Kinetic Study of the Prooxidant Effect of α-Tocopherol. Hydrogen Abstraction from Lipids by α-Tocopheroxyl Radical

A kinetic study of the prooxidant effect of α-tocopherol was performed. The rates of allylic hydrogen abstraction from various unsaturated fatty acid esters (ethyl stearate 1, ethyl oleate 2, ethyl linoleate 3, ethyl linolenate 4, and ethyl arachidonate 5) by α-tocopheroxyl radical in toluene were determined, using a double-mixing stopped-flow spectrophotometer. The second-order rate constants (k _p) obtained are <1 × 10⁻² M⁻¹ s⁻¹ for 1, 1.90 × 10⁻² M⁻¹ s⁻¹ for 2, 8.33 × 10⁻² M⁻¹ s⁻¹ for 3, 1.92 × 10⁻¹ M⁻¹ s⁻¹ for 4, and 2.43 × 10⁻¹ M⁻¹ s⁻¹ for 5 at 25.0 °C. Fatty acid esters 3, 4, and 5 contain two, four, and six –CH₂– hydrogen atoms activated by two π-electron systems (–C=C–CH₂–C=C–). On the other hand, fatty acid ester 2 has four –CH₂– hydrogen atoms activated by a single π-electron system (–CH₂–C=C–CH₂–). Thus, the rate constants, k _abstr/H, given on an available hydrogen basis are k _p/4 = 4.75 × 10⁻³ M⁻¹ s⁻¹ for 2, k _p/2 = 4.16 × 10⁻² M⁻¹ s⁻¹ for 3, k _p/4 = 4.79 × 10⁻² M⁻¹ s⁻¹ for 4, and k _p/6 = 4.05 × 10⁻² M⁻¹ s⁻¹ for 5. The k _abstr/H values obtained for 3, 4, and 5 are similar to each other, and are by about one order of magnitude higher than that for 2. From these results, it is suggested that the prooxidant effect of α-tocopherol in edible oils, fats, and low-density lipoproteins may be induced by the above hydrogen abstraction reaction.     

Processing of Oriented K(Ta,Nb)O3 Films Using Chemical Solution Deposition

K(Ta,Nb)O₃ (KTN) thin films have been prepared by the chemical solution deposition method. KTN precursors consisted of a uniform mixture of K[Ta(OC₂H₅)₆] and K[Nb(OC₂H₅)₆] with interaction at the molecular level. Perovskite KTN thin films with the desired composition (Ta/Nb = 65/35, 50/50, and 35/65) were synthesized from the precursor solutions by the dip coating method. KTN thin films with (100) preferred orientation were successfully synthesized on MgO(100) and Pt(100)/MgO(100) substrates. X-ray pole figure measurements showed that grains of KTN films had a prominent three-dimensional regularity on MgO(100) and Pt(100)/MgO(100) surfaces. The Curie temperatures of KTN films decreased with increasing Ta/Nb ratio. Typical P-E hysteresis loops were observed for KTN thin films of three compositions on Pt(100)/MgO(100) substrates. The values of remanent polarization ( P _r) of KTN films increased as the Ta/Nb ratio changed from 65/35 to 35/65.     

Photoreaction of Titanium-Based Metal-organic Compounds for Ceramic Fine Patterning

The photoreaction of metal-organic compounds prepared by the chemical modification of metal alkoxides was investigated for the patterning of ceramic films. The chemical stability and photoreactivity of these compounds were found to be greatly influenced by the kind of chemical additive applied during the syntheses of the precursor solutions. In this study, the photoreaction of the precursor thin films prepared by the addition of alkanolamines was achieved by tuning the wavelength of the incident UV light. The decomposition of the organic moieties of the percursors was clearly observed in IR spectra during UV irradiation. Furthermore, the spectrum of the titania precursor film in the visible and ultraviolet regions (UV-vis) changed in accordance with the irradiation time. The photolithography of the titanium precursor pattern was successfully achieved by means of these techniques.     

l-Ascorbic acid as an alternative fuel for direct oxidation fuel cells

l-Ascorbic acid (AA) was directly supplied to polymer electrolyte fuel cells (PEFCs) as an alternative fuel. Only dehydroascorbic acid (DHAA) was detected as a product released by the electrochemical oxidation of AA via a two-electron transfer process regardless of the anode catalyst used. The ionomer in the anode may inhibit the mass transfer of AA to the reaction sites by electrostatic repulsion. In addition, polymer resins without an ionic group such as poly(vinylidene fluoride) and poly(vinyl butyral) were also useful for reducing the contact resistance between Nafion membrane and carbon black used as an anode, although an ionomer like Nafion is needed for typical PEFCs. A reaction mechanism at the two-phase boundaries between AA and carbon black was proposed for the anode structure of DAAFCs, since lack of the proton conductivity was compensated by AA. There was too little crossover of AA through a Nafion membrane to cause a serious technical problem. The best performance (maximum power density of 16 mW cm⁻²) was attained with a Vulcan XC72 anode that included 5 wt.% Nafion at room temperature, which was about one-third of that for a DMFC with a PtRu anode.     

