Measurement and correlation of mutual diffusion coefficients for styrene-butadiene rubber(SBR)-n-nonane systems

The mutual diffusion coefficients for styrene-butadiene rubber(SBR)-n-nonane systems were measured using a sorption apparatus with a quartz spring at 100 and 130°C for mass fractions of n-nonane ranging from 0 to 0.16. The mutual diffusion coefficients were correlated with good agreement by the free-volume theory.     

Asymmetric oxidation of poly(vinyl sulfides) with percamphoric acid,aspergillus niger,and penicillium notatum

The asymmetric oxidation of poly(phenylvinyl sulfide) (poly-Ph VS) and poly(t-butylvinyl sulfide) (poly-t-BuVS) was carried out with optically active percamphoric acid, and the optically active polysulfoxides were obtained. The values of the specific rotation for the oxidation products of poly-PhVS and poly-t-BuVS were + 1.0 (having 56% of sulfoxide unit contents) and +9.1 (49%), respectively. The specific rotation of the product increased with increasing the contents of sulfoxide units. The optical rotatory dispersion curves of the oxidation products of poly-PhVS and poly-t-BuVS were positive curves and were found to fit the simple Drude equation. The λ_c values of the oxidation products (poly-PhVS, 271 mμ; poly-t-BuVS, 212 mμ) suggested that the chromophore which caused optically activity was the sulfoxide group. Similarly, the asymmetric oxidation of t-BuVS–MMA copolymer, t-BuVS–styrene copolymer, and PhVS–MMA copolymer was carried out, and the optically active copolysulfoxides were obtained. Furthermore, the biosynthetic oxidation of poly-PhVS and PhVS–maleic anhydride copolymer treated with aqueous KOH was carried out using Aspergillus niger or Penicillium notatum in Czapeck solution, and the optically active polymers were obtained.     

Asymmetric addition of thiol to diene polymer in the presence of optically active amines as catalyst

The asymmetric addition reaction of thiolacetic acid or benzylmercaptan to diene polymer (natural rubber, cis- and trans-1,4-polyisoprene, _cis-1,4-polybutadiene, various styrenebutadiene copolymers and alternating acrylonitrile-butadiene copolymer) by optically active catalysts such as d-bornylamine ([α]d?45.2°), l-aspartic diethyl ester (?11.2°), l-aspartic dibutyl ester (?5.3°) were carried out in benzene at room temperature to 90°C. The optically active polymers were obtained from natural rubber and cis-1,4- and trans-1,4-polyisoprene, but were not obtained from cis-1,4-polybutadiene, styrene-butadiene copolymers, and butadiene-acrylonitrile copolymer. The [α]²⁵_D value of optically active derivatives was ?0.1° ～ ?1.0° (in benzene), and the optical rotatory dispersion curves were found to fit the simple Drude equation.     

Development of an improved calibration method for the LFB ultrasonic material characterization system

We investigated standard specimens for accurately calibrating the line-focus-beam ultrasonic material characterization (LFB-UMC) system without system dependencies. We evaluated several types of lithium tantalate (LiTaO3) substrates using two LFB-UMC systems with different device/system characteristics to measure and calibrate the propagation characteristics of the leaky surface acoustic waves (LSAWs), and analyzed the variations between the calibrated results. We concluded from this analysis that, by selecting materials with the cut surfaces and propagation directions of standard specimens that are identical to the objects to be calibrated, calibration errors resulting from different performance characteristics between the two systems could be nearly eliminated. Also, analytical errors caused by the effects of spectra with two close peaks (another propagation wave mode), one of the most common problems of characterization in the past, could be eliminated at the same time by this method.     

Effects of dissolved carbonate on arsenate adsorption and surface speciation at the hematite--water interface

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite-water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [P(CO2) = 10(-3.5) atm and approximately 0; CO2-free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L(-1), [As(V)]0 = 1.5 mM and I = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L(-1), [As(V)]0 = 0.5 mM and I = 0.01 M NaCI], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems (P(CO2) = 10(-3.5) atm) than in the CO2-free argon system at pH 4-7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear ( 2.8 A) and bidentate binuclear (approximately equal to 3.3 A) bonding at pH 4.5-8 and loading levels of 0.46-3.10 microM m(-2). Using the results of the pseudo-equilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the P(CO2) = 10(-3.5) atm and the CO2-free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to electrical double-layer potentials caused by the adsorption of carbonate in the air-equilibrated system. Overall results suggest that the effects of dissolved carbonate on As(V) adsorption were influenced by the reaction conditions [e.g., available surface sites, initial As(V) concentrations, and reaction times]. Quantifying the effects of adsorbed carbonate may be important in predicting As(V) transport processes in groundwater, where iron oxide-coated aquifer materials are exposed to seasonally fluctuating partial pressures of CO2(g).     

Preparation and application of methacrylate-based cation-exchange monolithic columns for capillary ion chromatography

Polymer-based strong cation-exchange monolithic capillary columns with different capacities were constructed for ion chromatography by radical polymerization of glycidyl methacrylate (GMA) and ethylene dimethacrylate in a 250-microm-i.d. fused-silica capillary and its subsequent sulfonation based on ring opening of epoxides with 1 M Na(2)SO(3). The cation-exchange capacities can easily and reproducibly be controlled in the range of up to 300 microequiv/mL by changing the immersion time of the epoxy-containing polymer in the Na(2)SO(3) solution. The chromatographic performance of the produced monolithic capillary columns was evaluated through the separation of a model mixture of common cations such as Na(+), NH(4)(+), K(+), Mg(2+), and Ca(2+). As an example, these cations could be well separated from one another on a 15-cm-long cation-exchange monolithic column (column volume, 7.4 microL) with a capacity of 150 microequiv/mL by elution with 10 mM CuSO(4). The pressure drop of this 15-cm column was approximately 1 MPa at a normal linear velocity of 1 mm/s (a flow rate of 3 microL/min), and the numbers of theoretical plates for the cations were above 3000 plates/15 cm. This GMA-based cation-exchange monolithic column could withstand high linear velocities of at least 10 mm/s. Over a period of at least two weeks of continuous use, no significant changes in the selectivity and resolution were observed. The applicability of a flow rate gradient elution and the feasibility of direct injection determination of major cations in human saliva sample were also presented.     

Wind-flow measurement over the Subaru Telescope

Wind flows over the 8.2-m Subaru Telescope at Mauna Kea in Hawaii were analyzed with a correlation method. Three or four wind flows were detected from our measurements. Spatial and temporal resolution of the wind-flow analysis across the 8.2 m pupil were investigated experimentally. A three-dimensional spatiotemporal-frequency analysis was also applied to the wind-flow data.