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41.
Ochiai M Takeuchi Y Katayama T Sueda T Miyamoto K 《Journal of the American Chemical Society》2005,127(35):12244-12245
Reported here for the first time is the iodobenzene-catalyzed alpha-oxidation of ketones, in which diacyloxy(phenyl)-lambda3-iodanes generated in situ act as real oxidants of ketones and m-chloroperbenzoic acid serves as a terminal oxidant. Oxidation of a ketone with m-chloroperbenzoic acid in acetic acid in the presence of a catalytic amount of iodobenzene, BF3.Et2O, and water at room temperature under argon affords an alpha-acetoxy ketone in good yield. p-Methyl- and p-chloroiodobenzene also serve as efficient catalysts in this direct oxidation. We found that when the reaction was carried out in the absence of a catalytic amount of iodobenzene, Baeyer-Villiger oxidation of a ketone took place. It is noted that use of water and BF3.Et2O is crucial to the success of this alpha-acetoxylation. 相似文献
42.
Thermal decomposition of 1-tert-butylperoxy-1,2-benziodoxol-3(1H)-one in cyclic ethers and acetals at 50 degrees C generates alpha-oxy carbon-centered radicals, which undergo an addition reaction with vinyl sulfones and unsaturated esters. 相似文献
43.
Yasunori Fujikoshi 《Annals of the Institute of Statistical Mathematics》1981,33(1):279-285
Summary This paper deals with the likelihood ratio test for additional information in a multivariate linear model. It is shown that
the power of the likelihood ratio test procedure has a monotonicity property. Asymptotic approximations for the power are
also obtained. 相似文献
44.
45.
Nakayama T Kurosawa Y Furui S Kerman K Kobayashi M Rao SR Yonezawa Y Nakano K Hino A Yamamura S Takamura Y Tamiya E 《Analytical and bioanalytical chemistry》2006,386(5):1327-1333
Polymerase chain reaction (PCR) is an essential part of research based on genomics or cell analysis. The development of a
microfluidic device that would be suitable for high-temperature-based reactions therefore becomes an important contribution
towards the integration of micro-total analysis systems (μTAS). However, problems associated with the generation of air bubbles
in the microchannels before the introduction of the assay liquid, which we call the “initial start-up” in this study, made
the flow irregular and unstable. In this report, we have tried to address these problems by adapting a novel liquid-flow method
for high-temperature-based reactions. A PDMS-based microfluidic device was fabricated by soft-lithography techniques and placed
on a cartridge heater. The generation of the air bubbles was prevented by introducing the fluorinated oil, an inert and highly
viscous liquid, as the cap just before the introduction of the sample solutions into the microchannels. The technique was
applied for continuous-flow PCR, which could perform PCR on-chip in a microfluidic system. For the evaluation of practical
accuracy, plasmid DNA that serves as a reference molecule for the quantification of genetically modified (GM) maize was used
as the template DNA for continuous-flow PCR. After PCR, the products were collected in a vial and analyzed by gel electrophoresis
to confirm the accuracy of the results. Additionally, quantitative continuous-flow PCR was performed using TaqMan technology
on our PCR device. A laser detection system was also used for the quantitative PCR method. We observed a linear relationship
between the threshold cycle (Ct) and the initial DNA concentration. These results showed that it would be possible to quantify
the initial copies of the template DNA on our microfluidic device. Accurate quantitative DNA analysis in microfluidic systems
is required for the integration of PCR with μTAS, thus we anticipate that our device would have promising potential for applications
in a wide range of research. 相似文献
46.
Methylenecyclopentanones were synthesized by the nickel-catalyzed [3+1+1] cycloaddition reactions of alkenyl Fischer carbene complexes with methylenecyclopropanes. The methylenecyclopropane was transformed into the C(2)-symmetric bis-cyclopentapyridazine derivative by reacting with p-toluenesulfonyl hydrazine. 相似文献
47.
Yasunori Nishijima 《Journal of Macromolecular Science: Physics》2013,52(3-4):389-411
The characteristics of photoluminescence are affected by the molecular motions in the local environment of the excited molecule. Hence, by knowing the lifetime of the excited state, various relaxation times of the molecular motions can be estimated from the emission characteristics. In the present paper the effect of the molecular motions manifested in the fluorescence emission, such as the rotational depolarization of fluorescence, the internal quenching of fluorescence due to internal rotation, and the inter-and intramolecular excimer formation, are reviewed and the possible applications of such phenomena to the study of molecular motions in polymer systems are discussed. The application of fluorescence methods provide unique information about the molecular motions in the nanosecond range in polymer solutions, melts, and solids. 相似文献
48.
Molecular recognition of dicarboxylates by a dinuclear zinc(II) complex of 2,2?-binaphthalene bearing di(2-pyridyl)aminomethyl groups at 8- and 8?-positions ([Zn2L]4+) by UV-vis and fluorescence spectral titrations in an aqueous solvent was investigated. In a series of α,ω-dicarboxylate, receptor [Zn2L]4+ showed the highest binding affinity for succinate and UV-vis and fluorescence changes were also largest upon the addition of this guest. In a series of phthalate derivatives, phthalate was strongly bound by [Zn2L]4+. The characteristic UV-vis and fluorescence changes strongly depend on the dihedral angle of two naphthyl groups of the complex [Zn2L]4+· dicarboxylate estimated by spectral titrations and DFT calculations. 相似文献
49.
Anna V. Klassen Makoto Matsukura Osamu Nakamura Vladimir V. Kochurikhin Mikhail A. Ivanov Galina Yu. Orlova Akio Miyamoto Yasunori Furukawa 《Journal of Crystal Growth》2008,310(11):2895-2898
The applicability of the edge-defined film-fed growth (EFG) technique for YbxY(1−x)VO4 (x=0.05, 0.1 and 1) was approved by successful growth of crystals up to 80 mm in length as the thin plates. Low-angle grain boundaries and the crystal coloration as main defects were found. Optimal seed orientation was suggested on the strength of vanadate crystal plate morphology. Optical properties, chemical composition and the crystalline quality were investigated. 相似文献
50.
Anisotropic optical properties and nanostructures of thin films prepared by oblique co-deposition of Ag and SiO2 were studied. At low concentrations of Ag, a columnar structure grew towards the direction of the incident SiO2 vapor and small Ag particles were embedded in that structure. An inhomogeneous distribution of Ag was observed in cases where the Ag was deposited from the opposite side of the surface normal to the direction of the incident SiO2 vapor. This inhomogeneous distribution of Ag particles gives rise to optical anisotropy, i.e., the optical transmittance of p-polarized light varies drastically depending on the angle of incidence, while that of s-polarized light remains unchanged. A possible application of the anisotropic optical absorption properties of Ag---SiO2 hybrid films is in the manufactur of an inorganic thin film polarizer. 相似文献