适于复杂水溶液体系的高性能分子印迹聚合物微/纳尺度光化学传感材料的可控制备及其性能研究

To overcome the significant challenges in the molecular imprinting field including the relatively lower affinity and selectivity of the presently developed molecularly imprinted polymers (MIPs) towards small organic template molecules and their incompatibility with complex aqueous samples in comparison with the biological receptors, hydrophilic and fluorescent MIP micro- or nanoparticles that are applicable for the direct and rapid detection of small organic molecules with high affinity and selectivity in complex aqueous solutions (in particular in biological media) are to be synthesized via the combined use of controlled/"living" radical polymerization and molecular imprinting techniques as well as the template surface-anchoring strategy by stoichiometric noncovalent interaction and fluorescene labeling method on the basis of molecular design. The synthetic conditions for the desired hydrophilic and fluorescent MIP micro- or nanoparticles will be optimized, and the properties of such MIP micro- or nanoparticles via different synthetic routes will be compared. In addition, the effects of the structures of the MIP particles, the fluorescence labeling methods used, and the structural parameters of the hydrophilic polymer brushes (including their backbones, molecular weights, and grafting densities) on the properties of the MIPs will be investigated in detail. The above studies will provide theoretical and practical basis for the fabrication of advanced MIPs-based chemosensors compatible with real complex aqueous samples. The relevant studies on this topic have not been reported yet by others..This project opens up a facile and efficient way for the preparation of advanced micro- or nano-sized MIPs-based chemosensing materials that are applicable for the rapid, sensitive, and selective analyses of real complex aqueous samples. Its success will greatly promote the development of high-performance, multifunctional, and micro- or nano-sized MIPs and lay the foundation for their practical applications in such areas as analyses of foodstuffs, environmental monitoring, and clinical diagnostics.

从分子设计出发，将可控/“活性”自由基聚合与分子印迹技术相结合，并辅以表面锚定模板分子策略与荧光标记方法，制备在复杂水溶液(特别是生物样品)中对有机小分子具有高亲和性与选择性、且适于快速检测用的亲水性荧光分子印迹聚合物(MIPs)微/纳米粒子，以解决目前发展的MIPs与生物受体相比通常其亲和性与专一选择性较差且不适于复杂水溶液体系的挑战性难题。优化合成条件，比较由不同实验路线所得亲水性荧光MIPs的性能，研究MIPs的结构、荧光标记方式及亲水高分子壳层的各种参数对其性能的影响，为制备适于复杂水溶液体系的高性能MIPs光化学传感器提供理论与实验依据。上述研究尚未见文献报道。. 此研究为制备适于复杂水样分析的高性能MIPs微/纳传感材料开辟了一条简便高效的途径，必将极大地推动MIPs在高性能化、多功能化及微纳米化方向的发展，并为其在食品安全、环境监测及临床诊断等领域中的实际应用奠定基础。

适于复杂水溶液体系的高性能分子印迹聚合物(MIP)光化学传感材料因其在食品安全、环境监测及临床诊断等领域中巨大的应用前景而成为当前人们研究的热点。本项目以解决目前发展的MIP传感器与生物传感器相比通常其灵敏度与选择性较低(因MIPs印迹位点均匀性较差导致)且不适于复杂水溶液体系的挑战性难题为目标。从分子设计出发，将我们最近发展的可高效制备粒径均匀且表面含“活性”引发/链转移基团(或亲水性高分子刷)的聚合物微/纳米粒子的可控/“活性”自由基沉淀聚合(CRPP)技术引入分子印迹研究领域，并辅以表面锚定或未锚定模板策略与荧光标记方法，成功制备了一系列可高灵敏度、高选择性地直接检测复杂水样的荧光性MIP微/纳米粒子，得到了它们的最佳合成途径与一些有意义的规律。主要研究成果包括：1)将多种可控/“活性”自由基聚合技术与荧光标记方法相结合，在不锚定模板情况下，成功发展了“一步法”或“多步法”制备可在复杂生物样品中高灵敏度、高选择性地直接检测有机小分子(抗生素、除草剂及食品添加剂)的单荧光或双荧光MIP光化学传感微/纳米粒子的有效方法。2)将CRPP与表面锚定模板策略和荧光标记方法相结合，通过首先在由CRPP合成的“活性”(荧光)聚合物微球表面引入可锚定有机小分子(食品添加剂叶酸)或生物大分子(糖蛋白)的功能基团并以其锚定模板分子，然后以其为固载化“活性”引发剂进行可控表面印迹(可加入荧光单体)与亲水性高分子刷的可控接枝(糖蛋白体系无高分子刷)，成功得到了一系列表面具有均匀印迹位点且可在复杂生物样品中高灵敏度、高选择性地直接检测模板分子的MIP光化学传感材料。上述工作成功实现了利用MIP光化学传感材料在复杂生物样品(如未经稀释的纯牛/羊奶与牛/猪血清)中直接对有机小分子进行高灵敏度、高选择性快速检测的目标，解决了困扰MIP传感领域多年的挑战性难题，为MIP光化学传感器的最终实用化奠定了基础。相关工作已发表学术论文10篇，英文专著章节2章，并申请中国发明专利2项。