金属卟啉分子界面可控组装的高效电化学传感器研究

Electron transfer reactions play key roles in biological energy transduction and conversion as well as many other processes. Due to its good resemble to biomembrane interface, modified functional electrodes provide a good platform to study the electron transfer processes in biological systems. This project intends to study the relationship between spatial orientation and direct electrochemistry of metalloporphyrin molecules which are controlled assembled on electrode surfaces. Then, the study on how the electronic states and in turn the electrocatalytic activities of metalloporphyrins can be turned by axial ligands to the metal ions. Based on above knowledge, high performance bioelectrochemical sensors will be constructed and their applications to monitor small biomolecules like CO and NO will be investigated. This project is helpful toward the understanding of unique properties of interface molecules depending on orientation and electronic states of metal ions in porphyrins, and the structure-function relationship of assembled molecules at electrode surfaces. Realization of the project also promises the construction of high performance bioelectrochemical sensors.

生物体系中的电子转移是生命体进行物质传递、能量交换和信号转导的最基本过程之一。功能化电极界面是一种研究生命体系中电子转移过程的有效平台。本项目拟采用自组装技术将金属卟啉分子可控组装于电极界面，研究组装分子在电极界面的取向与其电子转移性质之间的关系，同时考察金属卟啉分子其轴向配体如何调控中心金属的能级及其对生命活性小分子的电催化性能，筛选高电催化活性的分子取向和轴向配体，构建相应的生物电化学传感器，探索其在细胞分析中的应用。该项目研究成果将对认识生物分子在表界面的基本特性，以及理解仿生催化领域金属活性中心能级与电催化活性之间的关系具有指导意义，同时也为发展高稳定性、高选择性、高灵敏生物分子识别器件提供理论基础和研究范例。

在项目资助的支撑下，成功构建了金属卟啉分子在电极界面的不同结合模型，并对分子的界面构象进行表征；通过ORR反应模型，阐明金属卟啉分子表界面构象对其直接电子转移性质的影响；并通过轴向配体分子调控了卟啉中心金属离子能级；同时，系统研究了采用轴向配位策略制备的卟啉敏化光电极的电化学性能，为设计高效光电传感器和器件提供了理论依据。通过努力，已顺利完成，取得了系列性的研究成果，发表与录用 SCI 论文共 15 篇。