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91.
Munetaka Takeuchi Yasuo Kameda Yasuhiro Umebayashi Sari Ogawa Takaaki Sonoda Shin-ichi Ishiguro Miho Fujita Mitsuru Sano 《Journal of Molecular Liquids》2009,148(2-3):99-108
Self-diffusion coefficients of Li+ DLi+, PF6− DPF6− and solvent propylene carbonate (PC) DPC in LiPF6−PC solutions were determined at 298 K by the pulse gradient spin echo (PGSE) NMR technique over the salt concentration range of 0.1–3.0 M (M = mol dm– 3). The order of the diffusion coefficients was found to be DLi+ < DPF6− < DPC over the concentration range examined, and they were monotonically decreased with increasing the salt concentration. Haven ratio Λ/ΛNMR, where Λ and ΛNMR represent the ionic conductivity measured electrochemically and that estimated via the Nernst-Einstein equation using the diffusion coefficient, respectively, was evaluated as the measure of the ion–ion interaction in the LiPF6–PC solutions. Though Λ/ΛNMR values for LiPF6-solutions decrease with increasing the salt concentration, they were greater than those for LiBF4–PC solutions over the whole concentration range examined, which indicates that the ion pair formation ability of PF6– ion is weaker than that of the BF4– ion. The smaller value of the ionic conductivity for the highly concentrated LiPF6–PC solution (above 2.0 M) than that of the LiBF4-solutions can be attributed to the more rapidly increased viscosity relative to the LiBF4-solution. Classic molecular dynamics (MD) simulations for the respective LiPF6 and LiBF4-solution of 0.5 and 1.0 M were also carried out based on the effective pair potentials. Diffusion coefficients, ionic conductivity and Haven ratio for these solutions were calculated from MD trajectories, and they qualitatively agree with those evaluated by experiments. Pair correlation functions gLiO(r) (for Li+–O (PC) pair) and gLiPF6(r) (for Li+–PF6– pair) or gLiBF4(r) (for Li+–BF4– pair) revealed that the lithium ion weakly forms the contact ion pairs with PF6–, whilst strongly with BF4–, which supports the present experimental results. Moreover, the simulation results show that both anions in the contact ion pairs predominantly take the monodentate form, which is in contrast to the multidentate coordination predicted by ab initio calculation in gas phase. 相似文献
92.
93.
Dr. Yoshikazu Ito Dr. Yoichi Tanabe Dr. H.‐J. Qiu Dr. Katsuaki Sugawara Dr. Satoshi Heguri Dr. Ngoc Han Tu Dr. Khuong Kim Huynh Dr. Takeshi Fujita Prof. Takashi Takahashi Prof. Katsumi Tanigaki Prof. Mingwei Chen 《Angewandte Chemie (International ed. in English)》2014,53(19):4822-4826
We report three‐dimensional (3D) nanoporous graphene with preserved 2D electronic properties, tunable pore sizes, and high electron mobility for electronic applications. The complex 3D network comprised of interconnected graphene retains a 2D coherent electron system of massless Dirac fermions. The transport properties of the nanoporous graphene show a semiconducting behavior and strong pore‐size dependence, together with unique angular independence. The free‐standing, large‐scale nanoporous graphene with 2D electronic properties and high electron mobility holds great promise for practical applications in 3D electronic devices. 相似文献
94.
Shitao Wang Dr. Tomohisa Sawada Dr. Kazuaki Ohara Prof. Dr. Kentaro Yamaguchi Prof. Dr. Makoto Fujita 《Angewandte Chemie (International ed. in English)》2016,55(6):2063-2066
Guest‐induced M18L6–M24L8 capsule–capsule conversion is reported. Both capsules are composed of PdII ethylenediamine units (M) and 1,3,5‐tris(3,5‐pyrimidyl)pyrimidine (L), and form trigonal bipyramidal (M18L6) and octahedral (M24L8) closed‐shell structures with huge hydrophobic inner spaces. The M18L6 trigonal bipyramid is converted to the M24L8 octahedron through encapsulation of large aromatic guests, with the latter capsule possessing a cavity volume three times larger than the former. Despite the dynamic properties of the capsule host, the encapsulated guests are difficult to extract and are thus isolated from the external environment. 相似文献
95.
