Photocatalytic Property and Electronic Structure of Lanthanide-based Oxysulfides

Lanthanide-based oxysulfides and sulfide, LnTaO_3.5S_0.5, Ln₁₀OS₁₄ (Ln = La, Pr, Nd, Sm) and La₄In₅S₁₃, were successively synthesized by sulfurization in a flowing H₂S. The sulfurization decreased the band-gap energies from >4 eV to <3eV, because of the formation of occupied S3p orbitals on the top of valence band. In accordance with the small band gap, the H₂ evolution from a 0.01 M Na₂S and 0.01 M Na₂SO₃ solution system was observed under irradiation of light up to >500 nm. The rate of H₂ evolution under light irradiation of >500 nm increased in the order of Ni/LaTaO_3.5S_0.5 < Ru/La₁₀OS₁₄ < Pt/La₄In₅S₁₃.     

Synthesis of polymeric microspheres employing SPG emulsification technique

Relatively uniform polymeric microspheres, the coefficients of variation being close to 10%, were obtained by the BPO-initiated suspension polymerization of styrenic monomers. Unlike the conventional stirred-tank system, a particular microporous glass membrane (SPG) provided uniform monomer droplets continuously when monomer was allowed to permeate through the micropores. The monomer droplets were suspended in an aqueous solution containing the stabilizing agents, transferred to a stirred vessel, and polymerized. Up to 10μm spheres, of a far narrower size distribution than those obtained by conventional microsuspension polymerization spheres, were obtained. The initial droplet size and distribution were retained with the successful suppression of secondary particle nucleation by the addition of hydroquinone in the aueous phase. Crosslinked polystyrene spheres were also synthesized in the presence of various low-molecular-weight diluents. While a good solvent, toluene, was not so effective; poor solvents, n-heptane and n-heptane, easily yielded the microporous structure, the specific surface area being as high as 160 m²/g. © 1994 John Wiley & Sons, Inc.     

Syntheses and structural properties of four Rb-aluminosilicate zeolites

Four types of Rb-aluminosilicate zeolites were hydrothermally synthesized in pure phase for the first time from Rb-aluminosilicate gels without using any organic structure-directing agent (SDA) under stirring conditions. The crystal structure of each zeolite was refined by Rietveld analysis of the X-ray diffraction (XRD) data. These crystal structures were confirmed to be Rb-mordenite, Rb-merlinoite, a new aluminosilicate zeolite with an ATT framework topology, and Rb-offretite denoted by RMA-1, RMA-2, RMA-3, and RMA-4, respectively. The Si/Al ratio of RMA-1 with an MOR topology varied from 5.3 to 8.0; however, the variation of the Si/Al ratios of the other zeolites was rather small. The crystal system of RMA-2 was tetragonal with space group I4/mmm, where two Rb sites were distributed at the center of an 8-membered ring (MR). On the other hand, two Rb sites in RMA-3 were located at the center of the 8-MR in small two cages. The structure of RMA-4 was identified as the OFF type with a local disorder or defect, which included a small amount of an intergrown ERI phase.     

CARBON ORDERING IN Fe-1.83C MARTENSITE Ⅰ. Crystal Structure of a Conventional Ordered Phase

采用电子衍射方法对Ｆｅ－１．８３Ｃ马氏体室温时效时产生的有序相结构进行研究，确定其结构为偏离化学计量成分Ｆｅ_４Ｃ的γ′－Ｆｅ_４结构，称为γ′－Ｆｅ_ｘＣ（Ⅰ）（ｘ＝４－１１）。碳原子位于单胞的１／２，１／２，１／２位置。该有序相单胞尺寸为：（ａ_Ｍ，ｃ_Ｍ分别为马氏体单胞的ａ和ｃ轴长度），它与母相完全共格，位向关系为（００１）_Ⅰ∥（００１）_Ｍ，［１００］_Ⅰ∥［１１０］_Ｍ。根据γ′－Ｆｅ_ｘＣ（Ⅰ）晶体结构计算出的有序相衍射花样与实验得到的衍射花样全部吻合。     

Age-related accumulation of phosphatidylcholine hydroperoxide in cultured human diploid cells and its prevention by α-tocopherol

