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981.
Kishi N Li Z Yoza K Akita M Yoshizawa M 《Journal of the American Chemical Society》2011,133(30):11438-11441
A new M(2)L(4) molecular capsule with an aromatic shell was prepared using two Pd(II) ions and four bisanthracene ligands. The self-assembled capsule possesses a cavity with a diameter of ~1 nm that can encapsulate medium-sized spherical and planar molecules as well as a very large molecule (C(60)) in quantitative yields. The encapsulated guests are fully segregated and shielded from the external environment by the large anthracene panels. 相似文献
982.
Mochida K Kawasumi K Segawa Y Itami K 《Journal of the American Chemical Society》2011,133(28):10716-10719
We have discovered that the combination of Pd(OAc)(2)/o-chloranil can catalyze the direct C-H bond arylation of polycyclic aromatic hydrocarbons (PAHs) with arylboroxins that occurs selectively at the K-region. The sequential integration of Pd-catalyzed direct arylation of PAHs and FeCl(3)-mediated cyclodehydrogenation is effective in rapidly extending a parent PAH π-system with high directionality. 相似文献
983.
Fujisaki J Matsumoto K Matsumoto K Katsuki T 《Journal of the American Chemical Society》2011,133(1):56-61
Aluminum(salalen) complex 1 [salalen = half-reduced salen, salen = N,N'-ethylenebis(salicylideneiminato)] was found to be a highly efficient catalyst for asymmetric oxidation of cyclic dithioacetals in the presence of 30% hydrogen peroxide as an oxidant. In the reaction of a series of 2-substituted 1,3-dithianes bearing alkyl, alkenyl, alkynyl, and aryl groups as the substituent, the trans-monoxides were obtained in high yields with 19:1 → >20:1 dr (diastereomeric ratio) and 98-99% ee (enamtiomeric excess). The reaction of nonsubstituted 1,3-dithiane also proceeded in a highly enantioselective manner to give the monoxide with a small formation of the trans-1,3-dioxide, an overoxidation product. Five-membered 1,3-dithiolanes and seven-membered 1,3-dithiepanes also underwent oxidation to give monoxides with high diastereo- and enantioselectivity. It was found that the equilibrium between the two chairlike conformers of dithianes has relevance to the observed diastereoselectivity in the first oxidation process, and the dioxide formation in the oxidation of 1,3-dithiane and its stereochemistry also can be explained by the conformational equilibrium of the product monoxide. 相似文献
984.
This paper presents detailed numerical results of the competitive diffusion Lotka-Volterra equation (May-Leonard type). First, we derive the global phase diagrams of attractors in the parameter space including the system size, where transition lines between simple attractors are clearly obtained in accordance with the results of linear stability analysis, but the transition borders become complex when multi-basin structures appear. The complex aspects of the transition borders are studied in the case when the system size decreases. Next, we show the statistical aspects of the turbulence with special attention to the onset of the supercritical Hopf bifurcation. Several characteristic quantities, such as correlation length, correlation time, Lyapunov spectra and Lyapunov dimension, are investigated in detail near the onset of turbulence. Our data show the critical scaling law near the onset only in the restricted parameter domain. However even when the critical indices are not determined accurately, it is shown that the empirical scaling relations are obtained in a wide parameter domain far from the onset point and those scaling indices satisfy several relations. These scaling relations are discussed in comparison with the result derived by the phase reduction method. Lastly, we make a conjecture about the stability of an ecosystem based on the bifurcation diagram: the ecosystem obeying the Lotka-Volterra equation in the case of May-Leonard type is stabilized more as the system size increases. 相似文献
985.
Takashi Kuchiyama Kenji YamamotoShigehiko Hasegawa Hajime Asahi 《Applied Surface Science》2011,258(4):1488-1490
Surface morphology and crystalline structure of high-stable zinc oxide films were evaluated by atomic force microscopy, scanning electron microscopy and X-ray diffraction (XRD) measurements. AFM measurement revealed that the higher stable samples have smaller roughness (average roughness and root mean square) parameters than the lower stable samples. Furthermore, in-plane XRD measurement showed that the crystallite size of high stable samples is smaller than that of the low stable samples. These results indicate that the larger surface area and lower film density deteriorates the stability of zinc oxide films through the adsorption and reaction of water or oxygen molecules. They also suggest that we can prepare the high stable zinc oxide transparent electrode films by controlling the surface morphology. 相似文献
986.
Visible light emission from atoms and ions sputtered on a polycrystalline Ti surface was observed under irradiation of 30 keV Ar3+ ions. A number of atomic lines of Ti I and II were observed in the wavelength of 250-850 nm. The intensity of Ti II emission increased 1.3-5.6 times by introducing oxygen molecules at a pressure of 5.8 × 10−5 Pa, whereas that of Ti I decreased 0.5-0.8 times. Factors enhancing or reducing photon intensities were plotted as a function of energy of the corresponding electrons in the excited states for Ti atoms and Ti+ ions. 相似文献
987.
