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111.
Kazukiyo Nagai Miyuki Mori Tetsuya Watanabe Tsutomu Nakagawa 《Journal of Polymer Science.Polymer Physics》1997,35(1):119-131
The poly(1-trimethylsilyl-1-propyne) (PMSP) has the potential to be an important membrane gas separation material due to the fact that it has the highest gas permeability of all polymeric membranes. One problem with PMSP is a decrease in the gas permeability with age. In order to understand the aging processes, we studied the change in free volume and the molecular motions of the PMSP and its membranes modified with 1-phenyl-1-propyne (PP) structures; that is, a copolymer and a blend of PMSP and PPP. During aging, the unrelaxed volume of the PMSP membrane was relaxed, and the molecular motion of carbons dropped, suggesting that the decrease in the microvoids caused a tighter chain packing. The copolymer and blend membrane had stable permeability compared to the PMSP. In particular, the addition of a small amount of the PP structure provided excellent stability with high gas permeability. A decrease in the unrelaxed volume of modified membranes was hardly observed with age; however, the molecular motion of some carbons slightly changed. This change did not affect the gas permeability. In this case, a larger unrelaxed volume was probably a dominant factor in the gas permeation of the PMSP rich membranes relative to the molecular motion in the T1 measurement. © 1997 John Wiley & Sons, Inc. 相似文献
112.
Itaru Natori Kimio Imaizumi Hideyuki Yamagishi Miyuki Kazunori 《Journal of Polymer Science.Polymer Physics》1998,36(10):1657-1668
The relationship between the microstructure and the properties of poly(1,3-cyclohexadiene)s, obtained by living anionic polymerization with an alkyllithium/amine system, and their hydrogenated derivatives are reported. The 1,2-bond/1,4-bond molar ratio of poly(1,3-cyclohexadiene) was determined by measuring 2D-NMR with the H H COSY method. The glass transition temperature of poly(1,3-cyclohexadiene) was found to rise with an increase in the ratio of 1,2-bonds to 1,4-bonds or with an increase of the number average molecular weight. The 1,2-bond of the polymer chain gives a high flexural strength and heat distortion temperature. Hydrogenated poly(1,3-cyclohexadiene) has the highest Tg (231°C) among all hydrocarbon polymers ever reported. 1,3-Cyclohexadiene–butadiene–1,3-cyclohexadiene triblock copolymer and 1,3-cyclohexadiene–styrene–1,3-cyclohexadiene triblock copolymer have high heat resistance and high mechanical strength. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1657–1668, 1998 相似文献
113.
Miyuki Harada Takeharu Miyamoto Mitsukazu Ochi 《Journal of Polymer Science.Polymer Physics》2009,47(18):1753-1761
The bisphenol‐A type epoxy resin was combined with layered clays. Three types of epoxy/clay nanocomposites were prepared by different clay pretreatment methods, that is, the slurry (clay swelling with polar solvent), organo, and solubilization (organoclay swelling with polar solvent) methods. The organo and solubilization systems showed good dispersibility. The basal spacing of the layered clays in the obtained nanocomposites was evaluated by XRD and TEM observations. The basal spacing of the nanoclay in the solubilization system drastically increased. The mechanical properties were improved with the increase in the clay dispersion. A high modulus and fracture toughness were obtained by improvement of the clay dispersion into the matrix. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1753–1761, 2009 相似文献
114.
Anzai K Saito K Takeshita K Takahashi S Miyazaki H Shoji H Lee MC Masumizu T Ozawa T 《Magnetic resonance imaging》2003,21(7):765-772
Blood-brain-barrier (BBB)-permeable, 3-methoxycarbonyl-2,2,5,5-tetramethylpyrrolidine-1-yloxy (MC-PROXYL) and BBB-impermeable carbamoyl-PROXYL were used to assess the ESR imaging technique by comparing with autoradiography. For this purpose, spin probes, 14C-labeled at their five-membered ring, [14C]MC-PROXYL and [14C]carbamoyl-PROXYL, were newly synthesized. These probes were i.p. or i.v. injected into rats and autoradiograms were recorded. The autoradiograms of rat head showed that [14C]MC-PROXYL distributed well in the brain compared to [14C]carbamoyl-PROXYL. In vivo ESR spectra and two-dimensional ESR images of isolated rat brain treated with MC- or carbamoyl-PROXYL also indicated the extensive distribution of MC-PROXYL but not carbamoyl-PROXYL in the rat brain. The three-dimensional ESR images of the head of rats and mice were consistent with the fact that MC-PROXYL but not carbamoyl-PROXYL is incorporated into the brain. The ESR-CT images were better for mice than rats. However, the quality of the ESR-CT images was still not satisfactory. Although the resolution and sensitivity of the ESR-CT images were worse than those of the autoradiographic images, the former technique has unique features and advantages; e.g., functional, noninvasive and three-dimensional detection. 相似文献
115.
3+3]Cycloalkyne dimers linked by an azo group: a stable cis-azo compound forms polymeric aggregates by nonplanar pi-pi interactions 总被引:1,自引:0,他引:1
Saiki Y Sugiura H Nakamura K Yamaguchi M Hoshi T Anzai J 《Journal of the American Chemical Society》2003,125(31):9268-9269
We previously reported that the structure of the linker moiety controlled intramolecular and bimolecular aggregation of [3+3]cycloalkyne oligomers, which are cyclic acetylene derivatives containing helicenes. Here, novel [3+3]cycloalkyne dimers linked by the azo group are synthesized, and aggregation behaviors are studied, which turned out to be considerably different. The trans- and cis-azo compounds were synthesized by the oxidative coupling of a [3+3]cycloalkyne amine derivative, and the stereochemistry was determined by UV-vis spectroscopy. 1H NMR, CD, gel permeation chromatography analysis, and vapor pressure osmometry in chloroform revealed that the trans-isomer forms a strong and selective bimolecular aggregate. The cis-isomer forms a trimolecular aggregate at a concentration below 1 mM and a polymeric aggregate at above 1 mM. Unlike known diaryl azo compounds, these azo isomers do not interconvert when subjected to heating or irradiation. In contrast, a model compound lacking the cyclic helicene structure isomerizes readily. 相似文献
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Nishida H Miyazaki Y Mukaihira T Saitoh F Fukui M Harada K Itoh M Muraoka A Matsusue T Okamoto A Hosaka Y Matsumoto M Ohnishi S Mochizuki H 《Chemical & pharmaceutical bulletin》2002,50(9):1187-1194
Intravascular clot formation is an important event in a number of cardiovascular diseases. The prevention of blood coagulation has become a major target for new therapeutic agents. Factor Xa (FXa) is a trypsin-like serine protease that plays a key role in the blood coagulation cascade and represents an attractive target for anticoagulant drug development. We have investigated substituents in the central part of a lead compound (3: M55113), and discovered that compound M55551 (34: (R)-4-[(6-Chloro-2-naphthalenyl)sulfonyl]-6-oxo-1-[[1-(4-pyridinyl)-4-piperidinyl]methyl]-2-piperazinecarboxylic acid) is a potent inhibitor of FXa (IC(50)=0.006 microM), with high selectivity for FXa over trypsin and thrombin. The activity of this compound is ten times more powerful than the lead compound. 相似文献