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The alkylperoxo O-O bond cleavage affords a Mn(v)-oxo complex and a hydroxylated substrate. This novel mechanism for the Mn(v)-oxo formation via an alkylperoxo Mn(iii) intermediate gives insight into the O-O bond activation by manganese complexes.Due to the adjustable band gap, the excellent radiation stability, and the high electron mobility of InGaN, the InGaN-based blue-light photodetectors (PDs) show great potential in visible light communication (VLC) systems. However, the applications of InGaN-based blue-light PDs in VLC systems are limited by the poor performance caused by the poor crystalline quality of InGaN materials. Herein, we report on the fabrication of high responsivity and high response speed InGaN-based metal-semiconductor metal (MSM) blue-light PDs using high-quality InGaN epitaxial films grown on Si substrates by the combination of low-temperature pulsed laser deposition (LT-PLD) and high-temperature metal organic chemical deposition (HT-MOCVD). The technology can not only suppress the interfacial reactions between films and substrates by LT-PLD growth, but also promote the lateral overgrowth of InGaN and improve the crystalline quality of InGaN-based epitaxial films by HT-MOCVD growth. Based on the high-quality InGaN-based materials, high-performance InGaN-based blue-light PDs are fabricated accordingly with a high responsivity of 0.49 A W-1 and a short rise/fall response time of 1.25/1.74 ms at an applied bias of -3 V. The performance is better than the results for the InGaN-based PDs previously reported. The InGaN-based blue-light PDs shed light on the potential for VLC system applications.In the present work, the adsorption mechanism and corrosion inhibition effect of coumarin as a green inhibitor was characterized. Quantum chemical calculation and molecular dynamics simulation of the coumarin molecule were performed to get insight into the adsorption model by assessing the frontier orbital parameters and adsorption configuration. The theoretical calculation disclosed that coumarin exhibited a higher adsorption reactivity in the water phase than that in the gas phase, and the C[double bond, length as m-dash]O structure in coumarin was the most favorable site for adsorption occurring. Coumarin could adsorb spontaneously on an aluminum surface in a parallel manner, where electron donation occurred from the aluminum surface to the inhibitor. Additionally, the experimental investigation determined that coumarin decreased the aluminum dissolution by suppressing both the anodic and cathodic reactions. The optimal coumarin concentration of 0.5 wt% resulted in a maximum inhibition efficiency (89.6%), but coumarin at a higher concentration would lead to the competitive and unstable adsorption of inhibitor molecules, thus decreasing the inhibition effect. Moreover, surface chemical characterization confirmed the formation of Al-coumarin complexes, which was in accordance with the theoretical calculation.Two kinds of CA-SA-based ternary phase change materials (PCMs), namely, capric acid-stearic acid-palmitic acid (CA-SA-PA) and capric acid-stearic acid-octadecanol (CA-SA-OD), were prepared by the melting-blending method. By the step cooling curve method, the optimum mass ratio of the two PCMs were determined to be CA  SA  PA = 77.4  8.6  14.0 and CA  SA  OD = 81.9  9.1  9.0, and the crystallization temperatures were 19.20 °C and 23.90 °C, respectively. The phase transition temperatures as measured by DSC were 18.60 °C and 24.82 °C, and the latent heat of phase transition were 129.15 J g-1 and 161.74 J g-1, respectively. The results are in good agreement with those measured by the step cooling curve method. The chemical and crystalline properties of the two PCMs were analyzed by FT-IR and XRD. It was found that CA-SA is combined with PA or OD by physical action, and the components have good compatibility and form a good eutectic structure. In addition, the results of heat storage and heat release experiments and the 500 times of accelerated melting-solidification cycling test showed that the two kinds of PCMs have good heat resistance and thermal reliability. Therefore, the prepared CA-SA-PA and CA-SA-OD have good performance and great application potential in building energy saving and solar energy utilization.Tin dioxide (SnO2) nanomaterials are important acid catalysts. It is therefore crucial to obtain details about the surface acidic properties in order to develop structure-property relationships. Herein, we apply 31P solid-state NMR spectroscopy combined with a trimethylphosphine (TMP) probe molecule, to study the facet-dependent acidity of SnO2 nanosheets and nanoshuttles. With the help of density functional theory calculations, we show that the tin cations exposed on the surfaces are Lewis acid sites and their acid strengths rely on surface geometries. As a result, the (001), (101), (110), and (100) facets can be differentiated by the 31P NMR shifts of adsorbed TMP molecules, and their fractions in different nanomaterials can be extracted according to deconvoluted 31P NMR resonances. The results provide new insights on nanosized oxide acid catalysts.An addition of H-phosphonates to aryl alkynes was realized under solvent- and metal-free conditions, affording Markovnikov-selective α-vinylphosphonates in moderate to good yields. A wide range of aryl alkynes could be applied for the reaction. A tentative mechanism of addition-substitution was proposed based on in situ 31P 1H NMR studies.Tumor associated macrophages (TAM) are key pathogenic factors in neoplastic diseases. They are known to have plasticity and can polarize into two opposing phenotypes, including the tumoricidal M1 and the protumoral M2 phenotypes with high prevalence of M2-phentoypes in patients with poor prognosis. Strategies for targeting M2-TAM may consequently increase the efficacy of therapeutic strategies for cancer treatment. Gold nanorod-assisted plasmonic photothermal therapy (PPTT) has emerged as a promising treatment for cancer but the effects of macrophage