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61.
A regioselective oxidation of allylic C–H bond to C–O bond catalyzed by copper (I) was developed with diacyl peroxides as oxidants. The oxidation of allylic C–H bond was accomplished with good yield and regioselectivity under mild reaction conditions. This method has a broad substrate scope including cyclic olefins, terminal and internal acyclic olefins and allyl benzene compounds. The reaction proceeds by a radical mechanism as suggested by spin trapping experiments. 相似文献
62.
Xia Zhang Lu Zhang Tan Jin Zhi-jun Pan Zhe-ning Chen Qiang Zhang Wei Zhuang 《化学物理学报(中文版)》2017,30(6):811-816
The solvation of carbon dioxide in sea water plays an important role in the carbon circle and the world climate. The salting-out/salting-in mechanism of CO2 in electrolyte solutions still remains elusive at molecule level. The ability of ion salting-out/salting-in CO2 in electrolyte solution follows Hofmeister Series and the change of water mobility induced by salts can be predicted by the viscosity B-coefficients. In this work, the chemical potential of carbon dioxide and the dynamic properties of water in aqueous NaCl, KF and NaClO4 solutions are calculated and analyzed. According to the viscosity B-coefficients, NaClO4 (0.012) should salt out the carbon dioxide relative to in pure water, but the opposite effect is observed for it. Our simulation results suggest that the salting-in effect of NaClO4 is due to the strongly direct anion-CO2 interaction. The inconsistency between Hofmeister Series and the viscosity B-coefficient suggests that it is not always right to indicate whether a salt belongs to salting-in or salting-out just from these properties of the salt solution in the absence of solute. 相似文献
63.
The physical properties, namely structural, mechanical, and thermodynamic properties, of Pd2Al intermetallic compound were explored through first-principles calculations within the framework of density functional theory. The calculated lattice constants were consistent with the available experimental data. The calculated elastic constants revealed that Pd2Al was mechanically stable. By the predicted elastic constants, several related properties, namely Cauchy pressures, shear anisotropy factors, directional Young's modulus, bulk, shear and Young's moduli, the ratio of K/G, Vickers hardness, sound velocity, and minimum thermal conductivity for Pd2Al were evaluated. According to the calculated results, it was found that Pd2Al possesses a highly anisotropic feature and behaves in a ductile manner with low stiffness. Finally, temperature-dependence of thermodynamic properties, namely Debye temperature and heat capacity, were also evaluated through the quasi-harmonic Debye model. 相似文献
64.
Carbohydrate components in glycoproteins play a critical role in health and disease and specificity of glycoprotein biomarkers can be greatly enhanced by analysis of their sugar components containing frequently different isomers. We show that two glycan isomers, 2,3-sialyllactose and 2,6-sialyllactose (important in cancer), can be distinguished voltammetrically after their modification with osmium(VI) complexes. Using SWV at different frequencies and CV at different scan rates we found conditions for simple discrimination between these isomers at mercury and carbon electrodes. 相似文献
65.
We study a coarsening process of one-dimensional cell complexes. We show that if cell boundaries move with velocities proportional to the difference in size of neighboring cells, then the average cell size grows at a prescribed exponential rate and the Poisson distribution is precisely invariant for the distribution of the whole process, rescaled in space by its average growth rate. We present numerical evidence toward the following universality conjecture: starting from any finite mean stationary renewal process, the system when rescaled by e ?2t converges to a Poisson point process. For a limited case, this makes precise what has been observed previously in experiments and simulations, and lays the foundation for a theory of universal asymptotic states of dynamical cell complexes. 相似文献
66.
