Prediction of Chameleonic Efficiency

Chameleonic properties, i. e., the capacity of a molecule to hide polarity in non-polar environments and expose it in water, help achieving sufficient permeability and solubility for drug molecules with high MW. We present models of experimental measures of polarity for a set of 24 FDA approved drugs (MW 405-1113) and one PROTAC (MW 1034). Conformational ensembles in aqueous and non-polar environments were generated using molecular dynamics. A linear regression model that predicts chromatographic apparent polarity (EPSA) with a mean unsigned error of 10 Ų was derived based on separate terms for donor, acceptor, and total molecular SASA. A good correlation (R²=0.92) with an experimental measure of hydrogen bond donor potential, Δlog P_oct-tol, was found for the mean hydrogen bond donor SASA of the conformational ensemble scaled with Abraham's A hydrogen bond acidity. Two quantitative measures of chameleonic behaviour, the chameleonic efficiency indices, are introduced. We envision that the methods presented herein will be useful to triage designed molecules and prioritize those with the best chance of achieving acceptable permeability and solubility.     

Water vapor volatilization and oxidation induced surface cracking of environmental barrier coating systems: A numerical approach

A numerical model is developed for surface crack propagation in brittle ceramic coatings, aiming at the intrinsic failure of rare-earth silicate environmental barrier coating systems (EBCs) under combustion conditions in advanced gas turbines. The main features of progressive degradation of EBCs in such conditions are captured, including selective silica vaporization in the top coat due to exposure to water vapor, diffusion path-dependent bond coat oxidation, as well as crack propagation during cyclic thermal loading. In light of these features, user-defined subroutines are implemented in finite element analysis, where surface crack growth is simulated by node separation. Numerical results are validated by existing experimental data, in terms of monosilicate layer thickening, thermal oxide growth, and fracture behaviors. The experimentally observed quasi-linear oxidation in the early stage is also elucidated. Furthermore, it is suggested that surface crack undergoes rapid propagation in the late stage of extended thermal cycling in water vapor and leads to catastrophic failure, driven by both thermal mismatch and oxide growth stresses. The latter is identified as the dominant mechanism of penetration. Based on detailed analyses of failure mechanisms, the optimization strategy of EBCs composition is proposed, balancing the trade-off between mechanical compliance and erosion resistance.     

Novel energy-saving window coating based on F doped TiO2 nanocrystals with enhanced NIR shielding performance

To reduce the energy consumption of cooling in the hot summer days, searching for novel NIR shielding materials for buildings is of great value. In this report, monodispersed F doped TiO₂ nanocrystals with an average size of 8.6 nm were synthesized as novel solar shielding materials for energy-saving windows. All the products adopted an anatase TiO₂ structure. After doping of F ions, the morphology of TiO₂ was transformed from an irregular shape to a pseudospherical shape. The Raman shift and XPS depth analysis confirmed the successful doping of F⁻ ions into the lattice oxygen sites in the TiO₂ structure. The introduction of F⁻ ions generated free electrons and bulk Ti³⁺ in TiO₂ crystals, which activated a localized surface plasmon resonance (LSPR) absorption in the NIR region. Correspondingly, the NIR shielding performance of the TiO₂ films improved with increasing F doping amounts. The NIR shielding value of the films increased from 1.3% to 43.2% when the molar ratio of F to Ti increased from 0 to 0.3. The reason can be attributed to the enhanced NIR absorption induced by the increased electron concentration after doping of fluorine ions. The F–TiO₂ films showed superior visible transmittance (90.1–96.7%). Moreover, the F–TiO₂ films lowered the indoor temperature of the heat box by 5.3 °C in the thermal tests. Overall, the prepared F–TiO₂ nanocrystals show a great potential to be used for energy-saving windows.     

Self-healing capacity of Mullite-Yb2SiO5 environmental barrier coating material with embedded Ti2AlC MAX phase particles

Repetitive heating and cooling cycles inevitably cause crack damage of hot gas components of gas turbine engines, such as blades and vanes. In this study the self-healing capacity is investigated of mullite + ytterbium monosilicate (Yb₂SiO₅) as EBC material with Ti₂AlC MAX phase particles embedded as a crack-healing agent. The effect of Ti₂AlC in the EBC was compared with the self-healing ability of the mullite + Yb₂SiO₅ material. After introducing cracks by Vickers indentation on the surface of each sample, crack healing was realized by controlling the temperature and time during the post-heat-treatment process. For the mullite + Yb₂SiO₅ composite with Ti₂AlC particles, crack healing occurred at 1000 °C, while in the case of the mullite + Yb₂SiO₅ composite without Ti₂AlC, a sustained temperature of 1300 °C or higher was required. Compared with the healing of the mullite + Yb₂SiO₅ composite by the formation of a eutectic phase, the addition of Ti₂AlC promoted healing via the oxidation of Ti and Al. Notably, the surface formation of a ternary oxide of Ti–Yb–O was confirmed, which completely covered the damage area. Consequently, the addition of a Ti₂AlC MAX phase to the EBC composite resulted in a complete strength recovery, while the mullite + Yb₂SiO₅ composite without Ti₂AlC showed a strength recovery of about 80%. Furthermore, by analyzing the indentation load–displacement curve to indicate the role of Ti₂AlC, the addition of Ti₂AlC improved both the hardness and stiffness of the composite.     

