共价有机骨架(COFs)由于其可控的结构和功能特性而成为新兴的有前途的传感材料。以及优异的物理化学特性。这里,基于三嗪的COF和大量使用的除草剂-草甘膦(GLY)之间的特定相互作用已用于设计用于GLY检测的一次性传感平台。这种除草剂已经广泛使用了几十年,然而,它对环境的有害影响和对人类的毒性最近得到了证实,调节严格控制和监测其使用及其在土壤中的存在的必要性,水,和食物。草甘膦是一种有机磷化合物,其在复杂的基质中的检测通常需要费力的预处理。这里,我们开发了一个直接的,小型化,健壮,草甘膦一次性电化学传感的绿色方法,利用COF的能力选择性地捕获和浓缩带负电荷的草甘膦分子在其纳米孔内。此过程产生GLY的浓度梯度,加速其向电极表面的扩散。同时,特异性COF-草甘膦结合催化C-P键的氧化裂解,连同孔隙纳米限制,使敏感的草甘膦检测。使用基于DFT的建模对详细的传感原理和选择性进行了审查。所提出的电化学方法的线性工作范围为0.1μM至10μM,检测下限为96nM,和320nM的定量限。详细的传感方法适用于实际样品基质,并可用于土壤和水样中的GLY测定。没有预处理,准备,或净化。结果显示了传感器在实际样品分析中的实用性,并建议其适用于可能的实验室外传感。
Covalent organic frameworks (COFs) are emerging as promising sensing materials due to their controllable structure and function properties, as well as excellent physicochemical characteristics. Here, specific interactions between a triazine-based COF and a mass-used herbicide - glyphosate (GLY) have been utilized to design a disposable sensing platform for GLY detection. This herbicide has been extensively used for decades, however, its harmful environmental impact and toxicity to humans have been recently proven, conditioning the necessity for the strict control and monitoring of its use and its presence in soil, water, and food. Glyphosate is an organophosphorus compound, and its detection in complex matrices usually requires laborious pretreatment. Here, we developed a direct, miniaturized, robust, and green approach for disposable electrochemical sensing of glyphosate, utilizing COF\'s ability to selectively capture and concentrate negatively charged glyphosate molecules inside its nanopores. This process generates the concentration gradient of GLY, accelerating its diffusion towards the electrode surface. Simultaneously, specific COF-glyphosate binding catalyses the oxidative cleavage of the C-P bond and, together with pore nanoconfinement, enables sensitive glyphosate detection. Detailed sensing principles and selectiveness were scrutinized using DFT-based modelling. The proposed electrochemical method has a linear working range from 0.1 μM to 10 μM, a low limit of detection of 96 nM, and a limit of quantification of 320 nM. The elaborated sensing approach is viable for use in real sample matrices and tested for GLY determination in soil and water samples, without pretreatment, preparation, or purification. The results showed the practical usefulness of the sensor in the real sample analysis and suggested its suitability for possible out-of-laboratory sensing.