Preparation of CLA ascorbyl ester with improved volumetric productivity by an ionic liquid-based reaction system

A new approach to the enzymatic production of conjugated linoleic acid (CLA) ascorbyl ester with a remarkably high volumetric productivity (120-200 g L(-1)) has been developed, in which strong solvation by tOMA.TFA (methyltrioctylammonium trifluoroacetate) enables a high concentration of ascorbic acid to be applied, and in which t-butanol enhances conversion by changing the equilibrium constant of the activity coefficients. This work has experimentally demonstrated the practicability of achieving efficient reactions of polar compounds at high concentrations in ionic liquids without significant loss of enzyme activity.     

Crown Ether Phase Transfer Catalysts for An Ionic Polymerization of Bisphenol A / 4,4′‐Dichlorodiphenyl Sulfone

Various crown ethers were prepared and applied as phase transfer catalysts for the an ionic copolymerization of bisphenol A and 4,4′‐dichlorodiphenyl sulfone monomers with alkali salts, e.g., NaNH₂, NaOH and KOH, as initiators. The catalytic abilities of various crown ethers for the an ionic polymerization of bisphenol A / 4,4′‐dichlorodiphenyl sulfone were found to be in the order: 15‐crown‐5 ? monobenzo‐15‐crown‐5 > 18‐crown‐6 > Dicyclohexano‐18‐crown‐6 > Dibenzo‐18‐crown‐6 > 12‐crown‐4 with sodium amide (NaNH₂) as initiator. Sodium amide was shown to be a better initiator than NaOH or KOH with monobenzo‐ 15‐crown‐5 as a catalyst. Effects of solvents and temperature on the crown ether catalytic polymerization were also investigated. Dimethyl sulfoxide (DMSO) exhibited much better for the polymerization than other organic solvents, e.g., toluene, p‐xylene, dimethyl formamide and dioxane. Higher polymerization was found at higher temperatures and about 100% yield of poly(bisphenol A / sulfone) was obtained at 125 °C in 3 hr. The molecular weight of poly(bisphenol A / sulfone) as a function of reaction time was determined with gel permeation chromatography. Concentration effects of crown ether on % yield and molecular weight of poly(bisphenol A / sulfone) were also investigated and discussed.     

JT-60U装置温度分布剖面不变性的实验研究

在一系列H模放电条件下，建立了一个旨在研究等离子体温度分布剖面不变性的数据库。介绍了数据库建立过程中要解决的关键问题和所用软件，对等离子体温度分布剖面不变性及芯部约束与边缘参数的关系进行了研究。     

Linear and nonlinear optical properties of hydrated and dehydrated silica micro-spheres under an electric bias

The linear refractive indices and nonlinear second-order susceptibility of hydrated and dehydrated silica micro-spheres are studied using attenuated total reflectance (ATR) and the second harmonic generation (SHG) method in direct transmission, respectively. A dramatic change of the effective dielectric constant of silica suspension under an electric bias was observed, which is attributed to particle redistribution in the fluid. Dielectric constants of dehydrated silica spheres change slightly under an electric field due to Pockels effect, for which we measure a linear electro-optical coefficient of r₃₃ ∼3.4±0.7 pm/V. The transmission second harmonic generation comes from the third-order susceptibility χ⁽³⁾, which is a coupling of two photons and the electrostatic field induced by the surface –OH charges as characterized by the Gouy-Chapman model. The SH signal from the dehydrated silica vanishes because of the loss of –OH groups on the particle surfaces. Dehydration of silica beads is irreversible. The optical properties of dried silica spheres do not recover their original hydrated state when distilled water is added.     

Tissue refractometry using Hilbert phase microscopy

We present, for the first time to our knowledge, quantitative phase images associated with unstained 5 mum thick tissue slices of mouse brain, spleen, and liver. The refractive properties of the tissue are retrieved in terms of the average refractive index and its spatial variation. We find that the average refractive index varies significantly with tissue type, such that the brain is characterized by the lowest value and the liver by the highest. The spatial power spectra of the phase images reveal power law behavior with different exponents for each tissue type. This approach opens a new possibility for stain-free characterization of tissues, where the diagnostic power is provided by the intrinsic refractive properties of the biological structure. We present results obtained for liver tissue affected by a lysosomal storage disease and show that our technique can quantify structural changes during this disease development.     

Variation of attenuated total reflection due to the birefringence of liquid crystals by excitation of surface plasmons

Attenuated total reflection (ATR) is a prominent effect in examining the excitation of surface plasmons. The Kretschmann–Raether and Otto configurations are implemented to generate surface plasmons and to examine the change of the refractive index of liquid crystals (LCs) by an applied field. A mixture of nematic and cholesteric liquid crystals is sandwiched between two glass substrates coated with conducting films. The minimum ATR angle changes by only 1° as the applied voltage increases to as much as 30 V (corresponding to 6×10⁵ Vm^-1), which does not agree with the calculation based on field-induced refractive-index change. This fact suggests that the orientation of LC molecules adjacent to an electrode surface is unaffected by the external field because of the strong-anchoring effect. A Jones-matrix simulation together with a multilayered structure of a LC clearly adduces this fact. Received: 30 November 2001 / Revised version: 1 February 2002 / Published online: 14 March 2002     

Benzotriazole-assisted synthesis of enamines

A new, facile preparation of enamines was achieved a two-step sequence: (i) the ready formation of an N-(-aminoalkyl)benzotriazole derivative from equimolar amounts of benzotriazole, an aldehyde, and a secondary amine, (ii) the elimination of benzotriazole from the derivative by sodium hydride in tetrahydrofuran (THF). The method provides enamines in good overall yields based on the quantity of amine used.     

Investigation of the scaling law on cellulose solution prepared at low temperature

Cellulose was dissolved rapidly in a 9.5 wt % NaOH/4.5 wt % thiourea aqueous solution pre-cooled to -5 degrees C to prepare its concentrated solution, in which inclusion complexes (ICs) associated with cellulose, NaOH, thiourea, and water clusters were created. Physical gels could form in the cellulose solution at either high temperature or after long storage time, because of aggregation between the ICs. To clarify whether the Winter and Chambon theory could describe the gelation process of this complex system, we have investigated carefully the viscoelastic behavior of the cellulose solution with the advanced rheological expanded system (ARES). In the temperature range from 10 to 25 degrees C, we have successfully measured the loss tangent (tan delta) at the gel point according to the Winter and Chambon theory, showing the independence of tan delta on the frequency for the cellulose solution. The exponents of the scaling laws eta 0 proportional, variant epsilon-gamma and Ge proportional, variant epsilon z for the cellulose solution at 10 degrees C before and beyond the gel point were confirmed to be in agreement with the predicted values based on the percolation theory. The high sensitivity of the cellulose solution on temperature poses a limit for the application of the scaling law for the wide temperature range. The gel formed from the cellulose solution at 30 degrees C at long storage time could undergo a transition to a transparent liquid state after stirring at -5 degrees C. At the same time, the loss modulus (G' ') exceeds the storage modulus (G'), indicating a partially reversible sol-gel transition, as a result of the reconstruction of the hydrogen-bond networks between the solvent and cellulose.