Better Together: Synergistic Enhancement of AuNPs and Bifunctional Monomers in a Dual-Channel Molecularly Imprinting Electrochemical Sensor for Simultaneous Detection of Diuron and Thidiazuron

IF 6.7 1区化学 Q1 CHEMISTRY, ANALYTICAL

Analytical Chemistry Pub Date : 2025-04-05 DOI:10.1021/acs.analchem.4c06793

Yi He, Chunyuan Tang, Yue Ren, Bingzheng Yuan, Libo Li, Tianyan You, Xuegeng Chen

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Abstract

The combination of diuron (DU) and thidiazuron (TDZ) is commonly used in cotton production for its excellent adaptability to low temperatures, which may lead to increased crop and soil pollution. The simultaneous detection of DU and TDZ poses significant challenges due to their weak and overlapping signals, along with an unclear electrochemical detection mechanism for TDZ. This study developed a dual-channel multifunctional molecularly imprinted electrochemical (MMIP-EC) sensing platform by optimizing the substrate material and MIP layer for high performance. First, amino-functionalized graphene-based poly(pyrrole)-poly(3,4-ethylenedioxythiophene) (NH₂-rGO/PPy-PEDOT) with high conductivity was synthesized as the substrate. Subsequently, MMIPs were prepared in one step using electropolymerization by introducing chloroauric acid (HAuCl₄) and bifunctional monomers (dopamine and thiophene). This method not only enhanced specific binding capacity of the MMIP layer but also amplified the signal through the synergistic effect of reduced AuNPs and bifunctional monomers. Furthermore, two independent modules (MMIP-DU and MMIP-TDZ) were integrated into a dual-channel EC platform for simultaneous transmission of DU and TDZ responses to separate windows. Finally, based on high-performance liquid chromatography–mass spectrometry (HPLC-MS) and electrochemical kinetics studies, it was speculated that the electrochemical oxidation of TDZ via the carbonylation of a secondary amine under strongly acidic conditions, followed by hydrolysis to form a carboxyl group, reveals the electrochemical oxidation mechanism of TDZ. The developed sensor exhibited excellent performance in selectivity and sensitivity, with low detection limits of 26.6 pg/mL (DU) and 39.2 pg/mL (TDZ). In conclusion, this sensing platform presents a novel perspective for the cost-effective and highly efficient detection of diverse environmental pollutants.

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更好地结合：双通道分子印迹电化学传感器中金纳米粒子和双功能单体的协同增效作用，用于同时检测杀草隆和噻草隆

双脲隆（DU）和噻脲隆（TDZ）因其对低温的良好适应性，在棉花生产中被广泛使用，但可能导致作物产量增加和土壤污染。由于DU和TDZ的信号微弱且重叠，以及TDZ的电化学检测机制不明确，因此同时检测DU和TDZ带来了很大的挑战。本研究通过优化衬底材料和MIP层，开发了双通道多功能分子印迹电化学（MMIP-EC）传感平台。首先，合成了具有高电导率的氨基功能化石墨烯基聚（吡咯）-聚（3,4-乙烯二氧噻吩）（NH2-rGO/ py - pedot）作为底物。随后，引入氯金酸（HAuCl4）和双功能单体（多巴胺和噻吩），通过电聚合一步制得MMIPs。该方法不仅增强了MMIP层的特异结合能力，而且通过还原AuNPs和双功能单体的协同作用放大了信号。此外，将两个独立的模块（MMIP-DU和MMIP-TDZ）集成到双通道EC平台中，同时将DU和TDZ响应传输到单独的窗口。最后，基于高效液相色谱-质谱（HPLC-MS）和电化学动力学研究，推测TDZ在强酸性条件下通过仲胺羰基化、水解形成羧基的电化学氧化过程，揭示了TDZ的电化学氧化机理。该传感器具有良好的选择性和灵敏度，检出限分别为26.6 pg/mL （DU）和39.2 pg/mL （TDZ）。总之，该传感平台为经济高效地检测各种环境污染物提供了一个新的视角。

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来源期刊

Analytical Chemistry 化学-分析化学

CiteScore

12.10

自引率

12.20%

发文量

1949

审稿时长

1.4 months

期刊介绍： Analytical Chemistry, a peer-reviewed research journal, focuses on disseminating new and original knowledge across all branches of analytical chemistry. Fundamental articles may explore general principles of chemical measurement science and need not directly address existing or potential analytical methodology. They can be entirely theoretical or report experimental results. Contributions may cover various phases of analytical operations, including sampling, bioanalysis, electrochemistry, mass spectrometry, microscale and nanoscale systems, environmental analysis, separations, spectroscopy, chemical reactions and selectivity, instrumentation, imaging, surface analysis, and data processing. Papers discussing known analytical methods should present a significant, original application of the method, a notable improvement, or results on an important analyte.