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191.
Fukuji Higashi Toshiharu Nishi 《Journal of polymer science. Part A, Polymer chemistry》1986,24(4):701-706
Mechanistic features of the reaction promoted by thionyl chloride and amides such as N-methylpyrrolidone (NMP) were studied. The reaction was effective in the amidation of carboxylic acids, but not effective in the esterification. The amidation was affected by the kind and the amount of amides used, most favorably by two equivalents of NMP with respect to the acid. These amides were assumed to be involved in the intermediate formation, and the reaction was proposed to proceed via Vilsmeier adducts derived from thionyl chloride and the amides, and through activation of a carboxylic acid different from an acyl chloride. The reaction was successfully applied to the direct polycondensation of aromatic dicarboxylic acids and diamines in NMP at 70°C to produce polyamides with high molecular weights. Initial reaction of dicarboxylic acids with the adducts, additive effect of tertiary amines, and polycondensation temperatures were studied in terms of the inherent viscosity of the polymers produced. 相似文献
192.
T. Ichino S. Sasaki T. Matsuura S. Nishi 《Journal of polymer science. Part A, Polymer chemistry》1990,28(2):323-331
A series of new polyimides containing fluorinated alkoxy side chains are prepared from novel fluorinated alkoxy diamines. The dieletric constant at 1 kHz in the fluorinated polyimides decreases from 3.3 to 2.6 as fluorine content increases. The refractive index also changes from 1.58 to 1.48, dependent on the fluorine content. In addition, the fluorinated polyimides exhibit lower water absorption than the reference polyimides prepared from m-phenylenediamine. 相似文献
193.
Enantiomer separation by capillary electrophoresis using DEAE-dextran and aminoglycosidic antibiotics 总被引:2,自引:0,他引:2
Summary Diethylaminoethyl (DEAE) dextran hydrochloride and three kinds of aminoglycosidic antibiotics; fradiomycin sulfate, kanamycin sulfate and streptomycin sulfate, were employed as chiral selectors in capillary electrophoresis, enantiomer separation. These selectors are cationic or basic because of amino functionality and therefore used for enantiomer separation of acidic compounds. To avoid adsorption of the basic or cationic selectors on the capillary inner surface, a coated capillary was employed. Among those tested, enantiomers of binaphthyl compounds and synthetic intermediates of diltiazem analogues were separated. Methanol addition was effective for the improvement of peak shape and resolution. 相似文献
194.
Fukuji Higashi Toshiharu Nishi 《Journal of polymer science. Part A, Polymer chemistry》1988,26(12):3235-3240
The direct polycondensation of terephthalic acid and p-phenylenediamine hydrochloride (PPD.2HCl) with thionyl chloride was found to be significantly promoted in N-methylpyrrolidone (NMP) by dissolved CaCl2 and tertiary amines. The inherent viscosity of the polymer obtained varied with the amount of CaCl2 and tertiary amines added. The reaction, when effectively promoted by CaCl2, proceeded homogeneously in the early state of polycondensation, and then resulted in a highly swollen gel. CaCl2 had to be present in the PPD.2HCl/tertiary amines/NMP solution as well as in the TPA/SOCl2/NMP mixture for the polycondensation to proceed to high molecular weight. Complexes of CaCl2, PPD.2HCl, and tertiary amines in NMP similar to the well known complex, CaCl2 · nNH3 (n = 2, 4, 8) was proposed to facilitate the polycondensation. 相似文献
195.
Improvement of Corrosion Resistance of Metals by an Environmentally Friendly Silica Coating Method 总被引:1,自引:0,他引:1
Satomi Ono Hiroyasu Tsuge Yasuo Nishi Shin-ichi Hirano 《Journal of Sol-Gel Science and Technology》2004,29(3):147-153
Corrosion resistance of stainless steel and Zn plated steel can be improved by a chromium-free environmentally friendly chemical solution deposition method. Precursor solutions were prepared from tetraethoxysilane with polymer, and were deposited on stainless steel, Zn plated steel and aluminum alloy by dip coating, followed by heat treatment. Addition of polymer to the precursor solution proved very effective in preparing films free from cracks on stainless steel and aluminum alloy substrates. The corrosion resistance was greatly improved by the resulting sub-micron thick silica-polymer hybrid film coatings on stainless steel and on Zn plated steel prepared at 200°C. The hardness of aluminum alloy coated with silica-PMMA hybrid film was improved by 7% over uncoated alloy. 相似文献
196.
