Metallocene QACs: The Incorporation of Ferrocene Moieties into monoQAC and bisQAC Structures

Inspired by the incorporation of metallocene functionalities into a variety of bioactive structures, particularly antimicrobial peptides, we endeavored to broaden the structural variety of quaternary ammonium compounds (QACs) by the incorporation of the ferrocene moiety. Accordingly, 23 ferrocene-containing mono- and bisQACs were prepared in high yields and tested for activity against a variety of bacteria, including Gram-negative strains and a panel of clinically isolated MRSA strains. Ferrocene QACs were shown to be effective antiseptics with some displaying single-digit micromolar activity against all bacteria tested, demonstrating yet another step in the expansion of structural variety of antiseptic QACs.     

Synthesis of Hollow Three-Dimensional Channels LiNi_(0.5)Mn_(1.5)O_4 Microsphere by PEO Soft Template Assisted with Solvothermal Method

A appropriate size with three-dimension(3 D) channels for lithium diffusion plays an important role in constructing highperforming LiNi_(0.5)Mn_(1.5)O_4(LNMO) cathode materials, as it can not only reduce the transport path of lithium ions and electrons, but also reduce the side effects and withstand the structural strain in the process of repetitive Li~+ intercalation/deintercalation. In this work, an e fficient method for designing the hollow LNMO microsphere with 3 D channels structure by using polyethylene oxide(PEO) as soft template agent assisted solvothermal method is proposed. Experimental results indicate that PEO can make the reagents mingle evenly and nucleate slowly in the solvothermal process, thus obtaining a homogeneous distribution of carbonate precursors. In the final LNMO products, the hollow 3 D channels structure obtained by the decomposition of PEO and carbonate precursor in the calcination can provide abundant electroactive zones and electron/ion transport paths during the charge/discharge process, which benefits to improve the cycling performance and rate capability. The LNMO prepared by adding 1 g PEO possesses the most outstanding electrochemical performance, which presented an excellent discharge capacity of 143.1 mAh g~(-1) at 0.1 C and with a capacity retention of 92.2% after 100 cycles at 1 C. The superior performance attributed to the 3 D channels structure of hollow microspheres, which provide uninterrupted conductive systems and therefore achieve the stable transfer for electron/ion.     

Toward a better understanding of multifunctional cement-based materials: The impact of graphite nanoplatelets (GNPs)

The impact of graphite nanoplatelets (GNPs) on the physical and mechanical properties of cementitious nanocomposites was investigated. A market-available premixed mortar was modified with 0.01% by weight of cement of commercial GNPs characterized by two distinctively different aspect ratios.The rheological behavior of the GNP-modified fresh admixtures was thoroughly evaluated. Hardened cementitious nanocomposites were investigated in terms of density, microstructure (Scanning Electron Microscopy, SEM and micro–Computed Tomography, μ-CT), mechanical properties (three-point bending and compression tests), and physical properties (electrochemical impedance spectroscopy, EIS and thermal conductivity measurements). At 28 days, all GNP-modified mortars showed about 12% increased density. Mortars reinforced with high aspect ratio GNPs exhibited the highest compressive and flexural strength: about 14% and 4% improvements compared to control sample, respectively. Conversely, low aspect ratio GNPs led to cementitious nanocomposites characterized by 36% decreased electrical resistivity combined with 60% increased thermal conductivity with respect to the control sample.     

Tuning of shear thickening behavior and elastic strength of polyvinylidene fluoride via doping of ZnO-graphene

ZnO rice like nonarchitects are grafted on the graphene carbon core via a rapid microwave synthesis route. The prepared grafted systems are characterized via XRD, SEM, RAMAN, and XPS to examined the structural and morphological parameters. Zinc oxide grafted graphene sheets (ZnO-G) are further doped in β-phase of polyvinylidene fluoride (PVDF) to prepare the polymer nanocomposites (PNCs) via mixed solvent approach (THF/DMF). β-phase confirmation of PVDF PNCs is done by FTIR studies. It is observed that ZnO-G filler enhances the β-phase content in the PNCs. Non-doped PVDF and PNCs are further studied for rheological behavior under the shear rate of 1–100 s⁻¹. Doping of ZnO-G dopant to the PVDF matrix changes its discontinuous shear thickening (DST) behavior to continues shear thickening behavior (CST). Hydrocluster formation and their interaction with the dopant could be the reason for this striking DST to CST behavioral change. Strain amplitude sweep (10⁻³% -10%) oscillatory test reveals that the PNCs shows extended linear viscoelastic region with high elastic modulus and lower viscous modulus. Effective shear thickening behavior and strong elastic strength of these PNCs present their candidature for various fields including mechanical and soft body armor applications.     

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.     

