具有介孔结构的无机/有机杂化荧光传感材料的构筑与性能研究

The fluorescent film sensor based molecular wire polymers effect has some advantages, such as the device may be re-used, the detected samples are uncontaminated, the reagents are unconsumed, and the materials favor to building the devices.However, the polymer sensing films have some defect, such as the poor permeability and the unaccepted the swelling in appliaction, which reducing the sensitivity and lifetime of the devices and limiting their application. Introducing the polymer to the porous inorganic materials may increase the permeability of the sensing film. Meanwhile, the anti-swelling ability of the film be also improved. In the program, the inorganic/organic hybrid mesoporous materials (1D, 2D, 3D,Periodic) with fluorensceent sensing units will be built by the incorporation of inorganic rigid polyhedral oligomeric silsesquioxanes (POSS) into the fluorescent conjugated polymers, and the periodic mesoporous hybrid materials based POSS will be created by using the in situ polymerization method. The effect of the structure and the porous sizes of the film materials on the permeability and anti-swelling property of the film will be investigated, and the enhancment mechanism in the sensing film will be studied. A simplicity, rapidity, high sensitivity method using detect the triazophos pesticide residue will be firstly proposed.

以分子导线聚合物制作的薄膜荧光传感器具有可反复使用、不污染待测体系、无试剂消耗、易于器件化的特点，但聚合物功能薄膜存在通透性差和易溶胀的缺点，导致传感灵敏度下降和器件寿命缩短，从而影响薄膜荧光传感器的性能，限制了其广泛应用。在聚合物分子中引入无机多孔材料，能增加聚合物膜的通透性，同时也能形成刚性稳定的膜结构,提高抗溶胀能力。本项目以刚性纳米结构的无机笼形倍半硅氧烷分子（POSS）与荧光共轭聚合物分子杂化，构筑不同介孔结构（一维、二维、三维网孔、有序）的无机/有机杂化荧光传感材料，同时以原位聚合技术构筑POSS基有序介孔结构的杂化材料；研究不同孔径与结构的多孔材料对功能薄膜通透性和抗溶胀能力的影响规律，探索杂化荧光传感材料结构、组成与传感性能之间的关系，揭示影响传感薄膜性能的微观机制；以三唑磷农药为检测对象，建立有机农药残留快速、高灵敏检测新方法。

荧光探针具有高的灵敏度，现已成为环境、生物体中重金属离子、活性氧、氮、硫及农药残留的重要研究手段。本项目主要开展了三方面的工作，一是基于聚炔的分子导线效应，构筑了新的具有荧光效率的聚二取代乙炔，实现了对重金属离子Cu2+、Pd2+的灵敏检测，建立了对农药草甘膦、甲基托布津的单光子荧光分析新方法。二是，鉴于双光子荧光探针更适合在生物活体观测，我们以咔唑为母体，构建了生物兼容性好、双光子吸收界面大、易于修饰的双光子荧光生色团，发展了一系列能用于Au3+、Cu2+、SO2、ClO-等双光子荧光探针分子，并实现了对它们的双光子共聚焦显微成像，为双光子荧光探针研究提供了一个有效的平台分子。 三是探索了POSS基杂化材料的合成及其荧光性能，尝试了荧光杂化分子用于探测Fe3+的技术。