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11.
Kakiuchi K Okada H Kanehisa N Kai Y Kurosawa H 《The Journal of organic chemistry》1996,61(9):2972-2979
Acid-catalyzed rearrangement of 5-cyclopentylidenecyclooctanone derivatives 9a-c was examined to obtain polyspiropolyquinanes 11a-c, considered to have a unique helical structure, through cascade rearrangement pathways consisting of continuous transannular cyclization followed by successive 1,2-alkyl shifts. The substrates were prepared easily by use of the Wittig or McMurry reaction. Reaction of the 5-cyclopentylidenecyclooctanone (9a) with acid gave the expected dispirotriquinane ketone 11a in high yield. The precise mechanism was elucidated by a deuterium-labeling experiment. In the case of the ketone 9b, having another spiroannulated cyclopentane ring attached on 9a, the trispirotetraquiane 11b was not obtained but the bis-propellane-type tetrahydrofuran 25 was produced exclusively. The 5-(5'-cyclopentylidenecyclooctylidene)cyclooctanone (9c) afforded the polycyclic compounds 27-31, depending on the acid used, instead of the desired tetraspiropentaquinane 11c. The structures of the products were determined by NMR spectral data including 2D (13)C INADEQUATE spectra and X-ray crystallographic analyses. The unexpected rearrangement pathways are also discussed. 相似文献
12.
Oscillating frequencies of a piezoelectric crystal were measured in various solutions. One side of the crystal surface was coated with a silicon sealant. This coating was useful for measuring the oscillation of crystals in solutions for a wide range of products of density (?) and viscosity (η) and in electrolyte solutions. For measurement in solutions, the frequency change depended on the circuit used, whereas for measurements in air the circuit did not influence the frequency change. All experimental data showed that the frequency change from pure water, ΔFw, followed ΔFw = ? K(√?η ? √?wηw) except for electrolyte and polymer solutions, where K is a proportionality constant, ηw the density of pure water and ηw the viscosity of water. 相似文献
13.
Yoshio Iwakura Keikichi Uno Shigeyoshi Hara Shigeru Kurosawa 《Journal of polymer science. Part A, Polymer chemistry》1968,6(12):3381-3393
A new ring-opening reaction of 1,3,4-oxadiazole by methylating reagents was developed in fuming sulfuric acid or polyphosphoric acid and then, by applying this reaction to poly-p-phenylene-1,3,4-oxadiazole, a high molecular weight poly-N-methylterephthalylhydrazide was obtained. Various methylating reagents were investigated as ring-opening reagents. The degrees of ring-opening in polymers were estimated and related to the properties of the polymers. 相似文献
14.
A quartz crystal microbalance (QCM) immunosensor was developed for the detection of 2,3,7,8-tetrachlorodibenzo-p-dioxins (TCDD) in environmental pollutants. An anti-TCDD antibody was immobilized on the gold surface of the QCM via chemical coupling, and its immunologic activity was then maintained by treatment with an artificial stabilizing reagent such as poly(2-methacryloyloxyethyl phosphorylcholine-co-n-butyl methacrylate). A competitive immunoreaction with TCDD conjugated ovalbumin (TCDD-ovalbumin) was used to detect TCDD. A calibration curve was obtained through the competitive immunoreaction, and linearity was shown from 100 ng mL(-1) to 0.1 ng mL(-1). Also, the cross-reactivities of the anti-TCDD monoclonal antibody were thoroughly evaluated with several TCDD derivatives. The relationships between GC-MS, ELISA, and QCM were compared using fly ash samples from a municipal solid waste, which were prepared using an accelerated solvent extractor. For 23 samples, the experimental relationship between the TCDD concentration by QCM vs. the TCDD concentration by ELISA was y= 1.07x + 2.70, r= 0.99, and the TCDD concentration by QCM vs. the toxic equivalent quantity (TEQ) value by GC-MS was y= 2.46x - 14.98, r= 0.89. 相似文献
15.
