Preparation of novel silica/poly(butylene succinate-co-adipate) organic–inorganic hybrid biodegradable material via sol–gel method

Silica/poly(butylene succinate-co-adipate) organic–inorganic hybrid biodegradable materials were prepared by the sol–gel method. Fourier-transform infrared spectroscopy (FT-IR) and Thermogravimetry/differential thermal analysis (TG/DTA) indicated that the inorganic (SiO₂, C₆H₅SiO_3/2) and organic (PBSA) components were well dispersed in the hybrid material. Heat resistant test shows that the hybrid material was both heat resistant and flexible. The presence of phenyl groups and siloxane network was responsible for the flexibility and heat resistance.     

Shielding effect of double microelectrode tips in a scanning electrochemical microscope

Electrochemical interaction of coaxial double microelectrodes, in which a ring microelectrode was surrounded by another ring microelectrode, was investigated. Mass-transfer reactions that occurred on both inner and outer microelectrodes interfered with each other and showed a “shielding” effect depending on potentials and geometries of microelectrodes. Application of the inner microelectrode of the double microelectrodes for a probing tip of a scanning electrochemical microscope (SECM) revealed that the shielding effect by the outer microelectrode affected the electrochemistry on the inner microelectrode in the vicinity of the substrate surface. The effect was intensified above the insulator but attenuated above the conductor as the microelectrodes approached in feedback mode of the SECM. Approach to a critical interelectrode distance also intensified the shielding effect in the substrate generation/tip collection mode. An SECM line-scan using a platinum/epoxy resin-model substrate was carried out to investigate the shielding effect on current sensitivity and lateral resolution of an SECM image.     

Dependence of property, cathode characteristics, thermodynamic stability, and average and local structures on heat-treatment condition for LiNi0.5Mn0.5O2 as a cathode active material for Li-ion battery

LiNi_0.5Mn_0.5O₂ was heat-treated under high oxygen-pressure and Ar-reducing conditions, and then the cathode properties, thermodynamic stability and average and local structures were investigated. From X-ray diffraction and ICP measurements, it was found that the pristine LiNi_0.5Mn_0.5O₂ had a single phase of the layered rock-salt structure although the Ni content was slightly rich compared with the nominal one. These characteristics were kept even after the heat-treatments. Charge–discharge cycle tests clarified that the cycle performance of LiNi_0.5Mn_0.5O₂ was improved by both the reducing and oxidizing treatments. From neutron diffraction and X-ray absorption fine structure measurements, the local distortion around the transition metal, especially Ni, was supposed to be one of the important factors to determine the cathode properties. It was also found that the sample with higher thermodynamic stability exhibited better capacity retention in the discharge–charge cycle tests.     

Phase structure in the blend of atactic poly(vinyl alcohol) with atactic poly(vinyl alcohol‐block‐vinyl acetate)

An almost fully saponified atactic poly(vinyl alcohol) and an atactic poly(vinyl alcohol‐block‐vinyl acetate) of which degree of saponification is 89 mol % were blended by a solution casting method. The phase structure of the blend film was analyzed by optical microscopy, ¹³C‐NMR, and differential scanning calorimetry. The most remarkable structure of the blend was composed of cylindrical domains penetrating the film. The swelling behavior of the blend films was also investigated in the dimethylsulfoxide and water mixed solvents to find differences in solubility and diffusion behavior between the matrix and the domain. The cylindrical domains could be selectively dissolved away in water and the film became porous. We tried to change the size of the cylindrical domain with various film preparation conditions. This aimed to turn the film into the useful filter membrane. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1807–1815, 2002     

Production of finely ground natural graphite particles with high electrical conductivity by controlling the grinding atmosphere

Natural graphite particles with high crystallinity sieved to obtain a particle size range of under 63 μm were ground with a ball mill, under various well-controlled grinding atmospheres such as N₂, O₂, He, H₂, and vacuum. The ratio, X_dif50/X_st50, i.e. between the 50 wt.% Stokes diameter and the 50 wt.% laser diffraction diameter, of the ground particles, was used as an index of the flakiness of the particles. The specific resistance of films composed of the ground graphite particles was systematically measured. The rate of reduction in the size of the particles by grinding was slow under an O₂-rich atmosphere such as 100% O₂ and dry air. On the other hand, it was relatively fast in vacuum, or under an N₂ or He atmosphere, and a gas mixture of 99% N₂ and 1% O₂. The rate of size reduction by grinding under a H₂ atmosphere was intermediate. In our experimental conditions, the flakiness of the ground particles increased with the decrease in the particles’ sizes. The electrical conductivity of the ground particles, however, tended to decrease with the decrease in their sizes. Under the condition that the Stokes diameter of the ground particles remains constant, the electrical conductivity of films made from the ground particles increases with the increase in the flakiness of the particles. It was finally determined from our systematic grinding experiments that small flaky particles, which had a size, X_st of ∼1 μm, with a high electrical conductivity can be produced by grinding in a gas mixture of 99% N₂ and 1% O₂. In this case, the flaky shape of the ground particles was visually confirmed by scanning electron microscopy.     

