Evaluation of dynamic modulus measurement for C/C-SiC composites at different temperatures

The determination of elastic properties at application temperature is fundamental for the design of fibre reinforced ceramic composite components. An attractive method to characterize the flexural modulus at room and high temperature under specific atmosphere is the nondestructive Resonant Frequency Damping Analysis (RFDA). The objective of this paper was to evaluate and validate the modulus measurement via RFDA for orthotropic C/C-SiC composites at the application temperature. At room temperature flexural moduli of C/C-SiC with 0/90° reinforcement were measured under quasi-static 4-point bending loads and compared with dynamic moduli measured via RFDA longitudinally to fibre direction. The dynamic modulus of C/C-SiC was then measured via RFDA up to 1250°C under flowing inert gas and showed an increase with temperature which fitted with literature values. The measured fundamental frequencies were finally compared to those resulting from numerical modal analyses. Dynamic and quasi-static flexural moduli are comparable and the numerical analyses proved that bending modes are correctly modeled by means of dynamic modulus measured via RFDA. The nondestructive RFDA as well as the numerical modeling approach are suitable for evaluation of C/C-SiC and may be transferred to other fibre reinforced ceramic composite materials.     

Aluminum to germanium inversion in mullite-type RAlGeO5: Characterization of a rare phenomenon for R = Y,Sm–Lu

Mullite-type RMn₂O₅ (R = Y, rare-earth element) ceramics are of ongoing research attentions because of their interesting crystal-chemical, physical, and thermal properties. We report a detailed structural, spectroscopic and thermal analysis of the series of mullite-type RAlGeO₅ (R = Y, Sm-Lu) phases. Polycrystalline samples are prepared by solid-state synthesis methods. Each sample is characterized by X-ray powder diffraction followed by Rietveld refinements, showing that they are isotypic and crystallize in the space group Pbam. The change of the metric parameters is explained in term of the lanthanide contraction effect. A rare inversion of Al/Ge between octahedral and pyramidal sites have been observed for these mullite-type so called O10 compounds, and the inversion parameter found to be between 0.22(1) and 0.30(1) for different R-cations. The <Al/Ge–O> bond distances and their bond valence sums (BVSs) support the respective inversions. Density functional theory (DFT) calculated phonon density of states (PDOS) and electronic band structures are compared for the vibrational and electronic band gap features respectively. Analysis of UV/Vis absorption spectra using both derivation of absorption spectra fitting (DASF) and Tauc's methods demonstrates that each of the RAlGeO₅ O10 compounds is high bandgap semiconductor, possessing direct transition between 4.1(1) and 5.4(1) eV. Both Raman and Fourier transform infrared spectra show clear red shift (quasi-harmonic) of the vibrational wavenumbers with respect to the ionic radii of the R-cations. Selective Raman bands at higher wavenumber region further complement the inversion of Al/Ge between two coordination sites. The higher decomposition temperature of the RAlGeO₅ compounds, compared to those of RMn₂O₅ phases, is explained in terms of higher bond strength of Al/Ge-O than those of Mn-O. Irrespective to the inversion between Al- and Ge-sites, the decomposition temperature also depends on the type of R-cation in RAlGeO₅.     

Gas Responsive Nanoswitch: Copper Oxide Composite for Highly Selective H2S Detection

A nanocomposite material based on copper(II) oxide (CuO) and its utilization as a highly selective and stable gas‐responsive electrical switch for hydrogen sulphide (H₂S) detection is presented. The material can be applied as a sensitive layer for H₂S monitoring, e.g., in biogas gas plants. CuO nanoparticles are embedded in a rigid, nanoporous silica (SiO₂) matrix to form an electrical percolating network of low conducting CuO and, upon exposure to H₂S, highly conducting copper(II) sulphide (CuS) particles. By steric hindrance due to the silica pore walls, the structure of the network is maintained even though the reversible reaction of CuO to CuS is accompanied by significant volume expansion. The conducting state of the percolating network can be controlled by a variety of parameters, such as temperature, electrode layout, and network topology of the porous silica matrix. The latter means that this new type of sensing material has a structure‐encoded detection limit for H₂S, which offers new application opportunities. The fabrication process of the mesoporous CuO@SiO₂ composite as well as the sensor design and characteristics are described in detail. In addition, theoretical modeling of the percolation effect by Monte‐Carlo simulations yields deeper insight into the underlying percolation mechanism and the observed response characteristics.     

Lab-Scale Microreactor Plant for the Study of Methylations with Liquid Chloromethane

Chloromethane is an important reagent for methylations in the process industry. However, as a gas suspected of causing cancer, it is rarely used at laboratory scale. Therefore, a setup is presented here for studies in a laboratory under safe and reproducible conditions. The use of a microreactor guarantees high heat transfer rates and a low holdup of the reagent. As a proof-of-concept, the reaction of chloromethane with the secondary amine morpholine in aqueous solution is investigated. By applying elevated pressures, a liquid-liquid system with enhanced solubility of chloromethane in the aqueous phase is accessible.     

