A General Catalyst Based on Cobalt Core–Shell Nanoparticles for the Hydrogenation of N-Heteroarenes Including Pyridines

Herein, we report the synthesis of specific silica-supported Co/Co₃O₄ core–shell based nanoparticles prepared by template synthesis of cobalt-pyromellitic acid on silica and subsequent pyrolysis. The optimal catalyst material allows for general and selective hydrogenation of pyridines, quinolines, and other heteroarenes including acridine, phenanthroline, naphthyridine, quinoxaline, imidazo[1,2-a]pyridine, and indole under comparably mild reaction conditions. In addition, recycling of these Co nanoparticles and their ability for dehydrogenation catalysis are showcased.     

Enantioselective hydrogenation of diaryl-substituted α,β-unsaturated nitriles

α,β-Unsaturated nitriles can be hydrogenated with enantioselectivities up to 88% ee using chiral ruthenium-diphenylphosphino bisaryl and bisheteroaryl complexes such as ruthenium(II)-BINAP and ruthenium(II)-BINP. Mechanistic investigations indicate that conversion is accelerated by electron-rich ligands and that an additional coordinative group needs be present in order to promote conversion. The chiral products are useful building blocks for the synthesis of histamine H₂ agonists of the arpromidine type.     

Discrete approximation of integral operators

A method to approximate the eigenvalues of linear operators depending on an unknown distribution is introduced and applied to weighted sums of squared normally distributed random variables. This area of application includes the approximation of the asymptotic null distribution of certain degenerated U- and V-statistics.

     

A Simpler Proof of the Excluded Minor Theorem for Higher Surfaces

We give a simple proof of the fact (which follows from the Robertson–Seymour theory) that a graph which is minimal of genusgcannot contain a subdivision of a large grid. Combining this with the tree-width theorem and the quasi-wellordering of graphs of bounded tree-width in the Robertson–Seymour theory, we obtain a simpler proof of the generalized Kuratowski theorem for each fixed surface. The proof requires no previous knowledge of graph embeddings.     

Dynamic stability of weakly damped oscillators with elastic impacts and wear

The dynamics of non-linear oscillators comprising of a single-degree-of-freedom system and beams with elastic two-sided amplitude constraints subject to harmonic loads is analyzed. The beams are clamped at one end, and constrained against unilateral contact sites near the other end. The structures are modelled by a Bernoulli-type beam supported by springs using the finite element method. Rayleigh damping is assumed. Symmetric and elastic double-impact motions, both harmonic and sub-harmonic, are studied by way of a Poincaré mapping that relates the states at subsequent impacts. Stability and bifurcation analyses are performed for these motions, and domains of instability are delineated. Impact work rate, which is the rate of energy dissipation to the impacting surfaces, is evaluated and discussed. In addition, an experiment conducted by Moon and Shaw on the vibration of a cantilevered beam with one-sided amplitude constraining stop is modelled. Bifurcation observed in the experiment could be captured.