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471.
The composition, formation constants, and molar absorptivities of the chelates of zirconium ion wtih xylenol orange and semi-xylenol orange are investigated spectrophotometrically in strong acid medium at ionic strength 3.0 (NaClO4 and HClO4). The data obtained were processed with a newly-constructed computer program and with LETAGROP/SPEFO. In the zirconium—xylenol orange system, Zr · H3 L, Zr· H4L, and Zr2 · L are present with logarithmic overall formation constants of 37.80, 38.68, 43.47, and molar absorptivities of 3.10 × 104 (485 nm), 5.98 × 104 (528 nm), 9.50 × 104 (551 nm) I mol-1 cm-1, respectively. The chelates Zr · L and Zr · HL were found in the zirconium—semi-xylenol orange system with logarithmic overall formation constants of 26.25 and 27.56, and molar absorptivities of 5.70 × 104 (532 nm) and 8.30 × 104 (535 nm) 1 mol-1 cm-1, respectively. Semi-xylenol orange is more sensitive and reliable than xylenol orange as a spectrophotometric reagent for zirconium. 相似文献
472.
The effect of initial panipenem (CAS No. 87726-17-8) concentration on its degradation in an aqueous solution was investigated. The degradation of panipenem followed pseudo-first-order kinetics at all the pH values tested. However, in an acidic solution, the degradation rate increased with the initial panipenem concentration. On the other hand, in an alkaline solution, the degradation rate was not affected by its initial concentration. In an acidic solution, the plots of the first-order rate constants versus initial panipenem concentrations showed a linear relationship. Theoretically, the first-order rate constant is independent of the initial concentration, and therefore, the results suggested unusualness. We investigated the results obtained under acidic conditions in detail to find a very complex reaction mechanism: panipenem and its degradation products are factors causing the unusual increase in the degradation rate. Moreover, it was shown that the dissociation of the carboxyl group played an important role in the degradation of panipenem. 相似文献
473.
Suzuki S Morita Y Fukui K Sato K Shiomi D Takui T Nakasuji K 《Inorganic chemistry》2005,44(23):8197-8199
The hexaazaphenalenyl anion (HAP, 3-), a highly symmetric heterocyclic pi system, has been synthesized and characterized. The crystal structures of its potassium salt K+.3- and copper complex Cu2+.(NH3)4.(3-)2 show pi-pi stacking and radially extended hydrogen bonds as well as coordination bonds constructed by the HAP anion. These in-plane and out-of-plane strong interactions demonstrate the multiple-networking ability of the HAP anion. 相似文献
474.
Mouri E Furuya Y Matsumoto K Matsuoka H 《Langmuir : the ACS journal of surfaces and colloids》2004,20(19):8062-8067
Detailed analysis of an interesting poly(methacrylic acid) (PMAA) brush structure in water of a diblock copolymer [(Et(2)SB(m)-b-(MMA)(n), where Et(2)SB is diethylsilacyclobutane] monolayer reported previously was performed by X-ray and neutron reflectometry and indicated that the hydrophilic layer formed with a relatively long PMAA chain is not a simple layer but is divided into two layers, that is, a "carpet"-like dense PMAA layer near the hydrophobic layer and a polyelectrolyte brush layer. The hydrophilic chain length dependence of the diblock copolymer monolayer was analyzed using m:n = 30:x polymer samples, especially of the PMAA double layer structure. With the increase in PMAA chain length in polymer samples, a carpet layer is mainly formed up to n approximately 50. With further increase in the PMAA chain length beyond n approximately 50, a well-defined brush layer appears. On the other hand, the variation in hydrophobic layer thickness with methacrylic acid unit is minimum at the critical PMAA length, that is, n approximately 50 under a constant surface pressure condition. It is strongly suggested that the two discrete layers contribute differently to surface pressure. Furthermore, from the comprehensive viewpoint, the major factor for brush formation was clarified not to be the absolute length of the PMAA chain, but the ratio of PEt(2)SB and PMAA chain length is an important factor. 相似文献
475.
Kozo Arai Michiharu Negishi 《Journal of polymer science. Part A, Polymer chemistry》1971,9(7):1865-1877
To determine the location of grafted poly(methyl methacrylate) in orthocortex structure of fine Australian Merino wool fibers, high-resolution electron microscopy was used. Optimal staining conditions for the observation of the deposited polymer were also studied. It was supposed that the grafted polymer is located mainly between the microfibril and matrix and around the protofibrillar subunits, but not in the matrix. The average space occupied by a grafted chain was estimated to be about four times as large as the total residue volume per polymer. It is supposed that the remarkably large space available per polymer chain is related to the excessive swelling seen with respect to the polymer uptake. 相似文献
476.
Hydrotalcite-like compounds (HTlcs) can be used as the catalysts as it is since they contain various transition metal cations
as the catalytically active species well dispersed on the basic support materials. Moreover, increasing numbers of the applications
of HTlcs after the heat treatment have been found since the oxides with very small crystal size, stable to thermal treatments,
are obtained after the calcination. The oxides possess interesting properties such as high surface area, basic properties
and further form small and thermally stable metal crystallites by reduction. Moreover, the calcined oxides show a unique property,
i.e., “memory effect,” which allows the reconstitution of the original hydrotalcite structure. We have developed the catalytic
applications of hydrotalcites as it is and moreover the mixed oxides derived from hydrotalcites for various catalytic reactions,
i.e., oxidation, dehydrogenation and reforming of hydrocarbons, and even for the reforming of methanol and the CO shift reaction.
