Effects of sintering additives and sintering methods on the mechanical, antimicrobial and optical properties of Si3N4 bioceramics.

Si3N4 bioceramics were fabricated using GPS and SPS method with MgO-RE2O3 (RE = La, Nd, Gd, Ho and Lu) sintering additives. The effect of sintering methods and sintering additives on the grain growth, mechanical, antimicrobial properties and color of Si3N4 bioceramics were studied. Samples sintered with GPS are composed of ß-Si3N4 and samples sintered with SPS are composed of α-Si3N4 and ß-Si3N4. The growth of ß-Si3N4 grains in samples sintered with GPS are more adequate. Samples sintered with GPS exhibit a S. aureus inactivation rate up to 98% and a bright color appearance with a hardness of about 13 GPa and a fracture toughness up to 7.5 MPa m1/2, suitable for dental implants. And samples sintered with SPS exhibit a hardness of about 17 GPa and a fracture toughness about 6 MPa m1/2.

Immunomodulatory Function of Pien Tze Huang in T Cell-Mediated Anti-tumor Activity against B16-F10, MC38 and Hep1-6 Tumor Models.

OBJECTIVE: To investigate the anti-tumor effects of Pien Tze Huang (PZH) in mouse models of B16-F10 melanoma, MC38 colorectal cancer, Hep1-6 hepatocellular carcinoma and chemically induced hepatocellular carcinoma model. METHODS: Various tumor models, including B16-F10, MC38 and Hep1-6 tumor hypodermic inoculation models, B16-F10 and Hep1-6 pulmonary metastasis models, Hep1-6 orthotopic implantation model, and chemically induced hepatocellular carcinoma model, were utilized to evaluate the anti-tumor function of PZH. Tumor growth was assessed by measuring tumor size and weight of solid tumors isolated from C57BL/6 mice. For cell proliferation and death of tumor cells in vitro, as well as T cell activation markers, cytokine production and immune checkpoints analysis, single-cell suspensions were prepared from mouse spleen, lymph nodes, and tumors after PZH treatment. RESULTS: PZH demonstrated significant therapeutic efficacy in inhibiting tumor growth (P<0.01). Treatment with PZH resulted in a reduction in tumor size in subcutaneous MC38 colon adenocarcinoma and B16-F10 melanoma models, and decreased pulmonary metastasis of B16-F10 melanoma and Hep1-6 hepatoma (P<0.01). However, in vitro experiments showed that PZH only had slight impact on the cell proliferation and survival of tumor cells (P>0.05). Nevertheless, PZH exhibited a remarkable ability to enhance T cell activation and the production of interferon gamma, tumor necrosis factor alpha, and interleukin 2 in CD4+ T cells in vitro (P<0.01 or P<0.05). Importantly, PZH substantially inhibited T cell exhaustion and boosted cytokine production by tumor-infiltrating CD8+ T cells (P<0.01 or P<0.05). CONCLUSION: This study has confirmed a novel immunomodulatory function of PZH in T cell-mediated anti-tumor immunity, indicating that PZH holds promise as a potential therapeutic agent for cancer treatment.

Syntheses of Cannabinoid Metabolites: Ajulemic Acid and HU-210.

Cannabinoid metabolites have been reported to be more potent than their parent compounds. Among them, ajulemic acid (AJA) is a side-chain analog of Δ9-THC-11-oic acid, which would be a good template structure for the discovery of more potent analogues. Herein, we optimized the key allylic oxidation step to introduce the C-11 hydroxy group with a high yield. A series of compounds was prepared with this condition applied including HU-210, 11-nor-Δ8-tetrahydrocannabinol (THC)-carboxylic acid and Δ9-THC-carboxylic acid.

Glycogen synthase kinase 3 controls T-cell exhaustion by regulating NFAT activation.

