Two Methods,One Goal: Structural Differences between Cocrystallization and Crystal Soaking to Discover Ligand Binding Poses

In lead optimization, protein crystallography is an indispensable tool to analyze drug binding. Binding modes and non-covalent interaction inventories are essential to design follow-up synthesis candidates. Two protocols are commonly applied to produce protein–ligand complexes: cocrystallization and soaking. Because of its time and cost effectiveness, soaking is the more popular method. Taking eight ligand hinge binders of protein kinase A, we demonstrate that cocrystallization is superior. Particularly for flexible proteins, such as kinases, and larger ligands cocrystallization captures more reliable the correct binding pose and induced protein adaptations. The geometrical discrepancies between soaking and cocrystallization appear smaller for fragment-sized ligands. For larger flexible ligands that trigger conformational changes of the protein, soaking can be misleading and underestimates the number of possible polar interactions due to inadequate, highly impaired positions of protein amino-acid side and main chain atoms. Thus, if applicable cocrystallization should be the gold standard to study protein–ligand complexes.     

Investigation of the microwave dielectric properties of the Li4x/3Zn2−2xTi1+2x/3O4 system by P–V–L theory and vibration spectroscopy

Li_4x/3Zn_2–2xTi_1+2x/3O₄ microwave dielectric ceramics with a spinel phase were prepared via a high-temperature solid-phase method. P–V–L theory, vibration spectra, and XPS were utilized to establish the links between the intrinsic and extrinsic factors and the microwave dielectric properties. According to the characterization, the change in permittivity (ε_r) was ascribed to the increase in the average bond ionicity of Ti–O(Af_iTi-O) and the polar mode of the lattice vibration; the change in quality factor(Q × f) resulted from the change in the Ti–O lattice energy (AU_Ti-O) and existence of oxygen vacancy; the increase in temperature coefficient of the resonance frequency (τ_f) was triggered by the increase in the Ti–O bond energy. The Li_0.6Zn_1.1Ti_1.3O₄ ceramics (x = 0.45) sintered at 1125 °C finally obtained optimal microwave dielectric constants of ε_r = 17.3, Q × f = 76,318 GHz and τ_f = -58 ppm/°C.     

Effect of lattice structure evolution and stacking fault energy on the properties of Cu–ZrO2/GNP nanocomposites

A hybrid nanocomposite comprising nanosized ZrO₂ and graphene nanoplatelet (GNP)-reinforced Cu matrix was synthesised via powder metallurgy. The influence of sintering temperature and GNP content on the electrical and mechanical behaviour of the Cu–ZrO₂/GNP nanocomposite was investigated. The ZrO₂ concentration was fixed at 10% for all the composites. Upon increasing the GNP concentration up to 0.5%, a significant improvement was observed in the compressive strength, microhardness, and electrical conductivity of the composite. Furthermore, the properties were significantly improved by increasing the sintering temperature from 900 to 1000 °C. The compressive strength, hardness, and electrical conductivity of Cu–10%ZrO₂/0.5%GNP were higher than those of the Cu–ZrO₂ nanocomposite by 60, 21, and 23.8%, respectively. This improvement in the mechanical properties is because of the decrease in the crystallite size and dislocation spacing, which increases the dislocation density, thereby increasing the impedance towards dislocation movement. The lower stacking fault energy of the hybrid nanocomposites enables easier electron transfer within and between the Cu grains, resulting in an improved electrical conductivity. The enhancement in strength and electrical conductivity were aided by the GNPs and ZrO₂ nanoparticles that were dispersed widely in the Cu matrix.     

Interfacial microstructure and mechanical properties of Ti3SiC2 ceramic and TC11 alloy joint diffusion bonded with a Cu interlayer

Reliable joints of Ti₃SiC₂ ceramic and TC11 alloy were diffusion bonded with a 50 μm thick Cu interlayer. The typical interfacial structure of the diffusion boned joint, which was dependent on the interdiffusion and chemical reactions between Al, Si and Ti atoms from the base materials and Cu interlayer, was TC11/α-Ti + β-Ti + Ti₂Cu + TiCu/Ti₅Si₄ + TiSiCu/Cu(s, s)/Ti₃SiC₂. The influence of bonding temperature and time on the interfacial structure and mechanical properties of Ti₃SiC₂/Cu/TC11 joint was analyzed. With the increase of bonding temperature and time, the joint shear strength was gradually increased due to enhanced atomic diffusion. However, the thickness of Ti₅Si₄ and TiSiCu layers with high microhardness increased for a long holding time, resulting in the reduction of bonding strength. The maximum shear strength of 251 ± 6 MPa was obtained for the joint diffusion bonded at 850 °C for 60 min, and fracture primarily occurred at the diffusion layer adjacent to the Ti₃SiC₂ substrate. This work provided an economical and convenient solution for broadening the engineering application of Ti₃SiC₂ ceramic.     

