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排序方式: 共有853条查询结果,搜索用时 15 毫秒
101.
Kei Fujise Eiji Tsurumaki Gaku Fukuhara Nobuyuki Hara Yoshitane Imai Shinji Toyota 《化学:亚洲杂志》2020,15(16):2456-2461
Polycyclic aromatic hydrocarbons consisting of three fused anthracene units were designed as new π‐conjugated compounds having helical structures. These expanded helicenes were synthesized by Pt‐catalyzed cycloisomerization of the corresponding ethynyl‐substituted precursors. The nonplanar and helical structure was confirmed by X‐ray analysis and DFT calculations, and the barrier to helical inversion was estimated to be 34 kJ mol?1. The enantiomers of the diphenyl derivative were successfully resolved by chiral HPLC. Enantiopure samples showed good chiroptical performance in the CD (|Δ?| 1380 L mol?1 cm?1) and CPL (|glum| 0.013) spectra, and these values were considerably large for simple organic molecules. The unique chiroptical properties are discussed on the basis of the molecular structure and the electronic state with the aid of time‐dependent DFT calculations. 相似文献
102.
Prof. Dr. Shunichi Fukuzumi Dr. Kei Ohkubo Dr. Yong‐Min Lee Prof. Dr. Wonwoo Nam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17548-17559
Redox‐inactive metal ions and Brønsted acids that function as Lewis acids play pivotal roles in modulating the redox reactivity of metal–oxygen intermediates, such as metal–oxo and metal–peroxo complexes. The mechanisms of the oxidative C?H bond cleavage of toluene derivatives, sulfoxidation of thioanisole derivatives, and epoxidation of styrene derivatives by mononuclear nonheme iron(IV)–oxo complexes in the presence of triflic acid (HOTf) and Sc(OTf)3 have been unified as rate‐determining electron transfer coupled with binding of Lewis acids (HOTf and Sc(OTf)3) by iron(III)–oxo complexes. All logarithms of the observed second‐order rate constants of Lewis acid‐promoted oxidative C?H bond cleavage, sulfoxidation, and epoxidation reactions of iron(IV)–oxo complexes exhibit remarkably unified correlations with the driving forces of proton‐coupled electron transfer (PCET) and metal ion‐coupled electron transfer (MCET) in light of the Marcus theory of electron transfer when the differences in the formation constants of precursor complexes were taken into account. The binding of HOTf and Sc(OTf)3 to the metal–oxo moiety has been confirmed for MnIV–oxo complexes. The enhancement of the electron‐transfer reactivity of metal–oxo complexes by binding of Lewis acids increases with increasing the Lewis acidity of redox‐inactive metal ions. Metal ions can also bind to mononuclear nonheme iron(III)–peroxo complexes, resulting in acceleration of the electron‐transfer reduction but deceleration of the electron‐transfer oxidation. Such a control on the reactivity of metal–oxygen intermediates by binding of Lewis acids provides valuable insight into the role of Ca2+ in the oxidation of water to dioxygen by the oxygen‐evolving complex in photosystem II. 相似文献
103.
Nakamura R Imanishi A Murakoshi K Nakato Y 《Journal of the American Chemical Society》2003,125(24):7443-7450
Multiple internal reflection infrared spectroscopy was applied to in situ investigations of surface intermediates of photocatalytic reactions on nanocrystalline TiO(2) films in contact with aqueous solutions. UV irradiation in the presence of dissolved O(2) caused the appearance of new bands peaked at 943, 838, and 1250-1120 cm(-)(1) together with intensity changes in other bands. Investigations of influences of the solution pH, the presence or absence of hole and electron scavengers, and isotopic H(2)O --> D(2)O exchange on the spectral changes have revealed that the primary step of photocatalytic O(2) reduction is the formation of the surface peroxo species, Ti(O(2)), giving the 943 cm(-)(1) band, probably with the surface superoxo species, TiOO., as a precursor, in neutral and acidic solutions. The surface peroxo species is then transformed to the surface hydroperoxo, TiOOH, giving the 838 and 1250-1120 cm(-)(1) bands, by protonation in the dark. This is, to our knowledge, the first direct in situ spectroscopic detection of primary intermediates for the photocatalytic O(2) reduction in aqueous solutions. On the basis of the assignment, a possible reaction scheme for various processes of the photocatalytic O(2) reduction is proposed, which is in harmony with other spectral changes induced by the UV irradiation. 相似文献
104.
Inside Back Cover: Plasmon‐Assisted Water Splitting Using Two Sides of the Same SrTiO3 Single‐Crystal Substrate: Conversion of Visible Light to Chemical Energy (Angew. Chem. Int. Ed. 39/2014) 下载免费PDF全文
105.
106.
Kei Ito 《Physics letters. [Part B]》1985,155(4):260-262
The derivation of the representations of BRS algebra in the Landau gauge is simplified by the superspace formalism. It is shown that the operation of the metric matrix can be interpreted as a kind of inversion of the superspace. 相似文献
107.
Absorption, pH and electric conductance of rhodamine BLiClH2O solutions are examined. The obtained results show that aqueous rhodamine B has a tendency to dimerize by the addition of LiCl. Other features on the structural properties of rhodamine B in aqueous LiCl solutions are discussed briefly. 相似文献
108.
109.
Kei Matsuzaki Muneshisa Okada Kojitsu Goto 《Journal of polymer science. Part A, Polymer chemistry》1972,10(3):823-828
The deuterium-decoupled methine proton spectra of polyacrylonitrile-β,β-d2 were measured at 156°C in dimethylsulfoxide-d6 solution. Splittings of triad peaks caused by pentad sequences were observed. The isotactic triad resonance was resolved into three peaks and the heterotactic resonance into two peaks, while the syndiotactic resonance was unresolved or resolved into three peaks. The splittings were assigned by comparing the probability of each pentad sequence with observed intensities. The pentad signal shifted to the higher magnetic field with increasing number of meso configurations as neighbors of the central triad. It was observed that the pentad of atactic polyacrylonitrile-β,β-d2 obeyed Bernoullian statistics but that of isotactic polymer obtained by γ-ray irradiation of the canal complex seemingly obeyed first-order Markov statistics. 相似文献
110.
Akihiro Fukabori Takayuki Yanagida Federico Moretti Yuui Yokota Rayko Shimura Shuji Maeo Jan Pejchal Kei Kamada Akira Yoshikawa 《Radiation measurements》2010,45(3-6):453-456
Micro-pulling down (μ-PD) method allows to prepare single crystals quickly and relatively inexpensively. Since it is a melt growth and taking into account segregation phenomena, the μ-PD method allows also to obtain single crystals characterized by dopant concentration gradients. Especially, taking the advantage of the grown crystal high aspect ratio, it allows to prepare crystalline samples with variable and wide range concentrations of dopants. These samples can help in understanding the correlation between dopant concentration and luminescence properties. 相似文献