Polymerization of methyl methacrylate by tri-n-butylborane in the presence of amino acid esters

The polymerization of methyl methacrylate by tri-n-butylborane in the presence of amino acid esters was investigated. The binary systems of tri-n-butylborane and amino esters were found to be more effective for initiating the polymerization than tri-n-butylborane alone. Co-catalytic effects of amino acid esters were in the order: tyrosinate > glutamate > aspartate ? phenyl alaninate > serinate > glycinate. The rate of polymerization in a mixture of dimethylsulphoxide and toluene was proportional to the square root of the concentration of the initiator system, to the monomer concentration, and to the concentration of dimethylsulphoxide in the solvent. The overall energy of activation was estimated to be 4.6 kcal/mol for the tri-n-butylborane/methyl tyrosinate system. Copolymerization curves gave a typical free-radical character.     

Lysozyme requires fluctuation of the active site for the manifestation of activity

Mutations around His15 which lie far away from the active site,stimulated glycol chitin activity of lysozyme at physiologicaltemperature. Del-Argl4Hisl5 lysozyme, a mutant lysozyme whoseArgl4 and Hisl5 were deleted together, and has the highest activityamong these mutant lysozymes, had a similar binding abilityto a trimer of N-acetyl-glucosamine, a substrate analogue, relativeto native lysozyme. This suggests that the increased activitywas due to an increased k_cat in the catalysis reaction. TheH-D exchange rate of the N-1 proton in the Trp63 which is locatedin the active site cleft, was enhanced in the Del-Argl4Hisl5lysozyme, while 2-D proton NMR analysis revealed no conformationalchange around Trp63. We conclude that some sort of fluctuationat the active site might be required for the manifestation ofactivity. This theory is supported by the finding that the Del-Argl4Hisl5lysozyme showed a shift in temperature dependency of activityto lower temperatures compared with that of native lysozyme.     

Studies on syntheses and permeabilities of special polymer membranes

Summary The permeabilities of various cellulose ester membranes and cellulose membranes were investigated using pure water and aqueous solution of glycerol as feed. In all membranes, the permeation rate for aqueous solution of glycerol was greater than for pure water. The permeation rates of cellulose ester membranes increased with an increase in number of carbon atoms of the substituent group in cellulose ester.     

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.     

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.     

Self-assembled monolayers of p-toluene and p-hydroxymethylbenzene moieties adsorbed on iron by the formation of covalent bonds between carbon and iron atoms for protection of iron from corrosion

An iron electrode was modified by electrolytic reduction in deaerated acetonitrile solution of p-toluenediazonium tetrafluoroborate CH₃C₆H₄N₂BF₄ (TDFB) or p-hydroxymethylbenzenediazonium tetrafluoroborate HOCH₂C₆H₄N₂BF₄ (HOTDFB) below 10 °C to form a self-assembled monolayer (SAM) of toluene CH₃C₆H₄- or hydroxymethylbenzene HOCH₂C₆H₄- (HOMB) moiety, probably adsorbed on the electrode by the formation of a covalent bond between carbon and iron atoms, as shown in references. The protective ability of the layer was examined by polarization measurement of the electrode in an aerated 0.5 M NaCl solution. The protective efficiencies of these two SAMs were not high, around 30%, a little higher than that of the toluenethiol CH₃C₆H₄SH SAM which was anchored on iron via a coordinate bond between sulfur and iron atoms. The iron surfaces modified with TDFB and HOTDFB were characterized by contact angle measurement, FTIR reflection spectroscopy and X-ray photoelectron spectroscopy. The persistence in protection of iron against corrosion by coverage with the HOMB SAM was confirmed by polarization measurements after immersion in 0.5 M NaCl for a long period of the time.     

Activity measurement of gallium in the B2 phase of the CoGa–Sb system by the EMF method with zirconia-based solid electrolyte

Gallium activity in the B2 phase regions of both binary Co–Ga and ternary Co–Ga–Sb systems was measured by EMF method with stabilized zirconia solid electrolyte The temperature range was 1073–1273 K and Sb concentrations were 1, 2 and 3 mol fractions. Ga activity at 1173 and 1273 K increases sharply in Ga rich region and the addition of Sb to the CoGa phase increases Ga activity. Activity change corresponds to the lattice parameter change with Sb addition to the CoGa phase.     

Cylindrical coils created with 3D X-ray lithography and metallization

The demand for microactuators is increasing recently. The key technology to realizing practical microactuators is microfabrication process. In the production of microminiature components, the technologies for processing high-aspect-ratio structures are essential. As one of these technologies, the LIGA process is widely known. Our laboratory researches the LIGA process to three-dimensional microfabrication and established the cylindrical-microcoil production process. In this paper, we have fabricated the cylindrical-microcoil for the solenoidal electromagnetic type microactuator. We designed and analyzed microactuators, and fabricated and evaluated microactuator coils produced by the combination of three-dimensional X-ray lithography and level copper plating. We succeeded in creating threaded groove-shaped structures with 10 μm line width, 20 μm pitch, and aspect ratio of 5 on the surface of an acrylic pipe by means of three-dimensional X-ray lithography. As a measure to suppress void generation, which is one of the shortcomings of electrolytic plating processes, the sputtering apparatus and plating equipment were improved, a pretreatment process was additionally provided, and the actual electrolytic plating method was improved. As a result, a void-free metallic deposit could be formed on a thin coil line. The processing technology enables the formation of thin-wire coil lines whose current paths feature a large allowable current-carrying capacity, enabling the production of miniature, high-output microactuators.     

Fabrication of large area diffraction grating using LIGA process

X-ray imaging is a very important technology in the fields of medical, biological, inspection, material science, etc. However, it is not enough to get the clear X-ray imaging with low absorbance. We have produced a diffraction gratings for obtaining high resolution X-ray phase imaging, such as X-ray Talbot interferometer. In this X-ray Talbot interferometer, diffraction gratings were required to have a fine, high accuracy, high aspect ratio structure. Then, we succeeded to fabricate a high aspect ratio diffraction grating with a pitch of 8 μm and small area using a deep X-ray lithography technique. We discuss that the diffraction gratings having a narrow pitch and an large effective area to obtain imaging size of practical use in medical application. If the pitch of diffraction gratings were narrow, it is expected high resolution imaging for X-ray Talbot interferometer. We succeeded and fabricated the diffraction grating with pitch of 5.3 μm, Au height of 28 μm and an effective area of 60 × 60 mm².     

Three-dimensional medical image recognition of cancer of the liver by a revised radial basis function (RBF) neural network algorithm

In this study, we propose a revised radial basis function (RBF) neural network algorithm and apply this algorithm to computer-aided diagnosis (CAD) of the liver. First, the revised RBF neural network algorithm is applied to recognition of the liver regions, and the recognition results are compared with those obtained using the conventional RBF neural network and the conventional multilayered neural network trained using the back-propagation algorithm. It is shown that the revised RBF neural network is accurate, and is a useful method because the parameters are automatically determined. Then, the revised RBF neural network is applied to CAD of the liver cancer called hepatocellular carcinoma (HCC).