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191.
CCl2自由基与H2O分子反应动力学研究 总被引:2,自引:0,他引:2
用213 nm激光光解CCl4产生CCl2自由基,用LP LIF技术测定了室温下基态CCl2自由基与H2O分子的反应速率常数为(5.45±0.95)×10-14 cm3•molecule-1•s-1.在G2MP2理论水平上计算了CCl2+H2O反应的最低单重态势能面,揭示了插入与加成 消除两种反应机理,得到了三个可能的产物通道:HCl+HClCO、HCl+trans ClCOH以及HCl+cis ClCOH.并用RRKM TST和传统过渡态理论计算了这三个通道的分支比及其温度效应.结果说明在低温下(273 K),插入机理的产物通道的分支比远大于加成 消除机理的产物通道, HCl+HClCO是主要产物,分支比为77.4%,其次是HCl+cis ClCOH,分支比为22.6%.而在高温下(3000 K),加成 消除机理的反应通道大于插入机理, HCl+trans ClCOH分支比为82.3%. 相似文献
192.
The controlled synthesis of SrCO3 nanostructures with different morphologies, such as rodlike, whiskerlike, ellipsoidlike, and spherelike, were successfully achieved by the cationic surfactant-CTAB-microemulsion-mediated solvothermal method. Various comparison experiments showed that fundamental experimental parameters, such as the molar ratio of H2O to CTAB and the concentration of reactants, played important roles in the morphological control of SrCO3 nanostructures. A lower molar ratio of H2O to CTAB favors rodlike products, whereas a higher molar ratio generally leads to the formation of spherical products. A rational mechanism based on fusion, aggregate, and coalescence of microemulsion droplets is proposed for the selective formation of various morphologies. X-ray powder diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and field-emission scanning electron microscope (FE-SEM) were used to characterize the products. 相似文献
193.
194.
Haoshuang Gu Yongming Hu Hao Wang Xiangrong Yang Zhenglong Hu Ying Yuan Jin You 《Journal of Sol-Gel Science and Technology》2007,42(3):293-297
Single crystalline nanowires of lead titanate (PbTiO3) were fabricated by hydrothermal method at 200°C using lead acetate and n-tetrabutyl titanate as starting materials, where sodium hydroxide was served as a mineralizer. Crystalline phases, microstructure
and optical properties of PbTiO3 nanowires were investigated. The PbTiO3 nanowires were uniform and continuous along the long axis, and were composed of single crystalline PbTiO3 with a tetragonal perovskite structure. The diameter of a single nanowire was around 12 nm and the length reached up to 3 μm.
The chemical composition of the samples and the valence states of elements were determined by X-ray photoelectron spectroscopy
(XPS). The ultraviolet/visible absorption spectroscopic investigation suggested that the absorption edge of optical transition
of the first excitonic state occurred at around 320 nm. A blue-green light emission peaking at about 471 nm (2.63 eV) is observed
at room temperature, and the intensity of this emission increased with increasing excitation wavelength. Oxygen vacancies
are responsible for the light emission of PbTiO3 nanowires. 相似文献
195.
Highly ordered rod-like large-pore periodic mesoporous organosilica (PMO) was successfully synthesized at low acid concentration with the assistance of inorganic salt using triblock copolymer P123 as a template. The roles of inorganic salt and acidity in the production of highly ordered mesostructure and the morphology control of PMOs were investigated. It was found that the inorganic salt can significantly widen the range of the synthesis parameters to produce highly ordered 2D hexagonal pore structure of p6mm symmetry. However, the uniform rod-like PMOs can only be synthesized in a narrow range of acid and salt concentrations, which were sensitive to induction time. The adsorption of lysozyme on PMO was studied at different pH values in comparison with adsorption on pure silica material under controlled morphology and pore structure. It was found that the adsorption capacity of lysozyme on the PMO was lower than that on pure SBA-15 silica material and the adsorption amounts are larger at pH 9.6 than at 7.0 for both materials. The results show that the electrostatic interaction between lysozyme and PMO/SBA-15 surface is more dominant than the hydrophobic forces and the interaction of neighboring lysozyme molecules also plays an important role. 相似文献
196.
