Influence of adsorption geometry in the heterogeneous enantioselective catalytic hydrogenation of a prototypical enone

Asymmetric catalysis is of paramount importance in organic synthesis and, in current practice, is achieved by means of homogeneous catalysts. The ability to catalyze such reactions heterogeneously would have a major impact both in the research laboratory and in the production of fine chemicals and pharmaceuticals, yet heterogeneous asymmetric hydrogenation of C═C bonds remains hardly explored. Very recently, we demonstrated how chiral ligands that anchor robustly to the surface of Pd nanoparticles promote asymmetric catalytic hydrogenation: ligand rigidity and stereochemistry emerged as key factors. Here, we address a complementary question: how does the enone reactant adsorb on the metal surface, and what implications does this have for the enantiodifferentiating interaction with the surface-tethered chiral modifiers? A reaction model is proposed, which correctly predicts the identity of the enantiomer experimentally observed in excess.

Evolution of functional diversity in the cupin superfamily

The cupin superfamily of proteins is among the most functionally diverse of any described to date. It was named on the basis of the conserved beta-barrel fold ('cupa' is the Latin term for a small barrel), and comprises both enzymatic and non-enzymatic members, which have either one or two cupin domains. Within the conserved tertiary structure, the variety of biochemical function is provided by minor variation of the residues in the active site and the identity of the bound metal ion. This review discusses the advantages of this particular scaffold and provides an evolutionary analysis of 18 different subclasses within the cupin superfamily.

Modeling based on the structure of vicilins predicts a histidine cluster in the active site of oxalate oxidase

It is known that germin, which is a marker of the onset of growth in germinating wheat, is an oxalate oxidase, and also that germins possess sequence similarity with legumin and vicilin seed storage proteins. These two pieces of information have been combined in order to generate a 3D model of germin based on the structure of vicilin and to examine the model with regard to a potential oxalate oxidase active site. A cluster of three histidine residues has been located within the conserved beta-barrel structure. While there is a relatively low level of overall sequence similarity between the model and the vicilin structures, the conservation of amino acids important in maintaining the scaffold of the beta-barrel lends confidence to the juxtaposition of the histidine residues. The cluster is similar structurally to those found in copper amine oxidase and other proteins, leading to the suggestion that it defines a metal-binding location within the oxalate oxidase active site. It is also proposed that the structural elements involved in intermolecular interactions in vicilins may play a role in oligomer formation in germin/oxalate oxidase.

Observed and simulated precursors of stratospheric polar vortex anomalies in the Northern Hemisphere

The Northern Hemisphere stratospheric polar vortex is linked to surface weather. After Stratospheric Sudden Warmings in winter, the tropospheric circulation is often nudged towards the negative phase of the Northern Annular Mode (NAM) and the North Atlantic Oscillation (NAO). A strong stratospheric vortex is often associated with subsequent positive NAM/NAO conditions. For stratosphere–troposphere associations to be useful for forecasting purposes it is crucial that changes to the stratospheric vortex can be understood and predicted. Recent studies have proposed that there exist tropospheric precursors to anomalous vortex events in the stratosphere and that these precursors may be understood by considering the relationship between stationary wave patterns and regional variability. Another important factor is the extent to which the inherent variability of the stratosphere in an atmospheric model influences its ability to simulate stratosphere–troposphere links. Here we examine the lower stratosphere variability in 300-year pre-industrial control integrations from 13 coupled climate models. We show that robust precursors to stratospheric polar vortex anomalies are evident across the multi-model ensemble. The most significant tropospheric component of these precursors consists of a height anomaly dipole across northern Eurasia and large anomalies in upward stationary wave fluxes in the lower stratosphere over the continent. The strength of the stratospheric variability in the models was found to depend on the variability of the upward stationary wave fluxes and the amplitude of the stationary waves.

Forward modelling to determine the observational signatures of white-light imaging and interplanetary scintillation for the propagation of an interplanetary shock in the ecliptic plane

Recent coordinated observations of interplanetary scintillation (IPS) from the EISCAT, MERLIN, and STELab, and stereoscopic white-light imaging from the two heliospheric imagers (HIs) onboard the twin STEREO spacecraft are significant to continuously track the propagation and evolution of solar eruptions throughout interplanetary space. In order to obtain a better understanding of the observational signatures in these two remote-sensing techniques, the magnetohydrodynamics of the macro-scale interplanetary disturbance and the radio-wave scattering of the micro-scale electron-density fluctuation are coupled and investigated using a newly constructed multi-scale numerical model. This model is then applied to a case of an interplanetary shock propagation within the ecliptic plane. The shock could be nearly invisible to an HI, once entering the Thomson-scattering sphere of the HI. The asymmetry in the optical images between the western and eastern HIs suggests the shock propagation off the Sun–Earth line. Meanwhile, an IPS signal, strongly dependent on the local electron density, is insensitive to the density cavity far downstream of the shock front. When this cavity (or the shock nose) is cut through by an IPS ray-path, a single speed component at the flank (or the nose) of the shock can be recorded; when an IPS ray-path penetrates the sheath between the shock nose and this cavity, two speed components at the sheath and flank can be detected. Moreover, once a shock front touches an IPS ray-path, the derived position and speed at the irregularity source of this IPS signal, together with an assumption of a radial and constant propagation of the shock, can be used to estimate the later appearance of the shock front in the elongation of the HI field of view. The results of synthetic measurements from forward modelling are helpful in inferring the in-situ properties of coronal mass ejection from real observational data via an inverse approach.