H. Shinohara H. Sato F. Misaizu K. Ohashi N. Nishi 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,20(1):197-200
Metastable uni-cluster dissociation for several hydrogen-bonded and van der Waals cluster ions are observed via resonance-enhanced two-photon ionization reflectron time-of-flight (TOF) mass spectrometry. All of the cluster ions studied show evaporation of a single molecule from the respective parent cluster ions as dominant metastable decay processes. Furthermore, the averaged metastable evaporation rate constants (k evap) of these cluster ions in a fixed time domain of 0.2–50 µs are obtained by analyzing the relative intensity of metastable ion peaks due to evaporation in the acceleration and the field-free drift regions of the TOF mass spectrometer. An intensity anomaly in some of the observed metastable ion peaks, indicative of magic number stability of the cluster ion, is also presented. 相似文献
197.
Oxidation Ability of Plasmon‐Induced Charge Separation Evaluated on the Basis of Surface Hydroxylation of Gold Nanoparticles
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Dr. Hiroyasu Nishi Prof. Tetsu Tatsuma 《Angewandte Chemie (International ed. in English)》2016,55(36):10771-10775
The oxidation ability of plasmonic photocatalysts, which has its origins in plasmon‐induced charge separation and has not yet been studied quantitatively and systematically, is important for designing practical photocatalytic systems. Oxidation ability was investigated on the basis of surface hydroxylation of Au nanoparticles on TiO2 at various irradiation wavelengths and electrolyte pH values. The reaction proceeds only when the sum of the flat band potential of TiO2 and the irradiated photon energy is close to, or more positive than, the theoretical potential for the reaction. 相似文献
198.
Treatment of beta-keto esters with terminal acetylenes in the presence of a catalytic amount of a manganese complex, MnBr(CO)5, and molecular sieves, gave multisubstituted aromatic compounds in good to excellent yields. This reaction employs [2 + 2 + 2] cycloaddition of beta-keto esters and 2 equiv of terminal acetylenes with dehydration. In the case of a 1,3-diketone, the corresponding acetophenone derivative and its deacylated compound can be synthesized selectively. 相似文献
199.
Five new 3-alkylpyridine alkaloids with a β-amino acid moiety, nakinadines B-F (1-5), have been isolated from an Okinawan marine sponge Amphimedon sp. (SS-1059), and the structures and stereochemistry were elucidated by spectroscopic data. Nakinadines B (1) and C (2) showed modest cytotoxicity. 相似文献
200.
Ochiai M Yoshimura A Mori T Nishi Y Hirobe M 《Journal of the American Chemical Society》2008,130(12):3742-3743
Reported here for the first time are the oxidative couplings of alkynes and primary alcohols yielding conjugated enones. Although the BF3-catalyzed reaction of terminal alkynes with p-trifluoromethylphenyl(difluoro)-lambda3-bromane results in the fluoro-lambda3-bromanation of triple bonds to afford (E)-beta-fluorovinyl-lambda3-bromanes, reaction of an alkyne with the difluoro-lambda3-bromane in the presence of an alcohol and BF3-Et2O affords directly conjugated enones in good yields. The reaction proceeds in a highly stereo- and regioselective manner under metal-free conditions. Interestingly, no formation of enones was detected, when difluoro-lambda3-iodane p-CF3C6H4IF2 was used instead of the lambda3-bromane. A mechanism involving a lambda3-bromane-induced oxidation of an alcohol to an aldehyde, [2 + 2] cyclization with alkynes yielding 2H-oxetes, and finally the electrocyclic ring opening is discussed. 相似文献