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排序方式: 共有6210条查询结果,搜索用时 10 毫秒
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
2.
Homohelicity induction of a series of propylene-linked zinc bilinone (ZnBL; linear tetrapyrrople-zinc(II) complex) dimers upon complexation with chiral amine and α-amino esters was investigated. Introduction of substituents such as dimethyl and diisobutyl to the central carbon of the propylene spacer gave rise to stabilization of the homohelical (PP and MM) conformers rather than the heterohelical (PM) conformer. As bulkiness of the substituent increased, stability of the homohelical conformers was raised. The preorganization of the homohelical structures led to significantly amplified homohelicity induction upon complexation with chiral amine and α-amino esters. 相似文献
3.
Xinyu Chen Yoshiro Oro Kenta Tanaka Norimichi Takenaka Hiroshi Bandow 《Analytical sciences》2004,20(7):1019-1023
A new stripping coil for the collection of nitrogen dioxide (NO2) has been developed to increase its versatility and efficiency. Nitrogen dioxide measurements based on quantitative collection through a reaction coil into an alkaline solution has been examined. Nitrogen dioxide is collected in a 0.1 N NaOH solution. This collection system has an efficiency of nearly 100%. The absorbed nitrogen dioxide has been measured by fluorescence detection with sub-ppbv detection limits. The excitation wavelength at 360 nm and the produced emission wavelength at 405 nm were suitable for nitrite ion measurements. 相似文献
4.
The electrode reaction of decamethylferrocene (DMFc) dissolved in a thin layer of a room-temperature molten salt (RTMS), 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C8mimC1C1N) or 1-octyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide (C8mimC2C2N), on a self-assembled monolayer-modified gold electrode is coupled with the ion transfer across the interface between the RTMS and the outer aqueous solution (W) to give a voltammogram whose shape resembles a voltammogram of a simple one-electron transfer process. The electroneutrality of the RTMS layer during the oxidation of DMFc to decamethylferricenium ion is maintained by the concomitant dissolution of C8mim+ ion from the RTMS phase to the W phase, and the reduction of decamethylferricenium ion to DMFc is accompanied by the transfer of either C1C1N- or C2C2N- from RTMS to W. The midpoint potential of the voltammogram varies with the concentration of the salt in the aqueous phase, C8mimCl or LiCnCnN (n = 1 or 2), in a Nernstian manner, showing that the phase-boundary potential between the RTMS and the W is controlled by the partition of these ions. Although the phase-boundary potential across the RTMS / W interface is Nernstian with respect to the ions common to both phases at the equilibrium, the polarization at the RTMS / W interface under current flow distorts the shape of the voltammograms, resulting in a wider peak separation in the voltammogram. 相似文献
5.
Yoshiyuki Watabe Takuya Kondo Hiroe Imai Masatoshi Morita Nobuo Tanaka Jun Haginaka Ken Hosoya 《Analytical sciences》2004,20(1):133-137
A new high-performance liquid chromatography (HPLC) method has been developed to detect ultra-low concentrations of bisphenol-A (BPA) (below 1 ng/L (ppt)) using column switching electrochemical detection (ECD). The results were superior to those obtained from manual pretreatment procedure with membrane stationary phase. BPA is inherently ubiquitous in the environment, including tools and solvents used for its analysis; to obtain meaningful results, therefore, the concentration of the overall BPA contamination must be below the detection limit for BPA using the analytical system. Therefore, purified water for preparing the standard BPA solution must be filtered with a hydrophobic membrane to suppress BPA background levels of contamination. In addition, we investigated methods for effectively preserving environmental water containing BPA. The addition of a small amount of ethylenediaminetetraacetic acid (EDTA) provided good recovery even after overnight storage. By employing these precautionary measures and procedures to reduce BPA contamination from the analytical procedure, we could accurately determine l(-10) ppt of BPA in environmental water samples using a column switching HPLC system. 相似文献
6.
It was found that a beta-fructofuranosidase produced by Microbacterium sp. H-1 has potent trans-beta-fructofuranosylation activity from sucrose (donor). By means of this enzyme system, rebaudioside A (RA), the second major sweet steviol glycoside of the leaves of Stevia rebaudiana, was subjected to transfructosylation, affording a mono-beta-fructofuranosylated product (RA-F) in a high yield. The structure of RA-F was elucidated as beta-D-fructofuranosyl-(2----6)-beta-D-glucopyranosyl ester of steviol-13-O-[beta-D-glucopyranosyl-(1----2)]- [beta-D-glucopyranosyl-(1----3)]-beta-D-glucopyranoside. Some improvement in the quality of sweetness was observed for RA-F. 相似文献
7.
Asymmetric Horner-Wadsworth-Emmons reactions of selected meso-α-dicarbonyl compounds with chiral phosphonate reagents, which possessed axially dissymmetric 1,1′-bi-2- or 8-naphthol at the carboxylate moiety as a chiral auxiliary, were examined. The reactions proceeded smoothly with good chemical yields as well as with high diastereoselectivities. Z-olefins were preferentially formed, and it was found that the free hydroxy group at the 2′- or 8′-position on the naphthalene ring plays a crucial role in the high diastereoselectivity, probably due to a complex-induced proximity effect. Mechanistic considerations are also described. 相似文献
8.
The propulsion methods of the aquatic lives are the results of optimization by evolution and are useful for the design of
swimming-robot, etc. Among them, loach has unique propulsion technique both bending its long body and shaking caudal fin.
Our purpose of the research is to clarify its swimming mechanism through flow field analysis. Two dimensional motion and flow
around it have been experimentally visualized by particle image velocimetry (PIV). Vortices around a loach and the interactions
between the loach body and surrounding water are analyzed. Generating and growing vortices by bending its body, it pushes
water backward to gain repulsing force, and it seems that moves through vortices reducing the resistance force at the same
time. When a vortex reaches to the caudal fin, it accelerates both sides of the vortex pushing water backward and seems gaining
propulsion utilizing the caudal fin. After moving forward, loach leaves a vortex street like reverse Karman vortices, which
means that loach gains propulsion. 相似文献
9.
10.
Syun-ichi Kiyooka Yushi Takeshita Yoshinori Tanaka Takafumi Higaki Yosuke Wada 《Tetrahedron letters》2006,47(26):4453-4456
A dicationic ((−)-sparteine)palladium complex underwent a superior catalytic enantioselective aldol reaction of aldehydes with 1-phenyl-1-trimethylsilyloxyethene performing satisfactorily, starting with ((−)-sparteine)PdCl2 and AgSbF6 as catalyst precursors (1 mol % loading) in the presence of 3 Å molecular sieves over the reaction. 相似文献