Preparation of core–shell particles by dispersion polymerization with a poly(ethylene oxide) macroazoinitiator

A macroazoinitiator (MAI) containing a poly(ethylene oxide) (PEO) block was used with a methyl methacrylate monomer to prepare polymer particles in ethanol/H₂O solutions. The effects of the monomer/MAI ratio (RMI) and H₂O content in the solutions on the molecular weight, particle diameters, and chemical structure of the resulting polymer particles were investigated. The reaction mixtures showed three kinds of states, which were milky colloid solutions, macrogels and/or precipitations, and clear solutions. The colloid solutions were obtained in the solutions with an H₂O content of about 50–90 vol % and a RMI of 20–400. In the colloid solutions, core–shell nanospheres consisting of PEO shells and poly(methyl methacrylate) (PMMA) cores were predominantly obtained. In the specific conditions close to the area of gel and/or precipitation formation, particles connected about 0.5–5 μm in length were obtained. Multiblock copolymers nanospheres tended to be obtained with lower RMIs, and PMMA‐PEO‐PMMA tri‐bloc and/or PMMA‐PEO di‐block copolymer nanospheres were obtained with higher RMIs. The solubility of the monomer and the generated polymer in solutions may have affected the polymerization development and the state of the products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Promotion Effect of FeOx Addition on the Catalytic Activity of Supported Cu Catalysts for the Water–gas Shift Reaction

Among the supported Cu–FeO_x catalysts, Al₂O₃-supported Cu–FeO_x catalyst exhibited the highest activity for WGS reaction. The enhancement of the catalytic activity by adding FeO_x to Cu/Al₂O₃ could be interpreted by the two possibilities; one is the formation of highly dispersed Cu⁰ and the other is the participation of reduced FeO_x in WGS reaction in the presence of Cu⁰.     

Screening of Inhibitors Targeting Heat Shock Protein 47 Involved in the Development of Idiopathic Pulmonary Fibrosis

Heat shock protein 47 (HSP47), a collagen-specific molecular chaperone, is causally related to fibrotic diseases, including idiopathic pulmonary fibrosis. The identification of Compounds that interfere with the HSP47-collagen interaction is essential for the development of relevant therapeutics. Herein, we prepared human HSP47 as a soluble fusion protein expressed in E. coli and established an assay system for HSP47 inhibitor screening. We screened a natural and synthetic Compound library established at Nagasaki University. Among 1023 Compounds, 13 exhibited inhibitory activity against human HSP47, of which three inhibited its function in a dose-dependent manner. Epigallocatechin-3-O-gallate, one of these three Compounds, is a typical polyphenol Compound derived from tea leaves. Structurally related Compounds were synthesized and examined for their activity, revealing a hydroxyl group at A-ring position 5 as important for its activity. The present findings provide valuable insight for the development of natural product-derived therapeutics for fibrotic diseases, including idiopathic pulmonary fibrosis.     

Influence of sputtering power on oxygen reduction reaction activity of zirconium oxides prepared by radio frequency reactive sputtering

Zirconium oxides (ZrO_2−x) have been investigated as new cathodes for direct methanol fuel cells without platinum. ZrO_2−x films were prepared using a radio frequency (RF) magnetron sputtering at RF powers from 75 to 175 W. The influence of the RF power on the catalytic activity for the oxygen reduction reaction (ORR) and properties of the ZrO_2−x films were examined. The ORR activity of the ZrO_2−x catalyst increased with the RF power in the range we studied. The onset potential for ORR over ZrO_2−x deposited at 175 W was 0.88 V vs RHE. In addition, the relationship between the ORR activity and the composition, crystallinity, electric conductivity, as well as the ionization potential has been investigated. The zirconium oxide with an oxygen defected state and the higher electric conductivity showed the higher ORR activity, and the electrocatalytic activity for ORR increased with the decreasing in the ionization potential of the ZrO_2−x catalyst.     

