Control of Oxidation State of Eu Ions in Na2O–Al2O3–SiO2 Glasses

Glasses doped with well‐controlled Eu³⁺ and Eu²⁺ ions have attracted considerable interest due to the possibility of tuning the wavelength range of the emitted light from violet to red by using their ⁵D₀→⁷F_j and 5d–4f electron transitions. Glasses were prepared to dope Eu³⁺ ions in a Na₂O–Al₂O₃–SiO₂ system, and the changes in the valence state of Eu³⁺ ions and the glass structure surrounding the Eu atoms during heating under H₂ atmosphere were investigated using fluorescence spectroscopy, X‐ray absorption fine‐structure spectroscopy, and ²⁷Al magic‐angle spinning solid‐state nuclear magnetic resonance spectroscopy. The reduction behavior of Eu³⁺ ions was dependent on the Al/Na molar ratio of the glass. For Al/Na < 1, the Al³⁺ ions formed the AlO₄ network structure accompanied by the Na⁺ ions as charge compensators; the Eu³⁺ ions occupied the interstitial positions in the SiO₄ network structure and were not reduced even under heating in H₂ gas. On the other hand, in the glasses containing Al₂O₃ with the Al/Na ratio exceeding unity, the Eu³⁺ ions commenced to be coordinated by the AlO₄ units in addition to the SiO₄ network structure. When heated in H₂ gas, H₂ gas molecules reacted with the AlO₄ units surrounding Eu³⁺ ions to form AlO₆ units terminated with OH bonds, and reduced Eu³⁺ ions to Eu²⁺ via the extracted electrons.     

Accelerated Discovery of Potent Bioactive anti-TNFα Aptamers by Microbead-Assisted Capillary Electrophoresis (MACE)-SELEX

Dysregulation of tumor necrosis factor-α (TNFα), a pro-inflammatory cytokine, causes several diseases, making it an important therapeutic target. Here, we identified a novel DNA aptamer against human TNFα using in vitro selection, which included a high exclusion pressure process against non-binding and weak binders through microbead-assisted capillary electrophoresis (MACE) in only three rounds. Among the 15 most enriched aptamers, Apt14 exhibited the highest inhibitory activity for the interaction between TNFα and its cognate receptor in mouse L929 cells. For further improving the bioactivity of the aptamer, dimerization programed by hybridization was evaluated, resulting in the Apt14 dimer exhibited a twofold higher binding affinity and stronger inhibition compared to the monomer counterpart. Rapid identification of bioactive aptamers using MACE in combination with facile dimerization by hybridization accelerates the discovery of novel bioactive aptamers, paving the way toward replacing current monoclonal antibody therapy with the less expensive and non-immunogenic aptamer therapy.     

Stabilizing effect of the cyclodextrins additive to spray-dried particles of curcumin/polyvinylpyrrolidone on the supersaturated state of curcumin

Although curcumin is considered to have various therapeutic effects, its use as a functional food or supplement is restricted owing to its low water solubility and bioavailability. To increase the solubility of curcumin in water, the use of polyvinylpyrrolidone (PVP) and vinylpyrrolidone-vinyl acetate copolymers with a pyrrolidone skeleton was noted to be promising. In particular, the bi-component formulations of curcumin/PVP prepared through spray drying exhibited an amorphous state in powder X-ray diffraction observations and temporally increased the apparent solubility of curcumin to over 5000 times that of untreated curcumin; nevertheless, after 24 h, the solubility decreased owing to the unstable supersaturated state of curcumin. The addition of α-cyclodextrin (α-CyD) in the bi-component curcumin/PVP formulation helped maintain the supersaturated state of curcumin, whereas the addition of β- and γ-CyD led to the collapse of the supersaturated state. The addition of α-CyD can likely help inhibit the nucleation and crystal growth of curcumin, through the interaction among the solubilized units of curcumin/PVP and α-CyD.     

Hydrothermal Synthesis and Formation Mechanisms of Lanthanum Tin Pyrochlore Oxide

Well-defined La₂Sn₂O₇ with a phase-pure pyrochlore structure was produced by hydrothermal synthesis at temperatures as low as 200°C. Production of phase-pure La₂Sn₂O₇ requires a pH above 10, and higher pH accelerates the crystallization process. The synthesis produced spherical particles of average particle size ∼0.59 μm (±0.12) and surface area ∼14.1 m²/g. SEM and TEM observation for morphologic evolution and kinetic analysis during crystallization indicated that La₂Sn₂O₇ formation probably proceeds via a two-step reaction. First a transient dissolution–precipitation occurs. Then the primary crystallites aggregate because of their colloidal instability, and heterocoagulation with the lanthanum hydrous oxide precursor particles also occurs. The sluggish reaction rate at the later stage of reaction is characterized by an in situ transformation, where the soluble tin species is diffused through the porous La₂Sn₂O₇ aggregates to react with entrapped lanthanum precursors.     

