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二维含丰富羰基的导电共价有机框架用于电化学生物传感。

2D Conductive Covalent Organic Frameworks with Abundant Carbonyl Groups for Electrochemical Sensing.

机构信息

CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, Liaoning 116023, P. R. China.

University of Chinese Academy of Sciences, 19 Yuquan Road, Beijing 100049, P. R. China.

出版信息

ACS Sens. 2022 Nov 25;7(11):3551-3559. doi: 10.1021/acssensors.2c02014. Epub 2022 Oct 20.

Abstract

Due to their permanent porosity, robust chemical stability, and tunable structure, covalent organic frameworks (COFs) are very attractive in the application of energy storage, catalysis, sorption, and sensing. However, the very low conductivity of COFs severely restricts their application in electrochemical sensing. Here, an aza-fused π-conjugated COFs with abundant carbonyl groups (COF1) was synthesized and deployed as electrode materials in electrochemical sensing for the first time. The current response of the acetylcholinesterase biosensor based on COF1 increases three times when compared to the electrode without COF1. The effects of carbonyl groups on signal enhancement were proved in depth by a series of characterization and comparison experiments with the prepared COF2 without carbonyl groups. The results demonstrated that exposed carbonyl active sites of COF1 can promote the effective immobilization and bioactivity preserving of enzyme molecules and contribute to the enrichment of analytes. Together with the good conductivity of COF1 derived from a fully extended 2D aromatized π-conjugated system, all of which improve the biosensor performance. The COF1-based biosensor exhibited fast response speed, high sensitivity, good selectivity and practicability, and robust stability for organophosphorus pesticide detection and proved to be a promising tool for the rapid and onsite detection of organophosphorus pesticides in the environment.

摘要

由于其永久的多孔性、强大的化学稳定性和可调节的结构,共价有机骨架(COFs)在储能、催化、吸附和传感应用中非常有吸引力。然而,COFs 的导电性非常低,严重限制了它们在电化学传感中的应用。在这里,首次合成了一种具有丰富羰基的氮杂稠合π共轭 COFs(COF1),并将其用作电化学传感中的电极材料。与没有 COF1 的电极相比,基于 COF1 的乙酰胆碱酯酶生物传感器的电流响应增加了三倍。通过一系列具有羰基的 COF2 和没有羰基的 COF2 的制备和对比实验,深入证明了羰基对信号增强的影响。结果表明,COF1 中暴露的羰基活性位点可以促进酶分子的有效固定和生物活性保持,并有助于分析物的富集。再加上完全扩展的 2D 芳构化 π共轭体系赋予 COF1 的良好导电性,所有这些都提高了生物传感器的性能。基于 COF1 的生物传感器在检测有机磷农药方面表现出快速的响应速度、高灵敏度、良好的选择性和实用性以及稳健的稳定性,并且有望成为环境中快速现场检测有机磷农药的一种有前途的工具。

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