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91.
Nishizawa M Hirakawa H Nakagawa Y Yamamoto H Namba K Imagawa H 《Organic letters》2007,9(26):5577-5580
The reaction of alkyl-substituted sec-ethoxyalkynyl acetates with water catalyzed by Hg(OTf)2 afforded alpha,beta-unsaturated esters in excellent yield with high catalytic turnover up to 1000 times under very mild reaction conditions with virtually complete E-selectivity, superior even to that of the HWE reaction. 相似文献
92.
Direct Transformation of Molecular Dinitrogen into Ammonia Catalyzed by Cobalt Dinitrogen Complexes Bearing Anionic PNP Pincer Ligands
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Dr. Shogo Kuriyama Dr. Kazuya Arashiba Prof. Dr. Hiromasa Tanaka Yuki Matsuo Dr. Kazunari Nakajima Prof. Dr. Kazunari Yoshizawa Prof. Dr. Yoshiaki Nishibayashi 《Angewandte Chemie (International ed. in English)》2016,55(46):14291-14295
The direct formation of ammonia from molecular dinitrogen under mild reaction conditions was achieved by using new cobalt dinitrogen complexes bearing an anionic PNP‐type pincer ligand. Up to 15.9 equivalents of ammonia were produced based on the amount of catalyst together with 1.0 equivalent of hydrazine (17.9 equiv of fixed nitrogen atoms). 相似文献
93.
The asymptotic stress and deformation fields associated with the contact point singularity of a nearly-flat wedge indenter impinging on a specially-oriented single face-centered cubic crystal are derived analytically in a companion paper. In order to investigate the extent of the asymptotic fields, the indentation process is simulated numerically using single crystal plasticity. The quasistatically translating asymptotic fields consist of four angular elastic sectors separated by plastically deforming sector boundaries, as predicted in the companion paper. The asymptotic stress distributions are in accord with the analytical predictions. In addition, simulations are performed for a wedge indenter with a 90° included angle in order to investigate the consequences of finite deformation and finite lattice rotation. Several salient features of the deformation field for the nearly-flat indenter persist in the deformation field for the 90° wedge indenter. The existence of the salient features is validated by comparison to experimental measurements of the lower bound on geometrically necessary dislocation (GND) densities. 相似文献
94.
Robust Inclusion Complexes of Crown Ether Fused Tetrathiafulvalenes with Li+@C60 to Afford Efficient Photodriven Charge Separation
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Dr. Mustafa Supur Yuki Kawashima Dr. Karina R. Larsen Dr. Kei Ohkubo Prof. Jan O. Jeppesen Prof. Shunichi Fukuzumi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(43):13976-13983
Inclusion complexes of benzo‐ and dithiabenzo‐crown ether functionalized monopyrrolotetrathiafulvalene (MPTTF) molecules were formed with Li+@C60 ( 1? Li+@C60 and 2? Li+@C60). The strong complexation has been quantified by high binding constants that exceed 106 M ?1 obtained by UV/Vis titrations in benzonitrile (PhCN) at room temperature. On the basis of DFT studies at the B3LYP/6‐311G(d,p) level, the orbital interactions between the crown ether moieties and the π surface of the fullerene together with the endohedral Li+ have a crucial role in robust complex formation. Interestingly, complexation of Li+@C60 with crown ethers accelerates the intersystem crossing upon photoexcitation of the complex, thereby yielding 3(Li+@C60)*, when no charge separation by means of 1Li+@C60* occurs. Photoinduced charge separation by means of 3Li+@C60* with lifetimes of 135 and 120 μs for 1? Li+@C60 and 2? Li+@C60, respectively, and quantum yields of 0.82 in PhCN have been observed by utilizing time‐resolved transient absorption spectroscopy and then confirmed by electron paramagnetic resonance measurements at 4 K. The difference in crown ether structures affects the binding constant and the rates of photoinduced electron‐transfer events in the corresponding complex. 相似文献
95.
96.
Yuki Kanazawa Prof. Hayato Tsuji Prof. Masahiro Ehara Prof. Ryoichi Fukuda Dr. Deborah L. Casher Prof. Kohei Tamao Prof. Hiroshi Nakatsuji Prof. Josef Michl 《Chemphyschem》2016,17(19):3010-3022
The photophysical properties of oligosilanes show unique conformational dependence due to σ‐electron delocalization. The excited states of the SAS, AAS, and AEA conformations of peralkylated n‐hexasilanes, in which the SiSiSiSi dihedral angles are controlled into a syn (S), anti (A), or eclipsed (E) conformation, were investigated by using UV absorption, magnetic circular dichroism (MCD), and linear dichroism spectroscopy. Simultaneous Gaussian fitting of all three spectra identified a minimal set of transitions and the wavenumbers, oscillator strengths, and MCD B terms in all three compounds. The results compare well with those obtained by using the symmetry‐adapted‐cluster configuration interaction method and almost as well with those obtained by time‐dependent density functional theory with the PBE0 functional. The conformational dependence of the transition energies and other properties of free‐chain permethylated n‐hexasilane, n‐Si6Me14, was also examined as a function of dihedral angles, and the striking effects found were attributed to avoided crossings between configurations of σσ* and σπ* character. 相似文献
97.
