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.     

Depolymerization of poly(fluoroalkyl methacrylate-co-methyl methacrylate) as studied with thermogravimetry

Thermal behaviors of a few kinds of poly(fluoroalkyl methacrylate-co-methyl methacrylate) prepared by γ-ray copolymerization were investigated by using thermogravimetric measurements together with the intermittent analysis of the gaseous products. The thermal degradation of copolymers composed of one of fluoroalkyl methacrylates of the following structures: CH₂?C(CH₃)COOCH₂(CF₂CF₂)_nH, where n = 1,2, and 3, and methyl methacrylate proceeded according to the depolymerization mechanism reproducing the pristine component comonomers exclusively, but their thermograms in inert atmosphere showed the feature of a two-step reaction. In air, however, thermograms of copolymers did not show such a stepwise decrease in weight with the elevating temperature, and temperatures at which depolymerization was introduced shifted to a much higher region. The overall aspects of depolymerization of copolymers seemed to be much similar to that of fluoroalkyl methacrylate homopolymer previously reported, and the retardation of depolymerization by air was considered to be due mainly to the stabilization of once-formed polymer radicals by oxygen.     

Hydrophobic effects on protein/nucleic acid interaction: enhancement of substrate binding by mutating tyrosine 45 to tryptophan in ribonuclease Tl

Hydrophobic effects on binding of ribonuclease Tl to guaninebases of several ribonucleotides have been proved by mutatinga hydrophobic residue at the recognition site and by measuringthe effect on binding. Mutation of a hydrophobic surface residueto a more hydrophobic residue (Tyr45 – Trp) enhances thebinding to ribonucleotides, including mononucleotide inhibitorand product, and a synthetic substrate-analog trinudeotide aswell as the binding to dinucleotide substrates and RNA. Enhancementson binding to non-substrate ribonucleotides by the mutationhave been observed with free energy changes ranging from –2.2 to – 3 .9 kJ/mol. These changes are in good agreementwith that of substrate binding, –2.3 kJ/mol, which iscalculated from Michaelis constants obtained from kinetic studies.It is shown, by comparing the observed and calculated changesin binding free energy with differences in the observed transferfree energy changes of the amino acid side chains from organicsolvents to water, that the enhancement observed on guaninebinding comes from the difference in the hydrophobic effectsof the side chains of tyrosine and tryptophan. Furthermore,a linear relationship between nucleolytic activities and hydrophobicityof the residues (Ala, Phe, Tyr, Trp) at position 45 is observed.The mutation could not change substantially the base specificityof RNase Tl, which exhibits a prime requirement for guaninebases of substrates.     

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.     

ARCOR,a new photolithography technique with antireflective coating on resist

The multiple interference effect is one of the major causes of the fluctuation in critical dimension control (CD) and in mark detection for alignment. Suppressing this effect is critical for future photolithography. We propose a new photolithography technique called anti reflective coating on resist (ARCOR), which improves linewidth accuracy and overlay accuracy by suppressing multiple interference. ARCOR consists of relatively simple processes: A clear antireflective film is spun onto the resist prior to the mark detecting for alignment and exposure. The film is subsequently removed and the resist developed in the conventional way. ARCOR differs from ARC, which suppresses the reflection at the resist/substrate interface. ARCOR suppresses the reflection at the air/resist interface. ARCOR allows mark detection and exposure without light intensity-loss and multiple interference. The experiments mainly examine polysiloxane and perfluoroalkylpolyether as ARCOR materials. It is shown that linewidth accuracy can be improved from 0.3 to 0.03 μm. The signal-to-noise ratio of the alignment signal is drastically improved, and the overlay error is about half that of the conventional method. ARCOR is also effective for directly measuring the reflectivity at the resist/substrate interface, which is a key parameter of the multiple interference effect and the halation. Using ARCOR and a thin resist film, the measured ratio of reflected light to incident light indicates the reflectivity at the resist/substrate interface. Because, the probe light does not reflect off the resist surface and the intensity-loss at the resist surface is suppressed. With perfluoroalkylpolyether film, the measurement error is ～ 1.5%.     

水性氯化物介质中对甲基苯烷基硫醚萃取钯的研究

p-Methylphenylalkylsulfide of various alkyl chain length as extractant were synthesized and the extraction of palladium was examined in terms of equilibrium and kinetics. Distribution ratio of Pd was independent of alkyl chain length. For aqueous chloride media, there was a significant difference in distribution ratios for the solution of NaC1 and HC1. The results of loading test and the slope analysis suggest that the extractant and Pd (Ⅱ) form 2:1 complex. Furthermore, the extraction rate based on the volume of aqueous phase was obtained in a stirred vessel, and the rate equation was presented. Unfortunately, it was difficult to construct surfactant liquid membrane system by use of the present extractant.     

