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131.
Shinji Suzuki Furitsu Suzuki Yasumasa Kanie Koji Tsujitani Asako Hirai Hironori Kaji Fumitaka Horii 《Cellulose (London, England)》2012,19(3):713-727
The structure and crystallization of carefully isolated sub-elementary fibrils (SEFs) of bacterial cellulose have been investigated
using TEM, WAXD, and high-resolution solid-state 13C NMR. The addition of a suitable amount of fluorescent brightener (FB) to the incubation medium of Acetobacter xylinum effectively suppressed the aggregation of the SEFs into the microfibrils, as previously reported. However, this study confirmed
for the first time that serious structural change in the SEFs occurs during the removal of excess FB by washing with buffer
solutions having pH values higher than 6 or with the alkaline aqueous solution that was frequently used in previous studies.
In contrast, the isolation of unmodified SEFs was successfully performed by utilizing a washing protocol employing pH 7 citrate–phosphate
buffer solution containing 1% sodium dodecyl sulfate. High-resolution solid-state 13C NMR and WAXD measurements revealed that the SEFs thus isolated are in the noncrystalline state in which the pyranose rings
of the almost parallel cellulose chains appear to be stacked on each other. The respective CH2OH groups of the SEFs adopt the gt conformation instead of the tg conformation found in cellulose I
α
and I
β
crystals, and undergo significantly enhanced molecular motion in the absence of intermolecular hydrogen bonding associated
with these groups. The main chains are also subject to rapid motional fluctuations while maintaining the parallel orientation
of the respective chains, indicating that the SEFs have a liquid crystal-like structure with high molecular mobility. Moreover,
the SEFs crystallize into cellulose I
β
when the FB molecules that may adhere to the surface of the SEFs are removed by extraction with boiling 70 v/v% ethanol and
0.1N NaOH aqueous solution. On the basis of these results, the crystallization of the SEFs into the I
α
and I
β
forms is discussed, including the possible formation of the crystalline-noncrystalline periodic structure in native cellulose. 相似文献
132.
Hiroshi Sakai Takashi Yamazaki Nobuya Machida Toshihiko Shigematsu Saburo Nasu 《Molecular Crystals and Liquid Crystals》2013,570(2):105-110
Abstract Mössbauer spectra of the FePS3-cobaltocene intercalation compound were measured in the temperature range of 300K to 10K. The spectra, distinct from those of pure FePS3, suggest the charge transfer from cobaltocene to Fe-S antibonding orbitals of the FePS3 host lattice. 相似文献
133.
Hideki Misaka Eisuke Tamura Kosuke Makiguchi Kensuke Kamoshida Ryosuke Sakai Toshifumi Satoh Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2012,50(10):1941-1952
For the living ring‐opening polymerization (ROP) of epoxy monomers, the catalytic activity of organic superbases, tert‐butylimino‐tris(dimethylamino)phosphorane, 1‐tert‐butyl‐2,2,4,4,4‐pentakis(dimethylamino)‐2Λ5,4Λ5‐catenadi(phosphazene), 2,8,9‐triisobutyl‐2,5,8,9‐tetraaza‐1‐phosphabicyclo[3.3.3]undecane, and 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris(dimethylamino)phosphoranylidenamino]‐2Λ5,4Λ5‐catenadi(phosphazene) (t‐Bu‐P4), was confirmed. Among these superbases, only t‐Bu‐P4 showed catalytic activity for the ROP of 1,2‐butylene oxide (BO) to afford poly(1,2‐butylene oxide) (PBO) with predicted molecular weight and narrow molecular weight distribution. The results of the kinetic, post‐polymerization experiments, and MALDI‐TOF MS measurement revealed that the t‐Bu‐P4‐catalyzed ROP of BO proceeded in a living manner in which the alcohol acted as the initiator. This alcohol/t‐Bu‐P4 system was applicable to the glycidol derivatives, such as benzyl glycidyl ether (BnGE) and t‐butyl glycidyl ether, to afford well‐defined protected polyglycidols. The α‐functionalized polyethers could be obtained using different functionalized initiators, such as 4‐vinylbenzyl alcohol, 5‐hexen‐1‐ol, and 6‐azide‐1‐hexanol. In addition, the well‐defined cyclic‐PBO and PBnGE were successfully synthesized using the combination of t‐Bu‐P4‐catalyzed ROP and click cyclization. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
134.
