High‐Temperature Creep Behavior of Dense SiOC‐Based Ceramic Nanocomposites: Microstructural and Phase Composition Effects

In this work, dense monolithic polymer‐derived ceramic nanocomposites (SiOC, SiZrOC, and SiHfOC) were synthesized via hot‐pressing techniques and were evaluated with respect to their compression creep behavior at temperatures beyond 1000°C. The creep rates, stress exponents as well as activation energies were determined. The high‐temperature creep in all materials has been shown to rely on viscous flow. In the quaternary materials (i.e., SiZrOC and SiHfOC), higher creep rates and activation energies were determined as compared to those of monolithic SiOC. The increase in the creep rates upon modification of SiOC with Zr/Hf relies on the significant decrease in the volume fraction of segregated carbon; whereas the increase of the activation energies corresponds to an increase of the size of the silica nanodomains upon Zr/Hf modification. Within this context, a model is proposed, which correlates the phase composition as well as network architecture of the investigated samples with their creep behavior and agrees well with the experimentally determined data.     

LAS glass–ceramic scaffolds by three-dimensional printing

Highly porous (>60% open porosity) glass–ceramic scaffolds with remarkable mechanical properties (compression strength of ～15 MPa) were produced by indirect 3D printing. Precursor glass powders were printed into 3D ordered structures and then heat treated to sinter and develop crystalline phases. The final glass–ceramic contained a β-spodumene solid solution together with a secondary phase of lithium disilicate.The precision of the printed geometry and the density of the struts in the scaffold depended on several processing parameters (e.g. powder size and flowability, layer thickness) and were improved by increasing the binder saturation and drying time. Two types of powders with different particle size distribution (PSD) and flowability were used. Powders with a larger PSD, could be processed within a wider range of printing parameters due to their good flowability; however, the printing precision and the struts density were lower compared to the scaffolds printed using the powder in a smaller average PSD.     

Synthesis and antiapoptotic activity of a novel analogue of the neutral sphingomyelinase inhibitor scyphostatin

The enantioselective synthesis of an analogue of scyphostatin, a potent inhibitor of the neutral sphingomyelinase, is described. The synthesis starts with cyclohexanone and a protected D-serine derivative. The key step is an asymmetric hydroxylation to access a hydroxycyclohexanone, which is transformed into a substituted hydroxycyclohexenone. This is converted into the scyphostatin analogue 14, a chemically and metabolically stabilised compound lacking the epoxy function of the natural congener and carrying a palmitic acid group instead of the native trienoyl residue. An evaluation of the biological activity of 14 revealed neutral sphingomyelinase inhibition in several in vivo test systems (monocytes, macrophages, hepatocytes) monitoring antiapoptotic effects and the inversion of phorbolester-induced translocation of green fluorescent protein labelled kinase (protein kinase C-alpha).     

Characterization of Cu/CeO2/γ-Al2O3 Thin Film Catalysts by Thermal Desorption Spectroscopy

Thermal desorption spectroscopy (TDS) under ultra high vacuum (UHV) condition has been used to investigate the desorption characteristics of Cu/CeO₂/γ-Al₂O₃ thin film catalysts coated onto the microchannel of a microreactor. TDS results demonstrate that surface desorption profiles and chemical properties (acid–base and redox properties) are remarkably influenced by the catalyst composition, i.e. the loading of copper and ceria. The enhanced basicity with the increase of ceria loading and the decrease of copper loading is evident from the shifted desorption maximum of CO₂ in TDS spectra. Three oxygen species, ranging from weakly bound oxygen desorbed at low temperature to the strongly held lattice oxygen desorbed at high temperature, are easily discernible and clearly identified by O₂ TDS spectra, depending on the catalyst compositions. The concomitant thermal desorption of O₂, CO₂, and H₂O at low temperature indicates the unique chemical properties of copper/ceria catalyst with appropriate copper and ceria contents. The observed low-temperature feature is ascribed to the role of porthole of copper/ceria interfacial area for several desorbed species. The weakly bound oxygen species is attributed to the enhanced abundance of copper/ceria interfacial anionic vacancies created by the intimate contact between copper and ceria entities and its impact on steam reforming of methanol (SRM) reaction is tentatively discussed in terms of reverse oxygen spillover.     

