College of Chemistry and Chemical Engineering, Institute for Conservation and Utilization of Agro-Bioresources in Dabie Mountains & Henan Key Laboratory of Utilization of Non-Metallic Mineral in the South of Henan, Xinyang Normal University, Xinyang, 464000, China.
Analyst. 2020 May 7;145(9):3245-3256. doi: 10.1039/d0an00278j. Epub 2020 Mar 25.
In this work, a disposable molecularly imprinted electrochemical sensor was developed towards the highly sensitive and selective detection of the organophosphorus insecticide phosalone (PAS), employing a home-made carbon paste microelectrode (CPME) modified with a Zr-based metal-organic framework catalyst (Pt-UiO-66) and a mesoporous structured conductive molecularly imprinted polymer (MIP). Pt-UiO-66 octahedra with isolated dispersed Pt nanoparticle active sites were firstly incorporated into the CPME to provide a remarkably amplified signal for voltammetric determination. The mesoporous MIP was then synthesized onto the Pt-UiO-66/CPME via electropolymerization and a subsequent sol-gel process, which could bind the PAS template molecules through hydrogen bond, coordinate bonding, hydrophobic interaction, and π-π stacking interaction. Morphological, structural, and electrochemical characterization studies revealed that this nano-sized MIP provided excellent features for PAS detection, including high porosity, large surface area, enhanced electron-transport ability, greatly improved diffusion capacity, and strong recognition specificity. Therefore, the resulting sensor exhibited an outstanding linearly proportional concentration domain of 0.50 nM-20 μM, low detection limit of 0.078 nM, marked selectivity over certain interferences with similar configurations, considerable repeatability, reproducibility, and stability for the analysis of PAS. Moreover, the sensor was successfully applied for the determination of PAS in agricultural products and environmental samples with results in good compatibility with a chromatographic method, indicative of the high reliability and practicability. Such an electrochemical sensor might open a novel window for the investigation of selective sensing of small organic species from their analogues coupled with the molecular imprinting technique.
在这项工作中,开发了一种一次性分子印迹电化学传感器,用于高灵敏度和选择性检测有机磷杀虫剂涕灭威(PAS),采用自制的碳糊微电极(CPME)修饰Zr 基金属有机骨架催化剂(Pt-UiO-66)和介孔结构的导电分子印迹聚合物(MIP)。首先将具有孤立分散的 Pt 纳米颗粒活性位点的 Pt-UiO-66 八面体掺入 CPME 中,为伏安法测定提供了显著增强的信号。然后通过电聚合和随后的溶胶-凝胶过程将介孔 MIP 合成到 Pt-UiO-66/CPME 上,该 MIP 可以通过氢键、配位键、疏水相互作用和π-π 堆积相互作用结合 PAS 模板分子。形态、结构和电化学表征研究表明,这种纳米级 MIP 为 PAS 检测提供了出色的特性,包括高孔隙率、大表面积、增强的电子传输能力、大大提高的扩散能力和强识别特异性。因此,所得传感器表现出出色的线性比例浓度范围为 0.50 nM-20 μM,检测限低至 0.078 nM,对具有相似结构的某些干扰物具有明显的选择性,具有良好的重复性、重现性和稳定性,可用于 PAS 的分析。此外,该传感器成功应用于农产品和环境样品中 PAS 的测定,结果与色谱法具有良好的兼容性,表明其具有较高的可靠性和实用性。这种电化学传感器可能为结合分子印迹技术选择性检测类似物中的小分子物种开辟了一个新的窗口。