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91.
Rational Design for Rotaxane Synthesis through Intramolecular Slippage: Control of Activation Energy by Rigid Axle Length
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Hiroshi Masai Dr. Jun Terao Dr. Tetsuaki Fujihara Dr. Yasushi Tsuji 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(19):6624-6630
We describe a new concept for rotaxane synthesis through intramolecular slippage using π‐conjugated molecules as rigid axles linked with organic soluble and flexible permethylated α‐cyclodextrins (PM α‐CDs) as macrocycles. Through hydrophilic–hydrophobic interactions and flipping of PM α‐CDs, successful quantitative conversion into rotaxanes was achieved without covalent bond formation. The rotaxanes had high activation barrier for their de‐threading, so that they were kinetically isolated and derivatized even under conditions unfavorable for maintaining the rotaxane structures. 1H NMR spectroscopy experiments clearly revealed that the restricted motion of the linked macrocycle with the rigid axle made it possible to control the kinetic stability by adjusting the length of the rigid axle in the precursor structure rather than the steric bulkiness of the stopper unit. 相似文献
92.
Dr. Jinying Zhang Zhen Zhu Prof. Dr. Yanquan Feng Hitoshi Ishiwata Dr. Yasumitsu Miyata Dr. Ryo Kitaura Dr. Jeremy E. P. Dahl Prof. Dr. Robert M. K. Carlson Dr. Natalie A. Fokina Prof. Dr. Peter R. Schreiner Prof. Dr. David Tománek Prof. Dr. Hisanori Shinohara 《Angewandte Chemie (International ed. in English)》2013,52(13):3536-3536
93.
Ishibashi Chiaki Ichiyama Mai Ishida Naoya Kitamura Naoto Idemoto Yasushi 《Journal of Solid State Electrochemistry》2022,26(3):663-682
Journal of Solid State Electrochemistry - The stable structures associated with the second charge of MgCo2−xMnxO4 (x = 0, 0.5), where Mg is removed from the stable first-discharge... 相似文献
94.
A. Matsekh M. Inoue T. Kiss A. Ibi S. Miyata Y. Yamada T. Izumi 《Physica C: Superconductivity and its Applications》2010,470(20):1288-1291
Recent process optimization allows improving homogeneity and a significant increase of Jc in GdBa2Cu3O7-δ deposited on ion-beam assisted deposited MgO template (GdBCO/IBAD-MgO). We applied low-temperature laser scanning microscopy and laser scanning thermo-electric microscopy (LSTEM) to investigate local dissipation and defects simultaneously in recent GdBCO/IBAD-MgO coated conductor. By using high-resolution LSTEM, we could detect current blocking obstacles which are responsible for the large scale local dissipation. Data on the present GdBCO/IBAD-MgO coated conductors point out a significant reduction of current blocking obstacles compared to the previous process. We have shown the improvement of spatial homogeneity in the recent GdBCO/IBAD-MgO coated conductors. Current blocking obstacles are much less densely distributed as compared to previous YBCO/IBAD-GZO coated conductor. Obstacles larger than several micrometer significantly increase local dissipation whereas smaller defects do not influence it noticeably. 2D map of the phase delay component of the thermoelectric voltage lock-in signal is effective to analyze current blocking obstacles having action upon local dissipation. 相似文献
95.
In recent years the so-called biomimetic chemistry has received much attention. Studies of the preparation and design of functional polymers which can serve as polymeric enzyme and nucleic acid models appear to be a particularly rapidly expanding areas of research. These polymers and their aggregates should require highly specific sites or, in other words, atmospheres around them, in order to facilitate a series of selective reactions under conditions similar to those of biochemical environments. In this connection, molecular design of certain three-dimensional, highly organized spaces which consist of various sorts of molecular aggregates and can incorporate definite molecules in a specified way within their space are of interest for performing controlled organic and polymer synthetic reactions. 相似文献
96.
Sulfonylurea derivatives including useful antidiabetics (Tolbutamide, Chlorpropamide) were synthesized in good yields from benzene-sulfonamides with thiocarbamates in the presence of DBU. Thiocarbamates were prepared by the selenium-assisted carbonylation of primary amines with carbon monoxide, sulfur, and methyl iodide under mild conditions. 相似文献
97.
