Organic–silicate hybrid catalysts based on various defined structures for Knoevenagel condensation

Two types of organic–inorganic hybrid base catalysts are prepared. Organic-functionalized molecular sieves (OFMSs), particularly “amine-immobilized porous silicates”, are designed based on common idea to immobilize catalytic active sites on silicate surface. Silicate–organic composite materials (SOCMs), such as “ordered porous silicate–quaternary ammonium composite materials”, are the precursors of ordered porous silicates obtained during the synthesis. Both the OFMS and the SOCM are used as the catalysts for Knoevenagel condensation. Among the OFMSs, there is clear tendency that the use of molecular sieve with larger pore volume and/or surface area gives the product in higher yield. Aminopropylsilyl (AP)-functionalized mesoporous silicates such as AP-MCM-41 gives the product in high yield under mild conditions. No loss of activity is observed after repeated use for three times. The SOCMs are also active for the same reaction. The precursors of the mesoporous silicates are more active than those of microporous silicates. This material can be repeatedly used without significant loss of activity. High activity is not due to the leached species. The active sites of the SOCM catalysts are considered to be SiO⁻ moieties located on the pore-mouth. Activity of the SOCM increases when the reaction is carried out without solvent, whereas decrease in activity of the OFMS is observed in the solvent-free system.     

Recognition of substrates by membrane potential of immobilized glucose oxidase membranes

The shifts in membrane potential, caused by the injection of glucose into a permeation cell, were measured using immobilized (entrapped) glucose oxidase membranes. No, pH change in the permeation cell was observed upon injection of glucose, but the shift in membrane potential was definitely detected. The shift in membrane potential was observed under nitrogen bubbling (in the absence of oxygen) using initially used enzyme membranes. It was, therefore, suggested that the shifts in membrane potential were not caused by an enzyme-substrate reaction, but by binding of the substrate to the enzyme, which indues a conformational change in the enzyme and leads to a change in charge density in the enzyme membrane. This mechanism is also supported by the fact that the shifts in membrane potential were observed upon injection of not only D-glucose but also L-glucose as reported in our previous study [J. Chem. Soc. Faraday Trans., 87 , 695 (1991)]. © 1994 John Wiley & Sons, Inc.     

One-Step Synthesis of Luminescent Nanoparticles of Complex Oxide, Strontium Aluminate

An organic aqueous solution of metal acetylacetonate precursors was subjected to spray pyrolysis in order to fabricate SrAl₂O₄:Eu (SAO) nanoparticles. Non-agglomerated luminescent SAO nanoparticles, having a spherical shape with a size of 10–30 nm, were achieved in a single step, while only submicrometer-sized SAO particles were obtained from the conventional ultrasonic pyrolysis of the metal nitrates. Without any post-annealing process, the as-prepared SAO nanoparticles were observed to exhibit a strong photoluminescence, which is comparable with that of the submicrometer-sized SAO particles. A mechanism for the formation of the nanoparticles is also discussed.     

Electro-rheological effect and dynamic rheological properties of a blend composed of two liquid crystalline materials with different molecular weight

Electro-rheological (ER) effect of a blend composed of two liquid crystalline materials with different molecular weights is described in this article. The results indicated that ER effect of the blend was observed at the temperature range where each neat sample did not show ER effect. Furthermore, both storage modulus (G′) and loss modulus (G″) decreased drastically at the temperature range for the blend in dynamic viscoelastic measurements. We show that steady ER effect could be obtained by using a blend made up of two liquid crystalline components, whereas remarkable increment in shear stress was not observed for each component under applied electric field.     

Hydrothermal Formation of Hydroxyapatite Layers on the Surface of Type-A Zeolite

Type-A zeolite evenly covered with hydroxyapatite thin layers was prepared using hydrothermal treatment at 120°C for 8 h under autogenous pressure. The hydroxyapatite needlelike nanocrystals, 100–200 nm in diameter and 30 nm in thickness, were grown under the reaction between discharged Ca²⁺ ions from type-A zeolite and PO₄³⁻ ions in (NH₄)₃PO₄ solution. The preferential orientations of the c -axis of hydroxyapatite crystals perpendicular to a zeolite surface were observed using transmission electron microscopy. The crystal structure of type-A zeolite was not destroyed under the reaction, but the surface morphology was changed only with complete covering of scaly hydroxyapatite particles.     