Reiko Saito Akifumi Fujita Ayako Ichimura Koji Ishizu 《Journal of polymer science. Part A, Polymer chemistry》2000,38(11):2091-2097
Novel structural microspheres of the Janus type, with microphase‐separated polystyrene (PS) and poly(tert‐butyl methacrylate) (PBMA) shells and crosslinked poly(2‐vinyl pyridine) (PVP) cores, were synthesized with the crosslinking of PVP spherical domains in poly(styrene‐block‐2‐vinyl pyridine‐block‐tert‐butyl methacrylate) ABC triblock terpolymer film with PS/PBMA lamellae–PVP spherical structures. For the formation of lamellae‐sphere structures, toluene, which was a selective solvent for the ABC triblock terpolymer, was used. With the crosslinking of PVP spheres in the microphase‐separated film with 1,4‐diiodobutane gas, the microphase structure of the terpolymer was fixed, and microspheres composed of microphase‐separated PS and PBMA shells and P2VP cores were obtained. The size distribution of the purified microspheres was narrow. The characteristics of the microspheres and their aggregation behaviors in selective solvents were investigated by transmission electron microscopy and light scattering methods. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2091–2097, 2000 相似文献
96.
Under atmospheric pressure, methanol was produced from CO2–H2 over Pd/ZnO and from CO–H2 over Pd/MgO catalyst. Similar support effects were observed over Cu catalysts. 相似文献
97.
Takahashi Y Nonogawa M Fujita K Yamaguchi R 《Dalton transactions (Cambridge, England : 2003)》2008,(27):3546-3552
Reaction of [Cp*Ir(micro-H)](2) (5) (Cp* = eta(5)-C(5)Me(5)) with bis(dimethylphosphino)methane (dmpm) gives a new neutral diiridium complex [(Cp*Ir)(2)(micro-dmpm)(micro-H)(2)] (3). Treatment of 3 with methyl triflate at -30 degrees C results in the formation of [(Cp*Ir)(H)(micro-dmpm)(micro-H)(Me)(IrCp*)][OTf] (6). Warming a solution of above 0 degrees C brings about predominant generation of 32e(-) Ir(II)-Ir(II) species [(Cp*Ir)(micro-dmpm)(micro-H)(IrCp*)][OTf] (7). Further heating of the solution of 7 up to 30 degrees C for 14 h leads to quantitative formation of a new complex [(Cp*Ir)(H)(micro-Me(2)PCH(2)PMeCH(2))(micro-H)(IrCp*)][OTf] (8), which is formed by intramolecular oxidative addition of the methyl C-H bond of the dmpm ligand. Intermolecular C-H bond activation reactions with 7 are also examined. Reactions of 7 with aromatic molecules (benzene, toluene, furan, and pyridine) at room temperature result in the smooth sp(2) C-H activation to give [(Cp*Ir)(H)(micro-dmpm)(micro-H)(Ar)(IrCp*)][OTf] (Ar = Ph (9); Ar = m-Tol (10a) or p-Tol (10b); Ar = 2-Fur (11)) and [(Cp*Ir)(H)(micro-dmpm)(micro-C(5)H(4)N)(H)(IrCp*)][OTf] (12), respectively. Complex also reacts with cyclopentene at 0 degrees C to give [(Cp*Ir)(H)(micro-dmpm)(micro-H)(1-cyclopentenyl)(IrCp*)][OTf] (13). Structures of 3, 8 and 12 have been confirmed by X-ray analysis. 相似文献
98.
Fully automated liquid chromatography-mass spectrometry determination of 17beta-estradiol in river water 总被引:1,自引:0,他引:1
Watabe Y Kubo T Nishikawa T Fujita T Kaya K Hosoya K 《Journal of chromatography. A》2006,1120(1-2):252-259
Surface modified molecularly imprinted polymers (SM-MIPs) for 17beta-estradiol (E2), utilizing 6-ketoecradiol as a pseudo template were prepared. MIPs for E2 were synthesized using 4-vinyl pyridine and ethylene dimethacrylate as a functional monomer and cross-linking agent, respectively. MIPs selectively retained E2 and provided excellent chromatographic resolution from interfering compounds inherent in river water sample matrices. Therefore, freshly prepared MIPs were applied to quantitative mass spectrometric (negative electrospray ionization mode) detection of low levels of E2 in river water sample. In order to pre-concentrate the target compound for HPLC analysis, column switching was coupled with a pretreatment column packed with the MIPs. The repeatability of actual determinations of river water sample, in which background E2 was not detected, spiked with 50 ng/L of E2 was 2.2% RSD with a detection limit and qualification limit of 1.8 and 5.4 ng/L, respectively. Surface modification of MIP particlefs packed in the pretreatment column provided selective affinity and on-line concentration of low levels of E2 while simultaneously eliminating sample matrix interference, resulting in a significant increase in sensitivity and reproducibility for liquid chromatography-mass spectrometry analysis of E2 in river water sample. 相似文献
99.
Chiral cationic palladium-phosphinooxazolidine catalysts in ionic liquid afforded excellent enantioselectivity in Diels-Alder reactions and the catalyst was easily recycled eight times without any significant decrease in chemical yields or enantioselectivity (89-99%, 88-99% ee). 相似文献
100.