Oxygen evolution on Ru1 − x Ni x O2 − y nanocrystalline electrodes

Nanocrystalline Ru_1 − x Ni _x O_2 − y with 0.02 < x < 0.30 were prepared by a sol–gel approach at temperatures between 300 and 600 °C. XRD patterns of the prepared materials indicate a single-phase character conforming to a tetragonal syngony. All prepared materials are sufficiently stable in acid media and show activity towards oxygen evolution. The activity towards oxygen evolution reaction of the materials with constant chemical composition decreases with increasing particle size. The increasing Ni content enhances the electrocatalytic activity in a stepwise manner with abrupt changes for materials containing approximately 5% or 15% of the cationic sites substituted by Ni.     

Molecular Dynamisc Simulation of Polyelectrolites

We carried out simulations of a polymer chain using molecular dynamics algorythm. As a model we used a three-dimensional set monomers (electrically charged material points) connected with its nearest neighbours by harmonic potential. Additionally all pairs of segments interacts by the Lennard-Jones (LJ) and Coulomb forces. The aim of the simulation was to determine chain conformation and other basic properties like radius of gyration and moment of inertia for various polymer length and electric charge distribution.Presented model could be alternative tool for structure prediction to typically used ones based on AMBER 99 [1] or another advanced force field.     

Composition and Antimicrobial Activity of Ilex Leaves Water Extracts

Plants from the Ilex genus are known for properties such as antimicrobial and anti-inflammatory activity, can act as antiobesity agents and thus can be helpful in medicine. Some holly species, such as Ilex paraguariensis (widely known in the form of popular beverage: yerba mate), have been investigated, while others have been partially researched or remain unknown. Therefore, we performed qualitative and quantitative phytochemical analyses and screened antimicrobial properties of lesser-studied species (I. aquifolium L., I. aquifolium ‘Argentea Marginata’ and I. × meserveae ‘Blue Angel’). I. paraguariensis was used as a standard species for comparison purposes. Investigations were performed on water extracts due to their expected activity and composition. Antimicrobial research included evaluating minimal inhibitory, bactericidal (Staphylococcus aureus and Escherichia coli) and fungicidal concentration (Candida albicans, Alternaria alternata, Fusarium oxysporum, and Aspergillus niger) of extracts. The influence of the extracts on the production, eradication, and viability of bacterial biofilms was also analysed. It was established that Ilex paraguariensis possesses the richest profile of hydroxycinnamic acids derivatives in terms of component concentration and diversity. Ilex spp., especially I. × meserveae, contain a slightly higher amount of flavonoids and more different flavonoid derivatives than I. paraguariensis. However, the strongest antibacterial activity was shown by I. aquifolium L. and its cultivar ‘Argentea Marginata’ in terms of minimal inhibitory, bactericidal and fungicidal concentration, and biofilm assays. Extracts from both species significantly reduced the biofilm viability of S. aureus as well, which may be of use in the production of multicomponent lavaseptics, antiseptics, diuretics (supporting urinary tract infection therapy) and, due to their action on fungi, additives to growth media for specific fungi. The significant content of saponins enables Ilex extracts to be used as natural emulsifiers, for example, in cosmetics. Moreover, relatively high chlorogenic acid and rutin content may suggest use of Ilex spp. to treat obesity, digestive problems, in chemoprevention, and as preservatives in the food industry.     

Velocity Multistability vs. Ergodicity Breaking in a Biased Periodic Potential

Multistability, i.e., the coexistence of several attractors for a given set of system parameters, is one of the most important phenomena occurring in dynamical systems. We consider it in the velocity dynamics of a Brownian particle, driven by thermal fluctuations and moving in a biased periodic potential. In doing so, we focus on the impact of ergodicity—A concept which lies at the core of statistical mechanics. The latter implies that a single trajectory of the system is representative for the whole ensemble and, as a consequence, the initial conditions of the dynamics are fully forgotten. The ergodicity of the deterministic counterpart is strongly broken, and we discuss how the velocity multistability depends on the starting position and velocity of the particle. While for non-zero temperatures the ergodicity is, in principle, restored, in the low temperature regime the velocity dynamics is still affected by initial conditions due to weak ergodicity breaking. For moderate and high temperatures, the multistability is robust with respect to the choice of the starting position and velocity of the particle.     