Development of Phosphodiesterase–Protein-Kinase Complexes as Novel Targets for Discovery of Inhibitors with Enhanced Specificity

Phosphodiesterases (PDEs) hydrolyze cyclic nucleotides to modulate multiple signaling events in cells. PDEs are recognized to actively associate with cyclic nucleotide receptors (protein kinases, PKs) in larger macromolecular assemblies referred to as signalosomes. Complexation of PDEs with PKs generates an expanded active site that enhances PDE activity. This facilitates signalosome-associated PDEs to preferentially catalyze active hydrolysis of cyclic nucleotides bound to PKs and aid in signal termination. PDEs are important drug targets, and current strategies for inhibitor discovery are based entirely on targeting conserved PDE catalytic domains. This often results in inhibitors with cross-reactivity amongst closely related PDEs and attendant unwanted side effects. Here, our approach targeted PDE–PK complexes as they would occur in signalosomes, thereby offering greater specificity. Our developed fluorescence polarization assay was adapted to identify inhibitors that block cyclic nucleotide pockets in PDE–PK complexes in one mode and disrupt protein-protein interactions between PDEs and PKs in a second mode. We tested this approach with three different systems—cAMP-specific PDE8–PKAR, cGMP-specific PDE5–PKG, and dual-specificity RegA–R_D complexes—and ranked inhibitors according to their inhibition potency. Targeting PDE–PK complexes offers biochemical tools for describing the exquisite specificity of cyclic nucleotide signaling networks in cells.     

Low thermal conductivity in porous SiC–SiO2–Al2O3–TiO2 ceramics induced by multiphase thermal resistance

The introduction of multiple heterogeneous interfaces in a ceramic is an efficient way to increase its thermal resistance. Novel porous SiC–SiO₂–Al₂O₃–TiO₂ (SSAT) ceramics were fabricated to achieve multiple heterogeneous interfaces by sintering equal volumes of SiC, SiO₂, Al₂O₃, and TiO₂ compacted powders with polysiloxane as a bonding phase and carbon as a template at 600 °C in air. The porosity could be controlled between 66% and 74% by adjusting the amounts of polysiloxane and the carbon template. The lowest thermal conductivity (0.059 W/(m·K) at 74% porosity) obtained in this study is an order of magnitude lower than those (0.2–1.3 W/(m·K)) of porous monolithic SiC, SiO₂, Al₂O₃, and TiO₂ ceramics at an equivalent porosity. The typical specific compressive strength value of the porous SSAT ceramics at 74% porosity was 3.2 MPa cm³/g.     

Optical properties of gadolinia-doped cubic yttria stabilized zirconia single crystals

Cubic zirconia single crystals stabilized with yttria and doped with Gd₂O₃ (0.10–5.00 mol%) were prepared by the optical floating zone method, and characterized by a combination of X-ray diffraction (XRD), and Raman, electron paramagnetic resonance (EPR), ultraviolet–visible (UV–Vis), photoluminescence excitation (PLE) and photoluminescence (PL) spectroscopic techniques. XRD and Raman spectroscopy showed that the crystal samples were all in the cubic phase, whereas the ceramic sample consisted of a mixture of monoclinic and cubic phases. The absorption spectrum showed four peaks at 245, 273, 308, and 314 nm in the ultraviolet region, and the optical band gap differed between samples with ≤3.00 mol% and those with >3.00 mol% Gd₂O₃. The emission spectrum showed a weak peak at 308 nm and a strong peak at 314 nm, which are attributed to the ⁶P_5/2 → ⁸S_7/2 and ⁶P_7/2 → ⁸S_7/2 transitions of Gd³⁺, respectively. The intensities of the peaks in the excitation and emission spectra increased with Gd³⁺ concentration, reached a maximum at 2.00 mol%, then decreased with higher concentrations. This quenching is considered to be the result of the electric dipole-dipole interactions, and this interpretation is supported by the Gd³⁺ EPR spectra, which showed progressive broadening with increasing Gd³⁺ concentration throughout the concentration range investigated.     

磨料有序排布电镀砂轮的制备及其把持力研究

为解决电镀砂轮磨削加工中容屑空间不足的问题，采用点胶微粘接的方法制备了磨料有序排布的电镀砂轮，分析了磨料粘接效果和镀层力学性能。通过SEM分析了磨料/镀层/导电胶的结合界面，并进行了干磨削试验。研究结果表明，直径约为磨料粒径40%的胶点可粘接住磨料，单个胶点上粘接多颗磨料的占比小于6%；双脉冲电镀工艺制备的镀层显微硬度大于500HV，表层残余应力小于100MPa，磨料/镀层/导电胶之间的界面贴合紧密，无明显缺陷；砂轮在磨削时没有出现磨料脱落现象。