Intercalated kaolinite as an emerging platform for cancer therapy

An innovative cancer therapy strategy regarding the interface engineering of kaolinite has been designed. The exposed silanol group facilitates more guest species with high dispersion on the supports. Mn_3O_4 magnetic nanoparticles are uniformly distributed on external surfaces of the Kaolin_(C12N)with the Al–O–Mn bond for the detection of the tumor microenvironment by T1-MRI; Doxorubicin(DOX) are loaded in the interlayer space with the electrostatic interaction for chemo-treating; and KI is coated on the outer layer of the nanocomposites based on the electrostatic interaction for thyroid cancer targeting. The synergetic effects and the treatment mechanism enhanced by the interface engineering, KI@DOX-Mn_3O_4-Kaolin_(C12N)can cause remarkably low cell viability(57%, 200 μg/mL), tumor shrinking(75%, 20 μg/kg), and accumulation into the tumor tissues. The novel kaolinite based drug delivery system is expected to incorporate imaging diagnosis, targeted therapy and drug delivery into one single system for postoperative residual thyroid cancer treatment and observation for metastasis of focal area.     

LiB6Si: An indirect band gap semiconductor

Using first-principle calculations, mechanical properties, electronic structure, and Raman spectra of LiB₆Si structure were investigated. The band structures calculated by GGA-PBE and HSE06 methods reveal that LiB₆Si is an indirect band gap semiconductor. The band gap estimated by HSE06 method is about 2.24 eV, which is in good agreement with that of experimental value 2.27 eV. The calculated tensile stress-strain curves of LiB₆Si reveal that [010] direction is the cleavage direction under tensile strains. The calculated Raman spectra of LiB₆Si are also in good agreement with that of measured. The position of the band gap may provide a basis for further photocatalysis research on LiB₆Si.     

Stimuli-Responsive Fluorescent Nanoswitches: Solvent-Induced Emission Enhancement of Copper Nanoclusters

Copper nanoclusters (CuNCs) as a new class of fluorescent materials have attracted a great deal of interest due to their outstanding fluorescence properties. In this work, a variety of organic solvents were used to induce self-assembly of glutathione-capped CuNCs (GSH-CuNCs) to form ordered assemblies with enhanced fluorescence properties. Assemblies with multicolor fluorescence emission were constructed on the basis of the aggregation-induced emission (AIE) of GSH-CuNCs and the solvent effect. The fluorescence emission from these GSH-CuNCs assemblies can also be tuned from yellow to purple by changing the organic solvent. A possible mechanism based on the size of the assemblies and electron transfer was explored to explain the solvent effects on GSH-CuNCs. Stimuli-responsive nanoswitches with excellent reversibility can be controlled by changing the type of organic solvent and the ratio of the organic solvent to the aqueous solution of GSH-CuNCs. As the CuNCs assemblies exhibit strong, stable, and color-tunable fluorescence, they were employed as color-conversion materials for recognizing different organic solvents.     

Double-Shelled C@MoS2 Structures Preloaded with Sulfur: An Additive Reservoir for Stable Lithium Metal Anodes

The growth of Li dendrites hinders the practical application of lithium metal anodes (LMAs). In this work, a hollow nanostructure, based on hierarchical MoS₂ coated hollow carbon particles preloaded with sulfur (C@MoS₂/S), was designed to modify the LMA. The C@MoS₂ hollow nanostructures serve as a good scaffold for repeated Li plating/stripping. More importantly, the encapsulated sulfur could gradually release lithium polysulfides during the Li plating/stripping, acting as an effective additive to promote the formation of a mosaic solid electrolyte interphase layer embedded with crystalline hybrid lithium-based components. These two factors together effectively suppress the growth of Li dendrites. The as-modified LMA shows a high Coulombic efficiency of 98 % over 500 cycles at the current density of 1 mA cm⁻². When matched with a LiFePO₄ cathode, the assembled full cell displays a highly improved cycle life of 300 cycles, implying the feasibility of the proposed LMA.     

Unravelling the Enigma of Nonoxidative Conversion of Methane on Iron Single-Atom Catalysts

The direct, nonoxidative conversion of methane on a silica-confined single-atom iron catalyst is a landmark discovery in catalysis, but the proposed gas-phase reaction mechanism is still open to discussion. Here, we report a surface reaction mechanism by computational modeling and simulations. The activation of methane occurs at the single iron site, whereas the dissociated methyl disfavors desorption into gas phase under the reactive conditions. In contrast, the dissociated methyl prefers transferring to adjacent carbon sites of the active center (Fe₁©SiC₂), followed by C−C coupling and hydrogen transfer to produce the main product (ethylene) via a key −CH−CH₂ intermediate. We find a quasi Mars–van Krevelen (quasi-MvK) surface reaction mechanism involving extracting and refilling the surface carbon atoms for the nonoxidative conversion of methane on Fe₁©SiO₂ and this surface process is identified to be more plausible than the alternative gas-phase reaction mechanism.     