The levels of phosphatidylcholine hydroperoxide in serially cultured human fetal diploid fibroblasts at various population doubling levels were determined by high-performance liquid chromatography combined with chemiluminescence detections. This methodology utilizes a mixture of cytochromec and luminol as post-column hydroperoxide group specific luminescent reagents. The cellular hydroperoxide content increased with age from 0.34 to 27.72 pmol/10⁶ cells. At the end of the cells'in vitro lifespan (51st population doubling level), the hydroperoxide content per 10⁶ cells reached about 80 times the level found in cells of the 20th population doubling level. Supplementation of exogenous α-tocopherol to the culture medium prevented hydroperoxide accumulation, but did not extent the lifespanin vitro. The results indicate that substantial intracellular phospholipid hydroperoxide accumulation occurred in the course of aging of human fetal liploid fibroblasts.     

Thermal strain of high strength polyethylene fiber in low temperature

High strength polyethylene fiber (Toyobo, Dyneema® fiber: hereinafter abbreviated to DF) has a negative thermal expansion coefficient. Relation between fiber structure and thermal strain of DF used as reinforcement of DF reinforced plastic (DFRP) for cryogenic use was investigated. The crystallinities and orientation angles of several kinds of polyethylene fibers having different modulus from 15 to 134Gpa (herein after abbreviated to DFs) were measured by NMR and X‐ray. We obtained the parameters of the mechanical series‐parallel model composed of crystal and amorphous by crystallinity and modulus. Thermal expansion coefficients of DFs were estimated by mechanical series‐parallel model. All DFs having different modulus showed negative thermal expansion coefficients in the temperature range from 180 to 300K, and absolute values of those markedly increased by increasing tensile modulus of DF. The estimated thermal expansion coefficients showed negative values, and thermal strains showed a similar curve to observed ones mostly. Average thermal expansion coefficients in the temperature range from 180 to 300K estimated by mechanical model agreed with the observed ones. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2918–2925, 2004     

Arrangements of uniformly sized particles in a powder bed

The volume of the unit cell of a powder bed in a general case is calculated, and an equation is proposed for calculating the porosity of the bed consisting of uniformly sized ellipsoidal particles in contact and regularly arranged. In the case of uniformly sized spherical particles in contact, the equation can be simplified.Three dimensions and face angles of the unit cell are given for each regular arrangement both in cases of ellipsoidal and spherical particles. The values of the porosity are calculated by using the author's equation: the results for both ellipsoids and spheres are equal when tire particle arrangements are the same.The face angles of the unit cells proposed by Graton and Fraser are modified in two cases by the author's method of calculation and a system omitted from their classification is described. Other equations for calculation of the porosity are discussed.     

Fractionation and enrichment of CLA isomers by selective esterification with Candida rugosa lipase

A commercial product of CLA contains almost equal amounts of cis-9,trans-11 (c9,t11)-CLA and trans-10,cis-12 (t10,c12)-CLA. We attempted to enrich the two isomers by a two-step selective esterification using Candida rugosa lipase that acted on c9,t11-CLA more strongly than on t10,c12-CLA. An FFA mixture containing CLA isomers was esterified with an equimolar amount of lauryl alcohol in a mixture of 20% water and the lipase. When the esterification of total FA reached 50%, two isomers were fractionated in a good yield: t10,c12-CLA was enriched in FFA, and c9,t11-CLA was recovered in lauryl esters. The FFA were esterified again to enrich t10,c12-CLA. At 27.3% esterification of total FA, the t10,c12-CLA content in FFA increased to 64.8 wt% with 89.3% recovery: The ratio of the content of t10,c12-CLA to that of two isomers was 95.9%. Lauryl esters obtained by the single esterification were employed for enrichment of c9,t11-CLA. After the esters were hydrolyzed, the resulting FFA were esterified again with lauryl alcohol. At 62.0% esterification of total FA, the c9,t11-CLA content in lauryl esters increased to 73.3 wt% with 79.4% recovery: The ratio of the content of c9,t11-CLA to that of two isomers was 95.6%. In a 600-g-scale purification, molecular distillation was effective in separating the reaction mixture into lauryl alcohol, FFA, and lauryl ester fractions.