Voltammetric study of electrocatalysis for dioxygen reduction by trinuclear rutheniumammine complex confined in a polymer membrane

Electrocatalytic O₂ reduction was studied using a modified electrode coated with a Nafion membrane (Nf) dispersing a trinuclear ruthenium ammine complex ([(NH₃)₅Ru^IIIORu^IV(NH₃)₄ORu^III(NH₃)₅]Cl₆, Ru-red). When measuring cyclic voltammogram under O₂ atmosphere (at 0.5 mV s⁻¹), catalytic currents due to O₂ reduction were found to develop below −0.2 V (vs. Ag/AgCl). Since Ru-red undergoes irreversible decomposition into the mononuclear complexes via the reduced state (Ru^III-Ru^III-Ru^III) (∼−0.1 V), it is suggested that the electrocatalysis originates from the decomposed species (initial active species: Ru^II(NH₃)₅(OH₂) and Ru^II(NH₃)₄(OH₂)₂) rather than from the Ru-red. Although the present electrocatalyst was also applied to H₂O₂ reduction system, the catalytic activity was found to be poor from the voltammetric behavior. It appeared that the kinetics of the electrocatalysis is much faster in the O₂ reduction than in the H₂O₂ one. A selective and direct catalysis for O₂ reduction into H₂O was suggested from a ring-disk voltammogram to take place by an aggregate of the mononuclear ruthenium complexes in the polymer matrix. In addition, it was found that electrocatalytic O₂ reduction involves a slow kinetic process, so that factors affecting the overall kinetics were discussed in terms of the catalysis mechanism.     

Bubble wake visualization by using photochromic dye

Wake structure of a single “clean bubble”, rising in rectilinear, zigzagging or spiraling path, is experimentally investigated. A single nitrogen gas bubble was produced in a silicone oil pool and the wake structure development in the rear of the rising bubble was visualized by using photochromic dye. The flexibility of this visualization method enabled us to distinguish wake from drift easily. Both bubble motion and wake structure were recorded by using stereo high-speed video camera simultaneously. We present the first experimental support for the existence of the standing eddy at the rear of the clean bubble, as predicted by a previous numerical study by Ryskin and Leal [1984. Journal of Fluid Mechanics 148, 19-35], Dandy and Leal [1986. Physics of Fluids 29(5), 1360-1366] and Blanco and Magnaudet [1995. Physics of Fluids 7(6), 1265-1274]. We study motion of a pair of vortex filaments, which is called double-threaded type wake, in the case of bubble rising in an axi-asymmetric path. Visualization results of multiple formations of horse-shoe type vortices in one period of zigzag motion of rising bubble with shape oscillations, which has not been observed in previous studies are also presented.     

Size Distribution of Gold Nanoparticles Used by Small Angle X-ray Scattering

The size distribution of gold nanoparticles was estimated based on the scattering intensity data obtained from small angle X-ray scattering (SAXS) and compared with the result of micrographs by transmission electron microscopy. The slope of the Guinier plot was used to estimate the mean size assuming a narrow particle size distribution. When the size distribution is narrow, the mean size can be easily obtained from slope of a Guinier plot of scattering data within 10% error. Additionally, assuming a lognormal size distribution, the size distribution and the mean size can be calculated using the experimental SAXS data in the fitting analysis. The histogram method, which utilizes the coefficient matrix of scattering intensity, was also applied to the estimation of the size distribution, and this method could be useful for a rough estimate of the size distribution.     

Helium gas permeability of montmorillonite/epoxy nanocomposites

Helium gas permeability of silicate clay (montmorillonite) particles/epoxy nanocomposites was examined. The incorporation of increasing amounts of montmorillonite particles reduced the helium gas permeability. Based on Fick’s law, gas permeation behavior of the nanocomposite was evaluated. With the increase of montmorillonite loading, gas diffusivity decreased, while gas solubility increased. Helium diffusion behavior is in agreement to the numerical results based on the Hatta–Taya–Eshelby theory. It has been revealed that dispersion of nanoscale platelets in polymer is effective in improving gas barrier property.     

Properties of novel diallyl phthalate resin modified with sulfur‐containing allyl ester compounds

Sulfur‐containing allyl ester, which reacts with diallyl phthalate (DAP) resin to have allyl groups, was synthesized by the reaction of allyl phthalic acid with bisphenol having sulfur atoms. The sulfur‐containing allyl ester compound was blended with DAP resin to improve the adhesive properties to copper. By modification with sulfur‐containing allyl ester compound, the T‐peel adhesive strength and the lap shear adhesive strength to copper was improved. In particular, the adhesive strength was greatly improved when the resin was modified with the allyl ester compound having a disulfide bond (?S?S?) (DADS). It is concluded that this result is due to the improvement of the interfacial adhesive strength because the sulfur atom was found to be located in the surface of the copper by Fourier transform infrared (FTIR) analysis. The glass transition temperature (T_g) and the thermal decomposition temperature (T_d) of the cured DAP resin modified with DADS slightly decreased with increasing concentration of DADS. The lowering of T_g is because the crosslinking density of the DAP resin modified with DADS is smaller than that of DAP resin. Moreover, from thermogravimetric analysis, the lowering of Td of the DAP resin modified with DADS is because DADS is likely to pyrolyze. © 2013 Society of Chemical Industry     