Four-Component Borocarbonylation of Vinylarenes Enabled by Cooperative Cu/Pd Catalysis: Access to β-Boryl Ketones and β-Boryl Vinyl Esters

We report here a general four-component synthetic procedure for the preparation of β-boryl ketones and β-boryl vinyl esters. Joint catalyzed by palladium and copper catalysts, borocarbonylative reaction between vinylarenes, aryl halides/triflates, B₂Pin₂, and carbon monoxide proceed successfully. A variety of synthetically useful β-boryl ketones were synthesized in good to high yields by using aryl iodides as the substrates. It is noteworthy that when aryl triflates were applied as the starting materials, β-boryl vinyl esters were synthesized in a similar manner and with broad functional group tolerance. A rational mechanism for this reaction was also proposed.     

Effect of Support on Catalytic Performance of Photothermal Fischer-Tropsch Synthesis to Produce Lower Olefins over Fe5C2-based Catalysts

Photothermal Fischer-Tropsch synthesis(FTS) has been extensively studied, but few reports were focused on systematically exploring the influence of support on catalytic performance. Herein, a series of Fe₅C₂-based catalysts with different supports was fabricated via a one-step wet-chemical method for photothermal conversion of syngas to lower olefins. Under light irradiation, the optimized Fe₅C₂/α-Al₂O₃ catalyst demonstrated remarkable photothermal FTS activity, delivering selectivity to lower olefins of 50.3% with a CO conversion rate of 52.5%. Characterization studies using X-ray diffraction and Mössbauer spectroscopy analysis revealed that the active catalyst mainly contained Fe₅C₂ nanoparticles on α-Al₂O₃ support. It was found that the weak interaction between active phase and α-Al₂O₃ could promote the formation of Fe₅C₂, which contributed to the high selectivity to lower olefins.     

Spleen and thymus metabolomics strategy to explore the immunoregulatory mechanism of total withanolides from the leaves of Datura metel L. on imiquimod-induced psoriatic skin dermatitis in mice

Our previous work demonstrated that total withanolides of Datura metel L. leaves (TWD) exhibited excellent therapeutic effects on psoriasis. However, current knowledge of its mechanisms is incomplete. In this study, integrated spleen and thymus untargeted metabolomics were used to analyze the changes in endogenous metabolites underlying the immunosuppressive activity of TWD on psoriasis animal models induced by imiquimod. The results suggested that TWD treatment markedly attenuated imiquimod-induced psoriasis and showed significant immunosuppressive activity as evidenced by decreased elevation index of spleen and thymus. Meanwhile, TWD significantly reversed the elevation of immunoregulatory factors, including IL-10, IL-17, IL-22 and IL-23. Multivariate trajectory analysis revealed that TWD treatment could restore the psoriasis-disturbed spleen and thymus metabolite profiles towards the normal metabolic status. A total of 25 and 27 metabolites associated with the immunomodulatory effects for which levels changed markedly upon treatment have been identified in spleen and thymus, respectively. These differential metabolites were mainly involved in amino acid metabolism, nucleotide metabolism, fatty acid metabolism and lipid metabolism. Our investigation provided a holistic view of TWD for intervention in psoriasis through immunoregulation and provided further scientific information in vivo about a clinical value of TWD for psoriasis.     

Interfacial Engineering FeOOH/CoO Nanoneedle Array for Efficient Overall Water Splitting Driven by Solar Energy

Interface engineering has been applied as an effective strategy to boost the electrocatalytic performance because of the strong coupling and synergistic effects between individual components. Here, we engineered vertically aligned FeOOH/CoO nanoneedle array with a synergistic interface between FeOOH and CoO on Ni foam (NF) by a simple impregnation method. The synthesized FeOOH/CoO exhibits outstanding electrocatalytic activity and stability for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline medium. For the overall water splitting, the bifunctional FeOOH/CoO nanoneedle catalyst requires only a cell voltage of 1.58 V to achieve a current density of 10 mA cm⁻², which is much lower than that required for IrO₂//Pt/C (1.68 V). The FeOOH/CoO catalyst has been successfully applied for solar cell-driven water electrolysis, revealing its great potential for commercial hydrogen production and solar energy storage.