Ir(III) and Ru(II) Complexes in Photoredox Catalysis and Photodynamic Therapy: A New Paradigm towards Anticancer Applications

Individually, photoredox catalysis (PC) and photodynamic therapy (PDT) are well-established concepts that have experienced a remarkable resurgence in recent years, leading to significant progress in organic synthesis for PC and clinical approval of anticancer drugs for PDT. But, very recently, new photoredox catalyst systems based on Ir(III) and Ru(II) complexes have garnered significant interest because they can simultaneously be used as PDT agents apart from their demonstrated PC activity. This highlight discusses the unique PC behavior of emerging Ir(III)- and Ru(II)-based systems while also examining their potential PDT activity in cancer treatment.     

Femtosecond Ti: Sa ultra short-pulse laser irradiation effects on the properties and morphology of the zirconia surface after ageing

Femtosecond pulses from a Ti:Sapphire laser were used to irradiate specimens of yttria-stabilised (35% mol) tetragonal zirconia (Y-TZP) with the purpose of studying the effects of the irradiations on their surface properties and morphology after ageing. Zirconia disks were divided into eight groups (n = 32) according to their surface treatment and subsequent ageing: Control: no treatment; sandblasting: Al₂O₃ sandblasting 50 μm; and ultrashort laser pulses irradiation with 25 μJ pulses, considering two different scanning steps based on the width between two grooves. These groups were duplicated and submitted to ageing. The surfaces were analysed using scanning electron microscopy (SEM), and X-ray diffraction. A finite element analysis, a biaxial flexure test, as well as fractographic and Weibull analyses, were performed. The strengths of the disks were statistically different for the treatment factor, and the principal stresses seemed to be concentrated at the centre of the specimens, as predicted by the computer simulations. Ageing decreased the strengths for all groups and increased the Weibull modulus for the laser group with the 40 μm-width between two grooves. The sandblasting group presented the highest monoclinic phase peak. Although the most significant strength was found within the sandblasting group, the phase transformation was favourable to the laser groups. The Weibull modulus was higher for the laser group with the 60 μm-width between two grooves, confirming the highest homogeneity of its failure distribution. Regardless of the surface treatment, strength was decreased with ageing in all groups. The femtosecond Ti:Sa ultra-short pulse laser irradiation can be suggested as an alternative to the gold standard sandblasting in long-term Y-TZP zirconia rehabilitations, such as crowns and veneers.     

Altered age-hardening behavior in the ultrafine-grained surface layer of Mg-Zn-Y-Ce-Zr alloy processed by sliding friction treatment

To gain insight into the ageing behavior of ultrafine grain(UFG)structure,the precipitation phenom-ena and microstructural evolutions of Mg-6Zn-1Y-0.4Ce-0.5 Zr(wt.％)alloy processed by sliding friction treatment(SFT)were systematically studied using hardness texting,transmission electron microscopy(TEM)equipped with high-angle annular dark-field scanning(HADDF-STEM),X-ray diffraction(XRD)and XRD line broadening analysis.The microhardness of the SFT-processed(SFTed)sample initially decreases from 109.6 HV to 104.8 HV at ageing for 8 h,and then increases to the peak-ageing point of 115.4 HV at 16 h.Subsequently,it enters the over-aged period.The un-SFTed sample,as the counterpart,follows a regular ageing behavior that increases from 89.9 HV to 99.6 HV when ageing for 12 h,and then drops.A multi-mechanistic model is established to describe the strengthening due to grain refinement,disloca-tion accumulation,precipitation etc.The analysis reveals that the temperature sensitive UFG structure has an obvious grain coarsening effect,which arouses the soft phenomenon in the early ageing stage.But precipitation hardening provides an excellent hardness enhancement for overcoming the negative influ-ence and helping to reach the peak-aged point.In our microstructural observations,a lot of equilibrium ultrafine MgZn2 precipitates precipitate along dislocations because defects can provide the favorable conditions for the migration and segregation of solute atoms.     

State-of-the-art technology: Recent investigations on laser-mediated synthesis of nanocomposites for environmental remediation

In both developing and industrialized/developed countries, various hazardous/toxic environmental pollutants are entering water bodies from organic and inorganic compounds (heavy metals and specifically dyes). The global population is growing whereas the accessibility of clean, potable and safe drinking water is decreasing, leading to world deterioration in human health and limitation of agricultural and/or economic development. Treatment of water/wastewater (mainly industrial water) via catalytic reduction/degradation of environmental pollutants is extremely critical and is a major concern/issue for public health. Light and/or laser ablation induced photocatalytic processes have attracted much attention during recent years for water treatment due to their good (photo)catalytic efficiencies in the reduction/degradation of organic/inorganic pollutants. Pulsed laser ablation (PLA) is a rather novel catalyst fabrication approach for the generation of nanostructures with special morphologies (nanoparticles (NPs), nanocrystals, nanocomposites, nanowires, etc.) and different compositions (metals, alloys, oxides, core-shell, etc.). Laser ablation in liquid (LAL) is generally considered a quickly growing approach for the synthesis and modification of nanomaterials for practical applications in diverse fields. LAL-synthesized nanomaterials have been identified as attractive nanocatalysts or valuable photocatalysts in (photo)catalytic reduction/degradation reactions. In this review, the laser ablation/irradiation strategies based on LAL are systematically described and the applications of LAL synthesized metal/metal oxide nanocatalysts with highly controlled nanostructures in the degradation/reduction of organic/inorganic water pollutants are highlighted along with their degradation/reduction mechanisms.     