Cellular immunity mediated by CD8+ T cells plays an indispensable role in bacterial and viral clearance and cancers. However, persistent antigen stimulation of CD8+ T cells leads to an exhausted or dysfunctional cellular state characterized by the loss of effector function and high expression of inhibitory receptors during chronic viral infection and in tumors. Numerous studies have shown that glycogen synthase kinase 3 (GSK3) controls the function and development of immune cells, but whether GSK3 affects CD8+ T cells is not clearly elucidated. Here, we demonstrate that mice with deletion of Gsk3α and Gsk3ß in activated CD8+ T cells (DKO) exhibited decreased CTL differentiation and effector function during acute and chronic viral infection. In addition, DKO mice failed to control tumor growth due to the upregulated expression of inhibitory receptors and augmented T-cell exhaustion in tumor-infiltrating CD8+ T cells. Strikingly, anti-PD-1 immunotherapy substantially restored tumor rejection in DKO mice. Mechanistically, GSK3 regulates T-cell exhaustion by suppressing TCR-induced nuclear import of NFAT, thereby in turn dampening NFAT-mediated exhaustion-related gene expression, including TOX/TOX2 and PD-1. Thus, we uncovered the molecular mechanisms underlying GSK3 regulation of CTL differentiation and T-cell exhaustion in anti-tumor immune responses.

Three nona-2,7-dienoic acid derivatives from saltern derived Micromonospora sp. FXY415.

Three new compounds, apocimycin A-C, were identified from a saltern-derived Micromonospora sp. strain FXY415, isolated from Dongshi saltern, Fujian, China. Their planar structures and relative configuration were confirmed mainly by analysis of 1D- and 2D- NMR spectra. Three compounds belong to 4,6,8-trimythyl nona-2,7-dienoic acid derivatives, apocimycin A also has a phenoxazine nucleus. Apocimycin A-C exhibited weak cytotoxic and antimicrobial activities. Our research showed again that microbial communities in extreme environments are a potential resource in looking for new and bioactive led compounds.

Effects of land clearing for agriculture on soil organic carbon stocks in drylands: A meta-analysis.

Agricultural activities have been expanding globally with the pressure to provide food security to the earth's growing population. These agricultural activities have profoundly impacted soil organic carbon (SOC) stocks in global drylands. However, the effects of clearing natural ecosystems for cropland (CNEC) on SOC are uncertain. To improve our understanding of carbon emissions and sequestration under different land uses, it is necessary to characterize the response patterns of SOC stocks to different types of CNEC. We conducted a meta-analysis with mixed-effect model based on 873 paired observations of SOC in croplands and adjacent natural ecosystems from 159 individual studies in global drylands. Our results indicate that CNEC significantly (p < .05) affects SOC stocks, resulting from a combination of natural land clearing, cropland management practices (fertilizer application, crop species, cultivation duration) and the significant negative effects of initial SOC stocks. Increases in SOC stocks (in 1 m depth) were found in croplands which previously natural land (deserts and shrublands) had low SOC stocks, and the increases were 278.86% (95% confidence interval, 196.43%-361.29%) and 45.38% (26.53%-62.23%), respectively. In contrast, SOC stocks (in 1 m depth) decreased by 24.11% (18.38%-29.85%) and 10.70% (1.80%-19.59%) in clearing forests and grasslands for cropland, respectively. We also established the general response curves of SOC stocks change to increasing cultivation duration, which is crucial for accurately estimating regional carbon dynamics following CNEC. SOC stocks increased significantly (p < .05) with high long-term fertilizer consumption in cleared grasslands with low initial SOC stocks (about 27.2 Mg ha-1 ). The results derived from our meta-analysis could be used for refining the estimation of dryland carbon dynamics and developing SOC sequestration strategies to achieve the removal of CO2 from the atmosphere.

Evaluation of Mutton Adulteration under the Effect of Mutton Flavour Essence Using Hyperspectral Imaging Combined with Machine Learning and Sparrow Search Algorithm.

