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1.
D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity
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Yohei Ohkoda Akane Asaishi Tomoya Namiki Tomoaki Hashimoto Midori Yamada Koichiro Shirai Yuta Katagami Dr. Tomoaki Sugaya Prof. Makoto Tadokoro Prof. Akiharu Satake 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(33):11745-11756
The one‐step synthesis of D3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η3‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η3‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands. 相似文献
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Motohiro Mizuno Yoji Aoki Darius Greenidge 《Journal of Physics and Chemistry of Solids》2006,67(4):705-709
The angular dependence of the 27Al NMR spectrum was measured for single crystals of smoky and colorless topaz, Al2SiO4(F,OH)2. Smoky topaz was obtained by irradiating high energy neutrons to colorless topaz. The quadrupole coupling constant e2Qq/h and the asymmetry parameter η were obtained from the analysis of the angular dependences of quadrupole splitting of the 27Al NMR spectrum. The local structures around the aluminum atoms in smoky and colorless topaz were discussed from the magnitude and the direction of the electric field gradient. The directions of principal axes of the EFG tensor of 27Al were close to the directions of Al-O and Al-F bonds. The difference in the bond lengths between Al(1)-F(1) and Al(1)-F(2) was found to affect the x and y components of the EFG tensor. 相似文献
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Tomohiro Kyotani Sonoko Kakui Takehito Mizuno Naoto Shimotsuma Soushi Inoue Junji Saito 《Analytical sciences》2006,22(7):1031-1034
A zeolite NaA (LTA) membrane supported by an alumina porous support tube for pervaporation (PV) dehydration of ethanol was characterized by transmission electron microscopy (TEM) using a focused ion beam (FIB) thin-layer specimen preparation technique and by Fourier transform infrared attenuated total reflectance method (FTIR-ATR) using a diamond prism as the waveguide. FIB-TEM clearly presented cross-section images up to about 15 microm depth from the membrane surface. FTIR-ATR monitored the Si-O asymmetric stretching vibration spectrum. The Si-O spectrum was compared with the TEM image and their relationships were discussed. By combining the two methods, we could study the thickness of surface LTA crystals, the grain boundary, the LTA/alumina interface structure and the crystallinity and density of materials inside of the alumina porous support. Consequently, fine structure changes of the LTA membrane corresponding to the hydrothermal synthesis condition could be sensitively detected. 相似文献
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K. M. A. Salam Hidekazu Konishi Masahiro Mizuno Hisashi Fukuda Shigeru Nomura 《Applied Surface Science》2002,190(1-4):88-95
Polycrystalline (1−x)Ta2O5−xTiO2 thin films were formed on Si by metalorganic decomposition (MOD) and annealed at various temperatures. As-deposited films were in the amorphous state and were completely transformed to crystalline after annealing above 600 °C. During crystallization, a thin interfacial SiO2 layer was formed at the (1−x)Ta2O5−xTiO2/Si interface. Thin films with 0.92Ta2O5–0.08TiO2 composition exhibited superior insulating properties. The measured dielectric constant and dissipation factor at 1 MHz were 9 and 0.015, respectively, for films annealed at 900 °C. The interface trap density was 2.5×1011 cm−2 eV−1, and flatband voltage was −0.38 V. A charge storage density of 22.8 fC/μm2 was obtained at an applied electric field of 3 MV/cm. The leakage current density was lower than 4×10−9 A/cm2 up to an applied electric field of 6 MV/cm. 相似文献
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Rikuhei Tanikaga Yoshimasa MatsumotoMaki Sakaguchi Yohei KoyamaKentaro Ono 《Tetrahedron letters》2003,44(35):6781-6783
Lipase-mediated acetylations of trans- and cis-2-substituted cyclohexanols gave the corresponding (1R)-cyclohexyl acetates and (1S)-cyclohexanols in high yields and ee, but c-4-tert-butyl-c-2-ethenyl-r-1-cyclohexanol was unreactive owing to the steric interaction between the axial OH group and the axial H atoms at the 3- and 5-positions. In the cis-isomer the OH group occupies an equatorial position to bind to the lipase, and less bulky axial alkenyl and alkynyl groups might not so much prevent acetylations than an alkyl group. 相似文献