Fluctuating Storage of the Active Phase in a Mn‐Na2WO4/SiO2 Catalyst for the Oxidative Coupling of Methane

Structural dynamics of a Mn‐Na₂WO₄/SiO₂ catalyst were detected directly under reaction conditions during the oxidative coupling of methane via in situ XRD and operando Raman spectroscopy. A new concept of fluctuating storage and release of an active phase in heterogeneous catalysis is proposed that involves the transient generation of active sodium oxide species via a reversible reaction of Na₂WO₄ with Mn₇SiO₁₂. The process is enabled by phase transitions and melting at the high reaction temperatures that are typically applied.     

Modification of carbon electrodes by vitamin B12-polymers

New types of electroactive polymers consisting of derivatives of vitamin B₁₂ and epoxy resins have been synthesized. Surface modification of carbon (carbon felt or basal plane pyrolytic graphite) has been achieved by thermal curing of the monomers on the electrodes. Electrochemical response from the Co (II)/Co (I) redox couple has been observed from sub-mono to multilayer coverages. The influence of the size of the epoxy spacer on charge propagation in the polymer has been studied. The B₁₂-modified electrodes have been applied to electrosynthesis and electroanalysis: They catalyze the reductive cross-coupling of alkyl halides and activated olefins and they are efficient sensors for alkylating agents.     

Argentophilic Interactions

The decade 1990–2000 saw a growing interest in aurophilic interactions in gold chemistry. These interactions were found to influence significantly a variety of structural and other physical characteristics of gold(I) compounds. The attention paid to this unusual and counterintuitive type of intra‐ and intermolecular bonding between seemingly closed‐shell metal centers has rapidly been extended to also include silver chemistry. Hundreds of experimental and computational studies have since been dedicated to the argentophilicity phenomenon. The results of this development are reviewed herein focusing on molecular systems where two or more silver(I) centers are in close contact leading to specific structural characteristics and a variety of novel physical properties. These include strongly modified ligand‐to‐metal charge‐transfer processes observed in absorption and emission spectroscopy, but also colossal positive and negative thermal expansion on the one hand and unprecedented negative linear compressibility of crystal parameters on the other.     

Tetraacylation of isobutene: first synthesis of 1,3,6,8-tetramethyl-2,7-naphthyridine

The tetxaacetylation of isobutene has been perfomed in AlCl₃/AcCl. Treatment of the crude reaction medium with liquid ammonia yields the title compound.     

The energy spectrum of fully developed turbulence generated by random stirring

For fully developed turbulence in an incompressible fluid described by the Navier-Stokes equations with Gaussian random forces the relation between the energy spectrum and the stirring mechanism is investigated within a variational approach. Therein, the effect of nonlinear mode coupling is approximated by a wave number dependent eddy viscosity determined via a nonlinear integral equation for the energy spectrum. For various stirring spectra analytic approximations are compared with the solution obtained numerically with a cutoff in the integral kernel which ensures in eddy relaxing processes that the stirring forces exert strain only on scales larger than the eddy size. The results are compared with renormalization group calculations and closure approximations. Random forces injecting energy at a ratek ^–1 into the wave number banddk aroundk lead to a Kolmogorov distribution of energy. The spectrum of small-scale velocity fluctuations is shown to be universal in the sense that it remains unchanged under variations of the long wavelength stirring spectra.     

Dynamics of 2D anisotropic solids,smectics and nematics

In this research we study the critical dynamics of anisotropic layers in the various transition and crossover regimes associated with a defect unbinding picture of the melting process. We derive dynamic equations of motion for anisotropic solids, smectics and nematics, in the presence of defects and predict the critical behavior of various transport coefficients. The theory is applicable to two-dimensional layers of freely suspended liquid crystals, on which dynamic light-scattering experiments can be performed to test the predictions of the theory.