The evaluation of mutton adulteration faces new challenges because of mutton flavour essence, which achieves a similar flavour between the adulterant and mutton. Hence, methods for classifying and quantifying the adulterated mutton under the effect of mutton flavour essence, based on near-infrared hyperspectral imaging (NIR-HSI, 1000-2500 nm) combined with machine learning (ML) and sparrow search algorithm (SSA), were proposed in this study. After spectral preprocessing via first derivative combined with multiple scattering correction (1D + MSC), classification and quantification models were established using back propagation neural network (BP), extreme learning machine (ELM) and support vector machine/regression (SVM/SVR). SSA was further used to explore the global optimal parameters of these models. Results showed that the performance of models improves after optimisation via the SSA. SSA-SVM achieved the optimal discrimination result, with an accuracy of 99.79% in the prediction set; SSA-SVR achieved the optimal prediction result, with an RP2 of 0.9304 and an RMSEP of 0.0458 g·g-1. Hence, NIR-HSI combined with ML and SSA is feasible for classification and quantification of mutton adulteration under the effect of mutton flavour essence. This study can provide a theoretical and practical reference for the evaluation and supervision of food quality under complex conditions.

An ultrasonication-aided self-assembly strategy toward a PTCDA/RGO film cathode for organic K-ion full batteries.

A free-standing PTCDA/RGO film was synthesized by an ultrasonication-aided self-assembly strategy to alleviate the solubility of PTCDA in organic electrolytes. The PTCDA/RGO-50% film cathode exhibits a high capacity of 135.1 mA h g-1 at 0.05 A g-1 and excellent cycling stability (capacity retention of 85% after 200 cycles) for potassium ion batteries.

Single atoms (Pt, Ir and Rh) anchored on activated NiCo LDH for alkaline hydrogen evolution reaction.

Here, we report the synthesis of activated NiCo LDH to immobilize Pt, Ir and Rh single atoms for hydrogen evolution reaction. The Pt/A-NiCo LDH electrocatalyst exhibits the highest catalytic ability with a low overpotential of 16 mV to achieve a current density of 10 mA cm-2 and a mass activity about 24.8-fold that of commercial Pt/C. The results suggest that the Pt single atom catalyst can not only accelerate the Volmer steps in alkaline media, but also optimize the hydrogen adsorption process, improving the HER catalytic activity.

Ni-Doped Mo2C Anchored on Graphitized Porous Carbon for Boosting Electrocatalytic N2 Reduction.

Facilitating the efficient activation of N2 molecules and inhibiting the competing hydrogen evolution reaction remain a challenge in the nitrogen reduction reaction (NRR). A heteroatom doping strategy is an effective way to optimize the energy barrier during the NRR process to improve the catalytic efficiency. Herein, we report Ni-doped Mo2C anchored on graphitized porous conductive carbon for regulating the electronic structure and catalytic properties of electrocatalysts toward NRR. Benefiting from the porous structure and graphitization features of the carbon matrix, more active sites and high electronic conductivity were achieved. Meanwhile, with the doping of Ni atoms, the electronic configuration near the Ni-Mo active sites was optimized and the adsorption of N2 on them was also promoted due to the increased electron transfer. Moreover, the lowered energy barrier of the NRR process and the suppressed hydrogen adsorption on the active site all resulted in the high catalytic activity and selectivity of the catalyst. Therefore, a high NH3 yield rate of 46.49 µg h-1 mg-1 and a faradic efficiency of 29.05% were achieved. This work not only validates the important role of heteroatom doping on the regulation of NRR catalytic activity but also provides a promising avenue for the green synthesis of NH3.

Metallic-State MoS2 Nanosheets with Atomic Modification for Sodium Ion Batteries with a High Rate Capability and Long Lifespan.

Exploring active materials with a high rate capability and long lifespan for sodium ion batteries attracts much more attention and plays an important role in realizing clean energy storage and conversion. The strategy of optimizing the electronic structure by atomic element substitution within MoS2 layers was employed to change the inherent physical property. The enhanced electronic conductivity from a decreased bandgap and increased surface Na+ adsorption energy can efficiently and dramatically optimize the electrochemical performance for sodium storage. Attempting to limit the large volume variation and avoid MoS2 nanosheet stacking and restacking, numerous nanosheets are in situ grown into a designed hierarchical mesopore carbon matrix. This structure can tightly capture the nanosheets to prevent them from aggregating and offer a sufficient buffer zone for alleviating severe volume changes during the discharging/charging process, contributing remarkably to the structural integrity and superior rate performance of electrodes.

