Production of antimicrobially active silk proteins by use of metal‐containing dyestuffs

The work presented here discusses a new technique for preparing silk fibers and films with persistent antimicrobial activity through use of metallic dyestuffs during the fiber dyeing process. The length of the silk fibers investigated contracted when the fibers were immersed in concentrated neutral salt solutions, such as calcium or potassium nitrate, at elevated temperature levels. The birefringence and molecular orientation of the silk fibroin molecules became less ordered by the action of the neutral salt solutions, resulting in increased dyestuff absorption. Subsequently, contracted silk fibers were dyed with metallic dyestuffs containing Cr or Cu for the purpose of obtaining silk fibers with antimicrobial activity. Silk fibers dyed with metallic dyestuffs showed significant antimicrobial activity against the plant pathogen Cornebacterium and the human pathogen Coli bacillus. Tensile strength of the silk fibers after the salt shrinking and dyeing processes did not show a significant change, whereas the elongation at break was increased slightly. The techniques described here for preparing significantly active antimicrobial silk fibers are effective and economic ways of providing new materials for industrial and biomedical applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1181–1188, 2002     

SEPARATION AND ENRICHMENT OF WEAK ORGANIC ACIDS OR BASES BY IMMOBILIZED LIQUID MEMBRANES

A new and effective liquid membrane process to achieve both separation and enrichment simultaneously of weak organic acids or bases was developed. The process utilizes effectively the difference in the apparent partition coefficient of the constituent species between the aqueous and organic phases, and uses the change of the apparent partition coefficients with the hydrogen ion concentration of the aqueous phase. For such a fundamental model apparatus as a diaphragm diffusion cell being operated batch wise, the effects of pK value of solutes, permeability of solutes through the membrane, volume ratio of liquids in two aqueous phases, and pH value of aqueous phase on enrichment factor and selectivity for the solute to be concentrated were discussed analytically. Separation and enrichment were demonstrated using aqueous mixed solutions of fumaric acid and L-malic acid. The results were in good agreement with the theoretical predictions.     

Low-temperature selective reduction of NO with propene over alkaline-exchanged mordenites

Partially protonated alkaline mordenites showed higher activity per acid amount below 573 K than acidic zeolites for the selective reduction of NO with C₃H₆ in the presence of O₂, which can be related to a high concentration of NO₃ ^- species in the zeolite channels. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structural development and mechanical properties on immiscible and miscible blends from isotactic polypropylene and ethylene-1-hexene copolymers under uniaxial drawing

Isotactic polypropylene and ethylene-1-hexene copolymers containing 32 and 57 mol% of 1-hexene copolymers blends (i-PP/EH32 and i-PP/EH57) were prepared by solution blending, precipitating followed by drying and hot pressing. The two blends were subject to investigation on structure and mechanical properties of these blends under uniaxial drawing. The i-PP/EH32 and i-PP/EH57 represented the immiscible and miscible blends, respectively. The tensile stresses and strains at breaking point of i-PP/EH57 were remarkably higher than those of i-PP/EH32 at room temperature. From wide-angle X-ray diffraction (WAXD) measurement, it was observed that the orientation of crystallites occurred early and then propagated gradually up to about drawing ratio 8 because chains of EH57 copolymer were incorporated into the amorphous regions between lamellae of i-PP. In the WAXD patterns of i-PP/EH57, the oriented spot reflections coexsisted with unoriented ring reflections up to draw ratio higher than in pure i-PP. On the other hand, the two-phase structure was observed from TEM and AFM in i-PP/EH32, and on the drawing, separation at the interface between two-phase was observed in i-PP/EH32 even at the low strain.     

Preparation of siloxane-like films by glow discharge polymerization

Glow discharge polymerizations of tetramethoxysilane (TMOS), tetramethylsilane/oxygen mixture (½ molar ratio) (TMS/O₂), hexamethyldisiloxane (HMDSO), and tetramethyldisiloxane (TMDSO) were carried out for the preparation of thin, polymeric films with siloxane structures. The chemical composition of the formed polymers was examined by elemental analysis, infrared spectroscopy, and electron spectroscopy for chemical analysis (ESCA) in connection with polymerization conditions, especially, a level of the radiofrequency (rf) input power per mass of the monomers (W/FM value). The polymers prepared from HMDSO at fairly low W/FM values resembled in chemical composition the conventionally polymerized polydimethylsiloxane. The surface properties of the formed polymers also were evaluated by the measurement of surface energy.     