Production of thin graphite sheets for a high electrical conductivity film by the mechanical delamination of ternary graphite intercalation compounds

Herein we propose a production scheme for conductive films composed of thin graphite sheets with high crystallinity and polymeric resin. The crystalline graphite sheets were successfully produced from natural graphite powder by solution-phase synthesis of graphite intercalation compounds (GICs), following a wet planetary-ball milling under mild conditions. The shear forces in the milling pot lead to a peeling of graphite flakes. Taking into consideration the interlayer bonding force, the delamination should be preferentially done from the expanded GICs interlayer rather than intrinsic graphite one. Some composite films derived from the phenolic resin and flaky graphite sheets displayed much higher electrical conductivities compared to the film from the feed graphite particles. We also demonstrate the stage structure of synthetic GICs affected the film conductivity. The composite films made from exfoliated products of ground (around stage IV) GICs exhibited high electrical conductivity with a small amount of the graphite sheets.     

Light-Wavelength-Based Quantitative Control of Dihydrofolate Reductase Activity by Using a Photochromic Isostere of an Inhibitor

Photopharmacology has attracted research attention as a new tool for achieving optical control of biomolecules, following the methods of caged compounds and optogenetics. We have developed an efficient photopharmacological inhibitor—azoMTX—for Escherichia coli dihydrofolate reductase (eDHFR) by replacing some atoms of the original ligand, methotrexate, to achieve photoisomerization properties. This fine molecular design enabled quick structural conversion between the active “bent” Z isomer of azoMTX and the inactive “extended” E isomer, and this property afforded quantitative control over the enzyme activity, depending on the wavelength of irradiating light applied. Real-time photoreversible control over enzyme activity was also achieved.     

Multistage bayesian autonomy for high‐precision operation in a large field

This paper presents a generalized multistage bayesian framework to enable an autonomous robot to complete high‐precision operations on a static target in a large field. The proposed framework consists of two multistage approaches, capable of dealing with the complexity of high‐precision operation in a large field to detect and localize the target. In the multistage localization, locations of the robot and the target are estimated sequentially when the target is far away from the robot, whereas these locations are estimated simultaneously when the target is close. A level of confidence (LOC) for each detection criterion of a sensor and the associated probability of detection (POD) of the sensor are defined to make the target detectable with different LOCs at varying distances. Differential entropies of the robot and target are used as a precision metric for evaluating the performance of the proposed approach. The proposed multistage observation and localization approaches were applied to scenarios using an unmanned ground vehicle (UGV) and an unmanned aerial vehicle (UAV). Results with the UGV in simulated environments and then real environments show the effectiveness of the proposed approaches to real‐world problems. A successful demonstration using the UAV is also presented.     

Organosulfonic acid-functionalized mesoporous composites based on natural rubber and hexagonal mesoporous silica

This study is the first report on synthesis, characterization and catalytic application of propylsulfonic acid-functionalized mesoporous composites based on natural rubber (NR) and hexagonal mesoporous silica (HMS). In comparison with propylsulfonic acid-functionalized HMS (HMS-SO₃H), a series of NR/HMS-SO₃H composites were prepared via an in situ sol–gel process using tetrahydrofuran as the synthesis media. Tetraethylorthosilicate as the silica source, was simultaneously condensed with 3-mercaptopropyltrimethoxysilane in a solution of NR followed by oxidation with hydrogen peroxide to achieve the mesoporous composites containing propylsulfonic acid groups. Fourier-transform infrared spectroscopy and ²⁹Si MAS nuclear magnetic resonance spectroscopy results verified that the silica surfaces of the NR/HMS-SO₃H composites were functionalized with propylsulfonic acid groups and covered with NR molecules. After the incorporation of NR and organo-functional group into HMS, the hexagonal mesostructure remained intact concomitantly with an increased framework wall thickness and unit cell size, as evidenced by the X-ray powder diffraction analysis. Scanning electron microscopy analysis indicated a high interparticle porosity of NR/HMS-SO₃H composites. The textural properties of NR/HMS-SO₃H were affected by the amount of MPTMS loading to a smaller extent than that of HMS-SO₃H. NR/HMS-SO₃H exhibited higher hydrophobicity than HMS-SO₃H, as revealed by H₂O adsorption–desorption measurements. Moreover, the NR/HMS-SO₃H catalysts possessed a superior specific activity to HMS-SO₃H in the esterification of lauric acid with ethanol, resulting in a higher conversion level.     

湖滨房屋 日本山梨

<正>这间房屋是一间单层别墅,坐落于山梨县富士山山脚的海滨地区。该地区面朝美丽的湖泊,是个非常迷人的地方。湖泊在微风和阳光的抚摸下泛起丝丝涟漪。湖泊两旁种植了高大的榉树和日本枫树。在设计房屋时,我们的主旨就是欣赏周围美丽的自然环境。整间房屋30米×6.3米,沿湖而建,因此在每个房间都可以欣赏湖泊的全景。房屋室内采用以白色为主题色的简约设计。没有任何装饰性元素的中性空间面朝美丽的大自然。室内采光十分充足,室