Microstructure-Dependent K+ Storage in Porous Hard Carbon.

Hard carbons (HCs) are emerging as promising anodes for potassium-ion batteries (PIBs) due to overwhelming advantages including cost effectiveness and outstanding physicochemical properties. However, the fundamental K+ storage mechanism in HCs and the key structural parameters that determining K+ storage behaviors remain unclear and require further exploration. Herein, HC materials with controllable micro/mesopore structures are first synthesized by template-assisted spray pyrolysis technology. Detailed experimental analyses including in situ Raman and in situ electrochemical impedance spectroscopy analysis reveal two different K+ storage ways in the porous hard carbon (p-HC), e.g., the adsorption mechanism at high potential region and the intercalation mechanism at low potential region. Both are strongly dependent on the evolution of microstructure and significantly affect the electrochemical performance. Specifically, the adequate micropores act as the active sites for efficient K+ storage and ion-buffering reservoir to relieve the volume expansion, ensuring enhanced specific capacity and good structural stability. The abundant mesopores in the porous structure provide conductive pathways for ion diffusion and/or electrolyte infiltration, endowing fast ionic/electronic transport kinetics. All these together contribute to the high energy density of activated carbon//p-HCs potassium ion hybrid capacitors (74.5 Wh kg-1 , at 184.4 W kg-1 ).

Optimized Kinetics Match and Charge Balance Toward Potassium Ion Hybrid Capacitors with Ultrahigh Energy and Power Densities.

Potassium ion hybrid capacitors (PIHCs) are of particular interest benefiting from high energy/power densities. However, challenges lie in the kinetic mismatch between battery-type anode and capacitive-type cathode, as well as the difficulty in achieving optimized charge/mass balance. These significantly sacrifice the electrochemical performance of PIHCs. Here, strategies including charge/mass balance pursuance, electrolyte optimization, and tailored electrode design, are employed, together, to address these challenges. The key parameters determining the energy storage properties of PIHCs are identified. Specifically, i) the good kinetic match between anode and cathode translates into the very small variation of cathode/anode mass ratio at various rates. This sets general rules for the pursuance of charge balance, and to maximize the electrochemical performance of hybrid devices. ii) A potassium bis(fluoroslufonyl)imide (KFSI)-based electrolyte promotes better electrode kinetics and allows for the formation of more stable and intact solid electrolyte interphase layer, with respect to potassium hexafluorophosphate (KPF6 )-based electrolyte. And iii) hierarchically porous N/O codoped carbon nanosheets (NOCSs) with enlarged interlayer spacing, disordered structure, and abundant pyridinic-N functional groups are advantageous in terms of high electronic/ionic transport dynamics and structural stability. All these together, contribute to the high energy/power density of the activated carbon//NOCSs PIHCs (113.4 Wh kg-1 , at 17,000 W Kg-1 ).

Synthesis of Ordered Mesoporous Zr-Al Composite Oxides with Excellent Structural and Textural Properties and Extremely High Stability.

Ordered mesoporous Zr-Al composite oxide materials (denoted as OMZA-x) with different Zr contents have been synthesized by a solvent evaporation-inducing self-assembly procedure associated with a thermal treatment at 100 °C. A cooperative co-assembly process of amphiphilic triblock copolymer F127 molecules and inorganic hydroxyl species originated from the hydrolysis of Zr and Al precursors was proposed to explain the synthesis of OMZA-x. Compared to ordered mesoporous alumina prepared without introducing Zr species, the resultant OMZA-x exhibited a much more ordered mesostructure combined with a distinct increase in the pore volume and specific surface area. The highly homogenous doping of Zr into the mesopore walls together with the formation of Zr-O-Al bonds can effectively enhance the thermal and hydrothermal stability of OMZA-x. For instance, the ordered mesostructure and excellent textural properties of OMZA-6 prepared with the optimum atomic ratio of Al to Zr of 6 could be well maintained even after a high-temperature treatment at 1000 °C for 1 h or a hydrothermal treatment at 100 °C for 6 h.