Improvement of both adsorption performance of silica gel and heat transfer characteristics by means of heat exchange modulation for a heat pump

In order to provide high performance silica gel for an adsorption heat pump (AHP), gels were synthesized using the sol-gel process modified with a new method of controlling the primary gel particle growth by the addition of aluminum ion. In this process, the pores of the silica gel synthesized became smaller when aluminum ion was added in the washing process. Furthermore, this silica gel adsorbed more water at a low region of water vapor pressure and its adsorption ability did not change after 100 repetitive times of adsorping/desorping water vapor. The experimental results from the water vapor adsorption on the silica gel agreed well with theoretical results obtained under the Lump model for heat transfer and intraparticle diffusion model for mass transfer. A new direct heat exchange silica gel module (DS-module) for the AHP was provided, and the heat transfer characteristics during the operation for the adsorption of water vapor were both experimentally and theoretically determined. The period of the adsorption for the DS-module was shorter than that for a silica gel/tube module. Therefore, with the addition of the DS-module the heat transfer in the AHP adsorber was sufficiently enhanced and the maximum heat generation power for the 2-mm-thick DS-module was obtained. © 1997 Scripta Technica, Inc. Heat Trans Jpn Res, 25(7): 420–433, 1996     

Models for circular data from time series spectra

Circular data are those for which the natural support is the unit circle and its toroidal extensions. Numerous constructions have been proposed which can be used to generate models for such data. We propose a new, very general, one based on the normalization of the spectra of complex-valued stationary processes. As illustrations of the new construction's application, we study models for univariate circular data obtained from the spectra of autoregressive moving average models and relate them to existing models in the literature. We also propose and investigate multivariate circular models obtained from the high-order spectra of stationary stochastic processes generated using linear filtering with an autoregressive moving average response function. A new family of distributions for a Markov process on the circle is also introduced. Results for asymptotically optimal inference for dependent observations on the circle are presented which provide a new paradigm for inference with circular models. The application of one of the new families of spectra-generated models is illustrated in an analysis of wind direction data.     

Direct Reprogramming and Induction of Human Dermal Fibroblasts to Differentiate into iPS-Derived Nucleus Pulposus-like Cells in 3D Culture

Intervertebral disc (IVD) diseases are common spinal disorders that cause neck or back pain in the presence or absence of an underlying neurological disorder. IVD diseases develop on the basis of degeneration, and there are no established treatments for degeneration. IVD diseases may therefore represent a candidate for the application of regenerative medicine, potentially employing normal human dermal fibroblasts (NHDFs) induced to differentiate into nucleus pulposus (NP) cells. Here, we used a three-dimensional culture system to demonstrate that ectopic expression of MYC, KLF4, NOTO, SOX5, SOX6, and SOX9 in NHDFs generated NP-like cells, detected using Safranin-O staining. Quantitative PCR, microarray analysis, and fluorescence-activated cell sorting revealed that the induced NP cells exhibited a fully differentiated phenotype. These findings may significantly contribute to the development of effective strategies for treating IVD diseases.     

Sonochemical decomposition of perfluorooctane sulfonate and perfluorooctanoic acid

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are shown to be globally distributed, environmentally persistent, and bioaccumulative. Although the toxicities of these compounds were reported, the cleanup procedure from the environment is not developed because of their inertness. In this report the sonochemical degradations of PFOS and PFOA to the products through the fission of the perfluorocarbon chains were observed and the half-life times of the PFOS and PFOA degradations under an argon atmosphere determined to be 43 and 22 min, respectively. The shortening of perfluorocarbon chain of PFOS and PFOA leads to the lowering of the toxicity in view of the decrease of the persistence, and the technique would contribute to the remediation of the environmental pollution by these compounds.     

Direct Formation of Crystalline Gadolinium-Doped Ceria Powder via Polymerized Precursor Solution

Synthesis of Ce_0.9Gd_0.1O_1.95 (CGO) powder from a polymeric precursor solution containing a mixture of nitrates, nitric acid, and ethylene glycol was investigated with emphasis on the effect of polymerization of the precursor solution on the crystallization and morphology of the derived solid intermediate and the final oxide powder. It is shown for the first time in this work that the solid intermediate derived from the polymerized solution is present in the form of well-crystallized cerium-gadolinium formate solid solution, Ce_{1− x} Gd _x (HCOO)₃, exhibiting anisotropic growth. Further polymerization of the precursor solution resulted in the direct formation of loosely agglomerated nanoscaled CGO oxide powder from the polymerized solution at temperatures as low as 130°C.     

Formation of Sm2+ lons in Sol-Gel-Derived Glasses of the System Na2 O-Al2O3-SiO2

Samarium ions (Sm²⁺) incorporated into aluminosilicate glasses by a sol-gel process showed persistent spectral hole burning at room temperature. Gels of the system Na₂O-Al₂O₃SiO₂ synthesized by the hydrolysis of Si(OC₂H₅)₄, Al(OC₄H₉)₃, CH₃ COONa, and SmCl₃·6H₂O were heated in air at 500°C, then reacted with H₂ gas to form Sm²⁺ ions. Whereas Al³⁺ ions effectively dispersed the Sm³⁺ ions in the glass structure, Na⁺ ions were not effective. The Al₂O₃-SiO₂ glasses proved appropriate for reacting the Sm³⁺ ions with H₂ gas and exhibited the intense photoluminescence of Sm²⁺ ions. The reaction of Sm³⁺ ions with H₂ in the Al₂O₂-SiO₂ glasses was determined by first-order kinetics, and the activation energy equaled 95 kJ/mol. At 800°C, the maximum photoluminescence of the Sm²⁺ ions was achieved within 20 min.