Re-examination of phase relations between solid solutions in R4Al2O9-R4Si2N2O7-R4Si2O10 (R=Y,Gd, Yb) systems

Samples in Si–Al-R-O-N (R = Y, Gd, Yb) systems were prepared by solid-state reactions using R₂O₃, Al₂O₃, SiO₂ and Si₃N₄ powders as starting materials. X-ray diffraction was done to investigate RAM-J(R) solid solutions [RAM = R₄Al₂O₉, J(R) = R₄Si₂N₂O₇] formation and their equilibrium with RSO (R₄Si₂O₁₀). Phase relations between RAM, J(R) and RSO at 1700 °C were summarized in a phase diagram. It was determined that a limited solid solution of RAM and RSO could be formed along RAM-RSO tie-line, while RAM and J(R) form a continuous solid solution along RAM-J(R) tie-line. In RAM-J(R)-RSO ternary systems, the RAM-J(R) tie-lines were extended towards the RSO corner to form a continuous solid solution area of JRAMss (R = Y, Gd, Yb). The established phase relations in the Si–Al-R-O-N (R = Y, Gd, Yb) systems may facilitate compositional selections for developing JRAMss as monolithic ceramics or for SiC/Si₃N₄ based composites using the solid-solutions as a second refractory phase.     

Pseudocapacitive contributions to electrochemical kinetics in NiOx electrochromic anodes

Because of its ability to change optical absorption dynamically by applied electric field, nickel oxide (NiO) is a promising anodic material in smart windows, which can improve energy conversion efficiency in construction buildings. Although many works have achieved high electrochromic performance with different method. The underlying mechanism is still not fully investigated. In this article, we prepared the NiO films with large specific surface area and high stability by electron beam evaporation. X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were employed to figure out the surface morphology and composition of as-deposited films. Afterwards, the electrochemical properties and optical performance of the prepared NiO films were investigated. On this basis, the origin of surface charge was fully analyzed by cyclic voltammetry and diffusion coefficient test. These experimental and theoretical results firmly confirm that both the surface reaction and capacitive effect bring about the excellent EC performance in NiO films. These results not only provide clear evidence about electrochemical kinetics in NiO films, but also offer some useful guidelines for the design of EC materials with higher performance and longer stability.     

Influence of SiC microstructure on its corrosion behavior in molten FLiNaK salt

The influence of the microstructure on the corrosion rate of three monolithic SiC samples in FLiNaK salt at 900 °C for 250 h was studied. The SiC samples, labeled as SiC-1, SiC-2, and SiC-3, had corrosion rates of 0.137, 0.020, and 0.043 mg/cm²h, respectively. Compared with grain size and the presence of special grain boundaries (i.e., Σ3), the content of high-angle grain boundaries (HAGBs) appeared to have the strongest influence on the corrosion rate of SiC in FLiNaK salt, since the corrosion rate increased six times as the concentration of high-angle grain boundaries increased from 19 to 32% for SiC-2 and SiC-1, respectively. These results stress the importance of controlling the content of HAGBs during the production process of SiC.     

Effect of nitrogen on the antibacterial behavior of oxynitride glasses

The main drawback of bioglasses is their restricted use in load bearing applications and the consequent need to develop stronger glassy materials. This has led to the consideration of oxynitride glasses for numerous biomedical applications. This paper investigated two different types of glasses at a constant cationic ratio, with and without nitrogen (a N containing and a N-free glass composition) to better understand the effect of N on the biological properties of glasses. The results revealed that the addition of N increased the glass transition temperature, isoelectric point (IEP) and slightly increased wettability. Moreover, compared to N including glass, N-free glass exhibited better anti-bacterial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), two key bacteria that infect implants. In summary, these in vitro results indicated that amine functional groups existing in N containing glasses which are missing in N-free glasses, caused a slight difference in wetting behavior and a more obvious change in isoelectric point and in bacterial response. N-free glasses exhibited better inhibitory results both against E. coli and S. aureus compared to N including glass suggesting that oxygen rich glasses should be further studied for their novel antibacterial properties.     

Identification of Novel Fragments Binding to the PDZ1-2 Domain of PSD-95

Inhibition of PSD-95 has emerged as a promising strategy for the treatment of ischemic stroke, as shown with peptide-based compounds that target the PDZ domains of PSD-95. In contrast, developing potent and drug-like small molecules against the PSD-95 PDZ domains has so far been unsuccessful. Here, we explore the druggability of the PSD-95 PDZ1-2 domain and use fragment screening to investigate if this protein is prone to binding small molecules. We screened 2500 fragments by fluorescence polarization (FP) and validated the hits by surface plasmon resonance (SPR), including an inhibition counter-test, and found four promising fragments. Three ligand efficient fragments were shown by ¹H,¹⁵N HSQC NMR to bind in the small hydrophobic P⁰ pockets of PDZ1-2, and one of them underwent structure-activity relationship (SAR) studies. Overall, we demonstrate that fragment screening can successfully be applied to PDZ1-2 of PSD-95 and disclose novel fragments that can serve as starting points for optimization towards small-molecule PDZ domain inhibitors.     