Reactive blending of polyamide with polyethylene: pull-out of in situ-formed graft copolymers and its application for high-temperature materials

Reactive blending of polyamide 6 (PA) with polyethylene (PE) having reactive sites, maleic anhydride (MAH content=0.1 wt%),and glycidyl methacrylate (GMA content=3-12 wt%), was carried out at 70/30 and 65/35 (PA/PE) blend ratios. Blend morphology evolved by reactive blending was analyzed by light scattering and transmission electron microscopy. The blends were then irradiated by electron beam. The degree of crosslinking was estimated by measuring the dynamic storage modulus at a temperature above melting point of PA. It was found that surface-to-surface interparticle distance τ was significantly reduced by the micelle formation via pull-out of in situ-formed graft copolymers. The blend with shorter τ was crosslinked by electron-beam irradiation at the lower dose level. A blend having the minimum τ (∼0.2 μm) was nicely crosslinked at a low dose level same as for PE, and even for the PA matrix system.     

Studies on the biaxial stretching of polypropylene film. XI. Type II orientation during [2-2FI]-type stretching and its change by subsequent thermal contraction

In order to study the deformation mechanism of type II stretching, the change in orientation during the restretching and subsequent thermal contraction was investigated by x-ray diffraction method. When a uniaxially oriented film is restretched, the lamellae which are stacked in the stretching direction by the stretching rotate as a whole toward the restretching axis. They rotate backward nearly reversibly during the thermal contraction, unless the restretching exceeds a balancing state, where the orientation in the film plane are equal in all directions. However, when the restretching degree is so high and the film orientation exceeds the balancing state, the lamellar rotation is accompanied by a complex phenomenon. It is considered from the wide-angle and small-angle x-ray diffraction patterns that the lamellar surface becomes indented because of slippage between microfibrils composing the lamellae, and the microfibrils themselves bend at the boundary between the amorphous and crystalline regions within which the tilting of c-axis also occurs. Upon contracting of the film; these changes recover, but even in the last stage of contraction the orientation approaches the symmetrical biaxial orientation but not the uniaxial orientation from which the biaxial orientation is started. These orientation and disorientation behaviors are not affected basically by a slight change in the restretching temperature and the degree of stretching.     

Effective renaturation of reduced lysozyme by gentle removal of urea

To increase the folding yield of concentrated reduced lysozyme,we developed a renaturation method by means of dialysis fromconcentrated urea with redox agents. After lysozyme was incubatedin the reducing buffer (8 M urea solution) with oxidized glutathione,renaturation of reduced lysozyme was started by dialysis againstthe dialyzing buffer containing 8 M urea with redox agents.The urea concentration of the dialyzing bottle was graduallydiluted with dialyzing buffer without urea at a flow rate of0.1 ml/min by high pressure pump. Using this systematic dialysis,a concentration as high as 5 mg/ml of reduced lysozyme couldbe renaturated in 80% yield, while the folding yield was <5%even at a concentration of 1 mg/ml using a conventional rapiddilution method [Goldberg et al. (1991) Biochemistry, 30, 2790–2797].Therefore, it was concluded that gentle removal of urea fromdenatured proteins, dissolved in concentrated urea solution,by means of dialysis should be useful to renature denaturedproteins effectively.     

Construction of living cellular automata using the Physarum plasmodium

The plasmodium of Physarum polycephalum is a unicellular and multinuclear giant amoeba that has an amorphous cell body. To clearly observe how the plasmodium makes decisions in its motile and exploratory behaviours, we developed a new experimental system to pseudo-discretize the motility of the organism. In our experimental space that has agar surfaces arranged in a two-dimensional lattice, the continuous and omnidirectional movement of the plasmodium was limited to the stepwise one, and the direction of the locomotion was also limited to four neighbours. In such an experimental system, a cellular automata-like system was constructed using the living cell. We further analysed the exploratory behaviours of the plasmodium by duplicating the experimental results in the simulation models of cellular automata. As a result, it was revealed that the behaviours of the plasmodium are not reproduced by only local state transition rules; and for the reproduction, a kind of historical rule setting is needed.