Aerobic oxidation of alcohols, Baeyer−Villiger oxidation of ketones and O3 oxidation of oxalic acid have been successfully carried out with the Mg−Al hydrotalcites containing Ni, Fe and Cu, respectively,
as the catalysts in liquid phase. In the O3 oxidation of oxalic acid, the catalytic activity was enhanced by the “memory effect,” i.e., Mg(Cu)–Al hydrotaclite was reconstituted
on the surface of Mg(Cu,Al)O periclase particles and oxalic acid was incorporated as anions in the hydrotalcite layer, resulting
in an enhanced oxidation of oxalic acid. As the catalysts in the vapor phase reactions, Mg/Fe/Al mixed oxides prepared from
Mg–Al(Fe) hydrotalcites and effectively catalyzed the dehydrogenation of ethylbenzene. Supported Ni metal catalysts have been
prepared from Mg(Ni)–Al hydrotalcites and successfully used in the steam reforming and the oxidative reforming of methane
and propane. Moreover, the Ni catalysts have been improved by combining a trace amount of noble metals by adopting the “memory
effect” and used in the production of hydrogen for the PEFC under the daily startup and shutdown operation. Also starting
from aurichalcite or hydrotalcite precursor as the precursor, Cu/Zn/Al catalysts with high Cu metal surface area have been
prepared and successfully applied in the steam reforming of methanol and dimethyl ether, and moreover in the CO shift reaction. 相似文献
477.
Matsuoka H Maeda S Kaewsaiha P Matsumoto K 《Langmuir : the ACS journal of surfaces and colloids》2004,20(18):7412-7421
Strongly ionized amphiphilic diblock copolymers of poly(styrene)-b-poly(styrenesulfonate) with various hydrophilic and hydrophobic chain lengths were synthesized by living radical polymerization, and their properties and self-assembling behavior were systematically investigated by surface tension measurement, foam formation, hydrophobic dye solubilization, X-ray reflectivity, dynamic light scattering, small-angle neutron scattering, small-angle X-ray scattering, and atomic force microscope techniques. These copolymer solutions in pure water did not show a decrease of surface tension with increasing polymer concentration. The solutions also did not show foam formation, and no adsorption at the air/water interface was confirmed by reflectivity experiments. However, in 0.5 M NaCl aq solutions polymer adsorption and foam formation were observed. The critical micelle concentration (cmc) was observed by the dye solubilization experiment in both the solutions with and without added salt, and by dynamic light scattering we confirmed the existence of polymer micelles in solution, even though there was no adsorption of polymer molecules at the water surface in the solution without salt. By the small-angle scattering technique, we confirmed that the micelles have a well-defined core-shell structure and their sizes were 100-150 A depending on the hydrophobic and hydrophilic chain length ratio. The micelle size and shape were unaffected by addition of up to 0.5 M salt. The absence of polymer adsorption at the water surface with micelle formation in a bulk solution, which is now known as a universal characteristic for strongly ionized amphiphilic block copolymers, was attributed to the image charge effect at the air/water interface due to the many charges on the hydrophilic segment. 相似文献
478.
Kozo Toyota 《Tetrahedron letters》2004,45(41):7609-7612
Reaction of 1,8-bis[5-{(2,4,6-tri-t-butylphenyl)phosphinoethynyl}-2-thienyl]octane with butyllithium followed by treatment with 1,2-dibromoethane afforded a new polymer containing 3,4-bis[(2,4,6-tri-t-butylphenyl)phosphinidene]-1,2-di(2-thienyl)cyclobutene units. The polymer was allowed to react with bis(benzonitrile)dichloropalladium to give the polymer complex. A Sonogashira coupling reaction between ethynyltrimethylsilane and 4-bromonitrobenzene proceeded in DMF at 100 °C to give 4-nitro(trimethylsilylethynyl)benzene in the presence of the polymer complex, CuI, and triethylamine. 相似文献
479.
Toshiaki Munakata Koichi Ohno Yoshiya Harada Kozo Kuchitsu 《Chemical physics letters》1981,83(2):243-245
The Ne1(3P2) Penning electron spectra and the Ne I photoelectron spectra were measured in the gas phase. The observed systematic differences in their relative intensities were interpreted in terms of the electron distributions of the relevant molecular orbitals and used for assignment of the deep π bands, π1 (12.4 eV) for naphthalene, and π2 (11.9 eV) and π1 (12.8 eV) for anthracene. 相似文献
480.
Surface morphology and biological activity of protein thin films produced by electrospray deposition
Uematsu I Matsumoto H Morota K Minagawa M Tanioka A Yamagata Y Inoue K 《Journal of colloid and interface science》2004,269(2):336-340
Protein thin films were prepared by the electrospray deposition (ESD) method from aqueous solutions of alpha-lactalbumin (alpha-LA) at different concentrations, and their surface morphologies and biological activities were characterized. The surface morphologies of the deposited films were observed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The SEM and AFM images showed that the film surfaces had a fine porous structure, in which the pore diameters ranged from 40 to 600 nm. The biological activities of the cross-linked protein films were tested by the mechanochemical method. The response to calcium ion (Ca(2+)) demonstrated that the biological activity of the films was preserved. These results indicate that the ESD method is potentially useful for the fabrication of active protein thin films. The freestanding protein thin films prepared by ESD and postdeposition cross-linking provide novel options for protein-based biomaterials. 相似文献