Optical Energy Gap and Below Gap Optical Absorption of Fullerene Films Measured by the Constant Photocurrent Method and Photothermal Deflection Spectroscopy

The CPM spectra of fullerene films was measured to obtain the below gap absorption. The optical energy gap E_o was obtained by using the Tauc's plots. E_o did not change greatly with intercalated impurities. The absorption due to intercalated impurities was found below 1.6eV.     

Taxonomy for protective ability of rust layer using its composition formed on weathering steel bridge

For a quantitative evaluation of the protectiveness of a rust layer formed on a weathering steel bridge, the relationship between the corrosion rate of the bridge and the composition of the rust layers formed on the girders was first investigated. These corrosion rates were clearly classified by the protective ability index (PAI) of α/γ^∗ and (β + s)/γ^∗, where α, γ^∗, β and s are the mass ratio of crystalline α-FeOOH, the total of γ-FeOOH, β-FeOOH and the spinel-type iron oxide (mainly Fe₃O₄), β-FeOOH and spinel-type iron oxide, analyzed by XRD, respectively. The inequality of the former index α/γ^∗ > 1 expressed the protectiveness criterion of the rust layer, while that of the latter index, (β + s)/γ^∗< 0.5 or > 0.5, classified the corrosion rate of the non-protective rust layer. The PAI is useful for a quantitative evaluation of the protectiveness of a rust layer formed on a weathering steel bridge and is an important item for the corrosion assessment of the bridge.     

First-principles calculation of phase equilibria and phase separation of the Fe-Ni alloy system

Theoretical investigation of the phase equilibria of the Fe-Ni alloy has been performed by combining the FLAPW total energy calculations and the Cluster Variation Method through the Cluster Expansion Method. The calculations have proved the stabilization of the LIE phase at 1：3 stoichiometry, which is in agreement with the experimental result, and predicted the existence of L1 0 as a stable phase below 550 K; this L1 0 phase has been missing in the conventional phase diagram. The calculations are extended to the Fe-rich region that is characterized by a wide range phase separation and has drawn considerable attention because of the intriguing Invar property associated with a Fe concentration of 65%. To reveal the origin of the phase separation, a P-V curve in an entire concentration range is derived by the second derivative of free energy functional of the disordered phase with respect to the volume. The calculation confirmed that the phase separation is caused by the breakdown of the mechanical-stability criterion. The newly calculated phase separation line combined with the L1 0 and L12Eorder-disordered phase boundaries provides phase equilibria in the wider concentration range of the system. Furthermore, a coefficient of thermal expansion （CTE） is attempted by incorporating the thermal vibration effect through harmonic approximation of the Debye-Gruneisen model. The Invar behavior has been reproduced, and the origin of this anomalous volume change has been discussed.     

Photoelectrochemical energy conversion system modeled on the photosynthetic process

Photo-excitable electrodes were prepared by incorporating magnesium chlorophyll (MgChl) or manganese chlorophyll (MnChl) into the thin layer of such liquid cyrstals as N-(p-methoxybenzylidene)-p-butylaniline (MBBA) and 4′-heptyl-4-cyanobiphenyl (HCB), being attached to the platinum surface. The MgChl—MBBA electrode gave the positive photo-induced potential shift in an acidic solution. In sharp contrast, the negative photo-induced potential shift was developed by the MnChl—HCB electrode in an alkaline solution. The involvement of a liquid crystal prominently enhanced the photo-response of the immobilized chlorophylls. The photoelectrochemical energy conversion system modeled on the photosynthetic process was assembled by employing the MgChl—MBBA and the MnChl—HCB electrodes as a cathode and an anode, respectively. The photocurrent derived from the system was concluded to result from the decomposition of water, since an evidence for the molecular oxygen evolution at the MnChl—HCB electrode was obtained. Furthermore, the incorporation of β-carotene was found to markedly enhance the stability of the MnChl—HCB electrode.     

Radiation-induced graft copolymerization of mixtures of styrene and n-butyl acrylate onto cellulose and cellulose triacetate

Mixtures of styrene and n-butyl acrylate of various compositions were grafted onto cellulose and cellulose triacetate fibers preirradiated with γ-rays at 0°C in air. Monomer reactivity ratios of the grafted copolymers were found to be different from those of the nongrafted copolymers or those of AIBN-initiated copolymers. The active species initiating the graft copolymerization were trapped radicals for cellulose and peroxides for cellulose triacetate. Kinetic investigations of the graft copolymerization of styrene onto preirradiated cellulose triacetate fibers were also carried out, and it was found that the kinetic scheme for radical polymerization is also applicable to graft copolymerization in a heterogeneous system.     