Anodic and Cathodic Platinum Dissolution Processes Involve Different Oxide Species

The degradation of Pt-containing oxygen reduction catalysts for fuel cell applications is strongly linked to the electrochemical surface oxidation and reduction of Pt. Here, we study the surface restructuring and Pt dissolution mechanisms during oxidation/reduction for the case of Pt(100) in 0.1 M HClO₄ by combining operando high-energy surface X-ray diffraction, online mass spectrometry, and density functional theory. Our atomic-scale structural studies reveal that anodic dissolution, detected during oxidation, and cathodic dissolution, observed during the subsequent reduction, are linked to two different oxide phases. Anodic dissolution occurs predominantly during nucleation and growth of the first, stripe-like oxide. Cathodic dissolution is linked to a second, amorphous Pt oxide phase that resembles bulk PtO₂ and starts to grow when the coverage of the stripe-like oxide saturates. In addition, we find the amount of surface restructuring after an oxidation/reduction cycle to be potential-independent after the stripe-like oxide has reached its saturation coverage.     

Facile One-Step Oxidation of N-Boc-Protected Diarylhydrazines to Diaryldiazenes with (Diacetoxyiodo)benzene under Mild Conditions

A study on the oxidation of N-Boc- and N,N'-bis-Boc-protected 1,2-diarylhydrazines with (diacetoxyiodo)benzene is reported. The reactions proceed quickly in acetic acid at slightly elevated temperatures, giving diaryldiazenes in good to excellent yields. Electron-donating and electron-withdrawing groups are well tolerated. This synthetic protocol also applies to synthesising (aryldiazenyl)pyridines and unsymmetrical 1,3,5-tris(arylazo)benzenes.     

Convergent Assembly of the Tricyclic Labdane Core Enables Synthesis of Diverse Forskolin-like Molecules

We report a new synthetic strategy for the flexible preparation of forskolin-like molecules. The approach is different from the previously published works and employs a convergent assembly of the tricyclic labdane-type core from pre-functionalized cyclic building blocks. Stereoselective Michael addition enabled the fragment coupling with excellent control over three newly created contiguous stereocenters, all-carbon quaternary centers included. Silyl enol ether-promoted ring-opening metathesis paired with ring closure were the other key steps enabling concise assembly of the tricyclic core. Late-stage functionalization sequences transformed the tricyclic intermediates into a set of different forskolin-like molecules. The modular nature of the synthetic scheme described herein has the potential to become a general platform for the preparation of analogs of forskolin and other complex tricyclic labdanes.     

Raman spectroscopic study of the hydrogen‐arsenate mineral pharmacolite Ca(AsO3OH)·2H2O—implications for aquifer and sediment remediation

The removal of arsenate anions from aqueous media, sediments and wasted soils is of environmental significance. The reaction of gypsum with the arsenate anion results in pharmacolite mineral formation, together with related minerals. Raman and infrared (IR) spectroscopy have been used to study the mineral pharmacolite Ca(AsO₃OH)· 2H₂O. The mineral is characterised by an intense Raman band at 865 cm⁻¹ assigned to the ν₁ (AsO₃)²⁻ symmetric stretching mode. The equivalent IR band is found at 864 cm⁻¹. The low‐intensity Raman bands in the range from 844 to 886 cm⁻¹ provide evidence for ν₃ (AsO₃) antisymmetric stretching vibrations. A series of overlapping bands in the 300‐450 cm⁻¹ region are attributed to ν₂ and ν₄ (AsO₃) bending modes. Prominent Raman bands at around 3187 cm⁻¹ are assigned to the OH stretching vibrations of hydrogen‐bonded water molecules and the two sharp bands at 3425 and 3526 cm⁻¹ to the OH stretching vibrations of only weakly hydrogen‐bonded hydroxyls in (AsO₃OH)²⁻ units. Copyright © 2009 John Wiley & Sons, Ltd.     

Wetting transition in polyolefin blends studied by profiling techniques

Based on segregation data, determined with profiling techniques, we analyze surface phase diagram of binary liquid mixtures composed of random olefinic copolymers. Blends with extended‐ and small‐critical point wetting regimes are discussed. First observation of wetting transition is presented. Surface enrichment‐depletion duality, a phenomenon prerequisite to the 2^nd order wetting transition, is described.