Raman Spectroscopic Studies on the Formation Mechanism of Hydrous-Zirconia Fine Particles

The Raman spectra of hydrous-zirconia fine particles produced by the hydrolysis of various ZrOCl₂ solutions were investigated. The Raman spectra of hydrous zirconia synthesized at HCl concentrations below 1 mol/L were similar to those of monoclinic, crystalline ZrO₂; those of hydrous zirconia synthesized at HCl concentrations greater than 1 mol/L showed a crystal structure change. The line width of the Raman bands increased with increasing H⁺ ion concentration. Analyzing the relationship between Raman band width and particle size revealed that the primary particle size of hydrous zirconia was controlled by the H⁺ and Cl⁻ ions, because these ions interfered with the polymerization in a hydrolysis reaction. Based on the experimental results, the formation mechanism for primary particles of hydrous zirconia was determined.     

Catalysis at the toluene/water interface: shape-selective hydrolysis of esters having some rings and lactones promoted by octadecyl immobilized H-ZSM-5 catalyst

Shape-selective properties of octadecyltrichlorosilane-treated H-ZSM-5, abbreviated as H-ZSM-5-C₁₈, have been observed in the hydrolysis of esters having some rings and lactones in toluene-water solvent system. The shape-selectivity for the reaction has been evaluated by the ratio of the relative rate constants in comparison with the rate constant of methyl acetate. The selectivity became higher with increase in bulkiness of the substrate. Substrates having the minimum diameter larger than 6.5 Å, significantly larger in size than the pore openings of ZSM-5, could not react in this system.     

Biomass-based composites from poly(lactic acid) and wood flour by vapor-phase assisted surface polymerization

To prepare biomass-based composites in an environmentally benign manner, vapor-phase assisted surface polymerization (VASP) was applied to prepare the composites from wood flour and poly(l-lactic acid) (PLLA) without solvent. VASP of l,l-lactide successfully proceeded on the wood flour surfaces, resulting in surface coverage by newly generated PLLA. For obtained PLLA/wood flour composites, it was clarified that grafting of PLLA on wood flour surfaces had occurred to form covalently bonded composites, with the accumulated PLLA layers having crystallized in situ during VASP. Resulting PLLA layers showed very high crystallinity of 79.2% and a high melting point close to the equilibrium melting point. Moreover, thermal degradation behavior of the composites suggested a cooperative degradation manner of the components.     

Synthesis of Condensed Tannin Derivatives and their Protein-Precipitating Capacity

Four regiospecifically methylated condensed tannin derivatives were synthesized by the condensation of regiospecifically methylated flavan-3, 4-diols protected by benzyl groups, and subsequent debenzylation. The monomeric flavan-3,4-diols were obtained via four reaction steps starting from phloroacetophenone derivatives and protocatechualdehyde derivatives. Protein—precipitating capacity of these synthetic condensed tannin derivatives was tested and a comparision of these capacity suggests the following results: 1) Phenolic hydroxyl groups in tannins are essential sites for protein precipitation. 2) Although the A-ring has been considered not to be important for tannin—protein interactions, it was proved that the A-ring also plays an important role together with the B-ring. 3) Both hydroxyl groups of A- and B-rings may synergistically interact with proteins.     

Oxygen release behavior of metastable tetragonal t′meta-(Ce0.5Zr0.5)2 phases prepared by reduction and successive oxidation of t′ phase

Tetragonal CaF₂-related-type t′-/Ce_0.5Zr_0.5)O₂ phase was reduced at 773 K ≤ T_red. ≤ 1073 K to prepare precursors with various oxygen compositions: Ce₂Zr₂O_712d /0.111 < δ < 0.379). Metastable tetragonal t^′_meta-(Ce_0.5Zr_0.5)O₂ phases were prepared by oxidizing in O₂ at 873 K the precursors, and subjected to evolved oxygen gas analysis by heating the samples at a constant rate. When the precursor was prepared at T_red: ? 773 K; i.e. δ ? 0:379; the oxygen release behavior of the tetragonal phase agreed approximately with that of the t^′. For δ < 0.29, distinct features of the t^′_meta-(Ce_0.5Zr_0.5)O₂ appeared in the XRD results and Raman spectra. The temperature exhibiting the maximum release rate of oxygen from the t^′_meta became lower with decreasing the d value. It could be concluded that the thermodynamic behavior of the t^′_meta is related closely to the precursor composition and becomes more unstable with decrease in the δ value. The t^′ and t^′_meta phases with disordered arrangement of Ce and Zr ions may belong to the same space group; nevertheless, difference in the random arrays of the Ce and Zr ions was suggested on the basis of the present experimental results.     

13 years’ operational experience of SPring-8 vacuum system

The first electron beam was stored in SPring-8 storage ring in March 1997. An overview of the 13 years’ operational experience concerning the vacuum system of the SPring-8 storage ring is presented. The evolution of the vacuum system and their performance are summarized. Moreover, the main vacuum failures and their impact on accelerator operation are described in detail. We analyze the relationship between the difference types of vacuum failure and downtime of user experiment.     

New surface forces apparatus using two-beam interferometry

We designed a new surface forces apparatus for measuring the interactions between two nontransparent substrates and/or in nontransparent liquids. The small displacement of a surface, the bottom one in this study, was measured by the two-beam (twin path) interferometry technique using the phase difference between the laser light reflected by the fixed mirror and that by the mirror on the back of the bottom surface unit. It is possible to determine the distance with a resolution of 1 nm in the working range of 5 microm. This apparatus was successfully applied to measure the forces between mica surfaces in pure water and aqueous KBr solutions.     

Vitamin E reduces cholesterol esterification and uptake of acetylated low density lipoprotein in macrophages

The effects of vitamin E on cholesteryl ester (CE) metabolism in 1774 cells were examined. Pretreatment of 1774 cells with vitamin E at concentrations above 50 μM significantly decreased acetylated low density lipoprotein (LDL)-induced incorporation of [¹⁴C]oleate into CF in cells in a dose-dependent manner. This was partly due to vitamin E Also significantly inhibiting the uptake of [³H]CE-labeled acetylated LDL by 1774 cells. A trend existed toward suppression of acyl-CoA:cholesterol acyltransferase (ACAT) activity in the cell lysate at high vitamin E concentration, but there was no effect on hydrolysis of CE. These data indicate that vitamin E reduces the uptake of modified LDL and suppresses ACAT activity, resulting in less cholesterol esterification in macrophages; a novel mechanism underlying the antiatherogenic properties of vitamin E.     

The Direct Spectroscopy of Positronium Hyperfine Structure Using a Sub-THz Gyrotron

Positronium is an ideal system for research on Quantum Electrodynamics (QED), especially in a bound state. A discrepancy of 3.9 standard deviations has been found between the measured hyperfine structure (Ps-HFS) and the QED predictions. This may be due to the contribution of unknown new physics or common systematic effects in previous measurements, in all of which the Zeeman effect was used. We propose a new method to directly measure the Ps-HFS using a high power gyrotron. We compare two resonators which have been developed to supply sufficient power to drive the direct transition, a Fabry-Pérot resonator and a ring resonator with a diffraction grating. We plan to perform first direct measurement of Ps-HFS within the next six months.