Monte Carlo simulation of the sol-gel process for the hydrolysis and polycondensation of tin tetra-n-butoxide

The sol-gel process for the hydrolysis and polycondensation of tin tetra-n-butoxide in butanol was followed by viscosity measurements. The precipitation of tin-containing ultrafine particles was observed without any variation in the solution viscosity in the absence of diethylene glycols, while the viscosity increase was made without any precipitation by the addition of diethylene glycol. The induction period and the rate of the viscosity increase after the induction period was independent of the diethylene glycol content but depended upon the water content. The Monte Carlo simulation data were consistent with data for the viscosity experiment. The simulation was based on a kinetic model of the slow hydrolysis of tin tetra-n-butoxide, the reverse reaction of hydrolysis, and the polycondensation of the hydroxy derivatives.     

Corrosion of silicon nitride ceramics under hydrothermal conditions

Corrosion behaviour of Si₃N₄ ceramics containing Y₂O₃, Al₂O₃ and AIN as sintering aids was investigated under hydrothermal conditions at 200–300 C and saturated vapour pressures of water for 1–10 days. Hydrothermal corrosion resulted in the dissolution of the Si₃N₄ matrix and the formation of a product layer consisting of the original grain-boundary phases and hydrated silica. The dissolution rate of Si₃N₄ ceramics decreased with decreasing crystallinity of the grain-boundary phase. The dissolution rate could be adequately described by a parabolic plot in the initial stage of the reaction. The apparent activation energies were 83.5–108 kJ mol^–1, and the bending strength of the corroded samples decreased from 600 to 400 MPa in the initial stage of the reaction upto a weight loss of 0.004 g cm^–2, and then was almost constant up to a weight loss of 0.012 g cm^–2.     

Experimental analyses for electronic structure of barium zirconate-strontium zirconate proton-conducting solid solution

In proton-conducting oxides, analyses for their electronic structure contribute to the understanding of interactions between defects in them. In this study, electronic band alignment of (1−x)BaZr_0.8Y_0.2O_3−δ(BZY)–xSrZr_0.95Y_0.05O_3−δ(SZY) proton-conducting solid-solution system (BSZY) which has high defect concentration and the deep valence band is experimentally investigated. By using thin-film specimens for optical absorption measurements, absorption edges derived from electron transition from the valence band to the conduction band which was insensitive to the proton incorporation were clearly observed in spite of the high defect concentration. The obtained optical band gap energy increased from 5.61 to 5.89 eV with increasing x, which was consistent with a composition dependence of Zr(Y)O₆ octahedral tilting. Ultraviolet photon-yield spectroscopy (UV-PYS) measurements under vacuum condition revealed that BZY and SZY had ionization energy of 6.98 and 7.31 eV, respectively, and thus the absolute energy levels of the valence band maximum and the conduction band minimum of BSZY were experimentally clarified. We propose that the combination of the optical absorption measurements using thin-film specimens and the UV-PYS measurements under vacuum condition is effective in evaluating fundamental electronic structures of proton-conducting oxides.     

An Advanced Oscillation Mixing Method for Improving the Cooling Uniformity in Quenching

In quenching, the cooling uniformity is most important to diminish distortion occurring on work pieces. As a trial to accomplish uniform cooling, therefore, there exist various mixing methods of a quenchant and the quenchant circulation with an external pump has so far been the well accepted mixing method. However, this study proposes an advanced oscillation mixing method that can improve more the cooling uniformity in quenching. The proposed method includes a stirrer in oscillating motion, so that the simultaneous oscillating and mixing movements of the stirrer are considered to provide efecfively the uniform cooling characteristics for the quenchant. In comparison with the case of the circulation pump mixing, the investigation using the oscillation mixing method has demonstrated the following two experimental facts:(1) the short vapor blanket stage caused by the quick breakage of the oil vapor blanket and (2) the reduced variation of the quenching distortion.