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41.
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
42.
A great number of studies of polyelectrolyte complexes have been carried out by various investigators; most of them concentrated on the reaction between oppositely charged polyelectrolytes [1-3]. The structure and properties of the resultant complexes have been investigated to a lesser extent, and the understanding of this new class of polymer materials is still insufficient. Thus, we have been investigating the sorption of water vapor by the complexes and the morphological changes caused by this sorption [4,5]. 相似文献
43.
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
44.
45.
46.
Dr. Yusaku Nomura Dr. Frédéric Thuaud Dr. Daisuke Sekine Prof. Dr. Akihiro Ito Satoko Maeda Dr. Hiroyuki Koshino Dr. Daisuke Hashizume Dr. Atsuya Muranaka Dr. Thomas Cruchter Prof. Dr. Masanobu Uchiyama Prof. Dr. Satoshi Ichikawa Prof. Dr. Akira Matsuda Prof. Dr. Minoru Yoshida Prof. Dr. Go Hirai Prof. Dr. Mikiko Sodeoka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8387-8392
A synthetic methodology to access all possible stereoisomers of spectomycin A1 (SMA1) and A2 (SMA2) has been established through late-stage diversification. The key reaction for the construction of all four diastereomers is an intramolecular cyclization based on the umpolung of π-allyl palladium species with bis(pinacolato)diborane (B2(pin)2). Silyl group assisted direct benzylic oxidation of each isomer enabled construction of the fragile β-hydroxytetralone skeleton to provide the SMAs. The relative and absolute stereochemistry of SMA2 was also determined, and the absolute stereochemistry of SMA1 was extrapolated based on the optical rotation of SMA2. The axial chirality of SMAs is discussed based on circular dichroism spectra and DFT calculations, and it is concluded that the M isomer is predominant in solution. Biochemical assessment of all isomers in vitro revealed that the C9 hydroxyl group and dimeric structure were both important for protein SUMOylation-inhibitory activity. 相似文献
47.
Hong Xia Yoshio Hashimoto Toru Morita Toshihiro Hirai 《Journal of Polymer Science.Polymer Physics》2014,52(13):887-892
Few solvents are capable of dissolving polyketones (PKs). 1,1,1,3,3,3‐Hexafluoro‐2‐propanol (hexafluoroisopropanol, HFIP) is a better solvent than trifluoroethanol and m‐cresol. When HFIP was evaporated from a PK/HFIP solution, a porous cast‐film with a microparticle structure was formed because the isotactic PKs adopted a helical conformation, and convection during evaporation of the high polarity and low‐boiling‐point HFIP caused aggregation and rolling of the polymer molecules. The addition of plasticizer suppressed particle formation, improving the surface structure and mechanical properties of the film. In particular, the dielectric properties of the film improved significantly. This will enable PKs, which are rigid insulating materials, to be used as dielectric materials, broadening their range of applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 887–892 相似文献
48.
Mostafa Abdelrahman Sho Hirata Takuya Mukae Tomohiro Yamada Yuji Sawada Magdi El-Syaed Yutaka Yamada Muneo Sato Masami Yokota Hirai Masayoshi Shigyo 《Molecules (Basel, Switzerland)》2021,26(5)
Garlic (Allium sativum) is the second most important Allium crop that has been used as a vegetable and condiment from ancient times due to its characteristic flavor and taste. Although garlic is a sterile plant that reproduces vegetatively through cloves, garlic shows high biodiversity, as well as phenotypic plasticity and environmental adaptation capacity. To determine the possible mechanism underlying this phenomenon and to provide new genetic materials for the development of a novel garlic cultivar with useful agronomic traits, the metabolic profiles in the leaf tissue of 30 garlic accessions collected from different geographical regions, with a special focus on the Asian region, were investigated using LC/MS. In addition, the total saponin and fructan contents in the roots and cloves of the investigated garlic accessions were also evaluated. Total saponin and fructan contents did not separate the garlic accessions based on their geographical origin, implying that saponin and fructan contents were clone-specific and agroclimatic changes have affected the quantitative and qualitative levels of saponins in garlic over a long history of cultivation. Principal component analysis (PCA) and dendrogram clustering of the LC/MS-based metabolite profiling showed two major clusters. Specifically, many Japanese and Central Asia accessions were grouped in cluster I and showed high accumulations of flavonol glucosides, alliin, and methiin. On the other hand, garlic accessions grouped in cluster II exhibited a high accumulation of anthocyanin glucosides and amino acids. Although most of the accessions were not separated based on country of origin, the Central Asia accessions were clustered in one group, implying that these accessions exhibited distinct metabolic profiles. The present study provides useful information that can be used for germplasm selection and the development of new garlic varieties with beneficial biotic and abiotic stress-adaptive traits. 相似文献
49.
Nobuyuki Otozawa Rio Hamajima Masataka Yoshioka Raito Kato Arisa Tanaka Hiroto Fukuma Toshiki Terao Kei Manabe Syuji Fujii Yoshinobu Nakamura Atsushi Takahara Tomoyasu Hirai 《Journal of polymer science. Part A, Polymer chemistry》2020,58(14):1960-1964
This study investigates the effect of ionic liquids (ILs) on the anionic polymerization of methyl methacrylate (MMA). Polymethyl methacrylate (PMMA), an isotactic polymer, is prepared by anionic polymerization at a high reaction temperature with an IL that acts as both solvent and additive. The most plausible reaction mechanism is determined using 1H NMR and Fourier-transform infrared spectroscopy. The electrostatic interaction between MMA and the IL increases the apparent steric hindrance in MMA, resulting in the isotactic PMMA. 相似文献
50.
Order - A modular semilattice is a semilattice generalization of a modular lattice. We establish a Birkhoff-type representation theorem for modular semilattices, which says that every modular... 相似文献