In-Situ Observation of SiC Bulk Single Crystal Growth by XRD System

In-situ analysis for SiC bulk single crystal growth was reported using vertical X-ray diffractometer system. A furnace for SiC sublimation growth combined with the XRD system which possessed three kinds of functions including topography, rocking curve measurement and crystal growth rate monitoring was developed. These functions could contribute as a powerful tool finding the optimum growth condition by dynamic observation in the crucible. In this study, the in-situ X-ray topographs succeeded to capture dynamic elongation of defects and dislocation generated in the SiC growing crystals. The in-situ rocking curve measurement reviled appearance of mosaic structure in the SiC crystal grown with high growth rate. The in-situ growth rate monitoring also succeeded very precisely using the direct X-ray beam absorption. On the base of findings and facts obtained by the in-situ observations, the importance for the SiC growth was discussed.     

Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence

Molecular vibrations in the solid-state, detectable in the terahertz (THz) region, are the subject of research to further develop THz technologies. To observe such vibrations in terahertz time-domain spectroscopy (THz-TDS) and low-frequency (LF) Raman spectroscopy, two supramolecular assemblies with the formula [Nd^III (phen)₃ (NCX)₃] 0.3EtOH (X = S, 1-S; Se, 1-Se) were designed and prepared. Both compounds show several THz-TDS and LF-Raman peaks in the sub-THz range, with the lowest frequencies of 0.65 and 0.59 THz for 1-S and 1-Se, and 0.75 and 0.61 THz for 1-S and 1-Se, respectively. The peak redshift was observed due to the substitution of SCN⁻ by SeCN⁻. Additionally, temperature-dependent TDS-THz studies showed a thermal blueshift phenomenon, as the peak position shifted to 0.68 THz for 1-S and 0.62 THz for 1-Se at 10 K. Based on ab initio calculations, sub-THz vibrations were ascribed to the swaying of the three thiocyanate/selenocyanate. Moreover, both samples exhibited near-infrared (NIR) emission from Nd (III), and very good thermometric properties in the 300–150 K range, comparable to neodymium (III) oxide-based thermometers and higher than previously reported complexes. Moreover, the temperature dependence of fluorescence and THz spectroscopy analysis showed that the reduction in anharmonic thermal vibrations leads to a significant increase in the intensity and a reduction in the width of the emission and LF absorption peaks. These studies provide the basis for developing new routes to adjust the LF vibrational absorption.     

Uterine Deletion of Bmal1 Impairs Placental Vascularization and Induces Intrauterine Fetal Death in Mice

Recently, it was demonstrated that the expression of BMAL1 was decreased in the endometrium of women suffering from recurrent spontaneous abortion. To investigate the pathological roles of uterine clock genes during pregnancy, we produced conditional deletion of uterine Bmal1 (cKO) mice and found that cKO mice could receive embryo implantation but not sustain pregnancy. Gene ontology analysis of microarray suggested that uterine NK (uNK) cell function was suppressed in cKO mice. Histological examination revealed the poor formation of maternal vascular spaces in the placenta. In contrast to WT mice, uNK cells in the spongiotrophoblast layer, where maternal uNK cells are directly in contact with fetal trophoblast, hardly expressed an immunosuppressive NK marker, CD161, in cKO mice. By progesterone supplementation, pregnancy could be sustained until the end of pregnancy in some cKO mice. Although this treatment did not improve the structural abnormalities of the placenta, it recruited CD161-positive NK cells into the spongiotrophoblast layer in cKO mice. These findings indicate that the uterine clock system may be critical for pregnancy maintenance after embryo implantation.     

Downregulation of miR-122-5p Activates Glycolysis via PKM2 in Kupffer Cells of Rat and Mouse Models of Non-Alcoholic Steatohepatitis

Non-alcoholic steatohepatitis (NASH) has pathological characteristics similar to those of alcoholic hepatitis, despite the absence of a drinking history. The greatest threat associated with NASH is its progression to cirrhosis and hepatocellular carcinoma. The pathophysiology of NASH is not fully understood to date. In this study, we investigated the pathophysiology of NASH from the perspective of glycolysis and the Warburg effect, with a particular focus on microRNA regulation in liver-specific macrophages, also known as Kupffer cells. We established NASH rat and mouse models and evaluated various parameters including the liver-to-body weight ratio, blood indexes, and histopathology. A quantitative phosphoproteomic analysis of the NASH rat model livers revealed the activation of glycolysis. Western blotting and immunohistochemistry results indicated that the expression of pyruvate kinase muscle 2 (PKM2), a rate-limiting enzyme of glycolysis, was upregulated in the liver tissues of both NASH models. Moreover, increases in PKM2 and p-PKM2 were observed in the early phase of NASH. These observations were partially induced by the downregulation of microRNA122-5p (miR-122-5p) and occurred particularly in the Kupffer cells. Our results suggest that the activation of glycolysis in Kupffer cells during NASH was partially induced by the upregulation of PKM2 via miR-122-5p suppression.     