Takayoshi Oshima Tom Ichibha Kenji Oqmhula Keisuke Hibino Hiroto Mogi Shunsuke Yamashita Kotaro Fujii Yugo Miseki Kenta Hongo Daling Lu Ryo Maezono Kazuhiro Sayama Masatomo Yashima Koji Kimoto Hideki Kato Masato Kakihana Hiroshi Kageyama Kazuhiko Maeda 《Angewandte Chemie (International ed. in English)》2020,59(24):9736-9743
Undoped layered oxynitrides have not been considered as promising H2‐evolution photocatalysts because of the low chemical stability of oxynitrides in aqueous solution. Here, we demonstrate the synthesis of a new layered perovskite oxynitride, K2LaTa2O6N, as an exceptional example of a water‐tolerant photocatalyst for H2 evolution under visible light. The material underwent in‐situ H+/K+ exchange in aqueous solution while keeping its visible‐light‐absorption capability. Protonated K2LaTa2O6N, modified with an Ir cocatalyst, exhibited excellent catalytic activity toward H2 evolution in the presence of I? as an electron donor and under visible light; the activity was six times higher than Pt/ZrO2/TaON, one of the best‐performing oxynitride photocatalysts for H2 evolution. Overall water splitting was also achieved using the Ir‐loaded, protonated K2LaTa2O6N in combination with Cs‐modified Pt/WO3 as an O2 evolution photocatalyst in the presence of an I3?/I? shuttle redox couple. 相似文献
988.
Hiromichi Egami Taiki Rouno Tomoki Niwa Kousuke Masuda Kenji Yamashita Yoshitaka Hamashima 《Angewandte Chemie (International ed. in English)》2020,59(33):14101-14105
A linked dicarboxylate phase‐transfer catalyst enables smooth asymmetric dearomative fluorination of 2‐naphthols with Selectfluor under mild conditions to give the corresponding 1‐fluoronaphthalenone derivatives in a highly enantioselective manner. This reaction, which is compatible with a range of functional groups, is the first example of catalytic asymmetric fluorination of 2‐naphthols, and is expected to be useful in the synthesis of bioactive molecules. 相似文献
989.
Stereospecific Cyclic Poly(methyl methacrylate) and Its Topology‐Guided Hierarchically Controlled Supramolecular Assemblies
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Jing Ming Ren Prof. Kotaro Satoh Dr. Tor Kit Goh Dr. Anton Blencowe Dr. Kanji Nagai Dr. Kenji Ishitake Dr. Andrew Joseph Christofferson Dr. George Yiapanis Prof. Irene Yarovsky Prof. Masami Kamigaito Prof. Greg Guanghua Qiao 《Angewandte Chemie (International ed. in English)》2014,53(2):459-464
In this study, the stereocomplexation between a novel stereospecific cyclic vinyl polymer, that is, cyclic syndiotactic poly(methyl methacrylate) (st‐PMMA), with the complementary linear isotactic (it‐) PMMA was investigated. Surprising new insight into the effects of the topology (i.e., end groups), size, and tacticity of the assembling components on stereocomplex formation was obtained. Characterization of the stereocomplexes revealed that the self‐assembly of cyclic st‐PMMAs and linear it‐PMMAs resulted in the formation of an unprecedented “polypseudorotaxane‐type” supramolecular assembly. This stereocomplex exhibited remarkably different physical properties as compared to the conventional PMMA triple‐helix stereocomplex as a result of the restricted topology imposed by the cyclic st‐PMMA assembling component. 相似文献
990.
Elucidation of Pseurotin Biosynthetic Pathway Points to Trans‐Acting C‐Methyltransferase: Generation of Chemical Diversity
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Dr. Yuta Tsunematsu Manami Fukutomi Dr. Takayoshi Saruwatari Prof. Dr. Hiroshi Noguchi Prof. Dr. Kinya Hotta Prof. Dr. Yi Tang Prof. Dr. Kenji Watanabe 《Angewandte Chemie (International ed. in English)》2014,53(32):8475-8479
Pseurotins comprise a family of structurally related Aspergillal natural products having interesting bioactivity. However, little is known about the biosynthetic steps involved in the formation of their complex chemical features. Systematic deletion of the pseurotin biosynthetic genes in A. fumigatus and in vivo and in vitro characterization of the tailoring enzymes to determine the biosynthetic intermediates, and the gene products responsible for the formation of each intermediate, are described. Thus, the main biosynthetic steps leading to the formation of pseurotin A from the predominant precursor, azaspirene, were elucidated. The study revealed the combinatorial nature of the biosynthesis of the pseurotin family of compounds and the intermediates. Most interestingly, we report the first identification of an epoxidase C‐methyltransferase bifunctional fusion protein PsoF which appears to methylate the nascent polyketide backbone carbon atom in trans. 相似文献