Enhanced Potassium-Ion Storage of the 3D Carbon Superstructure by Manipulating the Nitrogen-Doped Species and Morphology.

Potassium-ion batteries (PIBs) are attractive for grid-scale energy storage due to the abundant potassium resource and high energy density. The key to achieving high-performance and large-scale energy storage technology lies in seeking eco-efficient synthetic processes to the design of suitable anode materials. Herein, a spherical sponge-like carbon superstructure (NCS) assembled by 2D nanosheets is rationally and efficiently designed for K+ storage. The optimized NCS electrode exhibits an outstanding rate capability, high reversible specific capacity (250 mAh g-1 at 200 mA g-1 after 300 cycles), and promising cycling performance (205 mAh g-1 at 1000 mA g-1 after 2000 cycles). The superior performance can be attributed to the unique robust spherical structure and 3D electrical transfer network together with nitrogen-rich nanosheets. Moreover, the regulation of the nitrogen doping types and morphology of NCS-5 is also discussed in detail based on the experiments results and density functional theory calculations. This strategy for manipulating the structure and properties of 3D materials is expected to meet the grand challenges for advanced carbon materials as high-performance PIB anodes in practical applications.

Phosphine-Catalyzed Chemo- and Diastereoselective [2 + 2 + 2] and [3 + 2] Annulations of γ-Methyl Allenoates with Doubly Activated Olefins: Syntheses of Highly Substituted Cyclohexanes and Cyclopentenes.

Phosphine-catalyzed chemoselective [2 + 2 + 2] and [3 + 2] annulations of γ-methyl allenoates with doubly activated olefins have been developed, which afford highly substituted cyclohexanes bearing five continuous stereogenic centers and cyclopentenes bearing three continuous stereogenic centers, respectively, in generally high yields with excellent diastereoselectivity. The [2 + 2 + 2] annulation represents an unprecedented reactivity pattern of γ-methyl allenoates with activated C═C bonds to access six-membered carbocycles. In addition, the study herein also evidences that the acidic protic additives such as benzoic acid can exert influence on chemoselectivity of phosphine-catalyzed annulation reactions involving allenoates.

Solvothermal-assisted evaporation-induced self-assembly of ordered mesoporous alumina with improved performance.

A solvothermal-assisted evaporation-induced self-assembly (SA-EISA) approach has been developed for the synthesis of ordered mesoporous alumina (OMA) materials with high thermal stability and improved performance in catalysis. In conventional EISA process, the evaporation step is accompanied by the hydrolysis of organic aluminum precursors, thus the evaporation conditions have significant influences on the reaction and the final structure of OMA. In our approach, the solvothermal treatment step promotes the complete hydrolysis of aluminum precursors and produces partially condensed cluster-like aluminum hydroxyl species, which allows the formation of OMA in a broad range of evaporation conditions. Compared to mesoporous alumina obtained by conventional EISA process, OMA materials prepared by SA-EISA approach exhibit higher specific surface area, pore volume and thermal stability. When used as supporting materials for vanadium oxide catalyst, OMA materials obtained by the SA-EISA approach exhibit excellent activity, selectivity and stability for ethylbenzene dehydrogenation with carbon dioxide as a mild oxidant. Our contribution has provided new understanding in the synthesis of OMA materials with improved performance for catalytic applications.

Compact-Nanobox Engineering of Transition Metal Oxides with Enhanced Initial Coulombic Efficiency for Lithium-Ion Battery Anodes.