Theranostic Agent Combining Fullerene Nanocrystals and Gold Nanoparticles for Photoacoustic Imaging and Photothermal Therapy

Developing photoactivatable theranostic platforms with integrated functionalities of biocompatibility, targeting, imaging contrast, and therapy is a promising approach for cancer diagnosis and therapy. Here, we report a theranostic agent based on a hybrid nanoparticle comprising fullerene nanocrystals and gold nanoparticles (FGNPs) for photoacoustic imaging and photothermal therapy. Compared to gold nanoparticles and fullerene crystals, FGNPs exhibited stronger photoacoustic signals and photothermal heating characteristics by irradiating light with an optimal wavelength. Our studies demonstrated that FGNPs could kill cancer cells due to their photothermal heating characteristics in vitro. Moreover, FGNPs that are accumulated in tumor tissue via the enhanced permeation and retention effect can visualize tumor tissue due to their photoacoustic signal in tumor xenograft model mice. The theranostic agent with FGNPs shows promise for cancer therapy.     

Kinetic Study of the Prooxidant Effect of α-Tocopherol. Hydrogen Abstraction from Lipids by α-Tocopheroxyl Radical

A kinetic study of the prooxidant effect of α-tocopherol was performed. The rates of allylic hydrogen abstraction from various unsaturated fatty acid esters (ethyl stearate 1, ethyl oleate 2, ethyl linoleate 3, ethyl linolenate 4, and ethyl arachidonate 5) by α-tocopheroxyl radical in toluene were determined, using a double-mixing stopped-flow spectrophotometer. The second-order rate constants (k _p) obtained are <1 × 10⁻² M⁻¹ s⁻¹ for 1, 1.90 × 10⁻² M⁻¹ s⁻¹ for 2, 8.33 × 10⁻² M⁻¹ s⁻¹ for 3, 1.92 × 10⁻¹ M⁻¹ s⁻¹ for 4, and 2.43 × 10⁻¹ M⁻¹ s⁻¹ for 5 at 25.0 °C. Fatty acid esters 3, 4, and 5 contain two, four, and six –CH₂– hydrogen atoms activated by two π-electron systems (–C=C–CH₂–C=C–). On the other hand, fatty acid ester 2 has four –CH₂– hydrogen atoms activated by a single π-electron system (–CH₂–C=C–CH₂–). Thus, the rate constants, k _abstr/H, given on an available hydrogen basis are k _p/4 = 4.75 × 10⁻³ M⁻¹ s⁻¹ for 2, k _p/2 = 4.16 × 10⁻² M⁻¹ s⁻¹ for 3, k _p/4 = 4.79 × 10⁻² M⁻¹ s⁻¹ for 4, and k _p/6 = 4.05 × 10⁻² M⁻¹ s⁻¹ for 5. The k _abstr/H values obtained for 3, 4, and 5 are similar to each other, and are by about one order of magnitude higher than that for 2. From these results, it is suggested that the prooxidant effect of α-tocopherol in edible oils, fats, and low-density lipoproteins may be induced by the above hydrogen abstraction reaction.     

Kinetics and reaction scheme of coal liquefaction over molten tin catalyst

Rates of formation of gases, oils, asphaltenes and preasphaltenes during non-solvent liquefaction of coal over molten tin catalyst have been measured. A probable reaction scheme and the rate constants for the pathways comprising the scheme have been presented. The results show that the catalyst greatly accelerates the conversion of preasphaltenes to asphaltenes. It also accelerates two other reactions, i.e., coal to preasphaltenes and coal to asphaltenes. By contrast, the catalyst does little to promote gasification and formation of oils.     

Rh/γ-Al2O3 Catalytic Layer Integrated with Sol–Gel Synthesized Microporous Silica Membrane for Compact Membrane Reactor Applications

An efficient and compact catalytic membrane reactor for reforming of CH₄ was developed by integrating a hydrogen perm-selective silica membrane with an Rh/-Al₂O₃ catalyst layer. The catalytic layer was sandwiched between the outer surface of the -Al₂O₃ support tube and the silica membrane with an aim of improving the heat and mass transfer rates through the system and to simplify the reactor geometry. The system showed improved efficiency for reforming of CH₄ at comparatively lower operating temperatures and steam to C molar ratios than the conventional fixed-bed steam reforming systems. Under optimized conditions, a nearly 25-30% improvement from the equilibrium conversion level was achieved as a result of abstraction of hydrogen from the product stream by the silica membrane integrated with the catalyst layer. The performance of the system was evaluated as a function of various process parameters. Because of the compactness and efficiency, the present system emerges as a promising alternative to the conventional membrane reactors, which possess separate catalytic and membrane units.