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31.
Taichi Nakano Takashi Miyamoto Takanori Endoh Makoto Shimotani Naoki Ashida Toshishige Morioka Yutaka Takahashi 《应用有机金属化学》2004,18(2):65-67
The palladium‐catalyzed silastannation of acetylenes with tributyl(trimethylsilyl)stannane in the presence of triethylphosphite is reported for the first time. The reaction occurs at room temperature to give (Z)‐silyl(stannyl)ethenes in high yields. The protodemetallation of the resulting adducts with HCl–tetraethylammonium chloride is described first, which demonstrates that the reaction is governed only by the stability of a carbonium ion arising from the protonation to (Z)‐silyl(stannyl)ethenes rather than the hard and soft acid and base principle, i.e. the β‐cation stabilization effect (σ–π stabilization one) of a stannyl group in the carbonium ion is rather significant. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
32.
33.
T. Inui 《Reaction Kinetics and Catalysis Letters》1987,35(1-2):227-236
Conversion of light olefins to gasoline was investigated for various metallosilicates having the pentasil pore-opening structure. The metallosilicate was prepared by replacing the Al ingredient of the H-ZSM-5 with various metal salt at the stage of gel formation. Among various metallosilicates H–Fe-silicate was most effective and stable for the selective formation of high octane-number gasoline. The causes of this high catalytic performance was attributed to its proper acid strength and low diffusion resistance. 相似文献
34.
Versatile In Situ Generated N‐Boc‐Imines: Application to Phase‐Transfer‐Catalyzed Asymmetric Mannich‐Type Reactions
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Dr. Taichi Kano Ryohei Kobayashi Prof. Keiji Maruoka 《Angewandte Chemie (International ed. in English)》2015,54(29):8471-8474
The efficient construction of nitrogen‐containing organic compounds is a major challenge in chemical synthesis. Imines are one of the most important classes of electrophiles for this transformation. However, both the available imines and applicable nucleophiles for them are quite limited given the existing preparative methods. Described herein are imine precursors which generate reactive imines with a wide variety of substituents under mild basic conditions. This approach enables the construction of various nitrogen‐containing molecules which cannot be accessed by the traditional approach. The utility of the novel imine precursor was demonstrated in the asymmetric Mannich‐type reaction under phase‐transfer conditions. 相似文献
35.
Yoshikazu Giga Katsuya Inui Alex Mahalov Shin’ya Matsui Jürgen Saal 《Archive for Rational Mechanics and Analysis》2007,186(2):177-224
We prove time local existence and uniqueness of solutions to a boundary layer problem in a rotating frame around the stationary
solution called the Ekman spiral. We choose initial data in the vector-valued homogeneous Besov space for 2 < p < ∞. Here the L
p
-integrability is imposed in the normal direction, while we may have no decay in tangential components, since the Besov space
contains nondecaying functions such as almost periodic functions. A crucial ingredient is theory for vector-valued homogeneous
Besov spaces. For instance we provide and apply an operator-valued bounded H
∞-calculus for the Laplacian in for a general Banach space . 相似文献
36.
The electrochromic properties of a polythiophene polyrotaxane film consisting of a polythiophene backbone wrapped by the tetra-cationic cyclophane, cyclobis(paraquat-p-phenylene), were characterized. A naked reference polythiophene film, i.e., polythiophene without tetra-cationic cyclophane, was also characterized. The surface morphology and thickness of the film (L) were observed by atomic force microscopy. The surface of the naked reference polythiophene film has micrometer-scale polythiophene aggregates, which causes the darker color of the film and smaller color contrast in the electrochromic process. The polythiophene polyrotaxane gives a more homogeneous and brighter colored film owing to the suppression of molecular interactions between the polythiophene chains by the tetra-cationic cyclophanes. Potential-step chronoamperometric measurement provided the area density of the oxidizable sites (Γ) and the apparent diffusion coefficient of the charge transport in the film. From linear relationship between L and Γ, the concentrations of the oxidizable sites in the polythiophene polyrotaxane and naked reference polythiophene films were calculated to be 1.3 and 2.4 mmol cm(-3), respectively. Interestingly, the polythiophene polyrotaxane film afforded a significantly larger apparent diffusion coefficient than the naked reference polythiophene film. This result suggests that the rate-determining step of the charge transport is not the electron hopping between the polythiophene chains but the transport of charge-compensating counterions from the solvent into the polythiophene. We believe that the counteranions of the tetra-cationic cyclophane provide a pathway allowing the charge-compensating counteranions to migrate from the solvent to polythiophene. The polythiophene polyrotaxane film showed faster color change than the naked reference polythiophene film in the electrochromic reaction. These results indicate that our polythiophene polyrotaxane is a better electrochromic material than the naked reference polythiophene. 相似文献
37.