Strong tribocatalytic dye degradation by tungsten bronze Ba4Nd2Fe2Nb8O30

The triboelectric effect has recently demonstrated its great potential in environmental remediation and even new energy applications for triggering a number of catalytic reactions by utilizing trivial mechanical energy. In this study, Ba₄Nd₂Fe₂Nb₈O₃₀ (BNFN) submicron powders were used to degrade organic dyes via the tribocatalytic effect. Under the frictional excitation of three PTFE stirring rods in a 5 mg/L RhB dye solution, BNFN demonstrates a high tribocatalytic degradation efficiency of 97% in 2 h. Hydroxyl radicals (?OH) and superoxide radicals (?O₂－) were also detected during the catalysis process, which proves that triboelectric energy stimulates BNFN to generate electron-hole pairs. The tribocatalysis of tungsten bronze BNFN submicron powders provides a novel and efficient method for the degradation of wastewater dye by utilizing trivial mechanical energy.     

Preparation of carbon fibers@NiS/Ni3S4@MoS2 with core-sheath structure for high efficiency and wide-bandwidth microwave absorption

Numerous studies have focused on the preparation of carbon fibers (CFs)-based high-efficiency microwave absorbers with reasonable structural design and surface morphology control, which simultaneously meet the required impedance matching and loss ability. Here, CFs@NiS/Ni₃S₄@MoS₂ (CNNM) with core-sheath structure was prepared through several simple hydrothermal reactions. The morphology of the as-prepared CNNM nanocomposite is controlled by the amount of added sodium molybdate dihydrate, which causes the difference in minimum reflection loss (RL) and effective attenuation bandwidth among the samples. For the microwave absorbing performance, the minimum RL is ?18 dB and the effective attenuation bandwidth is 8.7 GHz, which appear at the thickness of 2.8 mm and cover most of the X- and Ku-bands. The excellent absorbing performance is attributed to optimized impedance matching and enhanced polarization loss. These results originate from the transition metal sulfides, which not only effectively prevent the skin effect by decreasing the conductivity of CFs but also increase interfaces and flaws, leading to interface polarization and dipole polarization losses.     

Effect of preparation method on the mechanism for oxidation of C/C-BN composites

C/C-BN composites and C_f/BN/PyC composites exhibiting different structures for pyrolytic carbon (PyC) and boron nitride (BN) were studied comparatively to determine their oxidation behavior. This study used five types of samples. Porous C/C composites were modified with silane coupling agents (APS) and then fully impregnated in water-based slurry of hexagonal boron nitride (h-BN); the resulting C/C-BN preforms were densified by depositing PyC by chemical vapor infiltration (CVI), resulting in three types of C/C-BN composites. The other two C_f/BN/PyC composites were obtained by depositing a BN interphase and PyC in carbon fiber preforms by CVI; one was treated with heat, and the other was not. This study was focused on determining how the PyC deposition mechanism, morphology and pore structure were affected by the method of BN introduction. In the 600–900 °C temperature range, the C_f/BN/PyC composites and C/C composites underwent oxidation via a mixed diffusion/reaction mode. The C/C-BN composites had a different pore structure due to the formation of nodules comprising h-BN particles; both interfacial debonding and cracking were reduced, resulting in higher resistance to gas diffusion, lower oxidation rate and larger activation energy (Ea) in the temperature range 600–800 °C. In addition, the mechanism for oxidation of C/C-BN composites gradually exhibited diffusion control at 800–900 °C because the formation of h-BN oxidation products healed the defects. The oxidation mechanism was more dependent on pore structure than on BN structure or content.     

One-step synthesis of t-ZrO2 from Zircon using magnesium-calcium minerals as stabilizers

Stabling crystal structure at room temperature is a classic problem in the study of Zirconium dioxide (ZrO₂). However, there are few investigations on making tetragonal zirconia (t-ZrO₂) in one step at a low cost. In this research, t-ZrO₂ is synthesized using a one-step high-temperature solid-state sintering technique with magnesite, dolomite, and limestone as stabilizers and zircon as the raw material. The most suitable stabilizers and reaction conditions are determined, and the mechanism of zirconia structure stabilization is explored. The findings suggest that magnesite has the lowest effect as a crystal structure stabilizer, whereas dolomite and limestone are pretty close, but dolomite introduces more impurities. The ideal reaction conditions were 60% mol limestone at 1500 °C. The stabilization mechanism is zirconia gap correction, according to XRD and EPR data. The characterization of the SEM demonstrates that the heat treatment temperature and stabilizer had little effect on the morphology of t-ZrO₂. When limestone was introduced throughout the process, EDS data revealed that some amorphous silicon-calcium compounds occurred in the product. The focus of follow-up work will be on how to lessen the impact in this area. This research offers vital reference value for reducing the cost of the synthetic t-ZrO₂ process.