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61.
[reaction: see text] Ab initio calculations using 6-311G**, cc-pVDZ, aug-cc-pVDZ, and a (valence) double-zeta pseudopotential (DZP) basis set, with (QCISD, CCSD(T)) and without (UHF) the inclusion of electron correlation, and density functional methods (BHandHLYP, B3LYP) predict that alpha,beta-unsaturated acyl radicals and alpha-ketenyl radicals exist as isomers. At the CCSD(T)/cc-pVDZ//BHandHLY/cc-pVDZ level of theory, energy barriers of 15.1 and 17.7-21.7 kJ mol(-)(1) are calculated for the isomerization of s-trans-propenoyl and s-trans-crotonoyl radical to ketenylmethyl and 1-ketenylethyl radical, respectively. Similar results are obtained for the reactions of s-trans isomers involving silyl, germyl, and stannyl groups with energy barriers (DeltaE++) of 12.2-12.4, 13.1-13.9, and 12.9-18.2 kJ mol(-)(1) at the CCSD(T)/DZP//BHandHLYP/DZP calculation, respectively. These results suggest that alpha,beta-unsaturated acyl radicals and alpha-ketenyl radicals are not canonical forms but are isomeric species that can rapidly interconvert. 相似文献
62.
Lee JM Min YJ Lee KB Jeon SG Na JG Ryu HJ 《Langmuir : the ACS journal of surfaces and colloids》2010,26(24):18788-18797
The awareness of symptoms of global warming and its seriousness urges the development of technologies to reduce greenhouse gas emissions. Carbon dioxide (CO(2)) is a representative greenhouse gas, and numerous methods to capture and storage CO(2) have been considered. Recently, the technology to remove high-temperature CO(2) by sorption has received lots of attention. In this study, hydrotalcite, which has been known to have CO(2) sorption capability at high temperature, was impregnated with K(2)CO(3) to enhance CO(2) sorption uptake, and the mechanism of CO(2) sorption enhancement on K(2)CO(3)-promoted hydrotalcite was investigated. Thermogravimetric analysis was used to measure equilibrium CO(2) sorption uptake and to estimate CO(2) sorption kinetics. The analyses based on N(2) gas physisorption, X-ray diffractometry, Fourier transform infrared spectrometry, Raman spectrometry, transmission electron microscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy were carried out to elucidate the characteristics of sorbents and the mechanism of enhanced CO(2) sorption. The equilibrium CO(2) sorption uptake on hydrotalcite could be increased up to 10 times by impregnation with K(2)CO(3), and there was an optimal amount of K(2)CO(3) for a maximum equilibrium CO(2) sorption uptake. In the K(2)CO(3)-promoted hydrotalcite, K(2)CO(3) was incorporated without changing the structure of hydrotalcite and it was thermally stabilized, resulting in the enhanced equilibrium CO(2) sorption uptake and fast CO(2) sorption kinetics. 相似文献
63.
Yunhua Yu Qing Yang Donghua Teng Xiaoping Yang Seungkon Ryu 《Electrochemistry communications》2010,12(9):1187-1190
Reticular tin nanoparticle-dispersed carbon (Sn/C) nanofibers were fabricated by stabilization of electrospun SnCl4/PAN composite fibers and subsequent carbonization at different temperatures. These Sn/C composite nanofibers used as anode materials for rechargeable lithium-ion batteries (LIBs) show that the Sn/C nanofibers at 700 and 850 °C present much higher charge (785.8 and 811 mA h g?1) and discharge (1211.7 and 993 mA h g?1) capacities than those at 550 and 1000 °C and the as-received CNFs at 850 °C, corresponding to coulombic efficiencies of 64.9% and 81.7%, respectively. The superior electrochemical properties of the intriguing Sn/C nanofibers indicate a promising application in high performance Li-ion batteries. 相似文献
64.
