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。     

二氧化硅纳米均孔膜修饰电极检测化妆水中的抗氧化剂

制备了氧化铟锡(ITO)电极支撑的二氧化硅纳米均孔膜,保留胶束模板在纳米通道内,得到二氧化硅和胶束复合膜修饰的电极,并将其用于化妆品中丁基羟基苯甲醚和叔丁基对苯二酚的电化学检测。该均孔膜孔径2.3 nm,具有精确的尺寸筛分能力;胶束尾部的碳氢长链提供了疏水微环境,能够在水溶液中快速萃取和富集疏水有机分子。该电极对两种抗氧化剂的检测均获得了较好的灵敏度、线性范围和检测限,加标回收率分别为96.4%和104%,表明该电化学传感器具有一定的应用潜力。     

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.     

基于氟代异靛蓝并[7,6-g]异靛蓝的共轭聚合物的合成及其半导体性质

采用Stille缩聚,合成了3个异靛蓝并[7,6-g]异靛蓝(DIID)和乙烯单元交替排列的共轭聚合物P0F、P2F和P4F,三者在DIID单元中分别含0、2和4个氟原子(F).3个聚合物均具有良好的平面性,前线分子轨道几乎在整个共轭骨架上离域.它们均具有宽的吸收光谱,吸收范围在400~1000 nm,光学带隙约为1.25 eV;随着氟原子数目的增加,聚合物的最高占有分子轨道(HOMO)和最低空分子轨道(LUMO)能级依次下降0.1~0.2 eV.以这3个聚合物作为活性层,制备了顶栅-底接触型有机场效应晶体管器件,随着氟原子数目的增加,聚合物的传输性质由双极传输变为n型传输.P0F和P2F是双极传输型聚合物,空穴迁移率(μ_h)分别达到0.11和0.30 cm~2 V~(-1) s~(-1),电子迁移率(me)分别达到0.22和1.19 cm~2 V~(-1) s~(-1).P4F是n型聚合物,me达到0.18 cm~2 V~(-1) s~(-1).     

Synthesis of Au nanoparticles with Bi adlayers using glucose as dispersant

Well-dispersed Au/Bi nanoparticles with average size below 10 nm were prepared by using NaBH₄ to reduce HAuCl₄ with glucose as dispersant. The obtained Au/Bi NPs were well characterized by UV-Vis spectra, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and electrochemical measurements. The electrochemical study found that Bi adlayers on the surface of Au nanoparticles owns two kinds of surface structures, including a low coverage (2 × 2)-Bi adlayer and a close-packed (p × √3)-2 Bi adlayer due to the strong interaction between the two Bi layers and the below Au atoms, which is same with that bulk on Au surface.     

Crown ether complexes of sodium and potassium 2-(benzotriazol-2-yl)phenolates: Synthesis and catalysis towards the ring-opening polymerization of rac-lactide

Crown ether complexes of sodium and potassium 2-(benzotriazol-2-yl)phenolates were synthesized and characterized. In the presence of BnOH these complexes are highly active catalysts for the controlled ring-opening polymerization of rac-lactide. The polymerizations are iso-selective and the P_m of polylactide reached 0.77 when the polymerization was performed in toluene at ?60°C; whereas heterorich-polylactide was obtained when the polymerization was carried out in CH₂Cl₂ or THF.     

Precise large deviations for sums of random vectors with dependent components of consistently varying tails

Let {X _i = (X _1,i ,...,X _m,i )^?, i ≥ 1} be a sequence of independent and identically distributed nonnegative m-dimensional random vectors. The univariate marginal distributions of these vectors have consistently varying tails and finite means. Here, the components of X ₁ are allowed to be generally dependent. Moreover, let N(·) be a nonnegative integer-valued process, independent of the sequence {X _i , i ≥ 1}. Under several mild assumptions, precise large deviations for S _n = Σ _i=1 ⁿ X _i and S _N(t) = Σ _i=1 ^N(t) X _i are investigated. Meanwhile, some simulation examples are also given to illustrate the results.     

Standard molar enthalpy of formation of [(C12H8N2)2Bi(O2NO)3] and its biological activity on Schizosaccharomyces pombe

The title complex [(C₁₂H₈N₂)₂Bi(O₂NO)₃] was synthesized by reaction of 1,10-phenanthroline (phen) and Bi(NO₃)₃·5H₂O. The structure of the complex was characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. An advanced solution-reaction isoperibol microcalorimeter was applied to determine the standard molar enthalpies of formation at 298.15 K of the complex and Bi(NO₃)₃·5H₂O, giving –(798.92 ± 5.99) and –(1986.87 ± 0.20) kJ mol⁻¹, respectively. The biological effect of the complex was evaluated by microcalorimetry on the growth of Schizosaccharomyces pombe (S. pombe). According to thermogenic curves, the corresponding thermokinetics and thermodynamic parameters were derived. The complex had good bioactivity on the growth metabolism of S. pombe, with the value of IC₅₀ being 2.8 × 10⁻⁵ mol L⁻¹.