Entropic Contributions to Sodium Solvation and Solvent Stabilization upon Electrochemical Sodium Deposition from Diglyme and Propylene Carbonate Electrolytes

The formation of an appropriate solid electrolyte interphase (SEI) at the anode of a sodium battery is crucially dependent on the electrochemical stability of solvent and electrolyte at the redox potential of Na/Na⁺ in the respective system. In order to determine entropic contributions to the relative stability of the electrolyte solution, we measure the reaction entropy of Na metal deposition for diglyme (DG) and propylene carbonate (PC) based electrolyte solutions by electrochemical microcalorimetry at single electrodes. We found a large positive reaction entropy for Na⁺ deposition in DG of Δ_R 234 J mol⁻¹ K⁻¹ (c.f.: Δ_R 83 J mol⁻¹ K⁻¹), which signals substantial entropic destabilization of Na⁺ in DG by about 0.73 eV, thus increasing the stability of solvent and electrolyte relative to Na⁺ reduction. We attribute this strong entropic destabilization to a highly negative solvation entropy of Na⁺, due to the low dielectric constant and high freezing entropy of DG.     

Structure Elucidation of the First Sex-Inducing Pheromone of a Diatom

Diatoms are abundant unicellular microalgae, responsible for ≈20 % of global photosynthetic CO₂ fixation. Nevertheless, we know little about fundamental aspects of their biology, such as their sexual reproduction. Pheromone-mediated chemical communication is crucial for successful mating. An attraction pheromone was identified in the diatom Seminavis robusta, but metabolites priming cells for sex and synchronizing search and mating behavior remained elusive. These sex-inducing pheromones (SIP) induce cell cycle arrest and trigger the production of the attraction pheromone. Here we describe the challenging structure elucidation of an S. robusta SIP. Guided by metabolomics, a candidate metabolite was identified and elucidated by labeling experiments, NMR, ESI MSⁿ analyses, and chemical transformations. The use of negative ion mode MS was essential to decipher the unprecedented hydroxyproline and β-sulfated aspartate-containing cyclic heptapeptide that acts in femtomolar concentrations.     

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.     

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.

     

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)     

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.