Peng Liu Hui Ruan Tiantian Li Jiaqi Chen Fuqiu Ma Duoqiang Pan Wangsuo Wu 《Molecules (Basel, Switzerland)》2021,26(4)
The low cost β-zeolite and ethylenediamine modified β-zeolite (EDA@β-zeolite) were prepared by self-assembly method and used for Cu(II) removal from contaminated aqueous solution. Removal ability of β-zeolite toward Cu(II) was greatly improved after ethylenediamine (EDA) modification, the removal performance was greatly affected by environmental conditions. XPS results illustrated that the amide group played important role in the removal process by forming complexes with Cu(II). The EDA@β-zeolite showed desirable recycling ability. The finding herein suggested that the proposed composite is a promising and suitable candidate for the removal of Cu(II) from contaminated natural wastewater and aquifer. 相似文献
67.
目前,手性配体辅助钯催化的区域和对映选择性碳氢键活化是过渡金属催化的前沿领域.在过去的十年中,它作为一种越来越重要的合成工具,用于合成含有各种不对称元素(中心手性、轴手性和平面手性)的手性分子,也是快速构建各种碳碳键和碳杂原子键的最有效方法之一.本文介绍了一些典型手性配体在钯催化不对称sp2和sp3碳氢键活化/官能团化反应中的应用,如单齿配体亚磷酰胺、手性磷酸(CPAs)和双功能氮端单保护的氨基酸(MPAAs)配体;探讨了这些手性配体辅助催化反应的创新性和特点,在理清这一研究领域发展脉络的同时,展望了未来研究工作的方向.此外,本文还介绍了这一不对称合成策略在天然产物、药物分子全合成中的应用. 相似文献
68.
We have designed and synthesized a new luminescent coordination polymer[Zn2(NO3)(NCP)3(H2O)3]n·2 nH2O(1,HNCP=2-(2-carboxyphenyl)imidazo-[4,5-f]-1,10-phenanthroline)under hydrothermal conditions,which has been structurally characterized by single-crystal X-ray diffraction analyses.1 crystallizes in monoclinic,space group P21/n,with a=13.7748(3),b=19.2651(4),c=19.9543(4)?,β=95.339(2)o,V=5272.35(19)?3,C60 H39.73 N13 O13.33 Zn2,Mr=1286.80,Dc=1.621 g/cm3,Z=4,μ(Mo Ka)=2.118,F(000)=2629,the final R=0.0598 and w R=0.1483.In 1,the organic ligand NCP-displays two different bridging modes to connect adjacent Zn(II)ions into a 1 D chain along the c-direction.Photoluminescent analyses reveal that 1 exhibits a strong green emission with a fluorescent lifetime of 5.57 ns.The first-principle calculation results show that the luminescence mainly originates from ligand-centered charge transition. 相似文献
69.
Electroreduction of CO2 to formic acid has attracted extensive attention,because it is a promising strategy to re-utilize CO2 and reduce greenhouse gas emissions that may favor the mitigation of energy and environment issues.Although great efforts have been made to tune the structure and composition of catalysts aiming to improve CO2 conversion efficiency,seldom studies have been focused on the support regulation.In this work,ordered,porous TiO2 nanotube arrays have been used as model support to study the impact of pore structure for CO2 electrochemical reduction.It has been revealed that Pd supported on TiO2 nanotube arrays substrate exhibits enhanced performance towards CO2 reduction,showing a higher formate Faradaic efficiency of 20%over than Pd supported on TiO2 film substrate.This study will shed new light on the design and synthesis of efficient catalysts by tuning the morphology of support for CO2 conversion. 相似文献
70.
Polymeric membranes with diverse structures have attracted much attention as new materials for nonlinear optical devices. In this report, a novel oligomer of poly(aromatic ether sulfone)(OAES) has been synthesized and characterized. The electronic structure as well as linear and nonlinear optical properties has been studied by density function theory. The effect for general nonlinear optical polarizability of various condition has been further researched such as absence of side chains and introduction of phenyl substituent on side chains. The static and frequency-dependent hyperpolarizabilities of OAES and its derivatives have been calculated. This work interprets an efficient adjustment for the frequency response and the intensity of nonlinear optical polarizability can be achieved by regulating the structure of system, which provides a new potential for the application of oligomeric materials on nonlinear optical field. 相似文献