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1.
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
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Hiroto Kudo Nobuhito Ito Keiji Nakajima Masami Ochiai Tadatomi Nishikubo 《Journal of polymer science. Part A, Polymer chemistry》2007,45(19):4421-4429
The polyaddition of fluorine‐containing bis(epoxide)s and fluorine‐containing triazine di(aryl ether)s were examined to give the corresponding fluorine‐containing poly(cyanurate)s. It was observed that the synthesized fluoropolymers had good thermal stabilities and good film‐forming properties. The glass transition temperatures (Tg's) and refractive‐indices (nD's) of synthesized polymers were determined by differential scanning calorimetry and ellipsometry, respectively, and it was found that the values of Tg's and nD's were supported by their fluorine containing ratios and skeletons. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4421–4429, 2007 相似文献
5.
Miyuki Harada Kentaro Aoyama Mitsukazu Ochi 《Journal of Polymer Science.Polymer Physics》2004,42(22):4044-4052
A liquid‐crystalline epoxy resin was cured at two different temperatures. The phases of the cured systems clearly showed isotropic and nematic polydomain structures, which depended on the curing temperature. The fracture toughness of the systems was measured, and the fracture mechanism was investigated with polarized IR measurements. The nematic polydomain structure system showed considerably higher fracture toughness than the isotropic structure. Moreover, both systems exhibited a reorientation of the network chains near the fracture surface during the fracture process, and the region of the network reorientation in the nematic polydomain structure system was larger than that in the isotropic structure system. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4044–4052, 2004 相似文献
6.
The running coupling and the Kugo-Ojima parameter of unquenched lattice Landau gauge are simulated and compared with the continuum
theory. Although the running coupling measured by the ghost and gluon dressing function is infrared suppressed, the running
coupling has a maximum of α0 ∼ 2 − 2.5 at around q = 0.5 GeV irrespective of the fermion actions (Wilson fermions and Kogut-Susskind (KS) fermions). The Kugo-Ojima parameter
c which saturated to about 0.8 in quenched simulations becomes consistent with 1 in the MILC configurations produced with the
use of the Asqtad action, after averaging the dependence on polarization directions caused by the asymmetry of the lattice.
The presence of the correction factor 1 + c
1/q
2 in the running coupling depends on the lattice size and the sea quark mass. In the large lattice size and small sea quark
mass, c
1 is confirmed of the order of a few GeV. The MILC configuration of a = 0.09 fm suggests also the presence of dimension-4 condensates with a sign opposite to the dimension-2 condensates. The
gluon propagator, the ghost propagator, and the running coupling are compared with recent pQCD results including an anomalous
dimension of fields up to the four-loop level. 相似文献
7.
Interface properties of BCN/GaN metal-insulator-semiconductor (MIS) structures are investigated by X-ray photoelectron spectroscopy (XPS) and capacitance versus voltage (C-V) characteristics measurements. The BCN/GaN samples are fabricated by in situ process consisting of plasma treatment and deposition of BCN film in the plasma-assisted chemical vapor deposition (PACVD) apparatus. XPS measurement shows that the oxide formation at the BCN/GaN interface is suppressed by nitrogen (N2) and hydrogen (H2) plasma treatment. The interface state density is estimated from C-V characteristics measured at 1 MHz using Terman method. The minimum interface state density appears from 0.2 to 0.7 eV below the conduction band edge of GaN. The minimum value of the interface state density is estimated to be 3.0 × 1010 eV−1 cm−2 for the BCN/GaN structure with mixed N2 and H2 plasma treatment for 25 min. Even after annealing at 430 °C for 10 min, the interface state density as low as 6.0 × 1010 eV−1 cm−2 is maintained. 相似文献
8.
Trifluoromethylation onto the tetrafluorophthalonitrile and tetrafluoroisophthalonitrile has been carried out using CF3TMS-CuI-KF system, and it was demonstrated that these trifluoromethylation enabled us to successfully construct di- and/or tri-trifluoromethylated benzonitriles via the decyanotrifluoromethylation. 相似文献
9.
We have investigated the photoluminescence (PL) properties of trace amounts of Pr and Tb in single-crystal samples of yttria-stabilized zironia (YSZ), and found that Pr of the order of 10−6 mass% and Tb of the order of 10−5 mass% in YSZ can be detected by the PL spectroscopy. The PL spectra of the YSZ samples for the 280 nm excitation were comprised of several peaks and a broad emission. The peaks were attributed to transitions of Pr3+ and Tb3+ in the YSZ samples, whereas the broad emission seemed to be attributed to the yttria-associated oxygen vacancies. The peak intensities corresponded to the amounts of Pr and Tb in the YSZ samples, the amounts of which were analyzed by glow discharge mass spectrometry. In the PL excitation spectra, but not in the photoabsorption spectra, small peaks at 376 and 381 nm were observed, and were attributed to the transitions of Tb3+ in the YSZ samples. The results of the PL excitation spectra corresponding to the Pr3+ line emissions suggest that the charge transfer occurs between the YSZ and Pr ion in it. The trace amounts of these lanthanoids in YSZ would disturb the decay process of the photoinduced electrons to the yttria-associated oxygen vacancies. 相似文献
10.