PAMAM树状大分子对酮基布洛芬溶解度的影响

以酮洛芬为模型药物,研究聚酰胺-胺(PAMAM)树状大分子对酮洛芬的增溶作用,并探讨其作用机理.采用紫外光谱法测定了G1.0、G1.5、G2.0、G2.5、G3.0、G3.5PAMAM在不同浓度和不同pH时对酮洛芬的增溶量.并运用计算机模拟方法对PAMAM与酮洛芬相互作用的机理进行了探讨.实验结果表明,酮洛芬的溶解度随溶液pH值变化而变化,在pH4.0～6.0范围内,PAMAM树状大分子对酮洛芬的增溶量随着PAMAM的代数、浓度和溶液pH的增加而增大.整代和半代都具有增溶作用.然而,在同一pH条件下,对于具有相同官能团数目的整代和半代,整代增溶效果要高于半代.计算机模拟结果表明PAMAM与酮洛芬主要靠静电作用力结合.增溶机理可能是酮洛芬的羧基与PAMAM的伯胺和叔胺发生静电作用.     

光谱法及热动力学法研究环糊精与三氟氯氰菊酯的包合作用

制备了β-环糊精(β-CD)-三氟氯氰菊酯(CHL)包合物,采用差示扫描量热分析法和核磁共振波谱法对包合物进行表征.实验采用1HNMR研究包合物的空间结构,推测出三氟氯氰菊酯同β-CD的包合方式是从大口端进入β-CD.用化学软件对β-CD与CHL包合方式计算发现,CHL从β-CD的大口端和小口端进入,总能量分别为108.1kJ/mol与129.2kJ/mol,表明CHL从β-CD的大口端进入形成的包合物能量最低,结构最稳定.在25℃下,实验测得β-CD-三氟氯氰菊酯包合物形成常数为340.6L?mol-1,包合比是1∶1.热动力学方法研究了温度变化对包合反应的影响,计算得出包合过程的焓变-50.29kJ?mol-1、熵变120.6J?K-1?mol-1及自由能变化-14.45kJ?mol-1,进而确定了包合反应的主要驱动力是焓.     

Effect of temperature on enantiomer separation of oxzepam and lorazepam by high-performance liquid chromatography on a beta-cyclodextrin derivatized bonded chiral stationary phase

A reversed-phase high-performance liquid chromatography (HPLC) method with beta-cyclodextrin (beta-CD) derivatized as chiral stationary phase is used to directly separate oxazepam (Oxa) and lorazepam (Lor) enantiomers. The effect of temperature on the direct HPLC separation of Oxa and Lor enantiomers is studied for the commercially available beta-CD derivatized bonded chiral stationary phase. Chromatographic peak coalescence, appearing as a plateau between the resolved peaks, is observed at column temperatures of above 13 degrees C. Peak coalescence on the beta-CD derivatized bonded column is attributable to racemization of the Oxa enantiomer. By reducing the column temperature to 13 degrees C, the enantiomeric composition of Oxa and Lor could be determined on the chiral column. This method is expected to be useful for the resolution of 3-hydroxybenzodiazepines. At the same time, the separation mechanism is studied by calculating the thermodynamic parameters. The results reveal that the separation of Oxa and Lor enantiomer is a case of enthalpy-controlled separation, inclusion mechanism does not control the separation. The interaction between Oxa and beta-CD is an additionally strong pi-pi interaction or hydrogen bonding, but that between Lor or beta-CD derivatized is a weak pi-pi interaction or hydrogen bonding.     

Core-shell nanoparticles coated with molecularly imprinted polymers: a review

Core-shell surface molecular imprinting technology represents a rather new trend in analytical sciences. In this kind of material, the imprinting sites are located on the surface of the cores or shells of nanoparticles (NPs). This material can improve the capability of recognizing target molecules (analytes), reduce nonspecific adsorption, increase the relative adsorption capacity and selectivity, and accelerate the rate of mass transfer. This review (with 158 references) focuses on recent trends in core-shell MIPs. Following an introduction into the field, a first main section covers common core-materials including silica, magnetic NPs, quantum dots (including semiconductor quantum dots and carbon dots), gold and silver nanoclusters, and up-conversion materials. A further section covers the materials and reagents required for preparing MIPs (with subsections on templates, functional monomers, cross-linkers, initiators, and effects of solvent). A next main section covers synthetic approaches such as precipitation polymerization, emulsion polymerization, and grafting approach. A final section gives examples for applications of core-shell MIPs in analytical assays and in sensing.

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Graphical abstract This review (with 158 references) focuses on recent trends in core-shell nanoparticles coated with molecularly imprinted polymers (core-shell MIPs). Three significant synthesis methods are introduced: precipitation, emulsion and grafting approach. Applications of core-shell MIPs concentrate on solid phase extraction, fluorescent probe, surface-enhanced Raman scattering-based sensors and electrochemical sensors.