Yuanchun Hu Xinmiao Liang Junwei Wang Zhuo Zheng Xinquan Hu 《Tetrahedron: Asymmetry》2003,14(24):3907-3915
A series of new phosphite–pyridine ligands, based on the H8-binaphthyl backbone, were synthesized and employed in the copper-catalyzed enantioselective 1,4-conjugate addition of diethylzinc to acyclic enones. Ligands derived from (S)-H8-NOBIN provided better results than their parent ligands in the reaction. Ligand L1 provided excellent ees for trans-4-aryl-3-buten-2-ones (up to 97.8% ee) as substrates. Ligand L2 was very efficient for various para-chalcones, and up to 97.2% ee was achieved. 相似文献
197.
Three ion-pair complexes, [RbzPy](+)[Ni(mnt)(2)](-) (mnt(2)(-) = maleonitriledithiolate; [RbzPy](+) = 4-R-benzylpyridinium; R = Br (1), Cl (2), and NO(2) (3)), with unusual magnetic properties have been synthesized and characterized. The crystal structures of 1 and 2 have been solved. The two complexes belong to the P2(1)/c space group with Z = 4 and C(20)H(11)BrN(5)NiS(4), a = 12.0744(17) A, b = 26.369(4) A, c = 7.440(3) A, and beta = 102.63(3) degrees for 1 and C(20)H(11)ClN(5)NiS(4), a = 12.105(2) A, b = 26.218(4) A, c = 7.374(2) A, and beta = 102.55(2) degrees for 2, respectively. The [Ni(mnt)(2)](-) anions in 1-3 form uniformly spaced one-dimensional (1-D) magnetic chains of s = 1/2 at room temperature. The temperature dependences of the susceptibility for 1-3 show that they undergo phase transitions. All three complexes are paramagnetic in their high-temperature (abbreviation HT) phase and diamagnetic in the low-temperature (abbreviation LT) phase because of strong dimerization along the stacking direction. The results of thermal analysis (DSC) further confirm that the phase transition for 1 and 2 is first-order but maybe second-order for 3. The phenomena observed in this study are similar to those of the 1-D radical systems. 相似文献
198.
Solid dispersions of silymarin were prepared by the fusion method with the intention of improving the dissolution properties of silymarin. Polyethylene glycol 6000 (PEG 6000) was used as the inert hydrophilic matrix. The dissolution studies of the solid dispersions were performed in vitro. And the results obtained showed that the dissolution rate of silymarin was considerably improved when formulated in solid dispersions with PEG 6000 as compared to original drug, and the increased dissolution rate might be favorable for further oral absorption. 相似文献
199.
Magnetically recoverable chiral catalysts immobilized on magnetite nanoparticles for asymmetric hydrogenation of aromatic ketones 总被引:1,自引:0,他引:1
Novel heterogenized asymmetric catalysts were synthesized by immobilizing preformed Ru catalysts on magnetite nanoparticles via the phosphonate functionality and were characterized by a variety of techniques, including TEM, magnetization, and XRD. These nanoparticle-supported chiral catalysts were used for enantioselective heterogeneous asymmetric hydrogenation of aromatic ketones with very high enantiomeric excess values of up to 98.0%. The immobilized catalysts were easily recycled by magnetic decantation and reused for up to 14 times without loss of activity and enantioselectivity. Orthogonal nature of the present catalyst immobilization approach should allow the design of other superparamagnetic nanoparticle-supported asymmetric catalysts for a wide range of organic transformations. 相似文献
200.
1,1-Difluoroethysilanes (R3SiCF2CH3, R = Me or Et) were synthesized from 1,1-difluoroethyl phenyl sulfone and chlorosilanes using magnesium metal via reductive 1,1-difluoroethylation. It was confirmed that 1,1-difluoroethylsilanes were effective 1,1-difluoroethylating reagents for carbonyl compounds. 相似文献