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排序方式: 共有3748条查询结果,搜索用时 15 毫秒
961.
Norio Tsubokawa Takeshi Ohyama Akihiro Yamada Yasuo Sone 《Journal of polymer science. Part A, Polymer chemistry》1985,23(2):489-500
The ring-opening copolymerization of alkylene carbonate with cyclic acid anhydride was found to be initiated by carbon black containing potassium carboxylate (COOK) groups to give an alternating polymer, i.e., polyester. The polyester was propagated from COOK groups and effectively grafted from carbon black surface: e.g., the grafting ratio of polyester from ethylene carbonate (EC) and phthalic anhydride (PAn) went up to over 100%. On the other hand, the initiating activity of alkali metal carboxylate groups increased, depending on the alkali metal countercation, in the following order: COOLi < COONa < COOK < COORb < COOCs. This order was in agreement with that of increasing electropositivity of the counteraction. The activation energy of the copolymerization of EC with PAn was determined to be 26.3 kcal/mol. The rate of the copolymerization was accelerated in an aprotic solvent such as N-methyl-2-pyrrolidone. Furthermore, the effect of solvent and polymerization temperature on the grafting ratio of polyester was investigated. 相似文献
962.
Kazuo Matsuyama Takeshi Komai Katsukiyo Ito 《Journal of polymer science. Part A, Polymer chemistry》1986,24(10):2425-2432
T-butylperoxy phenylcarbonate (BPPC) was prepared. Its decomposition rate constant in cumene is given by kd = 2.39 × 1015 exp(?17,300/T), where T is the absolute temperature. When BPPC decomposes to polymerize styrene at 100°C, it produces 12% phenoxy radical to total primary radicals. The phenoxy radical hardly adds to styrene and reacts the other primary radicals and polymer radical. Thus it retards the rate of polymerization. 相似文献
963.
Yoshifumi Bando Takeshi Dodou Yuji Minoura 《Journal of polymer science. Part A, Polymer chemistry》1977,15(8):1917-1926
Muconic acid (Mu-acid) was found to polymerize to trans-1,4-poly(Mu-acid) with the use of azobisisobutyronitrile (AIBN) as an initiator. Similarly, a muconic acid derivative, ethyl muconate (EMu), was readily polymerized through a trans-1,4 addition mechanism by the use of a radical or anionic catalyst, but did not polymerize when a cationic catalyst such as boron trifluoride etherate was used. Moreover, the copolymerization of Mu-acid and EMu with various comonomers such as styrene, acryronitrile, and 2-vinylpyridine was carried out and Q–e values of Mu-acid and EMu are discussed. These substituted diene monomers always polymerized through trans-1,4 addition with all catalysts and any comonomers. 相似文献
964.
Yasumitsu Uraki Takeshi Imura Takao Kishimoto Mokoto Ubukata 《Cellulose (London, England)》2006,13(3):225-234
The lower critical solution temperature (LCST) of hydroxypropylcellulose bearing lignin (HPC-L) prepared from unbleached pulp depends on the amount of residual lignin. An HPC-L gel having thermal properties reflective of original HPC-L was prepared using ethyleneglycol diglycidylether as a crosslinker, as previously reported [Uraki et al. (2004) Carbohydr. Polym. 58:123–130], and the volume transition temperature was detected as an endothermic peak by differential scanning calorimetry (DSC). The adsorption and release behavior of the guest molecules to/from this gel was then examined. When the adsorption of cationic and anionic guests was compared, cationic methylene blue (MB) was adsorbed in larger amounts than anionic methyl orange (MO). In addition, MB adsorption into the HPC-L gel was greater than MB adsorption into the HPC gel prepared from commercially available HPC. This suggests that residual lignin affects the adsorption of organic dyes. Significant differences were not observed with respect to the release of MB from HPC-L at 38 °C and lower temperatures. In the adsorption of surfactants, marked adsorption at around the critical micelle concentration of the ionic surfactants and gel swelling were observed. Such swelling did not occur in the aqueous nonionic surfactant solution, although the nonionic surfactant was adsorbed into the gel. Gel swelling may have been caused by the electrostatic repulsion of the ionic surfactants adsorbed onto the polymer chains within the gel structure. 相似文献
965.
We have investigated the binding of noble-gas (Ng) atoms (Ng=Ar,Kr,Xe) with Pt atom by the ab initio coupled-cluster CCSD(T) method, taking into account the relativistic effects. It is shown that two Ng atoms can bind with Pt atom in linear geometry in the singlet lowest state where the second Ng atom attaches to Pt with the larger binding energy than the first Ng atom. The binding energy is evaluated as 8.2, 17.9, and 33.4 kcal/mol for Ar-Pt-Ar, Kr-Pt-Kr, and Xe-Pt-Xe, respectively, relative to the triplet ground state of the dissociation limit Pt ((3)D)+2Ng. The present results indicate that these Ng-Pt-Ng compounds are possible new gas-phase or matrix species. 相似文献
966.
Tayagaki T Galet A Molnar G Muñoz MC Zwick A Tanaka K Real JA Bousseksou A 《The journal of physical chemistry. B》2005,109(31):14859-14867
The 1A1 left arrow over right arrow 5T2 spin transition has been investigated in the solid solutions of Fe(x)M(1-x)(pyrazine)[Pt(CN)4] (M = Ni or Co, 0 < or = x < or = 1) having a three-dimensional polynuclear structure. Both Ni and Co dilutions tend to decrease the hysteresis width and smooth the transition curves. The enthalpy (entropy) change associated with the spin transition was found to decrease from 26 kJ mol(-1) (84 J K(-1) mol(-1)) for x = 1 to 12 kJ mol(-1) (47 J K(-1) mol(-1)) for 47% Co dilution and to 15 kJ mol(-1) (54 J K(-1) mol(-1)) for 59% Ni dilution. Raman spectroscopy revealed a mixed one- and two-mode behavior in the solid solutions. For the first time, a correlation between vibrational frequencies exhibiting one-mode behavior and the entropy change, which drives the spin crossover, is established. 相似文献
967.
