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1.
D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity 下载免费PDF全文
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
2.
Yuta Yamamoto Shogo Nakano Fumio Seki Yasuteru Shigeta Sohei Ito Hiroaki Tokiwa Makoto Takeda 《Molecules (Basel, Switzerland)》2021,26(5)
Infection of hosts by morbilliviruses is facilitated by the interaction between viral hemagglutinin (H-protein) and the signaling lymphocytic activation molecule (SLAM). Recently, the functional importance of the n-terminal region of human SLAM as a measles virus receptor was demonstrated. However, the functional roles of this region in the infection process by other morbilliviruses and host range determination remain unknown, partly because this region is highly flexible, which has hampered accurate structure determination of this region by X-ray crystallography. In this study, we analyzed the interaction between the H-protein from canine distemper virus (CDV-H) and SLAMs by a computational chemistry approach. Molecular dynamics simulations and fragment molecular orbital analysis demonstrated that the unique His28 in the N-terminal region of SLAM from Macaca is a key determinant that enables the formation of a stable interaction with CDV-H, providing a basis for CDV infection in Macaca. The computational chemistry approach presented should enable the determination of molecular interactions involving regions of proteins that are difficult to predict from crystal structures because of their high flexibility. 相似文献
3.
We propose an extrapolation algorithm for initial value problems in ordinary differential equations. In the algorithm, an appropriately chosen stepsizeH is divided into smaller stepsizes by a sequence and a new stopping rule is proposed. The sequences applied to the algorithm are Romberg {2,4,8,16,32,...}, Bulirsch {2,4,6,8,16...} and Harmonic {2,4,6,8,10,12,...} types. The proposed algorithm is compared numerically with the algorithm introduced by Stoer. In view of the accuracy of numerical solutions, the relatively small number of calculations, the stability and reliability of the algorithm, we found that the algorithm with the Romberg sequence is the best. 相似文献
4.
Shinichi Kikkawa Kazuteru Nagasaka Mark Bailey Yoshinari Miyamoto 《Journal of solid state chemistry》2007,180(7):1984-1989
Gallium oxynitride, isostructural to hexagonal gallium nitride (h-GaN), was obtained by ammonia nitridation of a precursor prepared from the addition of citric acid to an aqueous solution of gallium nitrate. Gallium oxynitride produced at 750 °C had a small amount of gallium vacancies, and was formulated as (Ga0.89□0.11) (N0.66O0.34) where the symbol □ stands for gallium vacancy. Both the gallium vacancies and oxygen substituted for nitrogen were randomly distributed within the structure. The amount of vacancies decreased with nitridation temperatures in the range of 750-850 °C. Approximately, 10 at% Li+ was doped into the gallium oxynitride, using a similar preparation with the additional presence of lithium nitrate, resulted in the random substitution of Ga3+ in an atomic ratio of Li/Ga<1 at 750 °C. Oxygen was codoped with lithium and substituted nitrogen in the wurtzite-type crystal lattice. These substitutions reduced the electrical conductivity in the gallium oxynitride semiconductor. A new oxynitride, Li2Ga3NO4, was also obtained with Li2CN2 impurity using similar preparations from a mixture of Li/Ga?1. The crystal structure was isostructural with h-GaN, and was refined as P63mc with a=0.31674(1) nm, and c=0.50854(2) nm. The Ga and Li occupancies at the 2b site were refined to be 0.6085 and 0.3915, respectively, assuming that the other 2b site was randomly occupied with 1/5O and 4/5N. When the new compound was washed for over 1 min for the removal of Li2CN2 impurities, it was decomposed to a mixture of α-GaOOH and α-LiGaO2. The as-prepared product with Li/Ga=1 showed the highest intensity in yellow luminescence among the products under excitation at 254 nm. 相似文献
5.
