The scope and limitations of liquid-crystalline behaviour in monosaccharide amphiphiles Comparison of the thermal behaviour of several homologous series of D-glucose derived compounds with an amino-linked alkyl chain

A short review of the scope and limitations of liquid-crystalline behaviour in carbohydrate derivatives is presented. In order to investigate the influence of structure variations on the thermal behaviour of monosaccharide amphiphiles, six homologous series of D-glucose and 2-deoxy-D-glucose derivatives with an aminolinked n-alkyl chain were prepared. The observed thermal behaviour could be readily explained with the aid of a refinement of the qualitative model that was presented earlier [1]. All compounds were found to be mesogenic, and the observed mesophase was smectic A_d (i.e. a partially overlapping bilayer structure) in all cases.     

When Do Tracer Particles Dominate the Lyapunov Spectrum?

Dynamical instability is studied in a deterministic dynamical system of Hamiltonian type composed of a tracer particle in a fluid of many particles. The tracer and fluid particles are hard balls (disks, in two dimensions, or spheres, in three dimensions) undergoing elastic collisions. The dynamical instability is characterized by the spectrum of Lyapunov exponents. The tracer particle is shown to dominate the Lyapunov spectrum in the neighborhoods of two limiting cases: the Lorentz-gas limit in which the tracer particle is much lighter than the fluid particles and the Rayleigh-flight limit in which the fluid particles have a vanishing radius and form an ideal gas. In both limits, a gap appears in the Lyapunov spectrum between the few largest Lyapunov exponents associated with the tracer and the rest of the Lyapunov spectrum.     

Ring‐Closing and Cross‐Metathesis with Artificial Metalloenzymes Created by Covalent Active Site‐Directed Hybridization of a Lipase

A series of Grubbs‐type catalysts that contain lipase‐inhibiting phosphoester functionalities have been synthesized and reacted with the lipase cutinase, which leads to artificial metalloenzymes for olefin metathesis. The resulting hybrids comprise the organometallic fragment that is covalently bound to the active amino acid residue of the enzyme host in an orthogonal orientation. Differences in reactivity as well as accessibility of the active site by the functionalized inhibitor became evident through variation of the anchoring motif and substituents on the N‐heterocyclic carbene ligand. Such observations led to the design of a hybrid that is active in the ring‐closing metathesis and the cross‐metathesis of N,N‐diallyl‐p‐toluenesulfonamide and allylbenzene, respectively, the latter being the first example of its kind in the field of artificial metalloenzymes.     

How thermal curing of an organic paper coating changes topography, chemistry, and wettability

Celluloses are preferred renewable substrates, but hydrophilicity and porosity disfavor their water resistance. We present here an ecofriendly application of imidized nanoparticles and a method to flexibly tune the surface wettability of papers. The soft nanostructured coating is sensitive to thermal curing, which affects both the surface chemistry and morphology. The thermal stability of the coating is first investigated with conventional and modulated differential scanning calorimetry, revealing influences of the imide content and an endotherm reaction below the glass transition temperature at 120-150 °C. The latter is studied in detail for an appropriate selection of the copolymer precursors. According to diffuse reflection infrared spectroscopy, Raman spectroscopy, and UV/vis spectroscopy, the endotherm corresponds to an imidization reaction. The morphology of the coatings is followed at various scale levels by contactless roughness measurements and atomic force microscopy. Finally, the experimental values are fitted to the parameters of the Wenzel wetting model, and so-called calibration curves for the relation between contact angles, surface roughness, and surface chemistry are presented. They allow the prediction of the water contact angle of coated papers from the hydrophilic to the hydrophobic range, with a maximum in hydrophobicity after increasing the imide content at 120-150 °C curing.     

In search of oligo(2-thienyl)-substituted pyridine derivatives: a modular approach to di-, tri- and tetra(2-thienyl)pyridines

Herein, we describe our attempts to systematically prepare a series of oligo(2-thienyl)-substituted pyridine derivatives. The crucial starting material, a β-alkoxy-β-ketoenamide, is easily available on a large scale by the reaction of lithiated methoxyallene with thiophene-2-carbonitrile and thiophene-2-carboxylic acid. This three-component reaction is followed by intramolecular cyclization to yield the suitably functionalized 2,6-di(2-thienyl)-substituted pyridine derivates. The two oxygen atoms allow the programmed activation of positions C-3, C-4, or C-5 of the pyridine ring to perform palladium-catalyzed coupling reactions with thiophene-2-boronic acid or 2-(tributylstannyl)thiophene, and alternatively, reductive removal of groups. With this concept, we were able to prepare five pyridine derivatives with 2-thienyl substituents in the 2,6-, 2,3,6-, 2,4,6-, 2,3,4,6-, and 2,3,5,6-positions. 2,3,4,5,6-Penta(2-thienyl)pyridine was not available with our methods. The UV/Vis and fluorescence spectra of all pyridines were recorded and showed a dependence on the substitution pattern and protonation state. For the protonated 2,3,5,6-tetra(2-thienyl)-substituted pyridine, a Stokes shift of about 180 nm with an emission at 515 nm was observed.     

Large Eddy Simulation of the vortex end in reverse-flow centrifugal separators

The present work is a study of the gas-flow phenomenon known as the “end of the vortex” (EoV), which spontaneously occurs at the lower end, or under, reverse-flow centrifugal separators such as cyclones or swirl tubes. Different CFD models of swirl tubes have been built to study and analyse this phenomenon in detail. The present numerical work is based on—and compared with—previous experimental observations of this phenomenon. The numerical models were built in complete agreement with the geometrical configurations and operating conditions used in these earlier experimental studies [1]. Two different configurations of swirl tubes were analyzed. One configuration was an in principle long tube with variable length in which the dependence on the vessel length of the behaviour of the vortex core in a simple, well-defined geometry was studied. The other configuration was equipped with a wide “dust collection vessel” at the bottom, the depth of which was varied, to study the behaviour of the vortex core in a widely-used geometry. 3-D LES simulations were carried out using the commercial CFD package Star-CD. The bending of the vortex core to the wall of the vessel and its precessional motion, constituting the phenomenon of the EoV, was seen in both configurations, and the obtained results are in very good agreement, both qualitatively and to an extent quantitatively, with previous experimental results [1].     

Inequalities between successive minima and intrinsic volumes of a convex body

The second theorem of Minkowski establishes a relation between the successive minima and the volume of a 0-symmetric convex body. Based on this theorem we will prove a series of inequalities connecting the product of certain successive minima with certain intrinsic volumes.     

Existence of unique SRB-measures is typical for real unicritical polynomial families

We show that for a one-parameter family of unicritical polynomials {fc} with even critical order ??2, for almost all parameters c, fc admits a unique SRB-measure, being either absolutely continuous, or supported on the postcritical set. As a byproduct we prove that if fc has a Cantor attractor, then it is uniquely ergodic on its postcritical set.