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1.
Dr. Manussada Ratanasak Takumi Murata Taishin Adachi Prof. Jun-ya Hasegawa Prof. Tadashi Ema 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(58):e202202210
BPh3 catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 and PhSiH3; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C6F5)3 shows little or no activity. 11B NMR spectra suggested the generation of [HBPh3]−. The detailed mechanism of the BPh3-catalyzed N-methylation of N-methylaniline ( 1 ) with CO2 and PhSiH3 was studied by using DFT calculations. BPh3 promotes the conversion of two substrates (N-methylaniline and CO2) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N+CO2−⋅⋅⋅BPh3]. The carbamate and BPh3 act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH3 to generate [HBPh3]−, which is used to produce key CO2-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh3]− species. 相似文献
2.
Hisatoyo Morinaga Natsumi Ogawa Mayu Sakamoto Hiroshi Morikawa 《Journal of polymer science. Part A, Polymer chemistry》2019,57(24):2466-2473
The thiol‐ene reaction between trans‐limonene oxide (trans‐LO) and ethane‐1,2‐dithiol in the presence of triethylborane affords a bio‐based bis‐functional epoxide (bis‐trans‐LO). The crosslinking reaction of bis‐trans‐LO with branched polyethyleneimine (BPEI; Mn = 600; BPEI600) at a feed ratio of bis‐trans‐LO/BPEI600 = 57/43 (wt/wt) yields the corresponding network polymer with Td10 (10% thermal decomposition temperature) of 304.7 °C in 98% yield. In contrast, negligible amounts of network polymer are obtained by the reaction of bis‐LO (bis‐functional epoxide derived from cis and trans‐LO) and BPEI600 regardless of the feed ratio. The mechanical strengths as measured by direct tensile tests of the network polymers derived from bis‐trans‐LO and BPEI600,1800 (Mn = 600 and 1800) were approximately 16 and 11 times higher than that of bis‐LO and BPEI1800, respectively. The tensile shear strengths of the metal‐to‐metal adhesive bonds induced by bis‐trans‐LO and BPEI600,1800 were 9.5 and 14.1 MPa, respectively. DMA revealed that the storage modulus of the network polymer derived from bis‐trans‐LO and BPEI1800 in the rubber region was higher than that of the material prepared from bis‐LO and BPEI1800, indicating higher crosslink density of the bis‐trans‐LO/BPEI1800 system. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2466–2473 相似文献
3.
Dr. Nozomi Mihara Dr. Yasuyuki Yamada Dr. Hikaru Takaya Prof. Yasutaka Kitagawa Dr. Kazunobu Igawa Prof. Katsuhiko Tomooka Prof. Hiroshi Fujii Prof. Kentaro Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(13):3369-3375
Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 5+, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 5+ catalyzed ethane oxidation in the presence of H2O2 at a relatively low temperature. The site-selective complexation of 3 5+ with an additional anionic porphyrin (TPPS4−) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 5+ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS4− to 3 5+ enhanced the catalytic activity. 相似文献
4.
In this paper, we will propose algorithms for calculating a minimal ellipsoid circumscribing a polytope defined by a system
of linear inequalities. If we know all vertices of the polytope and its cardinality is not very large, we can solve the problem
in an efficient manner by a number of existent algorithms. However, when the polytope is defined by linear inequalities, these
algorithms may not work since the cardinality of vertices may be huge. Based on a fact that vertices determining an ellipsoid
are only a fraction of these vertices, we propose algorithms which iteratively calculate an ellipsoid which covers a subset
of vertices. Numerical experiment shows that these algorithms perform well for polytopes of dimension up to seven. 相似文献
5.
The structural properties of polycrystalline silicon films, prepared by plasma enhanced chemical vapor deposition system, with different flow rates of SiH4/SiF4 mixtures at 300 °C were investigated. This study indicates that the low hydrogen coverage on the growing surface, under optimum fluorine radicals, will be leaded to an improvement of crystallized area as compared with case of high hydrogen coverage surface. Moreover, the studies of the role of SiH4 and SiF4 radicals show that the SiH4 radicals are important in the nucleation and growth of grains. However, SiF4 radicals are effective in the structural change of grain boundaries regions and by this way, in the present system, establish the growth of grains under the dominant 〈1 1 0〉 direction. The stress investigation indicates that addition of high flow rate of SiF4 in amorphous film, results in the nearly stress free films. Finally, we found that the changes in g-value reflect the changes in the intrinsic compressive and tensile stress in the both polycrystalline and amorphous silicon films. 相似文献
6.
7.
Hiroshi Maruyama Tadao Ishii Naruhiko Bamba Hironobu Maeda Akihisa Koizumi Yuzo Yoshikawa Hitoshi Yamazaki 《Physica C: Superconductivity and its Applications》1989,160(5-6):524-532
The temperature dependence of the extended X-ray absorption fine structure (EXAFS) is studied in the high Tc superconductors, YBa2Cu3O7−δ. The measurements were done at the Cu K-edge for samples of two orthorhombic phases (Tc≈90 K and ≈58 K, respectively) and a nonsuperconducting tetragonal phase. Interatomic distances and mean square relative displacements σ2 for Cu-O bonds are determined by the least squares refinement. The results indicate that values of σ2 increase near Tc for both the orthorhombic samples. It is concluded that this anomalous behavior related to Tc is caused by an anomalous vibration of oxygen atoms in the Ba-O layer. Changes in the Cu-O distances from 300 to 20 K are not found. 相似文献
8.
Hiroshi Noguchi Masanori Ueda Yoshinobu Baba Masako Takasu 《Journal of Polymer Science.Polymer Physics》2003,41(12):1316-1322
The electrophoresis of DNA chains in uncrosslinked polymer solutions with a Brownian dynamics simulation with an anisotropic friction tensor was analyzed. According to the degree of anisotropy, three types of migration behavior are obtained: fluctuation without or with periodicity between U‐shaped and compact conformations, or migration with linear conformation. We found good agreement between our simulation results and the direct observations of DNA by fluorescence microscopy. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1316–1322, 2003 相似文献
9.
We measured the entire region of mesopic and photopic vision to determine the color zone covering the visual field with unique red, yellow, green, and blue hue components. Eight kinds of test stimuli in the natural color system (NCS) color notation system were used. These stimuli were presented at horizontal and vertical meridians, and at meridians inclined at 45° angles. The illuminance level was set at six levels: 0.01 lx-1000 lx. The evaluation method measured chromatic, white, and black components as well as the hue component of the stimuli. Results show that the color zone of the retina extended further into the periphery with increasing illuminance; the response of opponent colors y-b was shown to be greater than that of the opponent colors r-g. 相似文献
10.
Takeshi Murashige Hideo Fujikake Hiroto Sato Hiroshi Kikuchi Taiichiro Kurita Fumio Sato 《Optical Review》2004,11(6):349-352
We have confirmed light diffraction of aligned polymer fibers obtained by a phase separation of an anisotropic-phase solution of liquid crystal and polymer. He—Ne laser light passing through the polymer fibers was scattered in the axis vertical to the fibers, and had two peaks of light intensity symmetrical to the center of the transmitting laser spot. The two peaks were found to be caused by light diffraction due to the periodic polymer-fiber dispersion because the peaks corresponded to values calculated by intervals between the fibers. The periodical fiber networks are considered to be formed by anisotropic spinodal decomposition. This effect can be used to measure the dispersion order of the polymer fibers. © 2004 The Optical Society of Japan 相似文献