Synthesis and luminescence properties of Pr3+ doped CaxBa1?xTiO3 (0.3?x<1) fine particles

Ca _x Ba_1−x TiO₃ (CBT) fine particles doped with red luminescence center of Pr³⁺ ions (Pr: CBT) were successfully synthesized by salt assisted spray pyrolysis (SASP) process. Scanning electronic microscope (SEM) and laser scattering analysis demonstrate that salt can be removed from the surface of particles by washing with Milli-Q water and the particles can be further separated by ball-milling to get well-dispersed Pr³⁺ ions doped CBT fine particles. The luminescence properties, such as photoluminescence (PL) and mechanoluminescence (ML), of as-synthesized Pr: CBT particles were investigated. For Pr: CBT fine particles with different Ca molar ratios, all the samples show one emission at 612 nm, with increasing Ca molar ratio, PL intensity of Pr: CBT fine particles become stronger and stronger. When pressure was loaded on the Pr: CBT pellet, mechanoluminescence(ML) emission was measured. The results show that the ML intensity is proportional to the applied pressure.     

Anodic characteristics of amorphous ternary palladium-phosphorus alloys containing ruthenium,rhodium, iridium,or platinum in a hot concentrated sodium chloride solution

Amorphous ternary palladium-based alloys containing platinum group metals as an additional element were prepared by rapid quenching from the molten state and their anodic characteristics were investigated in a 4 mol dm^?3 NaCl solution of pH 4 and 80° C. The amorphous alloys containing sufficient quantities of rhodium, platinum or iridium were passivated by anodic polarization and their corrosion rates at high current densities in the chlorine evolution region were extremely low. This fact was attributed to the formation of a highly protective passive film due to both the transformation to the amorphous structure and the addition of rhodium, platinum or indium. The electrocatalytic activities for chlorine evolution of amorphous alloys were higher than those of pure platinum group metals except palladium. In particular, the amorphous Pd₄₁Ir₄₀P₁₉ alloy had the desired stable, high electrocatalytic activity for chlorine evolution and the high overvoltage for oxygen evolution.     

Machining accuracy for shearing process of thin-sheet metals—Development of initial tool position adjustment system

In the shearing process, clearance has a significant effect on machining accuracy. However, the relationship between uneven clearance caused by misalignment of tool position and machining accuracy remains unclear. This is attributed to the fact that, previously, the effect was small because the thickness of the workpiece was not so thin, and a method for precisely measuring and adjusting the tool position had not been established. Therefore, in the present study, a new method of adjusting the initial tool position is developed. In addition, punching experiments are conducted under the condition that the initial tool position is adjusted to an accuracy of 2 μm or better, and the effects of clearance on machining accuracy, shape of cross-section, and diameter of hole, are investigated in three types of materials. From these results, the importance of adjusting the initial tool position is clarified.     

A content search system considering the activity and context of a mobile user

People routinely carry mobile devices in their daily lives and obtain a variety of information from the Internet in many different situations. In searching for information (content) with a mobile device, a user’s activity (e.g., moving or stationary) and context (e.g., commuting in the morning or going downtown in the evening) often change, and such changes can affect the user’s degree of concentration on his or her mobile device’s display and information needs. Therefore, a search system should provide the user with an amount of information suitable for the current activity and a type of information suitable for the current context. In this study, we present the design and implementation of a content search system that considers a mobile user’s activity and context, with the goal of reducing the user’s operation load for content search. The proposed system switches between two kinds of content search systems according to the user’s activity: the location-based content search system is activated when the user is stationary (e.g., standing and sitting), while a menu-based content search system is activated when the user is moving (e.g., walking). Both systems present information according to user context. The location-based system presents detailed information via menus and a map according to location-based categories. The menu-based system presents only a few options to enable users to get content easily. Through user experiments, we confirmed that participants could get desired information more easily with this system than with a commercial search system.