Preparation of monodispersed polymer-modified colloidal silica particles of less than 50 nm diameter

The preparation of monodisperse, ultrafine polymermodified colloidal silica, 11 or 42 nm in diameter, were studied. The reaction of the colloidal silica with polymeric silane coupler in 1,2-dimethoxyethane and removal of the unreacted polymer with granular silica gel (10–20 mesh) in acetone gave a suspension of monodisperse composite particles.     

Adsorption of phosphate from seawater on calcined MgMn-layered double hydroxides

Adsorptive properties of MgMn-3-300 (MgMn-type layered double hydroxide with Mg/Mn mole ratio of 3, calcined at 300 degrees C) for phosphate were investigated in phosphate-enriched seawater with a concentration of 0.30 mg-P/dm3. It showed the highest phosphate uptake from the seawater among the inorganic adsorbents studied (hydrotalcite, calcined hydrotalcite, activated magnesia, hydrous aluminum oxide, manganese oxide (delta-MnO2)). The phosphate uptake by MgMn-3-300 reached 7.3 mg-P/g at an adsorbent/solution ratio of 0.05 g/2 dm3. The analyses of the uptakes of other constituents (Na+, K+, Ca(+, Cl-, and SO(2-)4) of seawater showed that the adsorbent had a markedly high selectivity for the adsorption of phosphate ions. Effects of initial phosphate concentration, temperature, pH, and salinity on phosphate uptake were investigated in detail by a batch method. The phosphate uptake increased slightly with an increase in the adsorption temperature. The adsorption isotherm followed Freundlich's equation with constants of logK(F)=1.25 and 1/n=0.65, indicating that it could effectively remove phosphate even from a solution of markedly low phosphate concentration as well as with large numbers of coexisting ions. The pH dependence showed a maximum phosphate uptake around pH 8.5. The pH dependence curve suggested that selective phosphate adsorption progresses mainly by the ion exchange of HPO(2-)4. The study on the effect of salinity suggested the presence of two kinds of adsorption sites in the adsorbent: one nonspecific site with weak interaction and one specific site with strong interaction. The effective desorption of phosphate could be achieved using a mixed solution of 5 M NaCl + 0.1 M NaOH (1 M = 1 mol/dm3), with negligible dissolution of adsorbent. The adsorbent had high chemical stability against the adsorption/desorption cycle; it kept a good phosphate uptake even after the repetition of the seventh cycle.     

Improvement of basic performances of a nickel-metal hydride battery

To develop a sealed-type nickel-metal hydride battery for use in portable equipment or in electric vehicles, investigations were conducted on negative electrodes using AB₅-type hydrogen storage alloy and positive electrodes. For the cycle life performance of the battery, alkaline treatment of the alloy and the substitution of more than 50% to the alloy with Co were effective. For the positive electrode, zinc as a solid solution in the nickel positive electrode obviously prevented γ-NiOOH from being formed in the charging process of β-Ni(OH)₂ and suppressed the migration of the electrolyte solution in the separator to the active material of the positive electrode. Also, hydrophobic treatment of the surface of the alloy was effective to prevent the elevation of the battery internal pressure of the battery in high rate charge.     

O-selectivity and utility of phosphorylation mediated by phosphite triester intermediates in the N-unprotected phosphoramidite method

Previously, O-selective phosphorylation on polymer supports in the N-unprotected phosphoramidite method could not be carried out because the amino groups of dA and dC have high reactivity toward tervalent phosphorus(III)-type phosphitylating reagents. In this paper, we developed a new coupling strategy named the "activated phosphite method" in which the phosphitylation is mediated by phosphite triester intermediates 1. Application of 1-hydroxybenzotriazole as the promoter to the solid-phase synthesis resulted in excellent O-selectivity of more than 99.7%. This O-selectivity was explained by the frontier molecular orbital interactions between the reactive intermediates and the nucleophiles such as the amino or hydroxyl groups of nucleosides. Furthermore, longer oligonucleotides were synthesized not only by a manual operation but also by a DNA synthesizer. The utility of our new method was demonstrated by the successful synthesis of a base-labile modified oligodeoxyribonucleotide having 4-N-acetyldeoxycytidine residues. Finally, DNA 20-mers containing dA or dC could be synthesized in good yields by use of a combined reagent of 6-trifluoromethyl-1-hydroxybenzotriazole and benzimidazolium triflate.     

Investigation of structural changes related to temperature: An understanding of H-bond based proton transfer in 4(5)-vinylimidazole and acrylic acid copolymer membrane

An attempt to understand how proton transfer proceeds in poly (acrylic acid-co-4(5)-vinylimidazole) has been carried out based on the temperature dependent characterization techniques, i.e., Fourier transform infrared spectroscopy (FTIR), wide angle X-ray diffraction (WAXD), Raman spectroscopy, including the atomic distance calculations. Systematical studies are achieved from a series of poly (acrylic acid-co-4(5)-vinylimidazole) with different acrylic acid content. When the copolymer is almost an ideal in equimolar ratio of an alternating structure, the hydrogen bond between carboxylic acid and imidazole is maintained and initiates the proton conductivity even at 120 °C. Whereas when the copolymer is carboxylic acid rich, the dehydration to form anhydride proceeds resulting in the decrease in proton conductivity at high temperature. The radial distribution function (RDF) calculated from the WAXD pattern shows that the inter-atomic distances reflect how the increase in temperature induces a favorable packing structure under the hydrogen bond network and the chain mobility to enhance the proton transfer at high temperature, especially in the case of the copolymer with an ideal alternating structure.     

Comparison of standard materials for the establishment of calibration curves in solid sampling graphite furnace atomic absorption spectrometry. Direct determination of copper in powdered biological samples

Summary The selection of standard materials for the establishment of calibration curves is one of the most important problems in the direct analysis of biological samples by GFAAS. Three kinds of standard materials, NBS tomato leaves, coprecipitates with magnesium oxinate and Ni/DMG/PAN were investigated. It was found that it is possible to use both the NBS-SRM and the synthetic reference material prepared by coprecipitation with magnesium oxinate as standard materials for the direct determination of copper in several biological samples issued from NBS and NIES. However, too low results are obtained when the synthetic reference material prepared by coprecipitation with Ni/DMG/PAN is used. In order to clarify this, the effects of nickel and magnesium were examined and the role of magnesium was discussed.     

Stress distribution in poly‐p‐phenylenebenzobisoxazole (PBO) fiber estimated from vibrational spectroscopic measurement under tension. II. Analysis of inhomogeneous stress distribution in PBO fiber

Fourier transform Raman spectra were measured for poly‐p‐phenylenebenzobisoxazole (PBO) fiber subjected to a tensile stress, and the Raman shift factor (the frequency shift caused by 1 GPa tensile stress) depended strongly on the sample‐preparation condition. To clarify the reasons of this dependency, a mechanical series parallel model was adopted that could successfully and quantitatively explain the observed Raman shift factors and gave a concreate heterogeneous stress distribution in the PBO fibers. As a result, a mechanical series model was reasonable for PBO fiber. Broadening of Raman bands, which was observed when the PBO fiber was tensioned, could also be interpreted on the basis of an idea of heterogeneous stress distribution. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1281–1287, 2002     

Removal of water adsorbed on flouride glass surfaces by NF3 plasma processing

A new method to remove water adsorbed on flouride glass preforms is reported. This method, using NF₃ plasma, can remove surface water on fluoride glasses