Long term stability of electrocaloric response in barium zirconate titanate

The stability of the electrocaloric effect under electric field cycling is an important consideration in the development of solid-state cooling devices. Here we report measurements carried out on Ba(Zr_0.2Ti_0.8)O₃ ceramics which reveal that the adiabatic temperature change, polarization-electric field hysteresis loops and dielectric permittivity/loss show stable behavior up to 10⁵ cycles. We further demonstrate that the loss in electrocaloric response observed after 10⁵ cycles is associated with the migration of oxygen vacancies. As a result, the electrical properties of the material are changed leading to an increase in leakage current and Joule heating. Reversing the polarity of the electric field after every 10⁵ cycles changes the migration direction of oxygen vacancies, thereby preventing charge accumulation at grain boundaries and electrodes. By doing so, the electrocaloric stability is improved and the adiabatic temperature remains constant even after 10⁶ cycles, much higher than achieved in commercially available barium titanate ceramics.     

Effect of pre-treatment and hydraulic retention time on biohydrogen production from organic wastes

This study investigated the effect of pre-treatment and hydraulic retention time (HRT) on biohydrogen production from organic wastes. Various pre-treatments including thermal, base, acid, ultrasonication, and hydrogen peroxide were applied alone or in combination to enhance biohydrogen production from potato and bean wastewater in batch tests. All the pre-treated samples showed higher hydrogen production than the control tests. Hydrogen peroxide pre-treatment achieved the best results of 939.7 and 470 mL for potato and bean wastewater, respectively. Continuous biohydrogen production from sucrose, potato and bean wastewater was significantly influenced by reducing the HRT as 24, 18 and 12 h. Sucrose and potato showed similar behavior, where the hydrogen production rate (HPR) increased with decreasing the HRT. Optimum hydrogen yield results of 320 mL-H₂/g-VS (sucrose) and 150 mL-H₂/g-VS (potato) were achieved at HRT of 18 h. Bean wastewater showed optimum HPR of 0.65 L/L.d with hydrogen yield of 80 mL-H₂/g-VS at 24 h HRT.     

Stray current-induced corrosion in cathodic protection installations of steel-reinforced concrete structures: FEM study of the critical parameters

A wide range of parameters was investigated by numerical calculations concerning their impact on DC stray current corrosion of reinforced concrete (RC) structures. A simplified model geometry was used to extract the relevant parameters and their interaction in terms of stray current-affected structures. This study mainly focuses on RC structures that are fitted with cathodic protection installations. The findings reveal a complex interaction between the investigated parameters. The possible relevance of further parameters, which is not the subject of this study, was emphasised.     

Extracellular Vesicles: Messengers of p53 in Tumor–Stroma Communication and Cancer Metastasis

Tumor progression to a metastatic and ultimately lethal stage relies on a tumor-supporting microenvironment that is generated by reciprocal communication between tumor and stromal host cells. The tumor–stroma crosstalk is instructed by the genetic alterations of the tumor cells—the most frequent being mutations in the gene Tumor protein p53 (TP53) that are clinically correlated with metastasis, drug resistance and poor patient survival. The crucial mediators of tumor–stroma communication are tumor-derived extracellular vesicles (EVs), in particular exosomes, which operate both locally within the primary tumor and in distant organs, at pre-metastatic niches as the future sites of metastasis. Here, we review how wild-type and mutant p53 proteins control the secretion, size, and especially the RNA and protein cargo of tumor-derived EVs. We highlight how EVs extend the cell-autonomous tumor suppressive activity of wild-type p53 into the tumor microenvironment (TME), and how mutant p53 proteins switch EVs into oncogenic messengers that reprogram tumor–host communication within the entire organism so as to promote metastatic tumor cell dissemination.     

N-Heterocyclization in Gliotoxin Biosynthesis is Catalyzed by a Distinct Cytochrome P450 Monooxygenase

Gliotoxin and related epidithiodiketopiperazines (ETP) from diverse fungi feature highly functionalized hydroindole scaffolds with an array of medicinally and ecologically relevant activities. Mutation analysis, heterologous reconstitution, and biotransformation experiments revealed that a cytochrome P450 monooxygenase (GliF) from the human-pathogenic fungus Aspergillus fumigatus plays a key role in the formation of the complex heterocycle. In vitro assays using a biosynthetic precursor from a blocked mutant showed that GliF is specific to ETPs and catalyzes an unprecedented heterocyclization reaction that cannot be emulated with current synthetic methods. In silico analyses indicate that this rare biotransformation takes place in related ETP biosynthetic pathways.     

Photocaged Hoechst Enables Subnuclear Visualization and Cell Selective Staining of DNA in vivo

Selective targeting of DNA by means of fluorescent labeling has become a mainstay in the life sciences. While genetic engineering serves as a powerful technique and allows the visualization of nucleic acid by using DNA-targeting fluorescent fusion proteins in a cell-type- and subcellular-specific manner, it relies on the introduction of foreign genes. On the other hand, DNA-binding small fluorescent molecules can be used without genetic engineering, but they are not spatially restricted. Herein, we report a photocaged version of the DNA dye Hoechst33342 (pcHoechst), which can be uncaged by using UV to blue light for the selective staining of chromosomal DNA in subnuclear regions of live cells. Expanding its application to a vertebrate model organism, we demonstrate uncaging in epithelial cells and short-term cell tracking in vivo in zebrafish. We envision pcHoechst as a valuable tool for targeting and interrogating DNA with precise spatiotemporal resolution in living cells and wild-type organisms.