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71.
Masahiro YoshimuraKazuomi Tsuda Hiroshi NakatsukaTomoya Yamamura Masato Kitamura 《Tetrahedron》2011,67(51):10006-10010
Catalytic reactivity in the hydrogenation of a cyclic anhydride to a biotin synthetic intermediate has been investigated on the basis of Lyons’ original method using Wilkinson Ru complex, revealing the high performance of DPPF and XANTPHOS diphosphines possessing wide bite angles. The results have shown a new trail for design of the corresponding asymmetric catalysts, and the potential utility of (S,S)-Et-FerroTANE and (S,S)-(R,R)-Ph-TRAP has been demonstrated. 相似文献
72.
Mitsumoto K Oshiro E Nishikawa H Shiga T Yamamura Y Saito K Oshio H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(35):9612-9618
Cyanide‐bridged metal complexes of [Fe8M6(μ‐CN)14(CN)10 (tp)8(HL)10(CH3CN)2][PF6]4?n CH3CN?m H2O (HL=3‐(2‐pyridyl)‐5‐[4‐(diphenylamino)phenyl]‐1H‐pyrazole), tp?=hydrotris(pyrazolylborate), 1 : M=Ni with n=11 and m=7, and 2 : M=Co with n=14 and m=5) were prepared. Complexes 1 and 2 are isomorphous, and crystallized in the monoclinic space group P21/n. They have tetradecanuclear cores composed of eight low‐spin (LS) FeIII and six high‐spin (HS) MII ions (M=Ni and Co), all of which are bridged by cyanide ions, to form a crown‐like core structure. Magnetic susceptibility measurements revealed that intramolecular ferro‐ and antiferromagnetic interactions are operative in 1 and in a fresh sample of 2 , respectively. Ac magnetic susceptibility measurements of 1 showed frequency‐dependent in‐ and out‐of‐phase signals, characteristic of single‐molecule magnetism (SMM), while desolvated samples of 2 showed thermal‐ and photoinduced intramolecular electron‐transfer‐coupled spin transition (ETCST) between the [(LS‐FeII)3(LS‐FeIII)5(HS‐CoII)3(LS‐CoIII)3] and the [(LS‐FeIII)8(HS‐CoII)6] states. 相似文献
73.
Sakamoto N Ikeda C Yamamura M Nabeshima T 《Journal of the American Chemical Society》2011,133(13):4726-4729
Novel pentacoordinate dipyrrin-silicon complexes showed efficient red or near-IR fluorescence, and the structural interconversion between silanol and siloxane derivatives resulted in significant changes in the optical properties. 相似文献
74.
Kawamoto S Takasu M Miyakawa T Morikawa R Oda T Futaki S Nagao H 《The Journal of chemical physics》2011,134(9):095103
Arginine-rich peptide and Antennapedia are cell-penetrating peptides (CPPs) which have the ability to permeate plasma membrane. Deformation of the plasma membrane with CPPs is the key to understand permeation mechanism. We investigate the dynamics of CPP and the lipid bilayer membrane by coarse-grained simulation. We found that the peptide makes inverted micelle in the lipid bilayer membrane, when the attractive potential between the peptide and lipid heads is strong. The inverted micelle is formed to minimize potential energy of the peptide. For vesicle membrane, the peptide moves from the outer vesicle to the inner vesicle through the membrane. The translocation of the peptide suggests inverted micelle model as a possible mechanism of CPPs. 相似文献
75.
We propose a modified mechanism for the inhibition of [NiFe]hydrogenase ([NiFe]H(2)ase) by CO. We present a model study, using a NiRu H(2)ase mimic, that demonstrates that (i) CO completely inhibits the catalytic cycle of the model compound, (ii) CO prefers to coordinate to the Ru(II) center rather than taking an axial position on the Ni(II) center, and (iii) CO is unable to displace a hydrido ligand from the NiRu center. We combine these studies with a reevaluation of previous studies to propose that, under normal circumstances, CO inhibits [NiFe]H(2)ase by complexing to the Fe(II) center. 相似文献
76.