Effect of suspension characteristics on the performance of thermal barrier coatings deposited by suspension plasma spray

This paper investigates the influence of suspension characteristics on microstructure and performance of suspensions plasma sprayed (SPS) thermal barrier coatings (TBCs). Five suspensions were produced using various suspension characteristics, namely, type of solvent and solid load content, and the resultant suspensions were utilized to deposit five different TBCs under identical processing conditions. The produced TBCs were evaluated for their performance i.e. thermal conductivity, thermal cyclic fatigue (TCF) and thermal shock (TS) lifetime. This experimental study revealed that the differences in the microstructure of SPS TBCs produced using varied suspensions resulted in a wide-ranging overall TBC performance. All TBCs exhibited thermal conductivity lower than 1 W/(m. K) except water-ethanol mixed suspension produced TBC. The TS lifetime was also affected to a large extent where 10 wt % solid loaded ethanol and 25 wt % solid loaded water suspensions produced TBCs exhibited the highest and the lowest lifetime, respectively. On the contrary, TCF lifetime was not as significantly affected as thermal conductivity and TS lifetime, and all ethanol suspensions showed marginally better TCF lifetime than water and ethanol-water mixed suspensions deposited TBCs.     

Salt-assisted solution combustion synthesis of NiFe2O4: Effect of salt type

The effects of three types of salt including NaF, KCl, and NaCl on the properties of NiFe₂O₄ nanoparticles using salt-assisted solution combustion synthesis (SSCS) have been investigated. The synthesized powders were evaluated by SEM, TEM, FTIR, XRD, and VSM analysis. Also, the specific surface area (SSA), as well as size distribution and volume of the porosities of NiFe₂O₄ powders were determined by the BET apparatus. The visual observations showed that the intensity and time of combustion synthesis of nanoparticles have been severely influenced by the type of salt. The highest crystallinity was observed in the synthesized powder using NaCl. The SSA has also been correlated completely to the type of salt. The quantities of SSA was achieved about 91.62, 64.88, and 47.22 m²g^-1 for the powders synthesized by KCl, NaCl, and NaF respectively. Although the magnetic hysteresis loops showed the soft ferromagnetic behavior of the NiFe₂O₄ nanoparticles in all conditions, KCl salt could produce the particles with the least coercivity and remanent magnetization. Based on the present study, the salt type is a key parameter in the SSCS process for the preparation of spinel ferrites. Thermodynamic evaluation also showed that the melting point and heat capacity are important parameters for the proper selection of the salt.     

Reconstructed Water Oxidation Electrocatalysts: The Impact of Surface Dynamics on Intrinsic Activities

Electroreduction of small molecules such as H₂O, CO₂, and N₂ for producing clean fuels or valuable chemicals provides a sustainable approach to meet the increasing global energy demands and to alleviate the concern on climate change resulting from fossil fuel consumption. On the path to implement this purpose, however, several scientific hurdles remain, one of which is the low energy efficiency due to the sluggish kinetics of the paired oxygen evolution reaction (OER). In response, it is highly desirable to synthesize high-performance and cost-effective OER electrocatalysts. Recent advances have witnessed surface reconstruction engineering as a salient tool to significantly improve the catalytic performance of OER electrocatalysts. In this review, recent progress on the reconstructed OER electrocatalysts and future opportunities are discussed. A brief introduction of the fundamentals of OER and the experimental approaches for generating and characterizing the reconstructed active sites in OER nanocatalysts are given first, followed by an expanded discussion of recent advances on the reconstructed OER electrocatalysts with improved activities, with a particular emphasis on understanding the correlation between surface dynamics and activities. Finally, a prospect for clean future energy communities harnessing surface reconstruction-promoted electrochemical water oxidation will be provided.     

Dual-phase rare-earth-zirconate high-entropy ceramics with glass-like thermal conductivity

A series of rare earth zirconates (RE₂Zr₂O₇) high-entropy ceramics with single- and dual-phase structure were prepared. Compared with La₂Zr₂O₇ and Yb₂Zr₂O₇, the smaller “rattling” ions (Yb³⁺, Er³⁺, Y³⁺) have been incorporated into pyrochlore lattice in (La_0.2Nd_0.2Y_0.2Er_0.2Yb_0.2)₂Zr₂O₇ (LNYEY) while larger ions (La³⁺, Nd³⁺, Sm³⁺, Eu³⁺) incorporated into fluorite lattice in (La_0.2Nd_0.2Sm_0.2Gd_0.2Yb_0.2)₂Zr₂O₇ (LNSGY). Due to high-entropy lattice distortion and resonant scattering derived from smaller ions Yb³⁺, Er³⁺, and Y³⁺, LNYEY shows a lower glass-like thermal conductivity (1.62-1.59 W m^-1 K^-1, 100-600℃) than LNSGY (1.74-1.75 W m^-1 K^-1, 100-600℃). Moreover, LNYEY and LNSGY exhibit enhanced Vickers’ hardness (LNYEY, H_v = 11.47 ± 0.41 GPa; LNSGY, H_v = 10.96 ± 0.26 GPa) and thermal expansion coefficients (LNYEY, 10.45 × 10^-6 K^-1, 1000℃; LNSGY, 11.02 × 10^-6 K^-1, 1000℃). These results indicate that dual-phase rare-earth-zirconate high-entropy ceramics could be desirable for thermal barrier coatings.