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Kajitani T Onouchi H Sakurai S Nagai K Okoshi K Onitsuka K Yashima E 《Journal of the American Chemical Society》2011,133(24):9156-9159
We report a unique macromolecule consisting of a rodlike helical polyisocyanide backbone with a narrow molecular weight distribution and rigid mesogenic chiral pendants linked via a flexible spacer that exhibits lyotropic nematic and latticelike new smectic (lat-Sm) liquid crystal phases at different concentrations. The unprecedented lat-Sm phase is associated with the smectic ordering of both the stiff polymer backbone and the rigid-rod side groups. A detailed investigation of the films using X-ray scattering and atomic force microscopy revealed a novel tilted smectic layer structure of the polymer backbone aligned perpendicular to the smectic layer of the mesogenic pendants, which arrange in an antiparallel overlapping interdigitated manner. 相似文献
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Shigehiro Morikawa Toshiro Inubushi Kan Takahashi Hisanari Ishii Shino Shigemori 《Magnetic resonance imaging》1996,14(10):1197-1204
The relationships among tissue edema, lactate accumulation, and intracellular pH in middle cerebral artery (MCA)-occluded rats were investigated with multiecho 1H magnetic resonance imaging and spatially resolved metabolic images constructed by 1H and 31P nuclear magnetic resonance (NMR) chemical shift imaging (CSI). For the effective and sensitive detection of NMR signals from the brain, outer volume suppression (OVS), reduced k-space sampling and proton irradiation were incorporated into the CSI sequences. The consecutive three measurements of calculated T2 image, lactate image, and pH image which were required for 3.75 h were repeated for four cycles of 1–16 h after MCA occlusion. Tissue edema and lactate accumulation in the infarcted region were gradually and consistently increased during the 15-h observation period. In contrast, severe acidosis was already detected on the first pH image (2–4.7 h after MCA occlusion); thereafter, the degree of acidosis became milder and showed no further progression. The dissociation between the time courses of the lactate accumulation and pH decrease was clearly demonstrated by the NMR metabolic images. Acid-base balance in cerebral infarction might be affected not only by lactate production but also by complicated interactions with tissue edema and some other factors. 相似文献
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Yuko Kamikawa Takashi Kato Hisanari Onouchi Daisuke Kashiwagi Katsuhiro Maeda Eiji Yashima 《Journal of polymer science. Part A, Polymer chemistry》2004,42(18):4580-4586
A series of optically active dendrons with a primary amino group at the terminal were prepared from L - or D -glutamic acid, and their helicity induction abilities for a poly(phenylacetylene) bearing a phosphonate pendant were characterized with ultraviolet–visible and circular dichroism spectroscopy. The magnitude of the Cotton effects of the polymer induced by the dendrons significantly increased upon complexation with a higher generation dendron. The effect of the chirality of the glutamate residues (L and D ) on the helicity induction was also studied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4580–4586, 2004 相似文献
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Onouchi H Okoshi K Kajitani T Sakurai S Nagai K Kumaki J Onitsuka K Yashima E 《Journal of the American Chemical Society》2008,130(1):229-236
Rodlike polymers with precisely defined architectures are ideal building blocks for self-assembled structures leading to novel nanometer-scale devices. We found that the living polymerization of a single isocyanide enantiomer bearing an l-alanine pendant with a long n-decyl chain simultaneously produced diastereomeric right- and left-handed helices with different molecular weights and narrow molecular weight distributions. Each single-handed, rodlike helical polymer with a controlled length and handedness isolated by a facile solvent fractionation method with acetone self-assembled to form well-defined two- and three-dimensional smectic ordering on the nanometer scale on a substrate and in a liquid crystalline state as evidenced by direct atomic force microscopic observations and X-ray diffraction measurements, respectively. 相似文献
