Pyryliumverbindungen. 42. Benzocycloalkenone und Dihydro-2H,7H-1-benzopyranone aus 2,4,6-Triaryl-pyryliumsalzen und Cycloalkan-1,2-dionen

Pyrylium Compounds. 42. Benzocycloalkenones and Dihydro-2H,7H-1-benzopyranones from 2,4,6-Triarylpyrylium Salts and Cycloalkane-1,2-diones 2,4,6-Triarylpyrylium salts 1 react with cycloalkane-1,2-diones 2 in the presence of an appropriate condensing agent to yield benzocycloalkenones 3 . Thus, sodium acetate and cyclo-hexane-1,2-dione ( 2a ) lead to the dihydro-2H-naphthalenones 3a – i , whereas with cycloheptane-1,2-dione ( 2b ) and piperidine acetate, triethylamine or sodium acetate the tetrahydro-5H-benzo-cyclohepten-5-ones 3j – r are formed. As shown for the example 3a, j → 4a, b , benzocycloalkenones of type 3 can be converted into phthalazines 4 on heating with hydrazine in ethanol. By reaction of the dione 2a and an equimolar mixture of triethylamine and acetic acid or morpholine acetate with the salts 1 5,6-dihydro-2H,7H-1-benzopyran-8-ones 5 are obtained as a result of a new type of ring transformation. The pyrans 5 can be cleaved with perchloric acid in ethanol to 5,6,7,8-tetrahydro-8-oxo-1-benzopyrylium perchlorates 6 . If the pyrans 5 are heated with sodium acetate in ethanol, a conversion to benzocycloalkenones 3 is achieved (cf. 5a → 3a ). The structure of the new compounds was established by spectroscopic methods.     

Thermophysical Properties of ZrB2 and ZrB2–SiC Ceramics

Thermophysical properties were investigated for zirconium diboride (ZrB₂) and ZrB₂–30 vol% silicon carbide (SiC) ceramics. Thermal conductivities were calculated from measured thermal diffusivities, heat capacities, and densities. The thermal conductivity of ZrB₂ increased from 56 W (m K)⁻¹ at room temperature to 67 W (m K)⁻¹ at 1675 K, whereas the thermal conductivity of ZrB₂–SiC decreased from 62 to 56 W (m K)⁻¹ over the same temperature range. Electron and phonon contributions to thermal conductivity were determined using electrical resistivity measurements and were used, along with grain size models, to explain the observed trends. The results are compared with previously reported thermal conductivities for ZrB₂ and ZrB₂–SiC.     

Fracture Statistics Based on Pore/Grain-Size Interaction

The statistics of fracture in ceramics are discussed based on a model that describes crack instability that occurs at a configuration of a microcrack positioned in the stress-concentrating effect of a large pore. The interaction of pore size and grain-size distribution is considered, and the effect of a locally varying stress field is included. Results are presented as predictions of the critical pore size and microcrack size that cause fracture for the two assumed average grain sizes of 1 and 5 µm.     

Luminescent Amphiphilic Aminoglycoside Probes to Study Transfection

We report the characterization of amphiphilic aminoglycoside conjugates containing luminophores with aggregation-induced emission properties as transfection reagents. These inherently luminescent transfection vectors are capable of binding plasmid DNA through electrostatic interactions; this binding results in an emission “on” signal due to restriction of intramolecular motion of the luminophore core. The luminescent cationic amphiphiles effectively transferred plasmid DNA into mammalian cells (HeLa, HEK 293T), as proven by expression of a red fluorescent protein marker. The morphologies of the aggregates were investigated by microscopy as well as ζ-potential and dynamic light-scattering measurements. The transfection efficiencies using luminescent cationic amphiphiles were similar to that of the gold-standard transfection reagent Lipofectamine® 2000.     

Structure-Activity Relationships of Benzamides and Isoindolines Designed as SARS-CoV Protease Inhibitors Effective against SARS-CoV-2

Inhibition of coronavirus (CoV)-encoded papain-like cysteine proteases (PL^pro) represents an attractive strategy to treat infections by these important human pathogens. Herein we report on structure-activity relationships (SAR) of the noncovalent active-site directed inhibitor (R)-5-amino-2-methyl-N-(1-(naphthalen-1-yl)ethyl) benzamide ( 2 b ), which is known to bind into the S3 and S4 pockets of the SARS-CoV PL^pro. Moreover, we report the discovery of isoindolines as a new class of potent PL^pro inhibitors. The studies also provide a deeper understanding of the binding modes of this inhibitor class. Importantly, the inhibitors were also confirmed to inhibit SARS-CoV-2 replication in cell culture suggesting that, due to the high structural similarities of the target proteases, inhibitors identified against SARS-CoV PL^pro are valuable starting points for the development of new pan-coronaviral inhibitors.     

Particle In-Flight and Coating Properties of Fe-Based Feedstock Materials Sprayed with Modern Thermal Spray Systems

New developments in the field of thermal spraying systems (increased particle velocities, enhanced process stability) are leading to improved coatings. Innovations in the field of feedstock materials are supporting this trend. The combination of both has led to a renaissance of Fe-based feedstocks. Using modern APS or HVOF systems, it is now possible to compete with classical materials for wear and corrosion applications like Ni-basis or metal-matrix composites. This study intends to give an analysis of the in-flight particle and spray jet properties achievable with two different modern thermal spraying systems using Fe-based powders. The velocity fields are measured with the Laser Doppler Anemometry. Resulting coatings are analyzed and a correlation with the particle in-flight properties is given. The experiments are accompanied by computational fluid dynamics simulations of spray jet and particle velocities, leading to a comprehensive analysis of the achievable particle properties with state-of-the-art HVOF and APS systems.     

Heteroatom Effect on Star‐Shaped Hole‐Transporting Materials for Perovskite Solar Cells

Three new star‐shaped hole‐transporting materials (HTMs) incorporating benzotripyrrole, benzotrifuran, and benzotriselenophene central cores endowed with three‐armed triphenylamine moieties ( BTP‐1 , BTF‐1 , and BTSe‐1 , respectively) are designed, synthesized, and implemented in perovskite solar cells (PSCs). The impact that the heteroatom‐containing central scaffold has on the electrochemical and photophysical properties, as well as on the photovoltaic performance, is systematically investigated and compared with their sulfur‐rich analogue ( BTT‐3 ). The new HTMs exhibit suitable highest‐occupied molecular orbitals (HOMO) levels regarding the valence band of the perovskite, which ensure efficient hole extraction at the perovskite/HTM interface. The molecular structures of BTF‐1 , BTT‐3 , and BTSe‐1 are fully elucidated by single‐crystal X‐ray crystallography as toluene solvates. The optimized (FAPbI₃)_0.85(MAPbBr₃)_0.15‐based perovskite solar cells employing the tailor‐made, chalcogenide‐based HTMs exhibit remarkable power conversion efficiencies up to 18.5%, which are comparable to the devices based on the benchmark spiro‐OMeTAD. PSCs with BTP‐1 exhibit a more limited power conversion efficiency of 15.5%, with noticeable hysteresis. This systematic study indicates that chalcogenide‐based derivatives are promising HTM candidates to compete efficiently with spiro‐OMeTAD.     

Transimpedance amplifier with 120 dB dynamic range

A transimpedance amplifier (TIA) with compression of the input current is presented. The proposed TIA has two regions of operation: a linear one for small input currents and one with compression for high currents, which would otherwise saturate the TIA. The measured -3 dB bandwidth is 102 MHz, the equivalent RMS input current noise is 20.2 nA and the maximal current overdrive is 20.5 mA, leading to a dynamic range at the input of 120 dB