Lv Jingjing, Shan Li, Xu Jiahui, Liang Jiaxin, Fu Kai, Yu Haihan, Wang Di, Zhang Lina, Li Li, Ji Wenliang, Yu Jinghua
School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, P. R. China.
Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, P. R. China.
Anal Chem. 2025 Jul 8;97(26):13940-13948. doi: 10.1021/acs.analchem.5c01849. Epub 2025 Jun 27.
Herein, we present a highly efficient electrochemiluminescence (ECL) sensor on a paper-based closed bipolar electrode (CBPE) for the sensitive detection of carbendazim (CBZ). This work leverages the tunable dynamics of the cathodic oxygen reduction reaction (ORR) to regulate the emission of anodic luminescence. The innovative design of the CBPE eliminates the need for analytes to directly participate in redox reactions, as required in conventional three-electrode-based ECL systems, while also minimizing interference between the sensing and reporting poles by physically decoupling the two electrodes, greatly improving sensitivity. To further improve the ECL performance, novel ECL-emitting copper nanoclusters (CuNCs), with excellent stability and strong anodic luminescence characteristics, were synthesized and employed as the ECL emitter in the anodic cell, effectively preventing hydrogen evolution associated with the cathodic ECL mode. For target analysis, a Cl-doped metal-free porous electrocatalyst (-pClNC), labeled with an aptamer that specifically recognizes CBZ, is introduced into the sensing electrode. Upon target binding, the electrocatalyst -pClNC dissociates from the electrode surface, increasing the reaction energy barrier of the ORR and consequently weakening the anodic CuNCs ECL signal, enabling ultrasensitive target quantification. As a proof-of-concept, the proposed CBPE sensor was effectively applied to detect CBZ in crops, achieving a broad linear range of 10 to 10 g mL and an exceptionally low detection limit of 3.33 pg mL. This study establishes a sensitive platform for rapid pesticide residue detection and offers a universal strategy for reaction-regulated CBPE-ECL, with strong potential for detecting a broad range of targets in bioanalysis and clinical diagnostics.
在此，我们展示了一种基于纸基封闭双极电极（CBPE）的高效电化学发光（ECL）传感器，用于灵敏检测多菌灵（CBZ）。这项工作利用阴极氧还原反应（ORR）的可调动力学来调节阳极发光的发射。CBPE的创新设计消除了传统三电极ECL系统中分析物直接参与氧化还原反应的需求，同时通过物理分离两个电极将传感极和报告极之间的干扰降至最低，大大提高了灵敏度。为了进一步提高ECL性能，合成了具有优异稳定性和强阳极发光特性的新型ECL发光铜纳米簇（CuNCs），并将其用作阳极池中的ECL发射体，有效防止了与阴极ECL模式相关的析氢现象。对于目标分析，将一种标记有特异性识别CBZ适配体的Cl掺杂无金属多孔电催化剂（-pClNC）引入传感电极。在目标结合后，电催化剂-pClNC从电极表面解离，增加了ORR的反应能垒，从而削弱了阳极CuNCs的ECL信号，实现了超灵敏的目标定量。作为概念验证，所提出的CBPE传感器有效地应用于检测作物中的CBZ，实现了10至10 g mL的宽线性范围和3.33 pg mL的极低检测限。本研究建立了一个用于快速农药残留检测的灵敏平台，并为反应调节的CBPE-ECL提供了一种通用策略，在生物分析和临床诊断中检测广泛目标具有强大潜力。
