Degradation of estrogen conjugates using titanium dioxide as a photocatalyst.

Estrogen conjugates (estradiol-3-glucuronide, -17-glucuronide, estrone-glucuronide and -sulfate) were subjected to photodegradation using titanium dioxide immobilized on glass beads as a catalyst. Their time courses were measured by HPLC and compared with those of the unconjugated estrogens. Estradiol, its 17-glucuronide and estrone, which have an unconjugated phenolic hydroxy group at the C-3 position, were almost completely degraded by UV irradiation within 4 h. On the other hand, significant amounts of estradiol- and estrone-3-glucuronide (ca. 20%, 25%) and estrone sulfate (ca. 90%), which were conjugated at the 3-hydroxy group, remained after a 6.5 h irradiation. These results supported the hypothesis that the photodegradation of estrogens was initiated at the phenolic hydroxy group.     

Recent Advances in Layered Metal Chalcogenides as Superconductors and Thermoelectric Materials: Fe‐Based and Bi‐Based Chalcogenides

Recent advances in layered (Fe‐based and Bi‐based) chalcogenides as superconductors or functional materials are reviewed. The Fe–chalcogenide (FeCh) family are the simplest Fe‐based high‐T_c superconductors. The superconductivity in the FeCh family is sensitive to external or chemical pressure, and high T_c is attained when the local structure (anion height) is optimized. The Bi–chalcogenide (BiCh₂) family are a new group of layered superconductors with a wide variety of stacking structures. Their physical properties are also sensitive to external or chemical pressure. Recently, we revealed that the emergence of superconductivity and the T_c in this family correlate with the in‐plane chemical pressure. Since the flexibility of crystal structure and electronic states are an advantage of the BiCh₂ family for designing functionalities, I briefly review recent developments in this family as not only superconductors but also other functional materials.

     

Controllable heterogeneity in a supramolecular hydrogel

A dispersion of a peptide amphiphile into water forms hierarchical fibril structures, leading to a supramolecular hydrogel. We here report that there exists dynamic heterogeneity in the gel, which might be induced by the heterogeneous fibril network. The network, and therefore, the heterogeneity, can be easily regulated by changing the temperatures used to dissolve the gelator in water.     

Crystal structure and lattice vibration of proton dissolved BaZr0.8Sc0.2O2.9

Heat capacity and neutron diffraction measurements were carried out to determine the location of protons in the crystal of proton conducting perovskite oxide BaZr_0.8Sc_0.2O_2.9. The heat capacity of proton- and deuteron-dissolved BaZr_0.8Sc_0.2O_2.9 showed a slight difference from that of the dry sample. It indicates that the librational motion of the OH(OD) group is not excited below room temperature. The neutron diffraction experiments on the deutron dissolved sample indicate that the deuteron exists near the 12h site.     

Note on the propagation of love waves in a half-space with an elastic triple superficial layer subject to a high two-dimensional stress

The propagation of Love waves is investigated involving a triple superficial layer on a half-space, the entire system being elastic and highly stressed in two horizontal directions. The non-linear problem is illustrated numerically. A graph displays the phase velocity dependence on the wave length.     

Betuletol,a Propolis Component,Suppresses IL-33 Gene Expression and Effective against Eosinophilia

Propolis, a resinous substance produced by honeybees, has been used in folk medicine since ancient times due to its many biological benefits such as antitumor, antioxidant, antimicrobial, anti-inflammatory, and immunomodulatory effects. Propolis contains flavonoids, terpenoids, aromatic aldehydes, and alcohols, which vary with different climate and environmental conditions. In our study, we examined the antiallergic activity of Brazilian green propolis (BGP) and isolated the active compound that can suppress an allergy-sensitive gene, IL-33, expression and eosinophilia. Ethanolic extract of BGP freeze-dried powder was fractionated with several solvent systems, and the active fractions were collected based on activity measurement. The single active compound was found by thin-layer chromatography. Using column chromatography and NMR, the active compound was isolated and identified as 3,5,7-trihydroxy-6,4’-dimethoxyflavone, also known as betuletol. Further, the antiallergic activity of that has been examined in PMA-induced up-regulation of IL-33 gene expression in Swiss 3T3 cells. Our data showed the IL-33 gene suppression both by BGP and the isolated active compound, betuletol. We also found that betuletol suppressed ERK phosphorylation, suggesting it could be effective in suppressing IL-33 mediated eosinophilic chronic inflammation and will provide new insights to develop potent therapeutics against allergic inflammations.     

Enhancement in thermal stability and resistance to denaturants of lipase encapsulated in mesoporous silica with alkyltrimethylammonium (CTAB)

We assembled a highly durable conjugate with both a high-density accumulation and a regular array of lipase, by encapsulating it in mesoporous silica (FSM) with alkyltrimethylammonium (CTAB) chains on the surface. The activity for hydrolyzing esters of the lipase immobilized in mesoporous silica was linearly related to the concentration of lipase, whereas that of non-immobilized lipase showed saturation due to self-aggregation at a high concentration. The lipase conjugate also had increased resistance to heating when stayed in the silica coupling with CTAB. In addition, encapsulating the enzyme with FSM coupled CTAB caused the lipase to remain stable even in the presence of urea and trypsin, suggesting that the encapsulation prevented dissociation and denaturing. This conjugate had much higher activity and much higher stability for hydrolyzing esters when compared to the native lipase. These results show that FSM provides suitable support for the immobilization and dispersion of proteins in mesopores with disintegration of the aggregates.     

Temperature dependence of pre‐edge features in Ti K‐edge XANES spectra for ATiO3 (A = Ca and Sr), A2TiO4 (A = Mg and Fe), TiO2 rutile and TiO2 anatase

XANES (X‐ray absorption near‐edge structure) spectra of the Ti K‐edges of ATiO₃ (A = Ca and Sr), A₂TiO₄ (A = Mg and Fe), TiO₂ rutile and TiO₂ anatase were measured in the temperature range 20–900 K. Ti atoms for all samples were located in TiO₆ octahedral sites. The absorption intensity invariant point (AIIP) was found to be between the pre‐edge and post‐edge. After the AIIP, amplitudes damped due to Debye–Waller factor effects with temperature. Amplitudes in the pre‐edge region increased with temperature normally by thermal vibration. Use of the AIIP peak intensity as a standard point enables a quantitative comparison of the intensity of the pre‐edge peaks in various titanium compounds over a wide temperature range.