Cheng Xingyang, Tang Jing, Chen Yu, Bai Xue, Liao Yibo, Ouyang Xilian, Wang Yuchen, Tang Lin
College of Environmental Science and Engineering and Key Laboratory of Environmental Biology and Pollution Control (Ministry of Education), Hunan University, Changsha 410082, PR China.
Key Laboratory of Integrated Regulation and Resource Development on Shallow Lake of Ministry of Education, College of Environment, Hohai University, Nanjing 210098, China; Yangtze Institute for Conservation and Development, Hohai University, Nanjing 210098, China.
J Hazard Mater. 2025 Aug 5;493:138422. doi: 10.1016/j.jhazmat.2025.138422. Epub 2025 Apr 27.
Electrochemical molecular imprinting technology (e-MIT) has gained significant attention for detecting emerging micropollutants like per- and polyfluoroalkyl substances (PFAS). However, designing efficient and reliable PFAS sensors based on e-MIT remains challenging. In this study, we explored a mechanism for synergistic adsorption recognition of dual-functional monomers (DM), based on which a molecularly imprinted electrochemical sensor with high sensitivity and stability was developed for PFOA detection. DFT simulations demonstrated that the synergistic interaction between DMs enhances both molecular adsorption capacity and structural stability. Response surface methodology was employed to optimize the MIP composition, revealing a strong correlation between the DM ratio and sensor performance. The optimized MIP-modified electrode exhibited a higher Langmuir adsorption coefficient (Kₐ = 8.92 × 10⁸ cm mol) and improved stability (RSD < 2 %) compared to single-functional monomer electrodes. Additionally, Al/Co-MOFs/rGO complexes are coupled as the sensor basement. The sensor displayed a wide linear detection range (10 pM to 100 nM), low detection limit (5 pM), and excellent recoveries (94 %-107 %) in river samples, demonstrating its robustness and reliability in real-world applications. This study highlights the potential of DM-based electrochemical sensors for sensitive and reliable detection of emerging micropollutants in complex water environments, paving the way for future monitoring and environmental protection.
电化学分子印迹技术（e-MIT）在检测全氟和多氟烷基物质（PFAS）等新型微污染物方面受到了广泛关注。然而，基于e-MIT设计高效可靠的PFAS传感器仍然具有挑战性。在本研究中，我们探索了一种双功能单体（DM）协同吸附识别机制，并在此基础上开发了一种用于检测全氟辛酸（PFOA）的高灵敏度和稳定性的分子印迹电化学传感器。密度泛函理论（DFT）模拟表明，双功能单体之间的协同相互作用增强了分子吸附能力和结构稳定性。采用响应面法优化分子印迹聚合物（MIP）的组成，揭示了双功能单体比例与传感器性能之间的强相关性。与单功能单体电极相比，优化后的MIP修饰电极表现出更高的朗缪尔吸附系数（Kₐ = 8.92 × 10⁸ cm mol）和更好的稳定性（相对标准偏差<2%）。此外，铝/钴金属有机框架/还原氧化石墨烯（Al/Co-MOFs/rGO）复合物作为传感器基底。该传感器在河流样品中显示出较宽的线性检测范围（10 pM至100 nM）、低检测限（5 pM）和优异的回收率（94% - 107%），证明了其在实际应用中的稳健性和可靠性。本研究突出了基于双功能单体的电化学传感器在复杂水环境中灵敏可靠地检测新型微污染物的潜力，为未来的监测和环境保护铺平了道路。
