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排序方式: 共有168条查询结果,搜索用时 15 毫秒
61.
Koki Yamaguchi Masashi Eto Yasuyuki Yoshitake Kazunobu Harano 《Journal of Physical Organic Chemistry》2013,26(1):64-69
The reaction of 3,5‐bis(methoxycarbonyl)‐4‐oxo‐4H‐pyrazole 1,2‐dioxide (1a) with 1,3,5‐cycloheptatriene (2b) gave a mixture of the novel endo‐[4 + 6]‐cycloadduct (4ab), anti‐exo‐[4 + 2]‐cycloadduct (5ab), and the heterocage (6ab) derived from the intramolecular 1,3‐dipolar cycloaddition reaction of the syn‐endo‐[4 + 2]‐cycloadduct. Analogous endo‐[4 + 6] selectivity in 1,3‐dipolar cycloadditions has not been reported previously. The X‐ray analysis indicates that 6ab has a very long Nsp3–Nsp3 bond distance of 1.617(4) Å. The cycloaddition behaviour is discussed on the basis of transition‐state structures optimized at the B3LYP/6‐31G(d) level of theory, from which predictions of the peri‐, regio‐, and stereoselectivities agreed well with the experimental results. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
62.
Koki YamguchiMasashi Eto Kenta HigashiYasuyuki Yoshitake Kazunobu Harano 《Tetrahedron letters》2011,52(46):6082-6085
2,5-Bis(methoxycarbonyl)-3,4-diphenylcyclopentadienone (1) reacts with 4-phenylbut-3-yn-2-one (2b) in the presence of DABCO to give the bicyclic carbocycles (6b) and the tetracyclic carbocycle (7b) under extremely mild reaction conditions. 相似文献
63.
Surface-enhanced Raman spectroscopy (SERS) is a highly sensitive vibrational technique to obtain the structural information of chemical species on their surface and interface. In this short article, we briefly review the current research regarding the reaction mechanism and kinetics on the cathode surface of the Li–O2 battery by in situ SERS observations, including reaction intermediates and products, influence of solvent, discharge/charge mechanisms, and mediation mechanism of redox mediators. 相似文献
64.
We report a successful attempt to derive a closed-form expression for the relaxation function of a complex system by solving a set of coupled kinetic equations connecting the excitation/de-excitation rates to the number of particles (such as electrical charges, dipoles, etc.) in excited states. Our approach, originating from developments in dielectric and mechanical relaxation studies, allows the use of a unified treatment for a wide array of natural processes which often pose challenges to theoretical modeling. We use the notions that (i) a dipole represents any pair formed by a particle in an excited state (such as an energy level in optically excited molecules, or an electrode in dielectric spectroscopy) and its image in the ground state (or reference electrode), that (ii) coupling between such dipoles may be described as particle transfer from one excited state to another with lower energy, and that (iii) the relaxation function for such a system of dipoles is mathematically equivalent to the cumulative distribution function of particles, i.e., the total number of particles that are still in an excited state at a time t following excitation. Taken together, these ideas naturally lead to the identification of two types of relaxation – parallel and serial relaxation – and allow one to tackle systems with either geometrical or physical self-similarity within a unified mathematical scheme. 相似文献
65.
Morphology and properties of globular polymeric materials in the solid state: A composite material of DNA with a cationic surfactant 下载免费PDF全文
Emmanuel C. Ossai Yuka Tomimori Shota Ohki Koki Okada Takeshi Yonekura Kazuya Furusawa Naoki Sasaki 《Journal of Polymer Science.Polymer Physics》2016,54(7):730-738
The aim of the present study was to control entanglements in order to regulate the properties of polymeric solids. Initially, fabrication of polymeric solids with few entanglements was attempted. Films of the DNA–cationic surfactant, cetyltrimethylammonium bromide (CTAB) (DNA–CTA), were cast from ethanol solution at room temperature. Morphological examination of DNA–CTA complex films using atomic force microscopy (AFM) revealed that these films were constructed by particle‐like substances. Geometrical analysis of AFM images showed that the particle‐like substances were the aggregates of several DNA–CTA globules. Mechanical characterization suggested that there were fewer entanglements than with normal plastic films. Small angle X‐ray scattering experiments during annealing indicated that molecular motions were highly excited in the surface region of each particle. In conclusion, a globular polymeric film with fewer entanglements was fabricated. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 730–738 相似文献
66.
