表面富氨基核-壳式复合磁球功能化设计与组装

Core-shell structured composite magnetic spheres (CMS) carrying amino groups have been subjected to extensive research due to their wide applications in the fields of organic catalysis, biosensors, drug controlled release, immunoassay, enzyme immobilization, and isolation of proteins and nucleic acids. In this application paper, we initiate our investigation from the synthesis of CMS carrying amino groups at low cost. Well-defined core-shell structured Fe3O4/PANI and Fe3O4/PPy spheres possessing high magnetization, good dispersity, and narrow size distribution can be obtained through interfacial polymerization method without organic stabilizer, cross-linking agent, and/or surfactant. Subsequently, the acquired CMS will be tested as solid amines participating in the Mannich reaction to synthesize two kinds of important amino acids (i.e., Tyrosine and Tryptophane), based on the nucleophilicity of amino groups. The well-recognized NHS/EDC method will be adopted for the assembly of Fe3O4/PANI/MTX, Fe3O4/PPy/MTX, Fe3O4/PANI/FITC/MTX, and Fe3O4/PPy/FITC/MTX magnetic targeting drugs, because condensations can occur between the surface amino groups of CMS and the carboxyls of MTX. Also, the efficacy of the obtained magnetic targeting drugs will be biologically evaluated by applying them on the model tumor cells, i.e., Hela cells, which is based on the kinetics for controllably releasing MTX in vitro. The research with respect to functional design and assembly on the CMS carrying amino groups are of great scientific and technological significance, because this is helpful to deeply understand the reaction mechanisms between amino groups on the surface of polymers and molecules of chemials or biochemicals. Moreover, this research facilitates to broaden the applications of CMS carrying amino groups in the fields of organic synthesis and magnetic targeting drugs.

表面富氨基核-壳式复合磁球在有机催化、生物传感、药物控释、免疫分析、及蛋白质和核酸的纯化等领域有许多重要的应用。本项目首先在无需表面活性剂的条件下，采用界面聚合复合方法，合成磁响应性高、分散性好、颗粒尺寸分布窄、表面富氨基核-壳式Fe3O4/PANI(or PPy)复合磁球；利用表面氨基的亲核性，将表面富氨基复合磁球作为固体胺参与曼尼希反应，设计合成酪氨酸和色氨酸；根据表面氨基能和甲氨蝶呤（MTX）分子中的羧基缩合的特点，采用NHS/EDC法，设计组装Fe3O4/PANI(or PPy)/MTX磁性靶药及Fe3O4/PANI(or PPy)/FITC/MTX荧光磁性靶药；研究磁性靶药对Hela细胞的抑制、杀灭功效。本项目的研究工作有助于加深理解聚合物表面氨基与化学、生物分子的作用机理及磁性靶药与Hela细胞的作用机制，拓宽表面富氨基复合磁球在有机合成和磁性靶药领域的应用范围。

表面富氨基核–壳式复合纳米复合物在DNA纯化、靶药载体、金属离子回收、有机合成及能量储存与转换等领域具有重要的应用。本项目合成了表面富氨基、核–壳式Fe3O4/PANI、Fe3O4/PPy和Fe3O4/SiO2复合磁球，分别将其用作磁吸附分离剂，成功地从黑曲霉A. niger细胞中分离出可用于聚合酶链反应扩增的染色体DNA；相比于传统的苯酚–氯仿提取法，该磁分离方法效率高、环境友好、DNA纯化程度高。.采用EDC/NHS 方法，将甲氨蝶呤(MTX)固定于磁球表面，获得了可用于生物体内的荧光Fe3O4/PPy/MTX 磁性靶药。该磁性靶药载药量大(109 μg/mg)，具有缓释性，对HeLa细胞具有靶向特异性。该磁性靶药合成成本低、对HeLa细胞杀灭效果好，是一种潜在的用于治疗过度表达叶酸受体的癌细胞的磁性靶药。.探索了Fe3O4/PANI、Fe3O4/PPy和Fe3O4/SiO2/cPPyTh对金属离子的吸附性能和吸附机理。Fe3O4/PANI对Cr(VI)具有较高的吸附能力(200 mg/g)，脱掺杂的Fe3O4/PPy对Ag(I)具有较高的吸附能力(143.3 mg/g)和吸附选择性。首次报道了采用类芬顿试剂，在水溶液中合成吡咯噻吩共聚物(cPPyTh)，并提出了cPPyTh LUMO能级较高有利于Au(III)吸附–还原的观点。Fe3O4/SiO2/cPPyTh对Au(III)具有很高的吸附能力(> 800 mg/g)和吸附选择性。.将Fe3O4/PANI用作催化剂，在超声辅助下催化降解甲基橙(MO)。Fe3O4/PANI对MO有较高的吸附和催化降解能力，首次发现了MO 降解动力学遵循准二级吸附动力学和准一级降解动力学的复合模型。.评价了Fe3O4/PANI和脱掺杂Fe3O4/PANI的表面氨基含量；发现脱掺杂后Fe3O4/PANI的表面氨基含量提高了197.4 μmol/g。探索了将Fe3O4/PPy 用作可回收固体胺，参与曼尼希反应以合成酪氨酸的实验研究。利用紫外-可见分光光谱和液相-质谱技术检测了产物中的酪氨酸。.合成了具有富勒烯结构单元的新型含氮聚合物(PPBP)、RGO/PPBP复合物和含氮聚合物量子点。由RGO/PPBP组装的对称式超级电容器，具有优良电化学性能。提出了芳香族化合物对含氮聚合物量子点的非光化学荧光猝灭机理。