Two types of thiophene-capped [2]rotaxanes, i.e., bithienyl (2T)- and bis(3,4-ethylenedioxythiophene)-yl (BEDOT)-capped [2]rotaxanes, were synthesized. The electron-deficient cyclophane of cyclobis(paraquat-p-phenylene) (CBPQT4+) was used as a macrocycle. Association constants for inclusion complexation of 2T- and BEDOT-derivatives with CBPQT4+ were obtained by 1H NMR titration. Due to the donor-acceptor charge transfer absorption band, 2T- and BEDOT-capped [2]rotaxanes have red and green colors, respectively. On the basis of electrochemical analysis, we confirmed that only BEDOT-capped [2]rotaxane is a promising candidate for [3]rotaxane synthesis through oxidation coupling of the thiophene unit. 相似文献
38.
Oshima S Kashihara I Moritani K Inui N Mochiji K 《Rapid communications in mass spectrometry : RCM》2011,25(8):1070-1074
In secondary ion mass spectrometry (SIMS) of organic substances, the dissociation of the sample molecules is crucial. We have developed SIMS equipment capable of bombardment, where the primary ions are argon cluster ions with kinetic energy per atom controllable down to 1 eV. We previously reported the detection of intact ions of insulin and cytochrome C using this equipment. In this paper, we present a detailed characterization of the emission of secondary ions from insulin, focusing on the difference in secondary ion yield between intact ions and fragment ions by varying the incident angle of the cluster ions. The emission intensity of the intact ions was changed drastically due to the exposed dosage and incident angle of the cluster ions in contrast to the fragment ions. We discuss these results based on the manner in which the argon-cluster ions collide with the organic solid. 相似文献
39.
Itoi H Nishihara H Kogure T Kyotani T 《Journal of the American Chemical Society》2011,133(5):1165-1167
Zeolite-templated carbon is a promising candidate as an electrode material for constructing an electric double layer capacitor with both high-power and high-energy densities, due to its three-dimensionally arrayed and mutually connected 1.2-nm nanopores. This carbon exhibits both very high gravimetric (140-190 F g(-1)) and volumetric (75-83 F cm(-3)) capacitances in an organic electrolyte solution. Moreover, such a high capacitance can be well retained even at a very high current up to 20 A g(-1). This extraordinary high performance is attributed to the unique pore structure. 相似文献
40.
Akiyama H Sakata K Makiyma D Nakamura K Teshima R Nakashima A Ogawa A Yamagishi T Futo S Oguchi T Mano J Kitta K 《Journal of AOAC International》2011,94(5):1540-1547
In many countries, the labeling of grains, feed, and foodstuff is mandatory if the genetically modified (GM) organism content exceeds a certain level of approved GM varieties. We previously developed an individual kernel detection system consisting of grinding individual kernels, DNA extraction from the individually ground kernels, GM detection using multiplex real-time PCR, and GM event detection using multiplex qualitative PCR to analyze the precise commingling level and varieties of GM maize in real sample grains. We performed the interlaboratory study of the DNA extraction with multiple ground samples, multiplex real-time PCR detection, and multiplex qualitative PCR detection to evaluate its applicability, practicality, and ruggedness for the individual kernel detection system of GM maize. DNA extraction with multiple ground samples, multiplex real-time PCR, and multiplex qualitative PCR were evaluated by five laboratories in Japan, and all results from these laboratories were consistent with the expected results in terms of the commingling level and event analysis. Thus, the DNA extraction with multiple ground samples, multiplex real-time PCR, and multiplex qualitative PCR for the individual kernel detection system is applicable and practicable in a laboratory to regulate the commingling level of GM maize grain for GM samples, including stacked GM maize. 相似文献