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121.
Hisatoyo Morinaga Yusuke Ujihara Naho Yuto Daisuke Nagai Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2011,49(24):5210-5216
Metal‐free controlled ring‐opening polymerization of glycidyl phenyl ether (GPE) was achieved using tetra‐n‐butylammonium fluoride (Bu4NF) as an initiator in the presence of water and ethanol as chain transfer agents (CTAs). Number‐averaged molecular weight of poly(GPE) increased with an increase of [GPE]0/([Bu4NF]0 + [CTA]0) values, showing relatively narrow molecular weight distributions. NMR spectroscopic analysis exhibited a formation of ethoxy groups as well as FCH2 at the initiating polymer chain‐end when ethanol was used as the CTA in the polymerization. These results indicate that Bu4NF acts as a catalyst as well as the initiator for this polymerization system. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
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Kazuhiro Nagata Daisuke Sano Yu Shimizu Michiko Miyazaki Takuya Kanemitsu Takashi Itoh 《Tetrahedron: Asymmetry》2009,20(21):2530-2536
The catalytic asymmetric alkylation of α-cyanocarboxylates and acetoacetates with an alkyl halide was performed under phase-transfer conditions to afford compounds which have a chiral quaternary carbon with up to 97% and 94% ee, respectively. As applications of this method, chiral 2-oxindole derivatives and a β-lactam derivative were synthesized. 相似文献
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Daisuke Kamei Hiroharu Ajiro Mitsuru Akashi 《Journal of polymer science. Part A, Polymer chemistry》2010,48(16):3651-3657
The effects of stereoregularity, temperature, and solvent on the specific recognition of syndiotactic (st)‐poly(methacrylic acid) (PMAA) in macromolecularly porous isotactic (it)‐poly(methyl methacrylate) films were investigated to give important insights into the regularity and stability of nanospaces in the it‐PMMA films as well as template polymerization. The porous it‐PMMA films were fabricated on quartz crystal microbalance (QCM) substrates via the layer‐by‐layer (LbL) assembly of it‐PMMA/st‐PMAA, plus the st‐PMAA extraction from the assembly. QCM analysis and infrared spectroscopy revealed the first case of stereocomplex formation using st‐PMAA with lower stereoregularity (rr = 73%) in the LbL films, while st‐PMAA obtained with conventional free radical polymerization (rr = 62%) was barely incorporated into the porous it‐PMMA films. The maximum st‐PMAA incorporation increased from 25 to 40 °C, but there were almost no difference between 40 and 55 °C, indicating that the it‐PMMA crystallization would also be accelerated with increasing temperature. The studies on st‐PMAA incorporation with various complexing solvents revealed that the host it‐PMMA in the porous films could only form the original stereocomplex with 2/1 unit‐molar stoichiometry (st‐PMAA/it‐PMMA) in acetonitrile/water or ethanol/water. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3651–3657, 2010 相似文献
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Daisuke Nagai Asuka Fujii Masayoshi Tanaka Bungo Ochiai Atsushi Sudo Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2009,47(6):1510-1521
Anionic polymerization of methacrylates under sterically confined environment in a spherical beads‐shaped networked polystyrene (NwPS) matrix is described. The initiator used herein is a samarium (Sm) (III) enolate, which was formed by treatment of 2‐bromoisobutylate immobilized in the side chain of NwPS with Sm (II) iodide. By using this NwPS‐bound initiator, polymerization of a series of methacrylates (=solid‐supported polymerization) was studied to find its two aspects: (1) In the early stages, the rate constant for each methacrylate was comparable to that for its conventional solution‐phase polymerization using a Sm (III) enolate, suggesting that methacrylate can be efficiently supplied to the propagating end by its free permeation without any interference by the networked structure of the matrix. (2) After the early stages, the rate constant decreased remarkably, implying that permeation of methacrylate was sterically interfered by the formed poly(methacrylate) that filled the confined space in NwPS, as supported by a SEM image of the resulting beads, of which pores were filled with the formed polymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1510–1521, 2009 相似文献
129.
Desmosine is a crosslinking pyridinium amino acid of elastin, which is a useful biomarker for the diagnosis of chronic obstructive pulmonary disease (COPD) by LC–MS/MS analysis. We previously reported a synthesis of desmosine-d4, which is useful as an internal standard for quantitative LC–MS/MS analysis of desmosines, by deuterogenation of an alkyne group; however, the isotopic purity of the desmosine-d4 was only ca. 50%. The present report describes a new synthesis of desmosine-d4 that improves the isotopic purity to ca. 90% by exchanging the protons of the amino groups to deuterium using deuterogenation. 相似文献
130.
Vapor–liquid equilibria and saturated density for carbon dioxide + tetrahydrofuran mixtures at high pressures were measured by the analytical method at the temperatures 298.15 and 313.15 K. The experimental apparatus equipped with three Anton Paar DMA 512S vibrating tube density meters was previously developed for measuring vapor–liquid–liquid equilibrium at high pressures. The equilibrium composition and saturated density of each phase were determined by gas chromatograph and vibrating tube density meters, respectively. The bubble point pressure at the temperature 313.15 K was further measured by the synthetic method. The experimental data were correlated with Soave–Redlich–Kwong (SRK) equation of state and the pseudocubic equation of state. 相似文献