Effects of amino acid replacements around the reactive site of chicken ovomucoid domain 3 on the inhibitory activity toward chymotrypsin and trypsin

We have previously shown that replacing the P1-site residue(Ala) of chicken ovomucoid domain 3 (OMCHI3) with a Met or Lysresults in the acquisition of inhibitory activity toward chymotrypsinor trypsin, respectively. However, the inhibitory activitiesthus induced are not strong. In the present study, we introducedadditional amino acid replacements around the reactive siteto try to make the P1-site mutants more effective inhibitorsof chymotrypsin or trypsin. The amino acid replacement AspTyrat the P2' site of OMCHI3(P1Met) resulted in conversion to a35000-fold more effective inhibitor of chymotrypsin with aninhibitor constant (K_i) of 1.17x10^–11 M. The K_i valueof OMCHI3(P1Met, P2'Ala) indicated that the effect on the interactionwith chymotrypsin of removing a negative charge from the P2'site was greater than that of introducing an aromatic ring.Similarly, enhanced inhibition of trypsin was observed whenthe AspTyr replacement was introduced into the P2' site of OMCHI3(P1Lys).Two additional replacements, AspAla at the P4 site and ArgAlaat the P3' site, made the mutant a more effective inhibitorof trypsin with a K_i value of 1.44x10^–9 M. By contrast,ArgAla replacement at the P3' site of OMCHI3(P1Met, P2'Tyr)resulted in a greatly reduced inhibition of chymotrypsin, andAspAla replacement at the P4 site produced only a small changewhen compared with a natural variant of OMCHI3. These resultsclearly indicate that not only the P1-site residue but alsothe characteristics, particularly the electrostatic properties,of the amino acid residues around the reactive site of the proteaseinhibitor determine the strength of its interactions with proteases.Furthermore, amino acids with different characteristics arerequired around the reactive site for strong inhibition of chymotrypsinand trypsin.     

One-step formation of ethyl methyl ketone from 1-butene and water on ultrastable Y-type zeolite catalyst

Proton exchanged ultrastable Y-type zeolite with silica/alumina = 40 showed a pronounced catalytic activity for the formation of ethyl methyl ketone directly from 1-butene and water. The formation rate of ethyl methyl ketone was much higher than those on MoO₃-based catalysts in the oxidation of 1-butene by oxygen. It was suggested that the basic site necessary for the formation of ethyl ketone directly from 1-butene and water would be the pentacoordinated Al.     

Promotion of hydrogen permeation on metal-dispersed alumina membranes and its application to a membrane reactor for methane steam reforming

A mesoporous membrane for selective separation of hydrogen was prepared usingthe sol-gel method. Some metal salts such as RuCl₃, Pd(NH₃)₄Cl₂, RhCl₃,, and H ₂PtCl₆, were added to the boehmite sol and coated on a porous alumina substrate before firing at 500°C. It was foundthat the permeability of hydrogen and the separation factor for a hydrogen-nitrogen gaseous mixture of these metaldispersed membranes exceeded the limitations of the Knudsen diffusion mechanism. Although the gas permeation through a neat alumina membrane is governed by the Knudsen diffusion, the metals dispersed in alumina membranes were effective in promoting hydrogen permeation. These metaldispersed alumina membranes were also used in a membrane reactor for methane steam reforming at low temperature. In the temperature range of 300 to 500°C, the membrane reactor attained a methane conversion twice as high as the equilibrium value of the packed bed catalytic reactor system as a result of the selective removal of hydrogen from the reaction system.     

Ni含量对TiNi形状记忆合金相变行为的影响

用示差扫描热分析仪和光学显微镜系统研究了Ｎｉ含量对ＴｉＮｉ形状记忆合金Ｒ相和Ｍ相相变温度，相变热，热滞的影响。结果表明：在加热和冷却过程中，Ｔｉ－３３．３％Ｎｉ和Ｔｉ－７５．０％Ｎｉ不发生相变；ＴＭ，ΔＭ，ΔＨＭ和ΔＨＲ是Ｎｉ是含量的函数，ＴＲ和ΔＲ基本为一定值，与Ｎｉ含量有关。