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.     

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.     

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.     

Intestinal absorption and biological effects of orally administered amorphous silica particles

Although amorphous silica nanoparticles are widely used in the production of food products (e.g., as anticaking agents), there is little information available about their absorption and biological effects after oral exposure. Here, we examined the in vitro intestinal absorption and in vivo biological effects in mice of orally administered amorphous silica particles with diameters of 70, 300, and 1,000 nm (nSP70, mSP300, and mSP1000, respectively) and of nSP70 that had been surface-modified with carboxyl or amine groups (nSP70-C and nSP70-N, respectively). Analysis of intestinal absorption by means of the everted gut sac method combined with an inductively coupled plasma optical emission spectrometer showed that the intestinal absorption of nSP70-C was significantly greater than that of nSP70. The absorption of nSP70-N tended to be greater than that of nSP70; however, the results were not statistically significant. Our results indicate that silica nanoparticles can be absorbed through the intestine and that particle diameter and surface properties are major determinants of the degree of absorption. We also examined the biological effects of the silica particles after 28-day oral exposure in mice. Hematological, histopathological, and biochemical analyses showed no significant differences between control mice and mice treated with the silica particles, suggesting that the silica nanoparticles evaluated in this study are safe for use in food production.     

Effects of supercritical carbon dioxide treatment on the morphology of poly(l‐lactide)

Synthetic l ‐lactide random copolymers can be employed as controlled release materials when prepared using supercritical carbon dioxide (scCO₂), since they are biodegradable via hydrolysis. To determine the effects of thermal properties on polymer performance following scCO₂ processing, three types of poly(l ‐lactide) having different properties were assessed. The T_m of one poly(l ‐lactide) sample (H‐100) was found to be approximately 170 °C over the processing pressure range from 8 to 18 MPa, while a second sample (H‐440) also showed a constant value of approximately 152 °C. In contrast, the poly(l ‐lactide) REVODE exhibited a T_m of 146 °C prior to processing but a higher value of 147 °C following treatment at 8 MPa. Unlike the H‐100 and H‐440, the T_m value of the REVODE tended to decrease with increasing pressure. The T_g values increased greatly under mild conditions of 8 MPa pressure and a temperature of 40 °C. In particular, the T_g values for the H‐440 and REVODE increased by 4 °C and 5 °C, respectively. All T_g values were lowest at 12 MPa and increased with increasing processing pressure, although the effect of processing temperature was minimal. The Χ_{c DSC} of the H‐100 was 18% initially but increased to 20% upon scCO₂ processing at 40 °C and 14 MPa, and showed further increases at higher processing temperatures. Although the relationship between processing temperature and Χ_{c DSC} values for the H‐440 showed the same trend as observed with the H‐100, a different trend was seen for the REVODE. The Χ_{c XRD} values obtained from the XRD analyses differed from the values generated by DSC analysis, and showed a maximum degree of crystallinity following processing at 80 °C both with and without scCO₂ treatment. ATR FT‐IR analyses identified peaks due to semicrystalline regions in poly(l ‐lactide) samples treated with scCO₂, even when applying low temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44006.