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一步电合成Cu-血红素金属有机框架/碳纳米管用于双测定草甘膦

One-step electrosynthesis of Cu-Hemin MOFs/CNTs for the dual determination of glyphosate.

作者信息

Zhao Fan, Liu Yunxi, Lan Jingyue

机构信息

Tianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry, Tianjin Normal University, Tianjin, 300387, China.

出版信息

Mikrochim Acta. 2024 Aug 27;191(9):564. doi: 10.1007/s00604-024-06626-4.

Abstract

A simple and efficient dual-signal electrochemical sensor was designed for glyphosate (GLYP) determination based on the one-step electro-synthesized Cu-Hemin MOFs/CNTs nanocrystals. Cu-Hemin MOFs/CNTs were directly modified on the electrode through electrodeposition, avoiding complicated synthesis and modification processes. The incorporation of CNTs greatly boosted the conductivity of Cu-Hemin MOFs and the sensitivity of the electrochemical sensor. Cu active sites in Cu-Hemin MOFs were converted to CuCl, allowing the specific detection of GLYP with the turn of CuCl into non-electroactive Cu-GLYP. Meanwhile, GLYP showed highly effective inhibition effect on the inherent peroxidase-like activity of Cu-Hemin MOFs, therefore generating the second electrochemical signal with Cu-Hemin MOFs-catalyzed o-phenylenediamine (o-PD) + HO system. The Cu-Hemin MOFs/CNTs based sensor with two electrochemical signals showed good linearities of 1.0 × 10 M - 3.0 × 10 M and 1.0 × 10 M - 5.0 × 10 M, with detection limits of 5.17 × 10 M and 6.81 × 10 M for the CuCl signal based assay and nanozyme catalyzed o-PD + HO procedure, respectively. This simple and robust dual-signal sensor with excellent selectivity, accuracy, and stability allowed GLYP quantification in real samples, highlighting the potential application of this approach for food and environmental monitoring.

摘要

基于一步电合成的铜-血红素金属有机框架/碳纳米管(Cu-Hemin MOFs/CNTs)纳米晶体,设计了一种简单高效的双信号电化学传感器用于草甘膦(GLYP)的测定。通过电沉积将Cu-Hemin MOFs/CNTs直接修饰在电极上,避免了复杂的合成和修饰过程。碳纳米管的引入极大地提高了Cu-Hemin MOFs的导电性和电化学传感器的灵敏度。Cu-Hemin MOFs中的铜活性位点转化为氯化铜(CuCl),通过将CuCl转化为非电活性的铜-草甘膦(Cu-GLYP)实现对GLYP的特异性检测。同时,GLYP对Cu-Hemin MOFs固有的过氧化物酶样活性表现出高效抑制作用,因此在Cu-Hemin MOFs催化邻苯二胺(o-PD)+H₂O₂体系中产生第二个电化学信号。基于Cu-Hemin MOFs/CNTs的具有两个电化学信号的传感器在1.0×10⁻⁹ M - 3.0×10⁻⁷ M和1.0×10⁻⁷ M - 5.0×10⁻⁶ M范围内呈现良好的线性关系,基于CuCl信号检测法和纳米酶催化o-PD+H₂O₂法的检测限分别为5.17×10⁻¹⁰ M和6.81×10⁻¹⁰ M。这种简单且稳健的具有优异选择性、准确性和稳定性的双信号传感器能够对实际样品中的GLYP进行定量分析,突出了该方法在食品和环境监测中的潜在应用价值。

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