新型三明治型酞菁卟啉基稀土配合物的设计、制备及超分子电化学识别性质研究

The electrochemical active materials with specific molecular recognition ability are crucial for the design of the non-enzymatic electrochemical (bio) sensor, which show great application potential in clinical devices, drug and food inspection. Due to their chemically stablility, excellent semi-conductivity, and ease in functional modifications, sandwich-type phthalocyaninato and/or porphyrinato rare earth complexes are excellent building blocks for the design and synthesis of novel electrochemical active materials with application potentials electrochemical supermolecular recognition. In the present work, calixarene, pillarene and cyclodextrin-based groups and electron-donating/accepting substituents will be introduced onto the tetrapyrrole periphery of sandwich complexes as molecular recognition and redox tuning functional groups, respectively, resulting in novel sandwich-type double- and triple-decker complexes with not only good electrochemical activity but more importantly excellent recognition ability depending on the three-dimensional conjugate structure and cavities of the calixarene/pillarene/cyclodextrin -based groups with different sizes. These sandwich-type molecules will be then self-assembled into nano/microstructures with different morphology depending on various intermolecular interactions and act as the active layer to identify different small biomolecules in nonenzymatic electrochemical sensors. This study aims at (i) understanding the mechanism of the synergistic responses and interactions between sandwich-type molecules and biomolecules based on the electrochemical supramolecular recognition and (ii) developing smart and efficient nonenzymatic electrochemical sensing material and devices.

具有特异分子识别能力的电化学活性材料是无酶电化学（生物）传感研究的关键，在临床医学、药物和食品检测等领域有巨大的应用潜力。本课题以高效无酶电化学（生物）识别功能为导向，以开发具有实际应用前景的智能电化学传感材料及器件为最终目标，利用具有三维高度共轭结构的三明治型双层和三层酞菁卟啉稀土配合物的高稳定性、优异的半导体性能和极易进行功能化修饰等特点，将具有分子识别特性的杯（柱）芳烃及环糊精类官能团和能调节分子氧化还原电位的吸/供电子取代基引入酞菁卟啉周边，设计合成以酞菁卟啉大环平面共轭分子作为电化学活性中心，官能团空腔作为特异识别位点的新型三明治型酞菁卟啉稀土配合物。借助各种分子间作用力构筑不同结构和形貌的超分子聚集体，研究其作为电化学活性层对不同生物小分子的选择性电化学识别。揭示该类新型功能分子材料的电化学超分子识别特性和规律，为发展高性能的无酶电化学传感材料及器件提供理论指导和技术依据。

本课题紧紧围绕具有特异分子识别能力的新型酞菁卟啉电化学活性材料的设计合成及其作为高性能传感及电催化应用研究这个方向, 主要在三个方面开展了工作：一是设计合成了一系列新型酞菁/卟啉金属配合物及聚合物，成功实现了通过分子设计对分子的主客体识别能力和催化活性的有效调节，确立了共轭卟啉/酞菁半导体分子的尺寸识别效应和催化活性的协同效应在电化学识别中的重要应用前景，为无酶电化学生物传感器材料的开发提供了新的思路。二是通过多策略（主客体识别、中心金属和取代基的调控、拓展π-共轭体系、构筑异质结等）调节材料分子结构和聚集体结构改善化学传感性质，优化得到了一批高灵敏性、高选择性的室温光电化学（柔性）传感器，实现了对多种nM水平生物小分子（如H2O2、葡萄糖、多巴胺、乙酰氨基酚等）以及多种ppb级有害气体的超灵敏室温快速响应，显示了四吡咯基材料在光电化学传感器领域的巨大潜能；三是利用卟啉/酞菁基M-N4（M=过渡金属）单元锚定\分散金属活性位点，制备出具有多种活性位点的碳基氧还原电催化材料，半波电位达到或接近商业化Pt/C催化剂的技术指标，进一步拓展了该类半导体材料的应用范围。通过本项目的研究，不仅得到了一批高性能光电化学传感器件，而且揭示了该类新型功能分子材料的电化学超分子识别特性和规律，为发展高性能的无酶电化学传感材料及器件提供了理论指导和技术依据。