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Bio‐Based Polyketones by Selective Ring‐Opening Radical Polymerization of α‐Pinene‐Derived Pinocarvone 下载免费PDF全文
Hisanari Miyaji Prof. Dr. Kotaro Satoh Prof. Dr. Masami Kamigaito 《Angewandte Chemie (International ed. in English)》2016,55(4):1372-1376
The most abundant naturally occurring terpene, α‐pinene, which cannot be directly polymerized into high polymers by any polymerization method, was quantitatively converted under visible‐light irradiation into pinocarvone, which possesses a reactive exo methylene group. The bicyclic vinyl ketone was quantitatively polymerized in fluoroalcohols by selective (99 %) ring‐opening radical polymerization of the four‐membered ring, which results in unique polymers containing chiral six‐membered rings with conjugated ketone units in the main chain. These polymers display good thermal properties, optical activities, and contain reactive conjugated ketone units. Reversible addition fragmentation chain transfer (RAFT) polymerization was successfully accomplished by using appropriate trithiocarbonate RAFT agents, enabling the synthesis of thermoplastic elastomers based on controlled macromolecular architectures. 相似文献
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Hisanari Onouchi Takashi Hasegawa Daisuke Kashiwagi Hiroyuki Ishiguro Katsuhiro Maeda Eiji Yashima 《Journal of polymer science. Part A, Polymer chemistry》2006,44(17):5039-5048
Stereoregular, cis–transoidal poly(phenylacetylene)s bearing strongly acidic functional groups as pendants, such as a phosphonic acid and its monoethyl ester and a sulfonic acid, were found to interact with various biomolecules such as peptides, proteins, amino sugars, and carbohydrates in water, and the complexes exhibited characteristic induced circular dichroisms in the ultraviolet–visible region of the polymer backbones, which resulted from the formation of predominantly one-handed helical conformations. On the other hand, the sodium salt of poly[(4-carboxyphenyl)acetylene], bearing a weak acidic carboxy group, showed induced circular dichroisms only in the presence of carbohydrates and some positively charged proteins. The sensitivity of the polymers to the chirality of various biomolecules was also investigated with circular dichroism spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5039–5048, 2006 相似文献
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Miyagawa T Yamamoto M Muraki R Onouchi H Yashima E 《Journal of the American Chemical Society》2007,129(12):3676-3682
A water-soluble amphiphilic poly(phenylacetylene) bearing the bulky aza-18-crown-6-ether pendants forms a one-handed helix induced by l- or d-amino acids and chiral amino alcohols through specific host-guest interactions in water. We now report that such an induced helical poly(phenylacetylene) with a controlled helix sense can selectively trap an achiral benzoxazole cyanine dye among various structurally similar cyanine dyes within its hydrophobic helical cavity inside the polymer in acidic water, resulting in the formation of supramolecular helical aggregates, which exhibit an induced circular dichroism (ICD) in the cyanine dye chromophore region. The supramolecular chirality induced in the cyanine aggregates could be further memorized when the template helical polymer lost its optical activity and further inverted into the opposite helicity. Thereafter, thermal racemization of the helical aggregates slowly took place. 相似文献
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Hideki Hayashi Masanobu Maeda Taiki Naruo Yukio Onouchi Masaki Harada Yuzo Ishigaki 《International Journal of Polymer Analysis and Characterization》2017,22(8):725-733
The effects of adding imipramine-containing polymer (PImip-Fl) in two kinds of polyester/lysine triisocyanate (LTI) blends were investigated. PImip-Fl was prepared by Suzuki–Miyaura coupling reaction of dibromoimipramine hydrochloride and dioctylfluorene diboronic acid. The addition of PImip-Fl gave fluorescence to resins [poly(lactic acid) (PLA) and poly(ε-caprolactone) (PCL)], and its fluorescent maximum wavelength (λmax) depended on the resin. PImip-Fl was used as a functional additive for the estimation of compatibility of PLA/PCL blend composite. The addition of LTI to the resins/PImip-Fl blend composites afforded a shorter wavelength shift of the fluorescent λmax. This suggested that the method using PImip-Fl is adaptive for the estimation of compatibility of the blend composite. 相似文献