Tetsuo Miyazaki Shigeru Nagasaka Isao Maeda Takuro Matsumoto Shinji Koyama Seiji Kodama Masami Watanabe 《Radiation Physics and Chemistry》1996,47(6):817-819
Emission from high-energy-electron-irradiated golden hamster embryo (GHE) cells has been studied over the temperature range 12–300 K both by a one-shot-single-photon-counting method and by photocurrent measurements with an oscilloscope. Emission from the irradiated phosphate buffered saline (PBS) also has been studied. The emission spectra from PBS at 12 and 77 K show a maximum around 330 and 380 nm, respectively, which are the same spectra as those from irradiated pure H2O. The emission from irradiated GHE consists of the new band at 480 nm in addition to the emission from H2O. The 480 nm emission is observed at the temperature range of 12–300 K, though the emission at 300 K is much lower than that at low temperature. The 480 nm emission is ascribed to the transition from excited organic substances in GHE cells. The intensity of 480 nm emission at 300 K increases linearly with increasing irradiation-dose in the range of 11–600 Gy. 相似文献
6.
Nakai I Kondoh H Amemiya K Nagasaka M Shimada T Yokota R Nambu A Ohta T 《The Journal of chemical physics》2005,122(13):134709
The mechanism of CO oxidation reaction on oxygen-precovered Pt(111) surfaces has been studied by using time-resolved near-edge x-ray absorption fine structure spectroscopy. The whole reaction process is composed of two distinct paths: (1) a reaction of isolated oxygen atoms with adsorbed CO, and (2) a reaction of island-periphery oxygen atoms after the CO saturation. CO coadsorption plays a role to induce the dynamic change in spatial distribution of O atoms, which switches over the two reaction paths. These mechanisms were confirmed by kinetic Monte Carlo simulations. The effect of coadsorbed water in the reaction mechanism was also examined. 相似文献
7.
M. Yamanaka Y. Takeda S. Tanigawa A. Nishizawa N. Noda J. Fujita M. Takai M. Shimobayashi Y. Hayashi T. Koizumi K. Nagasaka S. Okajima Y. Tsunawaki A. Nagashima 《International Journal of Infrared and Millimeter Waves》1980,1(1):57-76
A twin optically-pumped far-infrared CH3OH laser has been constructed for use in plasma diagnostics. The antisymmetric doublet due to the Raman-type resonant two-photon transition is reproducibly observed at 118.8 m. With the 118.8-m line, it is obtained from the frequency separation of the anti-symmetric doublet that CH3OH absorption line center is 16±1 MHz higher than the pump 9.7-m P(36) CO2 laser line center. It is shown that the Raman-type resonant two-photon transition is useful in order to get several-MHz phase modulation for the far-infrared laser interferometer. Some preliminary performances of this twin laser for the modulated interferometer are described.This work was carried out under the collaborating research program at the Institute of Plasma Physics, Nagoya University, Nagoya 464, Japan. 相似文献
8.
Optically active sulfinylaziridines having a 4-methoxyphenyl group on their nitrogen atom were synthesized from optically active 1-chloroalkyl p-tolyl sulfoxide and an imine derived from benzaldehyde and p-anisidine stereoselectively in good overall yields. The sulfinylaziridines were treated with ethylmagnesium bromide or tert-butyllithium to afford aziridinylmagnesiums or aziridinyllithiums, respectively, in quantitative yields. Cross-coupling of the aziridinylmagnesiums with iodoalkanes in the presence of Cu(I) iodide gave tri-substituted aziridines in high yields from which enantiomerically pure β,β-disubstituted β-amino acid derivatives were synthesized. A β-amino acid derivative having deuterium at the stereogenic center was also realized by this method. On the other hand, from the aziridinyllithium, enantiomerically pure quaternary phenylalanine and quaternary aspartic acid derivatives were synthesized. 相似文献
9.
10.
We will focus on estimating the integrated covariance of two diffusion processes observed in a nonsynchronous manner. The observation data is contaminated by some noise, which possibly depends on the time and the latent diffusion processes, while the sampling times also possibly depend on the observed processes. In a high-frequency setting, we consider a modified version of the pre-averaged Hayashi–Yoshida estimator, and we show that such a kind of estimator has the consistency and the asymptotic mixed normality, and attains the optimal rate of convergence. 相似文献