Effect of composition of sucrose fatty acid esters on formation of palladium nanoparticles in reverse micelles

Palladium (Pd) nanoparticles were prepared in the reverse micellar system containing sucrose fatty acid esters with various esterification degrees. The TEM showed that Pd nanoparticles were of spherical and relatively uniform. The size of Pd nanoparticles strongly depended upon the composition of sucrose fatty acid esters. The resultant Pd colloid could be preserved for at least 2 months without precipitation.     

Characterization of fibril reinforced membranes for fuel cells

Characteristics of fibril reinforced membranes developed by Asahi Glass Company are reviewed. PTFE-fibrils <1 μm in diameter are dispersed in ion-exchange membranes uniformly. Mechanical properties, such as tensile strength, tear strength, creep property and compressive property were examined and compared with non-reinforced membranes. Fibril reinforced membranes, even by the addition of a small amount of PTFE-fibrils (2.7 wt.%), show excellent mechanical strength, especially in creep and tear strength. Cell performance is nearly equal to the one using a non-reinforced membrane and cell voltage stays about the same during the cell operation at 80 °C for 3000 h.     

Peumusolide A, unprecedented NES non-antagonistic inhibitor for nuclear export of MEK

A new polyketide peumusolide A was disclosed as an unprecedented NES non-antagonistic inhibitor for nuclear export of MEK, a promising scaffold for antitumor agents with novel mechanism of action, from Peumus boldus Molina. The absolute stereostructure as well as optical purity was established by use of the two synthesized enantiomeric model lactones. In addition, the Δε values in their CD spectra were demonstrated to be the conclusive index for determination of not only configuration at C-3 but also optical purity of natural congeneric polyketides. Peumusolide A was revealed to show NES non-antagonistic action by the biotinylated probe and to inhibit proliferation of MEK-activated tumor cells selectively.     

A thermodynamic consistency test for the binary constant-temperature VLE data using numerically optimized binary parameters

A thermodynamic consistency (TC) test for the constant-temperature VLE data was investigated by numerically optimizing the binary parameters of the activity coefficient equations to satisfy the Gibbs–Duhem (GD) equation. It was shown that the one parameter Margules equation can best satisfy the GD equation, even if significant experimental errors are involved. A thermodynamic consistency (TC) criterion was defined using the one parameter Margules equation. The TC criterion showed that, of the 37 alkane–alkane, 18 methanol–water and 44 ethanol–water binaries, 36, 16 and 1 binaries are reliable, respectively. Simple liquid mixtures meet the TC criterion.     

Removal of fine powders from film surface. I. Effect of electrostatic force on the removal efficiency

A novel fine particle removal system composed of a corona-discharge neutralizer, a pulse-jet air unit and an image processing system has been developed. First of all, adhesion force between particle and film was directly measured and effect of electrostatic force on the adhesion force was calculated experimentally and theoretically. The electrostatic force was found to be significant, leading to the suggestion that the countermeasure for the electrostatic force was required to effectively remove fine particles. This system was then applied to the removal of fine particles from surface of a gelatin film used for conventional capsule material. The number of particles removed by the system was calculated by an image processing system and number base removal efficiency was computed with and without the elimination of electrostatic charge by the neutralizer. It was found that the difference between the removal efficiency of particles with elimination of electrostatic charge and that of without the elimination showed linear relationship with the electrostatic adhesion force. The data confirmed the necessity of electrostatic charge elimination for the effective removal of fine particles.     

Profiling analysis of oligosaccharides in antibody pharmaceuticals by capillary electrophoresis

Carbohydrate chains in glycoprotein pharmaceuticals have important roles for the expression of their biological activities. Therefore, development of an assessment method for the carbohydrate chains is an important parameter for quality control of glycoprotein pharmaceuticals such as newly developed therapeutic antibodies. In this report, we applied capillary electrophoresis with laser-induced fluorescence detection to the analysis of carbohydrate chains after releasing with glycoamidase followed by derivatization with 3-aminobenzoic acid. We found that four major oligosaccharides present in antibody pharmaceuticals were successfully separated with good resolution. The present method showed good precision in both migration times and relative peak areas, and gave comparable accuracy with that using a derivatization method with 8-aminopyrene-1,3,6-trisulfonate.     

