亲电取代反应中活性位点预测方法的比较

预测发生亲电取代反应的活性位点具有重要的理论和实际意义. 目前已提出了许多基于反应物自身电子结构的预测方法. 本文选择14 个单取代苯和8 个双取代苯作为测试集,对14 种预测方法的可靠性进行了详细的比较分析. 结果表明,福井函数、平均局部离子化能等体现局部电子软度的方法特别适合含有邻对位定位基的单取代苯和双取代苯体系,但对于含有单个间位定位基的体系,这类方法往往预测失败. 基于静电效应的预测方法整体表现明显不如体现局部软度的方法,但更适合含有单个间位定位基的体系. 对所有体系预测能力最稳健的是双描述符,因此可以作为普适性的预测方法.     

Synthesis and biological evaluation of 5,6,7-trimethoxy- 1- benzylidene-3,4-dihydro-naphthalen-2-one as tubulinpolymerization inhibitors

A series of new combretastatin-A4 analogs were synthesized, in which a six-membered ring connects the linking bridge and A ring, and their tumor cell growth and tubulin-polymerization inhibitory activity were evaluated. These compounds appear to be potential tubulin-polymerization inhibitors. Compounds 1b with amino substituted on position 3 of B ring conferred optimal bioactivity, higher than that of the lead compound 22b and equivalent to that of CA-4. The binding modes of these compounds to tubulin were obtained by molecular docking, which can explain the structure-activity relationship. The studies presented here provide a new structural type for the development of novel antitumor agents.     

Heterometallic zinc uranium oxyfluorides incorporating imidazole ligands

Two heterometallic uranium oxyfluorides with hybrid networks were hydrothermally synthesized by incorporating two imidazoles, 1-(biphenyl-4-yl)-1H-imidazole(bpi) and 1,4-di(1H-imidazol-1-yl)benzene(dib), formulated as Zn(bpi)2(UO2)2(H2O)F6(1) and Zn(dib)(UO2)F4 0.5H2O(2). Compound 1consists of chains of edge-sharing UO2F5 and UO2F4(H2O) pentagonal bipyramids, which are linked by Zn(bpi)2moieties to form the sheet structure with decorated bpi. While in compound 2, sheets of edgesharing dimers of UO2F5 pentagonal bipyramids and Zn F3N2 polyhedra are linked by dib, creating a pillared three-dimensional framework. The two compounds represent the few examples of heterometallic uranium oxyfluorides incorporating organic ligands. The syntheses, structure as well as the IR spectra, UV–vis spectra and luminescent properties of the bimetallic uranium oxyfluorides are studied.     

Electrochemical properties of niobium and phosphate doped spherical Li-rich spinel LiMn2O4 synthesized by ion implantation method

Spherical Li-rich lithium manganese oxide(LMO) spinel material was synthesized by an ion implanted method assisted by polyalcohol doped with Niobium and Phosphate simultaneously.The material was characterized by scanning electron microscopy,X-ray diffraction and BET specific surface area analysis.The electrochemical performances were investigated with galvanostatic techniques and cyclic voltammetry.The synthesis process was investigated with TG/DSC.The results show that the lithium ion can be immersed into the pore of manganese dioxide at a low temperature with the ion implanted method.The prepared materials have a higher discharge capacity and better crystallization than those prepared by solid phase method.The doped Nb can improve the capacity of the Li-rich LMO spinel and reinforce the crystal growth along(111) and(400) planes.The crystal grains show circular and smooth morphology,which makes the specific surface area greatly decreased.Phosphate-doped LMO spinel exhibits good high-rate capacity and structure stability.The prepared Li_(1.09)Mn_(1.87)Nb_(0.031)O_(3.99)(PO_4)_(0.021)delivers a discharge capacity of 119mAhg~(-1) at 0.2C(1C=148mAg~(-1)) and 112.8 mAhg~(-1) at 10 C,the discharge capacity retention reaches 98% at 1 ℃ after 50 cycles at 25 ℃ and 94% at 55 ℃.     

Anti-tumor effects of combined doxorubicin and siRNA for pulmonary delivery

Direct administration of drugs and genes to the lungs by pulmonary delivery offers a potential effective therapy for lung cancers.In this study,combined doxorubicin(DOX)and Bcl2 siRNA was employed for cancer therapy using polyethylenimine(PEI)as the carrier of Bcl2 siRNA.Most of the DOX and siRNA possessed high cellular uptake efficiency in B16F10 cells,which was proved by FCM and CLSM analysis. Real-time PCR showed that PEI/Bcl2 siRNA exhibited high gene silencing efficiency with 70% Bcl2 mRNA being knocked down.The combination of DOX and siRNA could enhance the cell proliferation inhibition and the cell apoptosis against B16F10 cells compared to free DOX or PEI/Bcl2 siRNA.Furthermore,the biodistribution of DOX and siRNA via pulmonary administration was studied in mice with B16F10 metastatic lung cancer.The results showed that most of the DOX and siRNA were accumulated in lungs and lasted at least for 3 days,which suggested that combined DOX and siRNA by pulmonary administration may have high anti-tumor effects for metastatic lung cancer treatment in vivo.     