High Ethene/Ethane Selectivity in 2,2′‐Bipyridine‐Based Silver(I) Complexes by Removal of Coordinated Solvent
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Dr. Matthew G. Cowan William M. McDanel Prof. Hans H. Funke Dr. Yuki Kohno Prof. Douglas L. Gin Prof. Richard D. Noble 《Angewandte Chemie (International ed. in English)》2015,54(19):5740-5743
Following removal of coordinated CH3CN, the resulting complexes [AgI(2,2′‐bipyridine)][BF4] ( 1 ) and [AgI(6,6′‐dimethyl‐2,2′‐bipyridine)][OTf] ( 2 ) show ethene/ethane sorption selectivities of 390 and 340, respectively, and corresponding ethene sorption capacities of 2.38 and 2.18 mmol g?1 when tested at an applied gas pressure of 90 kPa and a temperature of (20±1) °C. These ethene/ethane selectivities are 13 times higher than those reported for known solid sorbents for ethene/ethane separation. For 2 , ethene sorption reached 90 % of equilibrium capacity within 15 minutes, and this equilibrium capacity was maintained over the three sorption/desorption cycles tested. The rates of ethene sorption were also measured. To our knowledge, these are the first complexes, designed for olefin/paraffin separations, which have open silver(I) sites. The high selectivities arise from these open silver(I) sites and the relatively low molecular surface areas of the complexes. 相似文献
98.
Daiki Shimizu Yuki Ide Takahisa Ikeue Atsuhiro Osuka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(15):5077-5081
A bis(NiII‐porphyrinyl)aminyl radical with meso‐C6F5 groups was prepared as a spin‐delocalized stable aminyl radical with a doublet spin state. Upon addition of pyridine, both NiII centers became hexacoordinated by accepting two axial pyridines, which triggered a spin‐state change of the NiII centers from diamagnetic (S=0) to paramagnetic (S=1). The resulting high‐spin NiII centers interact with the aminyl radical ferromagnetically to give rise to an overall sextet state (S=5/2). Importantly, this coordination‐induced spin‐state switching can be conducted in a reversible manner, in that washing of the high‐spin radical with aqueous hydrochloric acid regenerates the original doublet radical in good yield. 相似文献
99.
Arakawa R Shimomae Y Morikawa H Ohara K Okuno S 《Journal of mass spectrometry : JMS》2004,39(8):961-965
A low molecular mass polyester was analyzed by desorption/ionization on porous silicon (DIOS) mass spectrometry. The results were compared with those of matrix-assisted laser desorption ionization (MALDI) mass spectrometry using matrixes of alpha-cyano-4-hydroxycinnamic acid (CHCA) and 10,15,20-tetrakis(pentafluorophenyl)porphyrin (F20TPP). The CHCA matrix was not suitable for characterization of low molecular mass components of the polyester because the matrix-related ions interfered with the component ions. On the other hand, the F20TPP matrix showed no interference because no matrix-related ions appeared below m/z 822. However, the solvent selection for determining optimal conditions of sample preparation was limited, because F20TPP does not dissolve readily in any of the available organic solvents. In the DIOS spectra, the polymer ions were observed at high sensitivity without a contaminating ion. No matrix is needed for DIOS spectra of low molecular mass polyesters, facilitating sample preparation and selectivity of a precursor ion in post-source decay measurements. 相似文献
100.
Dr. Tatsuki Kurokawa Dr. Shigeki Kiyonaka Dr. Eiji Nakata Dr. Masayuki Endo Shohei Koyama Emiko Mori Nam Ha Tran Huyen Dinh Dr. Yuki Suzuki Kumi Hidaka Dr. Masaaki Kawata Dr. Chikara Sato Prof. Hiroshi Sugiyama Prof. Takashi Morii Prof. Yasuo Mori 《Angewandte Chemie (International ed. in English)》2018,57(10):2586-2591
In native systems, scaffolding proteins play important roles in assembling proteins into complexes to transduce signals. This concept is yet to be applied to the assembly of functional transmembrane protein complexes in artificial systems. To address this issue, DNA origami has the potential to serve as scaffolds that arrange proteins at specific positions in complexes. Herein, we report that Kir3 K+ channel proteins are assembled through zinc‐finger protein (ZFP)‐adaptors at specific locations on DNA origami scaffolds. Specific binding of the ZFP‐fused Kir3 channels and ZFP‐based adaptors on DNA origami were confirmed by atomic force microscopy and gel electrophoresis. Furthermore, the DNA origami with ZFP binding sites nearly tripled the K+ channel current activity elicited by heterotetrameric Kir3 channels in HEK293T cells. Thus, our method provides a useful template to control the oligomerization states of membrane protein complexes in vitro and in living cells. 相似文献