A novel strategy is proposed to construct a compact-nanobox (CNB) structure composed of irregular nanograins (average diameter ≈ 10 nm), aiming to confine the electrode-electrolyte contact area and enhance initial Coulombic efficiency (ICE) of transition metal oxide (TMO) anodes. To demonstrate the validity of this attempt, CoO-CNB is taken as an example which is synthesized via a carbothermic reduction method. Benefiting from the compact configuration, electrolyte can only contact the outer surface of the nanobox, keeping the inner CoO nanograins untouched. Therefore, the solid electrolyte interphase (SEI) formation is reduced. Furthermore, the internal cavity leaves enough room for volume variation upon lithiation and delithiation, resulting in superior mechanical stability of the CNB structure and less generation of fresh SEI. Consequently, the SEI remains stable and spatially confined without degradation, and hence, the CoO-CNB electrode delivers an enhanced ICE of 82.2%, which is among the highest values reported for TMO-based anodes in lithium-ion batteries. In addition, the CoO-CNB electrode also demonstrates excellent cyclability with a reversible capacity of 811.6 mA h g-1 (90.4% capacity retention after 100 cycles). These findings open up a new way to design high-ICE electrodes and boost the practical application of TMO anodes.

Synthesis, characterization and n-hexane hydroisomerization performances of Pt supported on alkali treated ZSM-22 and ZSM-48.

ZSM-48 and ZSM-22 zeolites with similar Si/Al molar ratio have been treated with alkali to modify the pore structures and acidity, and alkali treated ZSM-22 and ZSM-48 samples have been characterized by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), N2 adsorption/desorption, Nuclear Magnetic Resonance (NMR), NH3-Temperature Programmed Desorption (NH3-TPD) and Pyridine-Fourier Transform Infrared Spectroscopy (Py-FTIR). Characterization results indicate that NaOH treatment could improve the mesoporous structure for both ZSM-22 and ZSM-48. NaOH treatment modifies the acidity of ZSM-22 and ZSM-48 diversely. The n-hexane hydroisomerization performances of Pt supported protonic form ZSM-22 and ZSM-48 (Pt/HZSM-22 and Pt/HZSM-48) bifunctional catalysts have been evaluated in a fixed bed reactor. Catalytic results indicate that catalytic activity and selectivity depend on both pore structure and acidity of zeolites. In comparison of Pt/HZSM-22 and Pt/HZSM-48, Pt/HZSM-22 shows better n-hexane hydroisomerization performance at relatively low temperature (<300 °C), meanwhile, at relatively high temperature (>300 °C) Pt/HZSM-48 exhibits better catalytic performance. Moreover, alkali treated Pt/HZSM-48 could produce more di-branched isomer compared with alkali treated Pt/HZSM-22.

Dual-Confined Sulfur Nanoparticles Encapsulated in Hollow TiO2 Spheres Wrapped with Graphene for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are attractive owing to their higher energy density and lower cost compared with the universally used lithium-ion batteries (LIBs), but there are some problems that stop their practical use, such as low utilization and rapid capacity-fading of the sulfur cathode, which is mainly caused by the shuttle effect, and the uncontrollable deposition of lithium sulfide species. Herein, we report the design and fabrication of dual-confined sulfur nanoparticles that were encapsulated inside hollow TiO2 spheres; the encapsulated nanoparticles were prepared by a facile hydrolysis process combined with acid etching, followed by "wrapping" with graphene (G-TiO2 @S). In this unique composite architecture, the hollow TiO2 spheres acted as effective sulfur carriers by confining the polysulfides and buffering volume changes during the charge-discharge processes by means of physical force from the hollow spheres and chemical binding between TiO2 and the polysulfides. Moreover, the graphene-wrapped skin provided an effective 3D conductive network to improve the electronic conductivity of the sulfur cathode and, at the same time, to further suppress the dissolution of the polysulfides. As results, the G-TiO2 @S hybrids exhibited a high and stable discharge capacity of up to 853.4 mA h g-1 over 200 cycles at 0.5 C (1 C=1675 mA g-1 ) and an excellent rate capability of 675 mA h g-1 at a current rate of 2 C; thus, G-TiO2 @S holds great promise as a cathode material for Li-S batteries.