Deoxygenation of Epoxides with Carbon Monoxide

The use of carbon monoxide as a direct reducing agent for the deoxygenation of terminal and internal epoxides to the respective olefins is presented. This reaction is homogeneously catalyzed by a carbonyl pincer-iridium(I) complex in combination with a Lewis acid co-catalyst to achieve a pre-activation of the epoxide substrate, as well as the elimination of CO₂ from a γ-2-iridabutyrolactone intermediate. Especially terminal alkyl epoxides react smoothly and without significant isomerization to the internal olefins under CO atmosphere in benzene or toluene at 80–120 °C. Detailed investigations reveal a substrate-dependent change in the mechanism for the epoxide C−O bond activation between an oxidative addition under retention of the configuration and an S_N2 reaction that leads to an inversion of the configuration.     

Prevalence of unstable attractors in networks of pulse-coupled oscillators

We present and analyze the first example of a dynamical system that naturally exhibits attracting periodic orbits that are unstable. These unstable attractors occur in networks of pulse-coupled oscillators, and become prevalent with increasing network size for a wide range of parameters. They are enclosed by basins of attraction of other attractors but are remote from their own basin volume such that arbitrarily small noise leads to a switching among attractors.     

Depletion-flocculation in oil-in-water emulsions using fibrillar protein assemblies

This paper shows that low concentrations of beta-lactoglobulin fibrils can induce depletion-flocculation in beta-lactoglobulin-stabilized oil-in-water emulsions. The minimum required fibril concentration for flocculation was determined experimentally for fibril lengths of about 3 and 0.1 microm. The minimum fibril concentration for flocculation is two orders of magnitude higher for the short fibrils than for the long ones. These experimental results correspond well with a theoretical prediction based on a model of spinodal decomposition. In addition, rheological measurements were performed, verifying that flocculation was induced by a depletion mechanism. The results of this study show that the minimum concentration required for depletion-flocculation can be tuned by varying the length of the fibrils.     

Optical sectioning in wide-field microscopy obtained by dynamic structured light illumination and detection based on a smart pixel detector array

Optical sectioning in wide-field microscopy is achieved by illumination of the object with a continuously moving single-spatial-frequency pattern and detecting the image with a smart pixel detector array. This detector performs an on-chip electronic signal processing that extracts the optically sectioned image. The optically sectioned image is directly observed in real time without any additional postprocessing.     

Unstable attractors induce perpetual synchronization and desynchronization

Common experience suggests that attracting invariant sets in nonlinear dynamical systems are generally stable. Contrary to this intuition, we present a dynamical system, a network of pulse-coupled oscillators, in which unstable attractors arise naturally. From random initial conditions, groups of synchronized oscillators (clusters) are formed that send pulses alternately, resulting in a periodic dynamics of the network. Under the influence of arbitrarily weak noise, this synchronization is followed by a desynchronization of clusters, a phenomenon induced by attractors that are unstable. Perpetual synchronization and desynchronization lead to a switching among attractors. This is explained by the geometrical fact, that these unstable attractors are surrounded by basins of attraction of other attractors, whereas the full measure of their own basin is located remote from the attractor. Unstable attractors do not only exist in these systems, but moreover dominate the dynamics for large networks and a wide range of parameters.