Progress in non-precious metal oxide-based cathode for polymer electrolyte fuel cells

The cathode catalysts for polymer electrolyte fuel cells should have high stability as well as excellent catalytic activity for oxygen reduction reaction (ORR). Group 4 and 5 metal oxide-based compounds have been evaluated as a cathode from the viewpoint of their high catalytic activity and high stability. Although group 4 and 5 metal oxides have high stability even in acidic and oxidative atmosphere, they are almost insulator and have poor ORR activity because they have a large band-gap. It is necessary to modify the surface of the oxides to improve the ORR activity. We have tried the surface modification methods of oxides into four methods: (1) formation of complex oxide layer containing active sites, (2) substitutional doping of nitrogen, (3) introduction of surface oxygen defect and (4) partial oxidation of carbonitrides. These modifications were effective to improve the ORR activity of the oxides. The solubility of the oxide-based catalysts in 0.1 mol dm⁻³ at 30 °C under atmospheric condition was mostly smaller than that of platinum black, indicating that the oxide-based catalysts had sufficient stability compare to the platinum. The onset potential of various oxide-based cathodes for the ORR in 0.1 mol dm⁻³ at 30 °C achieved over 0.9 V vs. a reversible hydrogen electrode.     

High temperature electrochemical heat pump using water gas shift reaction. Part I: Theoretical considerations

A new electrochemical heat pump using a combination of an electrolytic reaction at lower temperature to absorb low grade thermal energy and a thermochemical reaction at higher temperature to produce more efficient thermal energy is proposed. At a lower temperature, an endothermic reaction which cannot occur thermochemically proceeds with electrolysis. At a higher temperature, an exothermic reaction which is the reverse of the electrolysis reaction occurs thermochemically to produce high grade thermal energy. The water gas shift reaction, CO₂(g) + H₂(g) CO(g) + H₂O(g), in molten carbonate is one possible candidate for the new electrochemical heat pump and can lead to an increase in the temperature of the thermal energy from 1100 to 1200K. A heat pump system using the shift reaction is also considered theoretically.     

TWO-CRACK PROPAGATION PATHS IN A FUNCTIONALLY GRADED MATERIAL PLATE SUBJECTED TO THERMAL LOADINGS

Two-crack propagation paths in a ceramic/metal functionally graded material plate (FGP) under one-cycle temperature change of heating and cooling are considered. When the FGP is subjected to thermal shock, a single crack or multiple cracks often initiate on the ceramic surface during the cooling process and propagate in the FGP. Crack paths are influenced by the heating temperature conditions, a compositional profile of the FGP, the fracture toughness, interaction among multiple cracks, and so on. Transient thermal stresses are treated as a linear quasi-static thermoelastic problem for a plane-strain state. The crack paths are treated under fracture mechanics using the finite-element method. The effects of heating temperature conditions, a compositional profile of the FGP, the fracture toughness, and a crack space on the crack propagation pattern are discussed and are shown in figures.     

Infrared sea surface emissivity including multiple reflection effect for isotropic Gaussian slope distribution model

A method is described for incorporating surface-emitted surface-reflected (SESR) radiation into the calculation of infrared sea surface emissivity. Firstly, the direct emissivity is obtained by ignoring SESR emission. Next, the first order SESR emissivity is obtained by using the direct emission as a radiation source. Finally, the ith order SESR emissivity is iteratively obtained by using the i − 1st order SESR emission.Computational results are in good agreement with a Monte Carlo calculation, where the SESR emissivity increases from an emission angle of 50° showing a maximum value of about 0.03 at an emission angle of 80°. The direct emissivity is smaller than the measured emissivity by 0.02∼0.03 around a wavelength of 10 μm at an emission angle of 73.5°. By incorporating the SESR emission into the emissivity model, the discrepancy between the computed and the measured emissivity is significantly reduced.The advantage of the present method over the previous works is that we need not to specify a cutoff angle to differentiate the radiation from the sea and that from the sky for calculating SESR emission. Instead of using a cutoff angle, the probability that radiation originates from the sea is derived from the probability distribution function of sea surface slope. As a result, the uncertainty in the computation of sea surface emissivity attributed to the uncertainty in cutoff angle could be effectively suppressed.