Synthesis and crystal structure analysis of complex hydride Mg(BH4)(NH2)

Complex hydride Mg(BH₄)(NH₂), which consists of double anion BH₄⁻ and NH₂⁻, was synthesized and the crystal structure was analyzed by synchrotron X-ray diffraction. The mixture sample of Mg(BH₄)₂ + Mg(NH₂)₂ prepared by ball milling was reacted and crystallized to Mg(BH₄)(NH₂) by heating at about 453 K. This crystal phase transforms into amorphous phase above 473 K and subsequently the dehydrogenation begins. The crystal structure of Mg(BH₄)(NH₂) was determined from measurement data at 453 K (chemical formula: Mg_0.94(BH₄)₁(NH₂)_0.88, crystal system: tetragonal, space group: I4₁ (No.80), Z = 8, lattice constants: a = 5.814(1), c = 20.450(4) Å at 453 K). Mg(BH₄)(NH₂) is ionic crystal which the cation (Mg²⁺) and the anions (BH₄⁻ and NH₂⁻) are stacking alternately along the c-axis direction. Two BH₄⁻ and two NH₂⁻ tetrahedrally coordinate around Mg²⁺ ion.     

Immunohistochemical study of calpain-mediated alpha-crystallin proteolysis in the UPL rat hereditary cataract

The purpose of this study is to examine if microencapsulated PC12 cells may provide long term effects to the hemiparkinsonian rats. A modified technique was used to encapsulate PC12 cells into gelled microspheres. We found that the PC12 cells can survive in the modified microcapsules in vitro. Most of the PC12 cells formed cluster 3 weeks after incubation. The PC12 cell-loaded microcapsules were also examined in vitro. Adult Sprague-Dawley rats, anesthetized with chloral hydrate, were injected unilaterally with 6-hydroxydopamine into the medial forebrain bundle. The effectiveness of this lesion was tested by measuring apomorphine or methamphetamine-induced rotation one month after lesioning. The unilaterally lesioned rats were transplanted with microencapsulated PC12 cells. Results showed that apomorphine and methamphetamine-induced rotations were greatly suppressed after transplantation. One year after the grafting, the animals were anesthetized with urethane for the voltammetric study. Low dose of KCl was directly injected into the grafted striatum through pressure microejection. We found that KCl-induced DA release, as measured by voltammetric techniques, was regenerated in the striatum. The animals were later sacrificed for histological examination. We found that capsules were present in the lesioned striatum one year after grafting. Most of the capsules contained no PC12 cell. However, some capsules were filled entirely with PC12 cells. Taken together, our data suggested that PC12 cells can survive in the capsule in vitro and may provide long-term dopaminergic effects to the hemiparkinsonian rats.     

Microstructural investigation and indentation response of pressureless-sintered α- and β-SiC

The microstructure and indentation response of pressureless-sintered - and -SiC were studied using a high-resolution electron microscope and analytical electron microscopy. The materials were manufactured with boron and carbon as sintering aids. It was found that the overall porosity of the materials was very low but a large number of carbon inclusions were present. X-ray diffraction revealed the fabricated -SiC material was of the same 3C polytype as the initial starting powder; however, electron microscope observations indicated that the material contained a high density of faulting of the -forms. High-resolution imaging of grain boundaries in these materials indicated that the boundaries were very clean, and when they contained an amorphous intergranular film it was at most 0.5 to 1 nm thick. The presence of boron was not detected. Deformation due to identation took several forms. Firstly, radial cracks extending from the corners of the indent suffered little hindrance from the matrix microstructure, such that transgranular fracture was the dominant mode. Secondly, the deformation zone beneath the indentations showed copious lattice microcracks with some preferred orientation during crack formation and propagation.     

高质量密度储氢材料-氨基化合物的合成

采用真空蒸发法制备了氨基化锂LiNH2(+2·LiH)薄膜,即首先将Li真空镀膜到金属基板上,然后经氮化、氢化处理合成LiNH2薄膜.此外,真空蒸发法也用于Mg部分置换Li后薄膜的制备.实验结果证明,与传统的粉末状试样相比,薄膜状试样能够在更低的温度下释放出氢气.研究表明采用包括真空蒸发法等非传统方法合成金属络合物储氢材料对进一步提高其储放氢特性具有良好的效果.     

Preparation of flexible transparent acryl/alumina nano-hybrid materials exhibiting low thermal expansion coefficient

In this study, flexible transparent hybrid films with low thermal expansion coefficient were prepared by combination of alumina fillers and polymerizable/non-polymerizable surface modifiers with carboxyl group. Four types of alumina fillers with different shape and size were used in this study, and could modify with surface modifiers containing carboxyl groups by electrostatic interaction and disperse homogeneously in resulting hybrid films regardless of the shape and size. So the hybrid films obtained showed high transmittance around 90%T, and it was considered, from transmission electron microscopic analysis, alumina fillers were dispersed at near original filler size, without aggregation. Moreover, thermal mechanical analysis cleared that the use of pillar or fiber type filler is more effective to reduce CTE compared with plate type fillers, especially CTE of hybrid film prepared with fiber type filler was drastically decreased to 17 ppm/K, while the influence by the difference of filler shape/size was not observed on tensile properties, surface hardness. By use of fiber type alumina filler and combination of polymerizable surface modifier and non-polymerizable surface modifier which seems to interact with matrix, for optimizing of the crosslink density, it was possible to reduce CTE, while the good mechanical properties was kept. Finally, hybrid film indicating low CTE value as 19 ppm/K, high flexibility (windable against 0.4 mm radius steel bar), and good tensile properties and surface hardness which were equal to or higher than those of matrix could prepared.