Light scattering studies on crystallization in polyethylene terephthalate

The light scattering from the spherulites of polyethylene terephthalate grown near the glass transition temperature has been investigated. The Hv scattering profiles can be reproduced by the sum of the ideal spherulite scattering with the distribution of spherulite radius and the isotropic scattering from randomly oriented crystallites. The ratio of optical anisotropies in the isotropic scattering to the ideal spherulite scattering is obtained by the method established to eliminate the effects of the number density of spherulites and the coefficient depending on the experimental conditions. It is found that the anisotropy ratio is almost independent of the crystallization time and of temperature above 106 °C, while it is larger at a crystallization temperature of 103 °C. The spherulitic structure is discussed in terms of the anisotropy ratio.     

The effect of the N-linked glycans on structural features and physicochemical functions of soybean β-conglycinin homotrimers

β-Conglycinin is a trimeric protein consisting of three subunits, α,α′,and β, which are N-glycosylated. The α and α′ subunits contain extension regions in addition to core regions common to all subunits. We purified homogeneous trimers consisting of only α, α′, or β from mutant soybean cultivars containing β-conglycinin lacking one or two subunits: α homotrimers from an α′-lacking mutant, α′ homotrimers from an α-lacking mutant, and β homotrimers from an α-and α′-lacking mutant. Structural features and physicochemical functions of the three homotrimers were examined and compared with those of recombinant homotrimers having no N-linked glycans. The native homotrimers have secondary structures very similar to those of the recombinant ones. In analogy with the recombinant homotrimers, the native ones exhibit different thermal stabilities from one another (β>α′>α), and the native α and α′ homotrimers exhibit better solubility, emulsifying ability, and heat-induced association than the native β homotrimer. Further, the N-linked glycans contribute to solubilities of the three subunits at low ionic strength (μ=0.08) and to the emulsifying ability of the native β homotrimer. N-Linked glycans also prevent heat-induced associations of the native α and α′ homotrimers but do not contribute to the secondary structure and the thermal stability of β-conglycinin.     

Dietary conjugated linolenic acid in relation to CLA differently modifies body fat mass and serum and liver lipid levels in rats

The present study compared the effect of dietary conjugated linolenic acid (CLNA) on body fat and serum and liver lipid levels with that of CLA in rats. FFA rich in linoleic acid, α-linolenic acid, CLA, or CLNA were used as experimental fats. Male Sprague-Dawley rats (4 wk old) were fed purified diets containing 1% of one of these experimental fats. After 4 wk of feeding, adipose tissue weights, serum and liver lipid concentrations, serum tumor necrosis factor (TNF)-α and leptin levels, and hepatic β-oxidation activities were measured. Compared with linoleic acid, CLA and, more potently, CLNA were found to reduce perirenal adipose tissue weight. The same trend was observed in the weight of epididymal adipose tissue. CLNA, but not CLA, was found to significantly increase serum and liver IG concentrations. Serum FFA concentration was also increased in the CLNA group more than in the other groups. The activity of β-oxidation in liver mitochondria and peroxisomes was significantly higher in the CLNA group than in the other groups. Thus, the amount of liver TG exceeded the ability of hepatic β-oxidation. Significant positive correlation was found between the adipose tissue weights and serum leptin levels in all animals (vs. perirenal: r=0.557, P<0.001; vs. epididymal: r=0.405, P<0.05). A less significant correlation was found between adipose tissue weights and serum TNF-α level (vs. perirenal: r=0.069, P<0.1; vs. epididymal: r=0.382, P<0.05). Although the mechanism for the specific effect of CLNA is not clear at present, these findings indicate that in rats CLNA modulated the body fat and TG metabolism differently from CLA.     

Increasing the hydrophobic interaction between terminal W-motifs enhances the stability of Salmonella typhimurium sialidase. A general strategy for the stabilization of {beta}-propeller protein fold

Protein engineering of the ß-propeller protein aimedat enhancing the structural stability of the protein was carriedout using a monomeric single domain ß-propeller protein,Salmonella typhimurium sialidase, as a model. Ala53 and Ala69each located at strands B and C of the W1 motif were mutatedto Leu and Val, respectively, to increase the hydrophobic interactionbetween W1 and W6 motifs. The mutants showed enhanced stabilitytowards guanidine hydrochloride and thermal unfolding. Ala53Leushowed higher stability, probably owing to the capability ofthe mutated Leu to interact extensively with more residues involvedin the hydrophobic interactions between the terminal W-motifs.The mutations, which are located far from the active site, haveno significant effect on the enzymatic properties. The strategyto enhance the stability proposed here might be applied to theother ß-propeller proteins.     

EFFECTS OF OPERATIONAL CONDITIONS ON DRYING CHARACTERISTICS IN CLOSED SUPERHEATED STEAM DRYING

The effects of operational conditions on the drying performance in closed superheated steam drying were examined theoretically and experimentally. The vapor generated from the sample was circulated in the drying chamber. In the theoretical analysis, the replacement of air with vapor in drying chamber and the convective vapor transfer in sample were considered. At the start of drying, the drying chamber was filled with air. As the drying proceeded, the air was replaced with the vapor generated from sample. The calculated results explained the characteristics of experimental data. The pore diameter of sample had little effect on the drying characteristics. During the internal evaporation period, the evaporation occurred in the narrow zone, which moved from the surface to the bottom of sample. The convective vapor transfer in sample had a significant influence on the drying performance. The excess increments in temperature and velocity of drying gas hardly contributed to shortening the drying time.