Well‐Defined Palladium Nanoparticles Supported on Siliceous Mesocellular Foam as Heterogeneous Catalysts for the Oxidation of Water

Herein, we describe the use of Pd nanoparticles immobilized on an amino‐functionalized siliceous mesocellular foam for the catalytic oxidation of H₂O. The Pd nanocatalyst proved to be capable of mediating the four‐electron oxidation of H₂O to O₂, both chemically and photochemically. The Pd nanocatalyst is easy to prepare and shows high chemical stability, low leaching, and recyclability. Together with its promising catalytic activity, these features make the Pd nanocatalyst of potential interest for future sustainable solar‐fuel production.     

Absolute Asymmetric Synthesis of a Tetrahedral Silver Complex

Even though the isolation of tetrahedral stereoisomers usually presents a synthetic challenge, a highly enantioenriched tetrahedral silver complex could be easily accessed by either crystallization or Viedma ripening. The overall preparation may be regarded as an example of absolute asymmetric synthesis. Experimental results indicate that both crystallization and Viedma ripening follow a similar cluster‐controlled mechanism.     

Sustainability of microporous polymers and their applications

Microporous polymers (MPs) are studied for their intriguing chemistry and physics as well as their potential application in catalytic transformations, gas-separation processes, water purification and so on. Here, we critically review MPs with respect to the sustainability aspects of their synthesis as well as their applications that have sustainable character. Some MPs have been synthesized from monomers derived from biomass resources, but there is certainly a large potential for further developments. There are also opportunities to improve the sustainability of MP synthesis in terms of the use of solvents, catalysts, and related aspects. The applications of MPs in processes related to sustainability depend upon multiple properties. A rich and flexible chemistry is important to applications as catalysts for, among other useful reactions, the photoreduction of CO₂ and selective oxidation. The (ultra)micropore volume of MPs are crucial in gas-separation applications such as CO₂ capture, and the chemisorption of CO₂ on MP-tethered alkylamines could offer a means to remove that gas from dilute mixtures. When it comes to the storage of H₂ and CH₄ in MPs for onboard use in fuel cell or biogas cars, volumetric capacity is paramount, meaning that the density of the MPs must be considered. Finally, for use in separation and purifications from liquid mixtures (aqueous or hydrocarbon-based), crosslinked MPs are more limited than the solution-processable MPs that can be more easily processed into films and membranes.     

Metropolis-Hastings Importance Sampling Estimator

Based on the proposed states of the Metropolis-Hastings (MH) algorithm we construct a MH Importance Sampling estimator for the approximation of expectations. The new approximation scheme is asymptotically correct and numerical experiments indicate that it can outperform the classical MH Markov chain Monte Carlo estimator. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Constructing dynamical systems having homoclinic bifurcation points of codimension two

A procedure is derived which allows for a systematic construction of three-dimensional ordinary differential equations having homoclinic solutions. The equations are proved to exhibit codimension-two homoclinic bifurcation points. Examples include the non-orientable resonant bifurcation, the inclination-flip, and the orbit-flip. In addition, an equation is constructed which has a homoclinic orbit converging to a saddle-focus satisfying Shilnikov's condition. The vector fields are polynomial and non-stiff in that the eigenvalues are of moderate size.     

Free-standing biomimetic polymer membrane imaged with atomic force microscopy

Fluid polymeric biomimetic membranes are probed with atomic force microscopy (AFM) using probes with both normal tetrahedrally shaped tips and nanoneedle-shaped Ag(2)Ga rods. When using nanoneedle probes, the collected force volume data show three distinct membrane regions which match the expected membrane structure when spanning an aperture in a hydrophobic scaffold. The method used provides a general method for mapping attractive fluid surfaces. In particular, the nanoneedle probing allows for characterization of free-standing biomimetic membranes with thickness on the nanometer scale suspended over 300-μm-wide apertures, where the membranes are stable toward hundreds of nanoindentations without breakage.     

Monitoring the aggregation of single casein micelles using fluorescence microscopy

The aggregation of casein micelles (CMs) induced by milk-clotting enzymes is a process of fundamental importance in the dairy industry for cheese production; however, it is not well characterized on the nanoscale. Here we enabled the monitoring of the kinetics of aggregation between single CMs (30-600 nm in diameter) by immobilizing them on a glass substrate at low densities and subsequently imaging them with fluorescence microscopy. We validated the new method by a quantitative comparison to ensemble measurements of aggregation. Single-particle statistics allowed us to observe for the first time several heterogeneities in CM aggregation. We observed two types of CM growth: a slow increase in the size of CMs and a stepwise increase attributed to interactions between aggregates preformed in solution. Both types of growth exhibit a lag phase that was very heterogeneous between different CMs, suggesting significant differences in their composition or structure. Detailed size histograms of CMs during aggregation also revealed the presence of two distinct subpopulations with different growth amplitudes and kinetics. The dependence of these distinct nanoscale processes/parameters on aggregation conditions is not accessible to bulk measurements that report only ensemble-average values and may prove important to an in-depth understanding of CM aggregation.