Identification and Structure–Activity Relationship Studies of Small‐Molecule Inhibitors of the Methyllysine Reader Protein Spindlin1

The methyllysine reader protein Spindlin1 has been implicated in the tumorigenesis of several types of cancer and may be an attractive novel therapeutic target. Small‐molecule inhibitors of Spindlin1 should be valuable as chemical probes as well as potential new therapeutics. We applied an iterative virtual screening campaign, encompassing structure‐ and ligand‐based approaches, to identify potential Spindlin1 inhibitors from databases of commercially available compounds. Our in silico studies coupled with in vitro testing were successful in identifying novel Spindlin1 inhibitors. Several 4‐aminoquinazoline and quinazolinethione derivatives were among the active hit compounds, which indicated that these scaffolds represent promising lead structures for the development of Spindlin1 inhibitors. Subsequent lead optimization studies were hence carried out, and numerous derivatives of both lead scaffolds were synthesized. This resulted in the discovery of novel inhibitors of Spindlin1 and helped explore the structure–activity relationships of these inhibitor series.     

Me-DLC films as material for highly sensitive temperature compensated strain gauges

In technical applications strain gauges are widely used. Apart from conventional polymer foil based strain gauges that are glued to the work piece surface, sputtered strain gauges are already commercially used in special applications. Those sputter strain gauges are typically made of NiCr alloy and the sensor layer is as sensitive to strain as the ones used in the glued strain gauges with a gauge factor of 2, but neglecting problems of creeping and swelling of the involved polymer materials. Diamond-like carbon (DLC) films offer significantly higher strain sensitivity, but usually they are also very sensitive to temperature effects. Using metal doped diamond-like carbon (Me-DLC), higher strain sensitivity than conventional metal based systems, in combination with thermal compensation, is possible. The influence of different process parameters on the gauge factor and temperature coefficient of resistance (TCR) of DLC and Me-DLC films produced in industrial sputtering systems was investigated. Gauge factors up to 13 in combination with a high negative TCR in the range of a few thousand ppm/K were reached with sputtered DLC films. The substrate bias voltage in particular showed a strong influence on the resulting gauge factor of the films. For Me-DLC films different deposition methods (dc and rf sputtering) and various doping metals (Ag, Ni, Ti, and W) were investigated. Using dc sputtering of the Me-DLC films only Ni-DLC showed gauge factors slightly higher than 2. Furthermore, only for Ni-DLC zero crossing of the TCR was observed by variation of the metal content. Using rf excitation especially Ni-DLC films showed gauge factors exceeding values of 15 in combination with a TCR close to zero.     

The use of microwave irradiation for the easy synthesis of graphene-supported transition metal nanoparticles in ionic liquids

Stable ruthenium or rhodium metal nanoparticles were supported on chemically derived graphene (CDG) surfaces with small and uniform particle sizes (Ru 2.2 ± 0.4 nm and Rh 2.8 ± 0.5 nm) by decomposition of their metal carbonyl precursors by rapid microwave irradiation in a suspension of CDG in the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate. The graphene-supported hybrid nanoparticles were shown to be active and could be re-used at least 10 times as catalysts for the hydrogenation of cyclohexene and benzene under organic-solvent-free conditions with constant activities up to 1570 mol cyclohexane × (mol metal)⁻¹ × h⁻¹ at 4 bar and 75 °C.     

Polysilazane derived micro/nano Si3N4/SiC composites

The pyrolised polysilazanes poly(hydridomethyl)silazane NCP 200 and poly(urea)silazane CERASET derived Si–C–N amorphous powders were used for preparation of micro/nano Si₃N₄/SiC composites by hot pressing. Y₂O₃–Al₂O₃ and Y₂O₃–Yb₂O₃ were used, as sintering aids. The resulting ceramic composites of all compositions were dense and polycrystalline with fine microstructure of average grain size <1 μm of both Si₃N₄ and SiC phases. The fine SiC nano-inclusions were identified within the Si₃N₄ micrograins. Phase composition of both composites consist of , β modifications of Si₃N₄ and SiC. High weight loss was observed during the hot pressing cycle, 12 and 19 wt.% for NCP 200 and CERASET precursors, respectively. The fracture toughness of both nanocomposites (NCP 2000 and CERASET derived) was not different. Indentation method measured values are from 5 to 6 MPa m^1/2, with respect to the sintering additive system. Fracture toughness is slightly sensitive to the SiC content of the nanocomposite. Hardness increases with the content of SiC in the nanocomposite. The highest hardness was achieved for pyrolysed CERASET precursor with 2 wt.% Y₂O₃ and 6 wt.% Yb₂O₃, HV 23 GPa. This is a consequence of the highest SiC content as well as the chemical composition of additives.