Impact of defects on the decomposition of chemical warfare agent simulants in Zr-based metal organic frameworks

Metal organic frameworks (MOFs) containing zirconium secondary building units (SBUs) in UiO-67 and related MOFs, are highly active for neutralizing both the chemical warfare agents and simulants, such as dimethyl methylphosphonate (DMMP). However, two recent publications gave conflicting reports of DMMP reaction with UiO-67 under ultra high vacuum (UHV) conditions, with one reporting chemisorption and reaction (Wang et al., J Phys Chem C, 2017, 121, 11261–11272) and the other reporting only physisorption and reversible desorption (Ruffley et al., J Phys Chem C, 2019, 123, 19748–19758) from very similar temperature programmed desorption experiments. We show that the discrepancy between these experiments may be explained by different levels of missing linker defects in the UiO-67 samples. We present density functional theory calculations showing that SBU sites having two-adjacent missing linkers exhibit reaction barriers that are about 30 kJ/mol lower than SBU sites having a single missing linker. We also show that topology of the undercoordinated sites plays an important role in the reaction barrier under UHV conditions.     

Densification mechanism and microstructure characteristics of nano- and micro- crystalline alumina by high-pressure and low temperature sintering

Fully dense ceramics with retarded grain growth can be attained effectively at relatively low temperatures using a high-pressure sintering method. However, there is a paucity of in-depth research on the densification mechanism, grain growth process, grain boundary characterization, and residual stress. Using a strong, reliable die made from a carbon-fiber-reinforced carbon (C_f/C) composite for spark plasma sintering, two kinds of commercially pure α-Al₂O₃ powders, with average particle sizes of 220 nm and 3 μm, were sintered at relatively low temperatures and under high pressures of up to 200 MPa. The sintering densification temperature and the starting threshold temperature of grain growth (T_sg) were determined by the applied pressure and the surface energy relative to grain size, as they were both observed to increase with grain size and to decrease with applied pressure. Densification with limited grain coarsening occurred under an applied pressure of 200 MPa at 1050 °C for the 220 nm Al₂O₃ powder and 1400 °C for the 3 μm Al₂O₃ powder. The grain boundary energy, residual stress, and dislocation density of the ceramics sintered under high pressure and low temperature were higher than those of the samples sintered without additional pressure. Plastic deformation occurring at the contact area of the adjacent particles was proved to be the dominant mechanism for sintering under high pressure, and a mathematical model based on the plasticity mechanics and close packing of equal spheres was established. Based on the mathematical model, the predicted relative density of an Al₂O₃ compact can reach ～80 % via the plastic deformation mechanism, which fits well with experimental observations. The densification kinetics were investigated from the sintering parameters, i.e., the holding temperature, dwell time, and applied pressure. Diffusion, grain boundary sliding, and dislocation motion were assistant mechanisms in the final stage of sintering, as indicated by the stress exponent and the microstructural evolution. During the sintering of the 220 nm alumina at 1125 °C and 100 MPa, the deformation tends to increase defects and vacancies generation, both of which accelerate lattice diffusion and thus enhance grain growth.     

Matrix Manipulation of Directly-Synthesized PbS Quantum Dot Inks Enabled by Coordination Engineering

The direct-synthesis of conductive PbS quantum dot (QD) ink is facile, scalable, and low-cost, boosting the future commercialization of optoelectronics based on colloidal QDs. However, manipulating the QD matrix structures still is a challenge, which limits the corresponding QD solar cell performance. Here, for the first time a coordination-engineering strategy to finely adjust the matrix thickness around the QDs is presented, in which halogen salts are introduced into the reaction to convert the excessive insulating lead iodide into soluble iodoplumbate species. As a result, the obtained QD film exhibits shrunk insulating shells, leading to higher charge carrier transport and superior surface passivation compared to the control devices. A significantly improved power-conversion efficiency from 10.52% to 12.12% can be achieved after the matrix engineering. Therefore, the work shows high significance in promoting the practical application of directly synthesized PbS QD inks in large-area low-cost optoelectronic devices.     

Structural Aspects and Prediction of Calmodulin-Binding Proteins

Calmodulin (CaM) is an important intracellular protein that binds Ca²⁺ and functions as a critical second messenger involved in numerous biological activities through extensive interactions with proteins and peptides. CaM’s ability to adapt to binding targets with different structures is related to the flexible central helix separating the N- and C-terminal lobes, which allows for conformational changes between extended and collapsed forms of the protein. CaM-binding targets are most often identified using prediction algorithms that utilize sequence and structural data to predict regions of peptides and proteins that can interact with CaM. In this review, we provide an overview of different CaM-binding proteins, the motifs through which they interact with CaM, and shared properties that make them good binding partners for CaM. Additionally, we discuss the historical and current methods for predicting CaM binding, and the similarities and differences between these methods and their relative success at prediction. As new CaM-binding proteins are identified and classified, we will gain a broader understanding of the biological processes regulated through changes in Ca²⁺ concentration through interactions with CaM.