Effect of nanostructured grains in co-sputtered Ni-GDC thin-film anode on methane conversion kinetics for low temperature solid oxide fuel cells operating on nearly dry methane

Direct-methane solid oxide fuel cells (DMSOFCs) have recently attracted substantial attention due to their simplified system, reduced cost, and the direct availability of methane fuel obtained from natural gas. Among oxygen-ion conductive materials, doped-ceria such as gadolinium-doped ceria (GDC) or samarium-doped ceria can be incorporated into Ni-based anodes to reinforce their coking resistance, enlarge their electrochemical reaction area, and improve the kinetics of the internal reforming/electrochemical oxidation of methane. To reduce the range of operating temperatures of DMSOFCs while maintaining their performance, the thin film deposition technique of magnetron sputtering was adopted in this work. An Ni-GDC thin-film anode and a Pt thin-film cathode were deposited on scandia-stabilized zirconia (ScSZ) electrolyte supports. This fuel cell was tested with directly supplied methane fuel (3% H₂O) at 500 °C. The results demonstrated the effects of the GDC volume fraction in the anode—which was controlled by co-sputtering power—on open circuit voltage and electrochemical performance. The co-sputtered Ni-GDC anode was able to survive through 36-h operation, although there was some performance degradation. Field-emission scanning electron microscopy results revealed no formation of filamentous carbon on the Ni catalysts, despite the fact that both X-ray photoelectron spectroscopy and Raman spectroscopy analyses detected carbon coking. The relatively high performance and resistance to carbon coking of co-sputtered thin-film anode were attributed to its intrinsic small grain size.     

Controllable preparation of two-dimensional oriented BaTiO3 polycrystals from K0.8Ti1.73Li0.27O4 crystals by a one-step solvothermal process

Titanate precursors play an important role in obtaining oriented titanate materials via topochemical conversion. In this study, a two-dimensional (2D) K_0.8Ti_1.73Li_0.27O₄ (KTLO) crystal was successfully prepared by a one-step solvothermal process using TiO₂, LiOH?H₂O, and KOH as raw materials in ethanol/water mixed solvent for the first time. Meanwhile, the conditions and influencing factors for the solvothermal preparation of KTLO were investigated and analysed. With a ratio of ethanol/water of 20:5, better 2D KTLO can be obtained by reacting at 150 °C for 24 h. On this basis, KTLO was used directly to perform solvothermal treatment with Ba(OH)₂, and 2D BaTiO₃ (BT) was easily prepared by adjusting the reaction conditions (concentration, temperature, and time). When the solvothermal treatment was carried out in 0.5 mol/L Ba(OH)₂ solution at 80 °C for 1.5 h, 2D BT crystals could be easily obtained through the topochemical reaction mechanism. This strategy not only develops new methods for preparing precursors but also greatly simplifies the preparation process of BT and provides new research ideas for the preparation of functional materials.     

Microstructure evolution of CMAS glass below melting temperature and its potential influence on thermal barrier coatings

CaO–MgO–Al₂O₃–SiO₂ (CMAS) deposition significantly degrades the performance of thermal barrier coatings (TBCs). In this study, the microstructure evolution of CMAS glass at temperatures below its melting point was investigated in order to study the potential influence of temperature on the applicability of CMAS glass in TBCs. The CMAS glass fabricated in this study had a melting point of 1240 °C, became opaque, and underwent self-crystallization when the temperature reached 1000 °C. After heat treatment at 1050 °C, diopside and anorthite phases precipitated from the glass; at a higher temperature (1150 °C), diopside, anorthite, and wollastonite were formed as the self-crystallization products. An increase in the dwelling time resulted in the transformation of diopside to wollastonite and anorthite. At 1250 °C, all products formed a eutectic microstructure and melted. The results indicate that even at low temperatures, CMAS glass underwent microstructure evolution, which could influence the coating surface and stress distribution when deposited on TBCs.     

Physical and electrochemical behavior of affordable Na3SbS4 solid electrolyte at different heat treatment temperatures

High-capacity and affordable all-solid-state Na-ion batteries have gathered increasing interest in recent years owing to low-cost sodium, which contributes to reducing the price of these Na-ion batteries to approximately 70% of that in lithium batteries. However, in terms of electrolyte performance and battery cost, the complete replacement of lithium batteries has a long way to go. In this work, low-cost and high-safety Na₂S·9H₂O materials are used in synthesizing Na₃SbS₄ solid electrolyte, the price of which is only one-fifth that of high-purity Na₂S. The structure and electrochemical properties are studied through X-ray diffraction analysis, Raman spectroscopy, scanning electron microscopy, and electrochemical tests. Results indicate that a multiphase Na₃SbS₄ structure containing cubic and tetragonal phases formed after heat treatment at 300 °C. In addition, a third phase transition of Na₃SbS₄ is inferred after further heating at 600 °C. This phase structure contributes to the improvement of electrochemical performance by promoting increasing ionic conductivity to 0.54 mS cm^?1 at room temperature (25 °C) and reducing activation energy to 0.076 eV. This work provides an affordable material with good electrochemical properties and not only simplifies the preparation but also greatly reduces the risk of the process.