Yamaoka Y Taniguchi Y Yasuzuka S Yamamura Y Saito K 《The Journal of chemical physics》2011,135(4):044705
Quasi-binary (QB) picture of thermotropics, which regards a neat thermotropic liquid crystal as a binary system consisting of (semi)rigid core and molten alkyl chain, was assessed experimentally for the most famous (and representative) thermotropic mesogenic series nCB. By adding n-heptane as solvent, the smectic A phase was induced in 7CB-n-heptane system. Small angle x-ray diffraction showed that the QB picture holds not only in the phase behavior but also in the structure. It is suggested that the melting of 8CB and 9CB to isotropic liquid via smectic and nematic liquid crystals can be understood as a thermotropic-lyotropic crossover. 相似文献
77.
Dr. Yohei Hattori Shunsuke Tsubaki Dr. Ryota Matsuoka Dr. Tetsuro Kusamoto Prof. Hiroshi Nishihara Prof. Kingo Uchida 《化学:亚洲杂志》2021,16(17):2538-2544
Polychlorinated pyridyldiphenylmethyl radicals having substituents meta to the position bearing the carbon-centered radical (α-carbon) are synthesized. All of them are stable in ambient conditions in solutions and fluorescent in cyclohexane. The fluorescence of the radicals with bromo, phenyl, 4-chlorophenyl, or 2-pyridyl substituents are enhanced in chloroform, while the emission of the radicals with 2-thienyl or 2-furyl substituents are quenched in chloroform. DFT and TD-DFT calculations indicate that the first doublet excited states of the former are locally excited, while the first doublet excited states of the latter are charge transfer states from the π-electron-donating substituent to the accepting radical. The latter also show much higher photostability under 370-nm light irradiation compared with the first reported photostable fluorescent radical, (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (PyBTM), with pronounced bathochromic shifts of the fluorescence. 相似文献
78.
Ryota Kikuchi Takashi Misaka Shigeru Obayashi 《International Journal of Computational Fluid Dynamics》2016,30(4):285-306
An integrated method consisting of a proper orthogonal decomposition (POD)-based reduced-order model (ROM) and a particle filter (PF) is proposed for real-time prediction of an unsteady flow field. The proposed method is validated using identical twin experiments of an unsteady flow field around a circular cylinder for Reynolds numbers of 100 and 1000. In this study, a PF is employed (ROM-PF) to modify the temporal coefficient of the ROM based on observation data because the prediction capability of the ROM alone is limited due to the stability issue. The proposed method reproduces the unsteady flow field several orders faster than a reference numerical simulation based on Navier–Stokes equations. Furthermore, the effects of parameters, related to observation and simulation, on the prediction accuracy are studied. Most of the energy modes of the unsteady flow field are captured, and it is possible to stably predict the long-term evolution with ROM-PF. 相似文献
79.
Jie Zhu Dr. Ryota Osuga Prof. Ryo Ishikawa Prof. Naoya Shibata Prof. Yuichi Ikuhara Prof. Junko N. Kondo Prof. Masaru Ogura Prof. Jihong Yu Prof. Toru Wakihara Prof. Zhendong Liu Prof. Tatsuya Okubo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(44):19837-19842
Encapsulating metal nanoclusters into zeolites combines the superior catalytic activity of the nanoclusters with high stability and unique shape selectivity of the crystalline microporous materials. The preparation of such bifunctional catalysts, however, is often restricted by the mismatching in time scale between the fast formation of nanoclusters and the slow crystallization of zeolites. We herein demonstrate a novel strategy to overcome the mismatching issue, in which the crystallization of zeolites is expedited so as to synchronize it with the rapid formation of nanoclusters. The concept was demonstrated by confining Pt and Sn nanoclusters into a ZSM-5 (MFI) zeolite in the course of its crystallization, leading to an ultrafast, in situ encapsulation within just 5 min. The Pt/Sn-ZSM-5 exhibited exceptional activity and selectivity with stability in the dehydrogenation of propane to propene. This method of ultrafast encapsulation opens up a new avenue for designing and synthesizing composite zeolitic materials with structural and compositional complexity. 相似文献
80.
A versatile spectrophotometric method is described for the determination of microgram levels of silicon, as molybdenum blue. It combines the desirable features of existing spectrophotometric methods with three pretreatment procedures, namely (a) the removal of cations with a cation-exchange resin in the H(+)-form, (b) the conversion of all silicon species into the reactive monomer with an alkaline treatment, and (c) the decomposition of silicon fluoride with boric acid in the presence of cation-exchange resin. These pretreatments coupled with the colour development provide five procedures which are applicable to a wide variety of samples including natural and industrial waters and solutions of various nuclear reactor fuels and components. Provisions are included for the selective determination of total silicon. 相似文献