polarization parameters in the performance of this new treatment modality is still unknown. Herein, human monocytic THP-1 cells were polarized into two opposite phenotypic macrophages (M1-TAM and M2-TAM) and their response to PPTT was examined. M2-TAM exhibits a three-fold increase in AuNP uptake compared to M1-TAM. Laser irradiation results in selective killing of pro-tumoral M2-TAM after treatment with AuNPs with limited effects on anti-tumoral M1-TAM. A positive correlation between the expression of CD206 marker and the AuNP uptake may indicate the role of CD206 in facilitating AuNP uptake. Our findings also suggest that the differences in AuNP avidity and uptake between the M1-TAM and M2-TAM phenotypes may be the rationale behind the effectiveness of PPTT in the treatment of solid tumors.Three new titanium oxo-clusters Ti4O2(OiPr)10(OOCPhMe)2 (I), Ti6O4(OEt)8(OOCPhMe)8 (II) and Ti6O6(OEt)6(OOCCHPh2)6 (III) were obtained by easy one-step solvothermal reactions of titanium(iv) isopropoxide, alcohols and carboxylic acids. The three compounds were characterized by single-crystal and powder X-ray diffraction, TGA/DSC, optical and electron microscopy, and FTIR and NMR spectroscopy. X-ray powder diffraction and spectroscopy confirmed the purity of the compounds. Structural analysis indicates that in all compounds the titanium(iv) ions are six-coordinated (distorted octahedra). (I) is a tetranuclear complex containing a Ti4(μ4-O)(μ2-O) core, which is linked by two (μ2-OOCPhMe), four (μ2-OiPr) and six OiPr ligands. (II) and (III) are hexanuclear complexes with different cores, respectively Ti6(μ3-O)2(μ2-O)2 and Ti6(μ3-O)6. The coordination sphere of the Ti atoms is filled by eight (μ2-OOCPhMe), two (μ2-OEt) and six OEt in (II) and six (μ2-OOCHPh2) and six OEt in (III). Different steric hindrance of substituents attached to the carboxyl group or different concentrations lead to three main different cluster geometries with two ligands. The tetranuclear and the hexanuclear clusters were obtained with the OOCPhMe ligand, while the hexagonal prism cluster was obtained with the OOCCHPh2 ligand. Hirshfeld surface calculations indicated that the packing is driven by C-O⋯H-C weak hydrogen bonds. The clusters can be used as molecular models of organic molecules bonded to titania surface, used in organic photovoltaic (dye sensitized solar cells) or other optoelectronic applications.Pb-toxicity is associated with inflammation which leads to delay in wound healing. Pb2+ utilizes calcium ion channels to enter the cell. Therefore, to achieve effective healing in a Pb-poisoned system, capturing Pb2+ from the circulatory system would be an effective approach without hampering the activity of the calcium ion channel. In this work insulin-nickel fluorescent quantum clusters (INiQCs) have been synthesized and used for the specific detection of Pb2+ ions in vitro and in cell-free systems. INiQCs (0.09 μM) can detect Pb2+ concentrations as low as 10 pM effectively in a cell-free system using the fluorescence turn-off method. In vitro INiQCs (0.45 μM) can detect Pb2+ concentrations as low as 1 μM. INiQCs also promote wound healing which can easily be monitored using the bright fluorescence of INiQCs. INiQCs also help to overcome the wound recovery inhibitory effect of Pb2+ in vitro using lead nitrate. This work helps to generate effective biocompatible therapeutics for wound recovery in Pb2+ poisoned individuals.Due to the high demand for clean, economic, and recyclable energy, phase change materials (PCMs) have received significant attention in recent years. To improve the performance of PCMs, they are confined in micro- and nano-capsules composed of organic or inorganic materials. In this study, encapsulated phase change material (EPCM) systems were constructed with paraffin molecules as the core material and capped carbon nanotubes (CNTs) as the shell. We investigated the effects of different parameters including CNT diameter, length, and chirality and the length of the alkane molecule chain. We also investigated metal nanocluster-enhanced PCM systems via the addition of Cu, Ag, and Al clusters to the EPCM systems. Different thermodynamic, dynamic, and structural properties including configurational energy, melting range, mean square displacement, self-diffusion coefficient, radial distribution function (RDF), and average end-to-end distance of the confined molecules were examined. We also investigated the effect of metal doping in CNT on the different properties of the confined PCM. The results indicated that a longer CNT has a lower melting point than the normal CNT system. MM-102 Histone Methyltransferase inhibitor It was also observed that the bigger (30,0) CNT, (14,14) armchair CNT, and icosane systems have higher melting ranges than the normal (25,0) system. The metal cluster systems also have a lower starting melting point than the normal system. Furthermore, it was found that the Al cluster system has the lowest starting melting point among the studied systems.CaCu3Ti4O12 and CaCu2.95Mg0.05Ti3.95Al0.05O12 ceramics were fabricated via a solid-state reaction method. A single-phase of CaCu3Ti4O12 was found in these two ceramics. Very great grain size expansion was produced by co-doping with Mg2+ and Al3+. DFT results indicate that both Mg and Al atoms preferentially occupy Cu sites, creating liquid-phase sintering decomposition at grain boundary layers. Very high dielectric permittivity of ∼58 397 and low loss tangent of about 0.047 were achieved in a CaCu2.95Mg0.05Ti3.95Al0.05O12 ceramic. Additionally, the temperature stability of the dielectric response was improved. Better dielectric properties in the co-doped ceramic have possible origins from enhanced grain boundary responses, especially from the influences of metastable phases and oxygen enrichment at the grain boundaries. Experimental and computational results indicate that the colossal dielectric properties in CaCu3Ti4O12 ceramics might be correlated with an internal barrier layer capacitor structure.
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