Preparation of starch-<Emphasis Type="Italic">g</Emphasis>-PMMA,starch-<Emphasis Type="Italic">g</Emphasis>-P(MMA/BMA) and starch-<Emphasis Type="Italic">g</Emphasis>-P(MMA/MA) nanoparticles and their reinforcing effect on natural rubber by latex blending: a comparative study

Nanoparticles including starch-graft-methylmethacrylate, starch-graft-(methylmethacrylate/methyl acrylate), starch-graft-(methyl methacrylate/butyl methacrylate) were synthesized via emulsifier-free emulsion polymerization and were blended with natural rubber latex at various mass ratios. Chemical structure of graft copolymers was confirmed by Fourier transform infrared. Transmission electron microscopy demonstrated the core-shell structures of the nanoparticles distributed uniformly around the natural rubble particles. The tensile strength of blend films was significantly enhanced by addition of graft copolymers. Besides, scanning electron microscopy and atomic force microscopy showed the blend film had smooth surface.     

分子动力学模拟残基突变对芳香烃受体配体结合区的影响

芳香烃受体(Aryl hydrocarbon receptor,AhR)属于配体依赖性的转录因子蛋白。本文通过对AhR配体结合区域(Ligand binding domain,LBD)的结构功能及物种特异性分析,发现在其结合腔口有一些关键残基可能起到"门控"作用,进一步将野生型(WT)和3个突变模型(Phe289Ala、Tyr316Ala、Ile319Ala)进行分子动力学模拟,从蛋白稳定性、蛋白结构变化、蛋白结合腔变化及蛋白和配体结合能力4个方面分析3个残基的门控作用。研究发现,Phe289、Tyr316、Ile319氨基酸残基通过形成疏水作用为AhR LBD起到"门控"作用;而将这些氨基酸分别突变后,其蛋白稳定性降低,整体运动性增加,配体亲和力减弱,其中Tyr316、Ile319对腔内体积影响较大,Phe289使腔内环境稳定性降低。本研究可为基于芳香烃受体的药物设计提供相关理论指导。     

Enhancement of SrTiO<Subscript>3</Subscript>/BiPO<Subscript>4</Subscript> heterostructure for simulated organic wastewater degradation under UV light irradiation

A novel SrTiO₃/BiPO₄ heterostructure with different amounts of SrTiO₃ have been successfully prepared through the hydrothermal process. The photocatalysts were characterized by X-ray powder diffraction, UV–Vis diffuse reflectance spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. The photocatalytic performance was evaluated by degrading the methylene blue dye solution under UV light. Results showed that the samples displayed excellent photocatalytic degradation efficiency due to the highly efficient suppression of the recombination of electron–hole pairs. A possible mechanism of SrTiO₃/BiPO₄ heterojunctions was discussed. The research indicated that the as-prepared SrTiO₃/BiPO₄ heterogeneous photocatalyst can be used as an effective material for degrading industrial organic wastewater.     

AgBr@TiO<Subscript>2</Subscript>/GO ternary composites with enhanced photocatalytic activity for oxidation of benzyl alcohol to benzaldehyde

AgBr@TiO₂/GO (graphene oxide) ternary composite photocatalyst was synthesized by fabricating core–shell-structured AgBr@TiO₂ and anchoring it onto the surface of GO. The obtained samples were characterized by transmission electron microscopy, X-ray diffraction analysis, X-ray photoelectron spectroscopy, ultraviolet–visible (UV–Vis) diffuse reflectance spectrum, and photoluminescence (PL) spectroscopy. It was found that the AgBr nanoparticles were prone to aggregation while the core–shell-structured AgBr@TiO₂ possessed excellent dispersity. PL analysis revealed that the ternary-structured AgBr@TiO₂/GO could effectively promote the separation rate of electron–hole pairs. Photocatalytic oxidation of benzyl alcohol to benzaldehyde under visible-light irradiation was selected as probe reaction to evaluate the photocatalytic activity of the different samples. It was found that the AgBr@TiO₂/GO ternary composite exhibited evidently improved photocatalytic activity compared with AgBr, AgBr@TiO₂, and AgBr/GO. On the basis of the experiment results, the photocatalytic oxidation mechanism of benzyl alcohol over AgBr@TiO₂/GO is tentatively discussed.     

光响应超分子聚合物

超分子聚合物是超分子化学、高分子化学和材料化学领域的研究热点.将光响应的功能基团以非共价作用构筑到超分子聚合物体系中,得到光响应型超分子聚合物,从而能够将超分子聚合物的独特性质与光化学反应的优势有效地结合起来,从而构筑新型的光功能材料.本文总结了近年来本课题组有关光响应超分子聚合物方面的研究工作:介绍了主链型的光响应超分子聚合物的光调控组装和解离,超分子聚合物和共价聚合物的光控可逆切换和光调控组装形貌;另外还举例介绍了具有自修复和室温磷光发射等功能的侧链型光响应超分子聚合物,并对刺激-响应的超分子聚合物领域的发展做了展望.