High-entropy oxides: Harnessing crystalline disorder for emergent functionality

High-entropy materials defy historical materials design paradigms by leveraging chemical disorder to kinetically stabilize novel crystalline solid solutions comprised of many end-members. Formulational diversity results in local crystal structures that are seldom found in conventional materials and can strongly influence macroscopic physical properties. Thermodynamically prescribed chemical flexibility provides a means to tune such properties. Additionally, kinetic metastability results in many possible atomic arrangements, including both solid-solution configurations and heterogeneous phase assemblies, depending on synthesis conditions. Local disorder induced by metastability, and extensive cation solubilities allowed by thermodynamics combine to give many high-entropy oxide systems utility as electrochemical, magnetic, thermal, dielectric, and optical materials. Though high-entropy materials research is maturing rapidly, much remains to be understood and many compositions still await discovery, exploration, and implementation.     

Synthese,Struktur und photophysikalische Eigenschaften von polyarylierten Imidazolen und Oxazolen

Synthesis, Structure, and Photophysical Properties of Polyarylated Imidazoles and Oxazoles 23 tetraphenylimidazoles 1,2 and 11 triphenyloxazoles 4,5 with amino, nitro, methoxy, hydroxy, or halogeno substituents chiefly in the para position were prepared. The absorption and fluorescence emission properties were investigated in ethanolic solution. The effects of the substituents in 1,2 on the spectral shifts show that the arrangement of the phenyl rings in 1 position is not coplanar in relation to the heterocycle whereas the phenyl rings in 2 position are more coplanar. The spectral changes of compound 2a in solvents of various polarity (dielectric constants 2,02–47,24) are almost negligible. The Stokes shift is moderately increased. A remarkable increase in the fluorescence quantum yield is observed by chlorine substitution in phenyl ring 2.     

Aerosol-Jet-Printed Encapsulation of Organic Photovoltaics

Organic electronic devices (OEDs) are prone to oxygen- and water-induced degradation and therefore need to be encapsulated with barrier materials. In this work, an aerosol jet (AJ)-printing process is developed to coat perhydropolysilazane (PHPS) directly onto OEDs by adapting the print setup and systematically optimizing the process parameters. Furthermore, a novel curing process that converts PHPS to silica barrier layers is developed by combining damp heat (DH) exposure with subsequent vacuum–UV irradiation. This two-step treatment is shown to be considerably faster and gentler than the state-of-the-art curing processes and also yields a quantitatively higher conversion. Both the printing and the conversion process are fully compatible with OED devices, which is demonstrated by a damage-free direct encapsulation of organic solar cells. The encapsulated cells show a significant reduction of degradation in DH conditions (65 °C/85% r.h.), maintaining >95% of their initial performance for >100 h. Complementary electroluminescence measurements reveal that the AJ-printed barrier layers effectively prevent lateral water ingress into the devices. Herein, the proof of principle is provided that AJ printing can be used to print barrier layers directly onto OEDs and is thus an industrially highly relevant technology to precisely encapsulate such devices even on 3D objects.     

Cover Feature: Altering the Modular Architecture of Galectins Affects its Binding with Synthetic α-Dystroglycan O-Mannosylated Core M1 Glycoconjugates In situ (ChemBioChem 14/2023)

The multifunctionality of galectins helps regulate a broad range of fundamental cellular processes via cis-binding and trans-bridging activities and has gained widespread attention with respect to the importance of the natural specificity/selectivity of this lectin family to its glycoconjugate receptors. Combining galectin (Gal)-1, −3, −4, and −9 variant test panels, achieved via rational protein engineering, and a synthetic α-dystroglycan (DG) O-Mannosylated core M1 glycopeptide library, a detailed comparative analysis was performed, utilizing microarray experiments to delineate the design-functionality relationships within this lectin family. Enhancement of prototype Gal-1 and chimera-type Gal-3 cis-binding toward the prepared ligands is possible by transforming these lectins into tandem-repeat type and prototypes, respectively. Furthermore, Gal-1 variants demonstrated improved trans-bridging capabilities between core M1 α-DG glycopeptides and laminins in microarray, suggesting the possible translational applications of these galectin variants in the treatment of some forms of α-dystroglycanopathy.     

Polymer formation during thermal-oxidative ageing of aviation turbine oils

Oligomers/polymers formed during the thermal-oxidative ageing of ester-based aviation turbine oils have been investigated, using pentaerythritol tetraheptanoate as a model ester. The principal polymer structures in the primary ageing state were revealed by means of chromatographic and spectroscopic methods. The most probable structures are dicarboxylic acid polyesters with variable amounts of α,ω-dicarboxylic acids having chain lengths of C₂ up to C₇ The C⁷-branches also contained ester-bonded hydroxy as well as oxo substituents. Pentaerythritol triheptanoate discarboxylic acid mono esters were active precursors in polymer formation.     

Conversion of a polysilazane-modified cellulose-based paper into a C/SiFe(N,C)O ceramic paper via thermal ammonolysis

Cellulose-based paper samples were surface-modified by a polymeric single-source precursor prepared from perhydropolysilazane (PHPS) and iron(III)acetylacetonate (Fe(acac)₃) and ammonolyzed at 500°C, 700°C, 900°C, and 1000°C, leading to C/SiFe(N,C)O-based ceramic papers with in situ-generated hierarchical micro/nano-morphology. As reference, cellulose-free samples were prepared under the same conditions. Upon thermal treatment, the microstructure evolutions of the resulting ceramic paper and the reference sample were comparatively investigated. Scanning electron microscopy (SEM) showed that for all temperatures, the ceramic papers exhibit the same morphology as the template, however, with noticeable shrinkage and curling, particularly evident at higher temperatures. X-ray diffraction (XRD) measurements of the reference samples and the ceramic papers showed a similar crystallization behavior and phase evolution in both materials. In the ceramic paper, the crystallization process seems to occur at a later time. The results provide a comprehensive understanding of the investigated C/SiFe(N,C)O-based ceramic system. It was shown that use of the cellulose-based paper template has the benefit of retaining the microstructure and furthermore, apart from transforming the cellulose fibers into turbostratic carbon, does not change the phase evolution during the polymer-to-ceramic transformation, allowing at the same time the manufacturing of novel morphologically complex parts by a convenient one-pot synthesis approach.     

Overcoming Moisture-Induced Degradation in Organic Solar Cells

Unencapsulated organic solar cells are prone to severe performance losses in the presence of moisture. Accelerated damp heat (85 °C/85% RH) studies are presented and it is shown that the hygroscopic hole-transporting PEDOT:PSS layer is the origin of device failure in the case of prototypical inverted solar cells. Complementary measurements unveil that under these conditions a decreased PEDOT:PSS work function along with areas of reduced electrical contact between active layer and hole-transport layer are the main factors for device degradation rather than a chemical reaction of water with the active layer. Replacements for PEDOT:PSS are explored and it is found that tungsten oxide (WO₃) or phosphomolybdic acid (PMA)—materials that can be processed from benign solvents at room temperature—yields comparable performance as PEDOT:PSS and enhances the resilience of solar cells under damp heat. The stability trend follows the order PEDOT:PSS << WO₃ < PMA, with PEDOT:PSS-based devices failing after few minutes, while PMA-based devices remain nearly pristine over several hours. PMA is thus proposed as a robust, solution-processable hole extraction layer that can act as a one to one replacement of PEDOT:PSS to achieve organic solar cells with significantly improved longevity.