Kei Fujise Dr. Eiji Tsurumaki Prof. Dr. Kan Wakamatsu Prof. Dr. Shinji Toyota 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(14):4548-4552
Polycyclic aromatic compounds consisting of four or five fused anthracene units were synthesized by PtCl2-catalyzed cycloisomerization as novel long expanded helicenes. These compounds have helical structures with significant stacking of the terminal anthracene moieties at 0.33 nm interlayer distance. In the UV-vis and fluorescence spectra, the absorption and emission bands were red-shifted as the number of fused anthracene units was increased. The characteristic broad and long-lived emission bands of the long analogues are explained by the excimer-like stabilization of the excited state. These photophysical data as well as their cyclic voltammetric data are discussed on the basis of the π-conjugation and interlayer π⋅⋅⋅π interactions in the molecular structures and the molecular orbitals. The barrier and mechanism of helical inversion are also reported. 相似文献
135.
136.
Akira Mori Hitoshi Takeshita Ryoji Mori Shinji Takematsu Manabu Takemoto Seiji Ujiie 《Liquid crystals》2013,40(2):171-178
Two kinds of monocyclic troponoid mesogens, 2,5-dialkanoyloxytropones (4) and 5-alkanoyloxy2-alkoxytropones (5), were prepared. The former showed monotropic smectic A phases and the virtual isotropic liquid-smectic A transitions of the latter were determined by extrapolation of results in a binary phase diagram. Comparing the mesogenic properties between the tropones 4 and the 2-alkanoyloxy-5-alkoxytropones (1), the alkanoyloxy group at C-5 enhances both the melting points and the transition temperatures of the smectic A phases. From the comparison between 5 and 1, the alkanoyloxy group at C-2 lowers the melting points. 相似文献
137.
138.
V. V. Kaminskii Toshihiro Kuzuya Shinji Hirai S. M. Solov’ev N. V. Sharenkova M. M. Kazanin 《Physics of the Solid State》2012,54(7):1345-1347
The electrical conductivity of SmS polycrystals has been studied in the temperature range 300?C870 K. It has been shown that, at 300 K ?? T ?? 700 K, the concentration of conduction electrons is determined by electron transfer from impurity donor levels, and at T > 700 K, by that from the samarium 4f levels. 相似文献
139.
Shinji Ejiri Sinya Aoki Tetsuo Hatsuda Kazuyuki Kanaya Yoshiyuki Nakagawa Hiroshi Ohno Hana Saito Takashi Umeda 《Central European Journal of Physics》2012,10(6):1322-1325
We study the QCD phase structure at high temperature and density adopting a histogram method. Because the quark determinant is complex at finite density, the Monte-Carlo method cannot be applied directly. We use a reweighting method and try to solve the problems which arise in the reweighting method, i.e. the sign problem and the overlap problem. We discuss the chemical potential dependence of the probability distribution function in the heavy quark mass region and examine the applicability of the approach in the light quark region. 相似文献
140.
Yoko M. NAKAO Takashi MIYAWAKI Shinji YASUNO Kazuhiro NAKAO Sachiko TANAKA Midori IDA Masakazu HIRATA Masato KASAHARA Kiminori HOSODA Kenji UESHIMA Kazuwa NAKAO 《Proceedings of the Japan Academy. Series B, Physical and biological sciences》2012,88(8):454-461
Objective: To investigate the significance of intra-abdominal fat area (IAFA) on new onset of individual components of the metabolic syndrome: high blood pressure, dyslipidemia, or hyperglycemia. Methods: We conducted a longitudinal study using checkup data of a hospital from 1994 to 2010. Of 25,255 subjects, we examined 1,380 Japanese, who underwent computed tomography to measure IAFA and had no metabolic syndrome components at baseline. Results: During 3.6 years of the mean follow-up period, one of metabolic syndrome components occurred in 752 subjects. Of three components, high blood pressure was more prevalent. The multiple Cox regression analysis disclosed that IAFA is significantly associated with onset of metabolic syndrome components (HR: 1.05 per 10 cm2, 95%CI: 1.03–1.07). This finding was independent of BMI, and significant even in non-obese individuals with body mass index <25 kg/m2. Conclusions: MERLOT study demonstrates that IAFA is an independent predictor for new onset of individual components of the metabolic syndrome, even in non-obese healthy Japanese. 相似文献