基于Michael加成反应的稀土介孔杂化材料的设计合成及在水溶液中的发光性能研究

Rare mesoporous hybrid materials have received great interests in drug release, fluorescence immunoassay, disease diagnosis and biology and so on. However, the practical applications of these materials are limited to a large extent, essentially due to their poor luminescence properties in aqueous solution. Early studies showed that the luminescence of hybrid materials which grafted by lanthanide complexes, is mainly affected by the structure of organic ligands and the stability of chemical bond between the inorganic matrix and lanthanide complexes, especially in aqueous solution. So highly-binding-affinity organic group which also serve as efficient sensitizers, are necessary for ligands, and the ligands can also be assembled on the surface and pores of the mesoporous materials by stable covalent bonds. On the basis of our works, we will design and synthetize several dual-function organic ligands which contain electron-deficient double bond, And then, hybrid materials with excellent luminescent in aqueous solution were prepared by thiol-Michael addition reaction between thiol group of the mesoporous materials and electron-deficient double carbon bond of lanthanide complexes. The effects of surface microstructure of mesoporous materials, ligand structure, second ligand were investigated and the relationship between the structure and luminescence properties of hybrid materials is discussed in detail.

稀土介孔杂化材料在药物缓释、荧光免疫分析、疾病诊断、生物等领域获得广泛关注，该类材料能否在上述领域得到应用，关键在于其在水溶液中的发光性能。研究表明，有机配体的结构是影响稀土元素在水溶液中发光性能的主要因素之一，稀土配合物与无机基质连接的稳定性是影响其发光性能的另一因素。所以制备这类材料时，要求：一方面，在水溶液中，配体与稀土离子的配位能力强，且对稀土离子具有良好的敏化作用；另一方面，配体具有活性基团，能通过稳定的化学键嫁接到介孔材料中。本项目拟在前期研究的基础上，合成几种双功能型稀土有机配体（含缺电子双键），采用巯基与缺电子双键的Michael加成反应，使稀土配合物通过稳定的S-C键嫁接到巯基功能化的介孔材料中，制备几种在水溶液中具有稳定性高、发光性能强的稀土介孔杂化材料。研究介孔材料的表面微观结构、配体的结构、第二配体等与杂化材料发光性能之间的内在联系。

本项目主要围绕杂化发光材料的功能设计、复合机制、发光性能及应用等开展研究工作。主要包括：（1）稀土杂化材料合成方面，通过基质的表面修饰，有机配体的结构设计，复合条件的优选，采用自由基聚合、类Michael加成、自组装等方法制备了光功能型的水凝胶、氨基化黏土及介孔/高分子杂化材料。并探讨了稀土杂化材料在酸性气体传感领域的应用。（2）水溶性荧光材料合成方面，通过助溶基团的结构设计和功能调控，制备出两种水溶性的荧光材料，并探讨了它们在细胞成像领域的应用。（3）稀土纳米发光材料合成方面，系统研究了纳米材料的相结构、离子掺杂、形貌等对其发光性能的影响，并制备出具有多色发光性能的CdWO4：Eu3+纳米棒。