Zinc Oxide Based Coatings for the UV-Protection of Wood for Outdoor Applications

Summary: Nano-sized zinc oxide (ZnO) was chosen as a suitable candidate for the UV-protection of coatings. ZnO-based acrylate coatings were applied to polycarbonate plates, glass plates and impregnated wood. Coated samples were artificially weathered (Xenon test) for at least 1500 hours and studied with regards to their optical and mechanical properties, such as color shifts (yellowing), as well as to changes in brightness, transparency or hydrophobicity. The prepared wood coatings showed reduced yellowing and improved optical properties.     

Synthesis and Reactivity of Dithienopyrazines**

Heteroacenes developed to widely used building blocks in organic semiconductors for application in organic electronics due to their tunable structures and properties concomitant with inherent stability. Here, we report efficient preparation and investigation of so far unknown heterotriacenes, basic anti- and syn-dithienopyrazine 5 and 6 . The comparison of the two isomers with respect to electronic properties and follow-up reactions gives insights into structure-property and -reactivity relationships. Examples of transition metal-catalyzed C−C cross-coupling reactions of corresponding halogenated derivatives show the practical impact for extended π-conjugated systems applied in optoelectronic devices.     

Ruthenium Complexes of Rigid,Dianionic, Tetradentate N-Donor Ligands and their Potential as Catalysts for Water Oxidation

Two mononuclear ruthenium(II) complexes based on dianionic {N₄} ligands and with axial pyridines have been prepared and characterized crystallographically ( 1 ) or by 2D NMR spectroscopy using residual dipolar couplings ( 2 ). The {N₄} ligands provide a constrained equatorial coordination with one large N−Ru−N angle, and additional non-coordinating N atoms in case of 2 . Their redox properties have been investigated (spectro)electrochemically, and their potential to serve as water oxidation catalysts has been probed using cerium ammonium nitrate (CAN) at pH 1.0. Complex 1 undergoes rapid degradation, likely via ligand oxidation, whereas 2 is more rugged and exhibits 80 % efficiency in the Ce^IV-driven water oxidation, with a high initial turnover frequency (TOF_i) of 3.07×10⁻² s⁻¹ (at 100 equiv. CAN). The initial rate of O₂ evolution exhibits 1^st order dependence on catalyst concentration, suggesting a water nucleophilic attack mechanism. Repeated addition of CAN and control experiments show that high ionic strength conditions (both NO₃⁻ and Ce^III) significantly decrease the TOF.     

Application of a Viscoelastic Material Model in Electro-Mechanics

In this contribution, the numerical modeling of electro-viscoelastic material is considered. The electro-mechanical problem formulated in terms of a symmetrized stress tensor is extended to a viscoelastic material model. For the incorporation of the viscosity model, the logarithmic strain space setting is utilized which mimics the small strain setting. Therefore a rheological model for viscosity from the geometrically linear theory can be used. Numerical examples for a typical uniaxial tensile test show the capability of the method to demonstrate typical relaxation and creep behavior. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A Novel Type of Vesicles Based on Ionic and π–π Interactions

Electrostatic self‐assembly can be used to form supramolecular vesicles in aqueous solution. Vesicles consist of cationic G8 poly(amidoamine) dendrimers and the trivalent sulfonate dye Ar27. No classical amphiphiles are present but the interplay of electrostatics, π–π interaction and geometric factors influences the structure formation. Labeled guest molecules, both small molecules and peptides, can be included inside these vesicles and vesicles imaged by fluorescence techniques. The structure was studied by dynamic and static light scattering, small‐angle neutron scattering, confocal laser scanning microscopy, and fluorescence correlation spectroscopy. The study indicates the prospect of constructing functional nanoobjects by the self‐assembly of charged molecules in aqueous solution.

     

Back Cover: Manipulating Intermetallic Charge Transfer for Switchable External Stimulus-Enhanced Water Oxidation Electrocatalysis (Angew. Chem. Int. Ed. 44/2023)

Electrocatalytic processes involving the oxygen evolution reaction (OER) present a kinetic bottleneck due to the existence of linear-scaling relationships, which bind the energies of the different intermediates in the mechanism limiting optimization. Here, we offer a way to break these scaling relationships and enhance the electrocatalytic activity of a Co−Fe Prussian blue modified electrode in OER by applying external stimuli. Improvements of ≈11 % and ≈57 % were achieved under magnetic field (0.2 T) and light irradiation (100 mW cm⁻²), respectively, when working at fixed overpotential, η=0.6 V at pH 7. The observed enhancements strongly tie in with the intermetallic charge transfer (IMCT) intensity between Fe and Co sites. Density Functional Theory simulations suggest that tuning the IMCT can lead to a change of the OER mechanism to an external stimuli-sensitive spin crossover-based pathway, which opens the way for switchable electrocatalytic devices.     

Efficient Transfection via an Unexpected Mechanism by Near Neutral Polypiperazines with Tailored Response to Endosomal pH

Cationic pH-responsive polymers promise to overcome critical challenges in cellular delivery. Ideally, the polymers become selectively charged along the endosomal pathway disturbing only the local membrane and avoiding unintended interactions or cytotoxic side effects at physiological conditions. Polypiperazines represent a novel, hydrophilic class of pH-responsive polymers whose response can be tuned within the relevant pH range (5–7.4). The authors discovered that the polypiperazines are effectively binding plasmid DNA (pDNA) and demonstrate high efficiency in transfection. By design of experiments (DoE), a wide parameter space (pDNA and polymer concentration) is screened to identify the range of effective concentrations for transfection. An isopropyl modified polypiperazine is highly efficient over a wide range of concentrations outperforming linear polyethylenimine (l-PEI, 25 kDa) in regions of low N*/P ratios. A quantitative polymerase chain reaction (qPCR) surprisingly revealed that the pDNA within the piperazine-based polyplexes can be amplified in contrast to polyplexes based on l-PEI. The pDNA must therefore be more accessible and bound differently than for other known transfection polymers. Considering the various opportunities to further optimize their structure, polypiperazines represent a promising platform for designing effective soluble polymeric vectors, which are charge-neutral at physiological conditions.