Hydroamidation of 1,3‐Diynes

A chemo‐, regio‐, and stereoselective mono‐hydroamidation of (un)symmetrical 1,3‐diynes is described. Key for the success of this novel transformation is the utilization of an advanced palladium catalyst system with the specific ligand Neolephos. The synthetic value of this general approach to synthetically useful α‐alkynyl‐α, β‐unsaturated amides is showcased by diversification of several structurally complex molecules and marketed drugs. Control experiments and density‐functional theory (M06L‐SMD) computations also suggest the crucial role of the substrate in controlling the regioselectivity of unsymmetrical 1,3‐diynes.     

Long-range repulsive interaction between molecules on a metal surface induced by charge transfer

The adsorption of a molecular electron donor on Au(111) is characterized by the spontaneous formation of a superlattice of monomers spaced several nanometers apart. The coverage-dependent molecular pair distributions obtained from scanning tunneling microscopy data reveal an intermolecular long-range repulsive potential, which decreases as the inverse of the molecular separation. Density functional theory calculations show a charge accumulation in the molecules due to electron donation into the metal. Our results suggest that electrostatic repulsion between molecules persists on the surface of a metal.     

Superfluid-helium converter for accumulation and extraction of ultracold neutrons

We report the first successful extraction of accumulated ultracold neutrons (UCN) from a converter of superfluid helium, in which they were produced by downscattering neutrons of a cold beam from the Munich research reactor. Windowless UCN extraction is performed in vertical direction through a mechanical cold valve. This prototype of a versatile UCN source is comprised of a novel cryostat designed to keep the source portable and to allow for rapid cooldown. We measured time constants for UCN storage and extraction into a detector at room temperature, with the converter held at various temperatures between 0.7 and 1.3 K. The UCN production rate inferred from the count rate of extracted UCN is close to the theoretical expectation.