The total synthesis and an unambiguous structure confirmation of stevastelin B 1, a novel 15-membered cyclic depsipeptide, are described; the fatty acid moiety in 1, prepared stereoselectively from L-quebrachitol was converted into the amino carboxylic acid, whose macrolactamization by Shioiri's procedure effectively constructed the cyclic structure of 1. 相似文献
16.
Jun-Ichiro Makiura Takuma Higo Yutaro Kurosawa Kota Murakami Shuhei Ogo Hideaki Tsuneki Yasushi Hashimoto Yasushi Sato Yasushi Sekine 《Chemical science》2021,12(6):2108
Efficient activation of CO2 at low temperature was achieved by reverse water–gas shift via chemical looping (RWGS-CL) by virtue of fast oxygen ion migration in a Cu–In structured oxide, even at lower temperatures. Results show that a novel Cu–In2O3 structured oxide can show a remarkably higher CO2 splitting rate than ever reported. Various analyses revealed that RWGS-CL on Cu–In2O3 is derived from redox between Cu–In2O3 and Cu–In alloy. Key factors for high CO2 splitting rate were fast migration of oxide ions in the alloy and the preferential oxidation of the interface of alloy–In2O3 in the bulk of the particles. The findings reported herein can open up new avenues to achieve effective CO2 conversion at lower temperatures.Efficient activation of CO2 at low temperature was achieved by reverse water–gas shift via chemical looping (RWGS-CL) by virtue of fast oxygen ion migration in a Cu–In structured oxide, even at lower temperatures. 相似文献
17.
18.
Tadanori Kurosawa An-Dih Yu Tomoya Higashihara Wen-Chang Chen Mitsuru Ueda 《European Polymer Journal》2013
Two polyimides, PI(DAT-6FDA) and PI(DAPT-6FDA), from N-(2,4-diaminophenyl)-N,N-diphenylamine (DAT) or N-(4-(2′,4′-diaminophenoxy)phenyl-N,N-diphenylamine (DAPT) and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) were prepared to clarify the structural effect on the resulting memory properties. The memory device based on PI(DAT-6FDA) showed an unstable volatile behavior, while the device based on PI(DAPT-6FDA) with a more bulky donor (D) unit exhibited a stable non-volatile FLASH type memory characteristic with a long retention time over 104 s. The theoretical simulation based on the density functional theory (DFT) suggested that the greater distinct charge separation between the ground and charge transfer (CT) states led to a highly stable memory behavior. Also, it was clarified that PI(DAPT-6FDA) had a highly twisted conformation compared to PI(DAT-6FDA) in the ground state, and a more twisted dihedral angle between the D and acceptor (A) units was induced in the CT state, which led to the non-volatile memory characteristic. 相似文献
19.
20.
Self‐Replication and Amplification of Enantiomeric Excess of Chiral Multifunctionalized Large Molecules by Asymmetric Autocatalysis
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Prof. Dr. Tsuneomi Kawasaki Mai Nakaoda Yutaro Takahashi Yusuke Kanto Nanako Kuruhara Kenji Hosoi Prof. Dr. Itaru Sato Arimasa Matsumoto Prof. Dr. Kenso Soai 《Angewandte Chemie (International ed. in English)》2014,53(42):11199-11202
Self‐replication of large chiral molecular architectures is one of the great challenges and interests in synthetic, systems, and prebiotic chemistry. Described herein is a new chemical system in which large chiral multifunctionalized molecules possess asymmetric autocatalytic self‐replicating and self‐improving abilities, that is, improvement of their enantioenrichment in addition to the diastereomeric ratio. The large chiral multifunctionalized molecules catalyze the production of themselves with the same structure, including the chirality of newly formed asymmetric carbon atoms, in the reaction of the corresponding achiral aldehydes and reagent. The chirality of the large multifunctionalized molecules controlled the enantioselectivity of the reaction in a highly selective manner to construct multiple asymmetric stereogenic centers in a single reaction. 相似文献