Influences of fatty acid moiety and esterification of polyglycerol fatty acid esters on the crystallization of palm mid fraction in oil-in-water emulsion

We examined the crystallization of palm mid fraction (PMF) in oil-in-water (O/W) emulsion, after adding polyglycerol fatty acid esters (PGFEs). We employed ultrasonic velocity measurements and DSC techniques, with special emphases on the influences of fatty acid moiety and esterification of PGFE. Twelve types of PGFEs were examined as additives. PGFEs have a large hydrophilic moiety composed of 10 glycerol molecules to which palmitic, stearic and behenic acids were esterified as the fatty acid moiety with different degrees of esterification. Crystallization temperature (T(c)) of PMF remarkably increased with increasing concentrations of the PGFEs as the chain length of the fatty acid moiety increased, and the PGFE became more hydrophobic in accordance with increasing degree of esterification. We observed that the heterogeneous nucleation of PMF in the O/W emulsion was activated at the oil-water interface, where the template effect of very hydrophobic long saturated fatty acid chains of the PGFE might play the main role of heterogeneous nucleation.     

Adsorption of humic acid on goethite: isotherms, charge adjustments, and potential profiles

The adsorption of natural organic matter (NOM) on mineral (hydr)oxide plays an important role in the evaluation of the speciation of toxic metal ions in the environment. Because both NOM and mineral oxide have variable charges that adjust upon adsorption, a good understanding of proton binding is required before the binding of metal ions can be understood. In this study, the adsorption of purified Aldrich humic acid (PAHA) on goethite was examined as a function of the environmental conditions (pH, salt concentration, and free concentration of PAHA) together with the proton adsorption to PAHA, goethite, and their mixtures. The induced charges on both components were separated on the basis of the difference between the charge/pH curves of the mixture and those of the single components. The electrostatic potential profile across the adsorbed layer was obtained as a numerical solution of the Poisson-Boltzmann equation using the charge density of the adsorbed PAHA and the goethite surface. From the quantitative evaluation of the induced charge on both components, it is revealed that the degree of the charge adjustment is related to the electrostatic affinity between the PAHA segments and the goethite surface, the electrostatic repulsion between the PAHA segments, and the electrostatic shielding by salt ions. Considering the charge distribution of the adsorbed PAHA at the goethite surface, it is concluded that the change of the charge adjustment is sensitive to that of the conformation of the adsorbed PAHA. From the detailed inspection of the assumptions made and the comparison with the reported theoretical calculations, the obtained potential profiles are considered to broadly reflect the true potential profiles. Because a charge adjustment is not frequently considered in detail in relation to the NOM adsorption on metal (hydr)oxides, the obtained results can form the basis for the further development of modeling of the adsorption of NOM on (hydr)oxide surfaces.     

Role of the special pair in the charge-separating event in photosynthesis

We synthesized special-pair/electron-acceptor systems consisting of a complementary slipped cofacial dimer of imidazolyl-substituted zinc porphyrin, bearing pyromellitdiimide as the electron acceptor. In the case of the dimer, the first and second oxidation potentials were split into a total of four peaks in the differential pulse voltammetry measurement. Furthermore, the shift values of the first oxidation potentials obtained by changing the solvent polarity for the dimer were almost half of those observed for the monomer. These results indicate that the radical cation is delocalized over the whole pi system of the dimer. Time-resolved transient absorption measurements revealed that, relative to the corresponding monomer, the dimer accelerated the charge separation rate, but decelerated the charge recombination rate. The smaller reorganization energy of the slipped cofacial dimer relative to that of the monomeric system demonstrates the significance of the special-pair arrangement for efficient charge separation in photosynthesis.     

Non-C2-symmetrical antimony-phosphorus ligand, (R/S)-2-diphenylphosphano-2′-di(p-tolyl)stibano-1,1′-binaphthyl (BINAPSb): preparation and its use for asymmetric reactions as a chiral auxiliary

A new non-C₂-symmetrical antimony-phosphorous ligand, (±)-2-diphenyl-phosphano-2′-di(p-tolyl)stibano-1,1′-binaphthyl (BINAPSb) 3, has been prepared from 2-bromo-2′-diphenylphosphano-1,1′-naphthyl 4 via its borane complex 6, and could be resolved by the separation of a mixture of the diastereomeric palladium complexes 8A and 8B derived from the reaction of (±)-3 with optically active palladium reagent (S)-7. The enantiomerically pure BINAPSb 3 has proved to be highly effective in the palladium-catalyzed asymmetric hydrosilylation of styrene as a chiral auxiliary.