     

碳纳米管在药物和基因转运领域的应用

当前国内外的许多研究小组都致力于开发出新型有效的药物和基因转运系统,用于改善多种治疗因子的药理学作用并降低其毒性.在新型纳米材料中,碳纳米管(carbon nanotubes,CNTs)正逐步引起人们的关注.功能化CNTs的两个关键优势在于它具有很强的细胞穿透能力和较低的细胞毒性,使其在药物和基因转运领域中的应用成为可能.CNTs可通过形成稳定的共价键或形成以非共价键为基础的超分子结合物来运载肽类、蛋白质、核酸和药物等活性分子,并将其运送至特定的组织和器官中以表达特殊的生物学功能.针对这一研究热点,本文综述了近几年国内外关于碳纳米管在药物和基因转运领域中的应用进展,并探讨了其毒性,以期为这一领域中的研究工作者提供参考.     

洛美沙星-Tb3+配合物与BSA相互作用的荧光光谱研究

以洛美沙星-Tb3 作为荧光探针,利用荧光光谱研究了洛美沙星-Tb3 配合物与BSA的相互作用.实验发现:牛血清白蛋白与洛美沙星分子之间有较强的结合作用,而且洛美沙星对BSA的构象有一定的影响;同时BSA与Tb3 之间存在静电作用,可置换出配合物中的水分子,使体系的荧光强度增强.结果表明:在实验最佳条件下,牛血清白蛋白能增强洛美沙星-铽的荧光强度,据此建立了一种检测白蛋白的新方法,该法的检测限可达mg水平,线性范围为16.5～148.5μg·mL-1,检测限为68.8 ng·mL-1,RSD为1.4%.此法简便易行,而且不受共存物质的干扰.     

Magnetic carbon nanotubes: synthesis by a simple solvothermal process and application in magnetic targeted drug delivery system

A poly(vinyl chloride) (PVC) main chain was grafted with poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) containing a quaternary amine group using atom transfer radical polymerization. The successful synthesis of a PVC-g-PDMAEMA graft copolymer was confirmed by Fourier transform infrared, nuclear magnetic resonance, thermogravimetric analysis, and transmission electron microscopy. The PVC-g-PDMAEMA graft copolymer was used as a structure-directing agent (SDA) for the fabrication of a mesoporous thin film containing a titanium dioxide (TiO₂) layer. To control the porosity of the resultant inorganic layer, the ratio of SDA to TTIP as well as the concentration of the sol?Cgel was varied. The structure and porosity of the mesoporous film were characterized by XRD and SEM analysis. The mesoporous TiO₂ film fabricated on the FTO surface was used as a photoanode for the dye-sensitized solar cell (DSSC). DSSC performance was the greatest when using TiO₂ film with a higher porosity and lower interfacial resistance. The highest energy conversion efficiency reached 3.2?% at 100?mW/cm², which was one of the highest reported values for a quasi-solid-state DSSC with 600-nm-thick TiO₂ film.     

荧光光谱法研究G3.0 PAMAM树状大分子与牛血清白蛋白的相互作用

聚酰胺-胺型(PAMAM)树状大分子是一类新型的纳米级、球型、高度分支、单分散性的聚合物,并具有安全、低毒、无免疫原性等许多独特的生物学性质。正是由于这些优势使其有望成为一种新型有效的生物材料,用于作为寡核苷酸的转运因子和药物转运载体。因此,深入了解树状大分子的生物学性质对进一步研究其在治疗方面的应用是至关重要的。文章应用荧光光谱法在生理条件下研究了具有表面氨基的3.0代聚酰胺-胺型(G3.0 PAMAM)树状大分子与牛血清白蛋白(BSA)间的相互作用。结果表明,加入G3.0 PAMAM树状大分子后,BSA内源性荧光发生猝灭,其猝灭机制属于静态猝灭,符合Stern-Volmer方程。通过计算得到该树状大分子与BSA间的结合常数为(1.067±0.025)L·mmol-1。通过同步荧光、红边激发荧光位移(REES)等方法的研究发现,树状大分子的存在会改变BSA的构象。此外还考查了体系的pH值和离子强度对该树状大分子与BSA相互作用的影响,由实验结果可推断静电作用是二者结合的主要作用机制。     

Bounds of weighted multilinear Hardy-Cesàro operators in p-adic functional spaces

We introduce the p-adic weighted multilinear Hardy-Cesàro operator. We also obtain the necessary and sufficient conditions on weight functions to ensure the boundedness of that operator on the product of Lebesgue spaces, Morrey spaces, and central bounded mean oscillation spaces. In each case, we obtain the corresponding operator norms. We also characterize the good weights for the boundedness of the commutator of weighted multilinear Hardy-Cesàro operator on the product of central Morrey spaces with symbols in central bounded mean oscillation spaces.     

荧光光谱法研究碳纳米管与牛血清白蛋白间相互作用

作为一类新型的纳米材料,碳纳米管(CNTs)所具有的独特结构、强细胞穿透能力和低免疫原性等特性引发了生物医学领域的广泛关注,并有望作为一类新型的药物和基因转运载体。因此,研究碳纳米管与生物大分子间的相互作用对其在体内的进一步应用具有极其重要的意义。本文运用荧光猝灭法、同步荧光法以及红边激发荧光位移法(REES法)研究了生理条件下碳纳米管与牛血清白蛋白(BSA)间的相互作用。结果表明,碳纳米管可引起BSA内源性荧光的静态猝灭,但同步荧光和REES的研究结果表明碳纳米管对BSA的构象基本没有影响。同时,通过对碳纳米管与BSA相互作用的机制的探讨,我们推测碳纳米管主要通过非特异性吸附的方式与BSA相互作用。