Katsunobu Yamamoto Tianshu Zhou Min Zhu Takeshi Kato Litong Jin 《Analytica chimica acta》2003,480(1):109-117
In this paper, preparation of a novel pH ultramicrosensor and its physiological application has been discussed. A tungsten nanoelectrode was produced by an etching method in 0.1 mol/l NaOH solution at the potential of +0.4 V (versus Ag/AgCl reference electrode) for about 100 s and the diameters ranged from 500 to 800 nm. The pH ultramicrosensor was fabricated by producing WO3 at W nanoelectrode surface by electrooxidation in 2.0 mol/l H2SO4 solution between 1.0 and 2.0 V. At last, Nafion was coated on the surface of WO3 to protect the pH ultramicrosensor. The W/WO3 pH ultramicrosensor exhibited a good pH linear region from 2.0 to 12.0 with a super-Nernstian slope of −53.5 ± 0.5 mV/pH unit. Response times ranged from 3 s at about pH 6.0-7.0 up to 15 s at high pH. An interference of various ions to the pH measurement was also studied in this paper. We also studied the lifetime, stability and reproducibility of the W/WO3 pH ultramicrosensor. In order to testing the performance of W/WO3 ultramicrosensor, we applied it to measure the extracellular pH values and a pH variation was also given about the normal, damaged and recovery endothelial cells. 相似文献
968.
Mitsumori T Bendikov M Dautel O Wudl F Shioya T Sato H Sato Y 《Journal of the American Chemical Society》2004,126(51):16793-16803
We report here the synthesis, X-ray structures, optical and electrochemical properties, fabrication of light-emitting devices, and density functional calculations for indolizino[3,4,5-ab]isoindole (INI) derivatives. Strongly luminescent heterocycles based on the INI unit were synthesized by 1,3-dipolar cycloaddition reactions between pyrido[2,1-a]isoindole (PIS) and acetylene or ethylene derivatives. They are indolizino[3,4,5-ab]isoindoles 2-9 and 14-15, benzo[1',2'-1,2]indolizino[3,4,5-ab]isoindoles 10, pyridazino[4',5':1,2]indolizino[3,4,5-ab]isoindoles 12-13, and 2,3-hydropyridazino[4',5':1,2]indolizino[3,4,5-ab]isoindole-1,4-dione 11. The relative luminescence quantum yield can be as high as 90%. Their reduction and oxidation potentials and high luminescence can make these heterocycles possible alternatives to tris(8-hydroxyquinolinato)aluminum (Alq(3)). The brightness of the light-emitting device reached as high as 10(4) cd/m(2) and indolizino[3,4,5-ab]isoindole 3 emits beautifully blue light. The X-ray crystal structures of INI derivatives were obtained for the first time. The geometries obtained from X-ray data and density functional theory calculations shed more light on an interesting formally antiaromatic 16pi system, which is divided into 10pi and 6pi aromatic systems. We also report a relatively easy protonation of INI, which occurs at a carbon, rather than nitrogen atom. 相似文献
969.
Takebayashi Y Yoda S Sugeta T Otake K Sako T Nakahara M 《The Journal of chemical physics》2004,120(13):6100-6110
The (13)C-NMR chemical shift of acetone delta((13)C[Double Bond]O) was measured in aqueous solution at high temperatures up to 400 degrees C and water densities of 0.10-0.60 g/cm(3) for the study of hydration structure in the supercritical conditions. The average number N(HB) of hydrogen bonds (HBs) between an acetone and solvent waters and the energy change DeltaE upon the HB formation were evaluated from the delta and its temperature dependence, respectively. At 400 degrees C, N(HB) is an increasing function of the water density, the increase being slower at higher water densities. The acetone-water HB formation is exothermic in supercritical water with larger negative DeltaE at lower water densities (-3.3 kcal/mol at 0.10 g/cm(3) and -0.3 kcal/mol at 0.60 g/cm(3)), in contrast to the positive DeltaE in ambient water (+0.078 kcal/mol at 4 degrees C). The corresponding Monte Carlo simulations were performed to calculate the radial and orientational distribution functions of waters around the acetone molecule. The density dependence of N(HB) calculated at 400 degrees C is in a qualitative agreement with the experimental results. In the supercritical conditions, the HB angle in a neighboring acetone-water pair is weakly influenced by the water density, because of the absence of collective HB structure. This is in sharp contrast to the hydration structure in ambient water, where the acetone-water HB formation is orientationally disturbed by the tetrahedral HB network formation among the surrounding waters. 相似文献
970.
Contracted Gaussian-type function sets to describe valence correlation are developed for the sixth-period d-block atoms Lu through Hg. A segmented contraction scheme is employed for their compactness and efficiency. Contraction coefficients and exponents are determined by minimizing the deviation from accurate natural orbitals generated from configuration interaction calculations, in which relativistic effects are incorporated through the third-order Douglas-Kroll approximation. The present basis sets yield more than 99% of atomic correlation energies predicted by accurate natural orbital sets of the same size. Relativistic model core potential calculations with the present correlating sets give the spectroscopic constants of the AuH molecule in excellent agreement with experimental results. 相似文献