The first synthesis of MnO@Mn O nanoparticles embedded in an N-doped porous carbon framework (MnO@Mn O /NPCF) through pyrolysis of mixed-valent Mn clusters is reported. The unique features of MnO@Mn O /NPCF are derived from the distinct interfacial structure of the Mn clusters, implying a new methodological strategy for hybrids. The characteristics of MnO@Mn O are determined by conducting high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and electron energy loss spectroscopy (EELS) valence-state analyses. Due to the combined advantages of MnO@Mn O , the uniform distribution, and the NPCF, MnO@Mn O /NPCF displays unprecedented lithium-storage performance (1500 mA h g at 0.2 A g over 270 cycles). Quantitative analysis reveals that capacitance and diffusion mechanisms account for Li storage, wherein the former dominates. First-principles calculations highlight the strong affiliation of MnO@Mn O and the NPCF, which favor structural stability. Meanwhile, defects of the NPCF decrease the diffusion energy barrier, thus enhancing the Li pseudocapacitive process, reversible capacity, and long cycling performance. This work presents a new methodology to construct composites for energy storage and conversion.
Background: Curcumin, the active ingredient in curcuma rhizomes, has a wide range of therapeutic effects. However, its atheroprotective activity in human acute monocytic leukemia THP-1 cells remains unclear. We investigated the activity and molecular mechanism of action of curcumin in polarized macrophages. Methods: Phorbol myristate acetate (PMA)-treated THP-1 cells were differentiated to macrophages, which were further polarized to M1 cells by lipopolysaccharide (LPS; 1 µg/ml) and interferon (IFN)-γ (20 ng/ml) and treated with varying curcumin concentrations. [3H]thymidine (3H-TdR) incorporation assays were utilized to measure curcumin-induced growth inhibition. The expression of tumor necrosis factor-a (TNF-a), interleukin (IL-6), and IL-12B (p40) were measured by quantitative real-time polymerase chain reaction (PCR) and enzyme-linked immunosorbent assay (ELISA). Macrophage polarization and its mechanism were evaluated by flow cytometry and western blot. Additionally, toll-like receptor 4 (TLR4) small interfering RNA and mitogen-activated protein kinase (MAPK) inhibitors were used to further confirm the molecular mechanism of curcumin on macrophage polarization. Results: Curcumin dose-dependently inhibited M1 macrophage polarization and the production of TNF-a, IL-6, and IL-12B (p40). It also decreased TLR4 expression, which regulates M1 macrophage polarization. Furthermore, curcumin significantly inhibited the phosphorylation of ERK, JNK, p38, and nuclear factor (NF)-γB. In contrast, SiTLR4 in combination with p-JNK, p-ERK, and p-p38 inhibition reduced the effect of curcumin on polarization. Conclusions: Curcumin can modulate macrophage polarization through TLR4-mediated signaling pathway inhibition, indicating that its effect on macrophage polarization is related to its anti-inflammatory and atheroprotective effects. Our data suggest that curcumin could be used as a therapeutic agent in atherosclerosis.
Postsynthetic decoration of the Mn, {Mn⊂Mn}, core with Cd in the outer shell to form the next generation MnCd, {Mn⊂MnMn⊂ MnCd}, core-shell disc was achieved and confirmed by single-crystal X-ray diffraction. The formation of MnCd has only been successful with Cd and if the Cd salt is added within the first half hour window when the inner Mn has formed. EDX and ICP-AES gave the accurate content and confirm the average found by X-ray diffraction. HR-ESI-MS was even more precise by revealing three prominent molecular species, MnCd, MnCd and MnCd, having a distribution of metals. The presence of nonmagnetic metal on the periphery reduces the exchange between these clusters as well as the low magnetic moment decreases the dipolar interaction resulting in a paramagnet compared to the ferrimagnetism found for the parent Mn, {Mn⊂MnMn⊂Mn}, disc. This study opens the way for the syntheses of heterometallic core-shell clusters in a controllable fashion.
The present study is an attempt to formulate a new approach to the modeling of the injection moldings of semicrystalline polymers. A phenomenological approach is employed to develop the qualitative description of crystallization phenomena under nonisothermal flow occurring in various polymer processing operations. The unified crystallization model, which is suitable to describe the multilayer microstructure arising in the injection moldings of semicrystalline polymers, is proposed. The “competing mechanisms” of crystallization in terms of the induction time indices for introducing various microstructure layers are utilized to quantitatively distinguish between the highly oriented skin layer and spherulitic core in the moldings. The application of the equations of continuity, momentum and energy, along with the rheological model, the equation of state and the unified crystallization model, to the injection molding process leads to the modeling of crystallinity and microstructure development in the moldings. The material parameters to be used in the modeling of the crystallinity and microstructure development in the injection moldings of isotactic polypropylenes (i‐PP's) with various molecular weights are determined. The melt viscosity as a function of shear rate and temperature is measured and fitted to the modified Cross model. Quiescent crystallization kinetics, including the induction time and the heat release due to crystallization, is characterized using differential scanning calorimetry. The spherulite growth rate of i‐PP's under isothermal and nonisothermal quiescent crystallization conditions is measured by optical microscopy. The molecular deformation factor during the induction period of shear‐in‐duced crystallization is obtained from the extrusion‐quenching and extrusion‐relaxation‐quenching experiments with a slit die. The variation of the induction time with shear rate obtained by Lagasse and Maxwell from the shearing‐crystallization experiments is used to determine the shear enhancement coefficient of crystallization.
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