Hemin was physically adsorbed onto porous carbon felt (CF), a microelectrode ensemble of micro-carbon fiber (ca. 7 μm in diameter) and possessing a three-dimensional random structure. The hemin-CF exhibited a well-defined redox wave that is due to Fe(III)/Fe(II) redox process in hemin, with a formal potential of ?0.32 V (vs. Ag/AgCl) in deoxygenated buffer solution of pH 7.0. The surface coverage of the electroactive hemin molecules on the surface of the CF was calculated to be 5.0?×?10?11 mol cm?2, and the apparent heterogeneous electron transfer rate constant is 3.35 s?1. The hemin-CF electrode displays excellent electrocatalytic activity for the reduction of dissolved oxygen (DO), and the magnitude of the cathodic current increases with increasing concentrations of DO in the sample solution. The electrode was used as a flow-through detector for sensitive and rapid consecutive determination of DO. Deoxygenated pH 7.0 solutions were analyzed at a flow rate of 8.0 mL min?1 at an applied potential of ?0.2 V, and highly reproducible cathodic peak current responses to DO were observed in the 0.72 to 13.3 mg L?1 concentration range. The maximum throughput is 170 samples h?1. The hemin-CF-based amperometric flow-sensor was applied to determine the concentration of DO in environmental water samples. Graphical abstract
Hemin was physically adsorbed onto porous carbon felt (CF), a microelectrode ensemble of micro-carbon fiber (ca. 7 μm in diameter). The hemin-CF electrode was used as a flow-through detector for highly sensitive and rapid determination of dissolved oxygen. 相似文献
98.
Takashi Kitayama Maki Nakahira Kae Yamasaki Hiromi Inoue Chika Imada Yuji Yonekura Masataka Awata Hikaru Takaya Yasushi Kawai Kohta Ohnishi Akira Murakami 《Tetrahedron》2013
Zerumbone 1, having powerful latent reactivity and containing two conjugated double bonds and a double conjugated carbonyl group is the major component of the essential oil of wild ginger, Zingiber zerumbet Smith. The conjugation system plays an important role in the expression of biological activity. N-Bromosuccinimide (NBS) reaction of 1 gave high reactive intermediate 2 with an exo-methylene group, which was obtained from 1 quantitatively. Treatment of 2 with nucleophiles gave various zerumbone-pendant derivatives, including C–H, C–O, C–N, and C–C bond formation, maintaining the conjugation system through SN2′-type reaction. Almost all zerumbone-pendant derivatives showed a good value of IC50 against the suppressive effect of NO generation. Among them, amine derivative 5, binding with 2 mol of zerumbone, showed the strongest activity (IC50: 0.24 μM). 相似文献
99.
Yasushi Imada Takahiro Kitagawa Han-Kun Wang Naruyoshi Komiya Takeshi Naota 《Tetrahedron letters》2013,54(7):621-624
An aerobic, organocatalytic, and aqueous method for the oxidation of sulfides is described. Synthetic flavin, 5-ethyl-3,7,8,10-tetramethylisoalloxazinium perchlorate, acts as an efficient catalyst for the oxidation of sulfides in water under an oxygen atmosphere (1 atm) with the assistance of ascorbic acid as a reductant. This is an inexpensive, convenient, and environmentally benign method for the selective oxidative transformation of sulfides into sulfoxides. 相似文献
100.
Atsumu Abe Soichi Furukawa Shinya Watanabe Yasushi Morinaga 《Applied biochemistry and biotechnology》2013,171(1):72-79
We previously found that some Saccharomyces cerevisiae and Lactobacillus plantarum remarkably formed mixed-specie biofilm in a static co-culture and deduced that this biofilm had potential as immobilized cells. We investigated the application of mixed-specie biofilm formed by S. cerevisiae BY4741 and L. plantarum HM23 for ethanol fermentation in repeated batch cultures. This mixed-specie biofilm was far abundantly formed and far resistant to washing compared with S. cerevisiae single biofilm. Adopting mixed-specie biofilm formed on cellulose beads as immobilized cells, we could produce enough ethanol from 10 or 20 % glucose during ten times repeated batch cultures for a duration of 10 days. Cell numbers of S. cerevisiae and L. plantarum during this period were stable. In mixed-specie biofilm system, though ethanol production was slightly lower compared to S. cerevisiae single-culture system due to by-production of lactate, pH was stably maintained under pH 4 without artificial control suggesting high resistance to contamination. Inoculated model contaminants, Escherichia coli and Bacillus subtilis, were excluded from the system in a short time. From the above results, it was indicated that the mixed-specie biofilm of S. cerevisiae and L. plantarum was a promising immobilized cell for ethanol fermentation for its ethanol productivity and robustness due to high resistance to contamination. 相似文献