E. Krentsel S. Fusselman H. Yasuda T. Yasuda M. Miyama 《Journal of polymer science. Part A, Polymer chemistry》1994,32(10):1839-1845
The depth of surface modification by low-temperature cascade arc torch is investigated. A stack of 10 sheets of nonwoven fabrics of polyester fibers is exposed to a low-temperature cascade arc torch containing CF4 or C2F4, and the fluorination effect is examined by ESCA. It is shown that interaction of chemically reactive species, created in a low-temperature cascade arc torch, with the surface is not limited to the surface contacted by the torch (flame). The results indicate that the fluorination effect is observed on surfaces which are shadowed from the torch by overlying fibers. The highest degree of fluorination is found on the second layer, rather than on the first layer which the torch contacts directly. No significant differences in the trends of penetration of CF4 and C2F4 treatment through porous samples are observed. However, ESCA data show principal differences in chemical structures of the surfaces treated with CF4 (nonpolymer-forming gas) and C2F4 (polymer-forming gas). These results indicate that chemically reactive species induced by the excited species of argon rather than primary species created by the ionization process seem to play predominant roles in the surface treatment as well as the low-temperature cascade arc torch polymerization of perfluorinated compounds. © 1994 John Wiley & Sons, Inc. 相似文献
67.
E. Krentsel H. Yasuda M. Miyama T. Yasuda 《Journal of polymer science. Part A, Polymer chemistry》1995,33(17):2887-2892
The depth and possible mechanisms of the penetration of surface modification into porous media by a low temperature cascade are torch are investigated. Two different modes of such penetration (“flow controlled” and “diffusion controlled”) are evaluated. Three porous samples [stacks of 10 sheets of nonwoven fabrics of poly(ethylene terephthalate)each], placed at an axial distance of 24, 28, and 32 cm from the cascade are anode, are exposed to a low temperature cascade arc torch containing argon and CF4 or C2F4, and surface properties of each of the sheets within treated porous samples are examined by ESCA. It is shown that interaction of chemically reactive species, created in the low temperature cascade arc torch, with the surface is not limited to the surface directly contacted by the torch. The flow controlled penetration is more pronounced for the outer layers, while diffusion controlled penetration is within the inner layers of the porous structure. Substantial differences in the fluorination effect of CF4 (nonpolymer forming gas) and C2F4 (polymer forming gas) discharges for the second and third stacks are observed, that can be explained by the fact that the major effect of the CF4 cascade arc torch treatment is based on the reaction of reactive species with the surface polymer molecules. The effect of C2F4 cascade arc torch treatment is based on the reactions of reactive species with polymers as well as reactions of reactive species themselves at the surface (plasma polymerization). Reactivity of the species created in C2F4 discharge is much higher compared to that created in CF4 discharge, which is one of the major factors influencing penetration trends of low temperature cascade arc treatment into porous media. © 1995 John Wiley & Sons, Inc. 相似文献
68.
ON THE TWO FORMS OF INTERMEDIATE M OF BACTERIORHODOPSIN 总被引:1,自引:0,他引:1
Abstract— The decay time course of intermediate M of bacteriorhodopsin was investigated by flash spectrophotometry. The decay was composed of two exponentials showing the existence of two forms of intermediate absorbing around 410 nm. The two were very different in kinetic character whereas the absorption spectra were almost the same. The relative yield of the two components was a function of the intensity of the exciting flash and the slower component disappeared when the flash intensity was made very small. A model based on the trimeric cluster structure of bacteriorhodopsin is proposed. 相似文献
69.
The rate constant for the reaction NH3 + OH → NH2 + H2O was determined by the comparison of the calculated induction period data with experiments by the shock tube technique in the range 1360–1840 K, for NH3-H2-O2-Ar mixtures. The rate constants can be represented by the expression k = 1012.49±0.04exp[(?1.95±0.15) kcal/,RT] cm3 mol?1 s?1. 相似文献
70.
Dr. Shunsuke Kato Koki Takeuchi Motonao Iwaki Prof. Dr. Kentaro Miyazaki Prof. Dr. Kohsuke Honda Prof. Dr. Takashi Hayashi 《Angewandte Chemie (International ed. in English)》2023,62(31):e202303764
Affinity purification of recombinant proteins is an essential technique in biotechnology. However, current affinity purification methods are very cost-intensive, and this imposes limits on versatile use of affinity purification for obtaining purified proteins for a variety of applications. To overcome this problem, we developed a new affinity purification system which we call CSAP (chitin- and streptavidin-mediated affinity purification) for low-cost purification of Strep-tag II fusion proteins. The CSAP system is designed to utilize commercially available chitin powder as a chromatography matrix, thereby significantly improving the cost-efficiency of protein affinity purification. We investigated the CSAP system for protein screening in 96-well format as a demonstration. Through the screening of 96 types of purified hemoproteins, several proteins capable of the catalytic diastereodivergent synthesis of cyclopropanes were identified as candidates for an abiotic carbene transfer reaction. 相似文献