Lee BH Ryu MK Choi SY Lee KH Im S Sung MM 《Journal of the American Chemical Society》2007,129(51):16034-16041
We report a new layer-by-layer growth method of self-assembled organic multilayer thin films based on gas-phase reactions. In the present molecular layer deposition (MLD) process, alkylsiloxane self-assembled multilayers (SAMs) were grown under vacuum by repeated sequential adsorptions of C=C-terminated alkylsilane and titanium hydroxide. The MLD method is a self- limiting layer-by-layer growth process, and is perfectly compatible with the atomic layer deposition (ALD) method. The SAMs films prepared exhibited good thermal and mechanical stability, and various unique electrical properties. The MLD method, combined with ALD, was applied to the preparation of organic-inorganic hybrid nanolaminate films in the ALD chamber. The organic-inorganic hybrid superlattices were then used as active mediums for two-terminal electrical bistable devices. The advantages of the MLD method with ALD include accurate control of film thickness, large-scale uniformity, highly conformal layering, sharp interfaces, and a vast library of possible materials. The MLD method with ALD is an ideal fabrication technique for various organic-inorganic hybrid superlattices. 相似文献
65.
Ryu Sato Toshiyuki Fujio Shiduko Nakajo Satoshi Ogawa Ashraful Alam 《Tetrahedron letters》2007,48(17):3013-3016
The synthesis of benzopentathiepin having a hydroxyl group at the neighboring position of polysulfur ring was performed by demethylation of 6-ethyl-9-methoxybenzopentathiepin with hydrogenbromide. Benzotrithiole having hydroxyl group was not isolated at all. The hydroxyl group was also alkylated with alkyl iodide in the presence of weak base. 相似文献
66.
Monodisperse poly(methyl methacrylate) (PMMA) particles containing various concentrations of stearyl methacrylate (SMA) were prepared, and a liquid crystal (LC) was swollen into the particles using a solute co-diffusion method (SCM). Phase separation behaviors between the polymer and LC were monitored by utilizing an optical and a polarized microscope (OM/POM). The monodisperse LC microcapsules were then applied to a polymer-dispersed liquid crystal (PDLC), and the electro-optical properties were investigated. As a result, the threshold and driving voltages were improved when the SMA content increased. The long alkyl chains of SMA in the capsules should exist at the interface of the LC and polymer resulting in an enhancement of phase separation between the polymer and LC, which largely influences the electro-optical properties of PDLC. 相似文献
67.
Young Bok Ryu Ji Sun Kim Kyeong Ho Kim Yangdo Kim Man Sig Lee 《Research on Chemical Intermediates》2016,42(1):83-93
Zn/Al mixed oxide was prepared by the coprecipitation or the hydrothermal method under different conditions and used as catalyst for synthesis of glycerol carbonate by carbonylation of glycerol with urea. The physical properties of the prepared Zn/Al mixed oxide particles were investigated, as well as their activity as catalyst in the mentioned synthesis. The dried Zn/Al mixed-oxide particles prepared by the coprecipitation method showed higher activity in synthesis of glycerol carbonate than those prepared by the hydrothermal method. The Zn/Al mixed oxide prepared by the coprecipitation method without NaNO3 showed the highest catalytic activity in synthesis of glycerol carbonate. 相似文献
68.
S. C. Chae Y. N. Jang I. K. Bae K. W. Ryu T. S. Yudintseva S. V. Yudintsev 《Journal of Radioanalytical and Nuclear Chemistry》2007,273(1):73-77
This study was aimed at the synthesis, study of phase relations and characterization of the garnet ([Ca1.5GdCe0.5]VIII[ZrFe]VI[Fe
x
Al3−x
]IVO12, x = 0−2) intended as promising matrix for actinides (Pu) immobilization. The optimum temperatures of the fabrication of the
garnets ceramics are 1400 °C at x = 2 and 1500 °C at x = 0−1. The garnets lattice parameters and the content of Ce, as an imitator of Pu, increased with the content of iron. It
was suggested that the ability of the garnet for incorporation of Pu was closely related to the ionic radii of the elements
occupied the four-and six-coordinated sites of the structure. 相似文献
69.
70.