Dual-mode fluorescence and colorimetric detection of pesticides realized by integrating stimulus-responsive luminescence with oxidase-mimetic activity into cerium-based coordination polymer nanoparticles

The great threat of pesticide residues to the environment and human health has drawn widespread interest to explore approaches for pesticide monitoring. Compared to commonly developed single-signal pesticide assays, multi-mode detection with inherent self-validation and self-correction is expected to offer more reliable and anti-interference results. However, how to realize multi-mode analysis of pesticides still remains challenging. Herein, we propose a dual-mode fluorescence and colorimetric method for pesticide determination by integrating stimulus-responsive luminescence with oxidase-mimetic activity into cerium-based coordination polymer nanoparticles (CPNs(Ⅳ)). The CPNs(Ⅳ) exhibit good oxidase-like activity of catalyzing the colorless 3,3',5,5'-tetramethylbenzidine (TMB) oxidation to its blue oxide, offering a visible color signal; by employing acid phosphatase (ACP) to hydrolyze ascorbic acid 2-phosphate (AAP), the generated ascorbic acid (AA) can chemically reduce the CPNs(Ⅳ) to CPNs(Ⅲ), which exhibit a remarkable fluorescence signal but lose the oxidase-mimicking ability to trigger the TMB chromogenic reaction; when pesticides exist, the enzymatic activity of ACP is restrained and the hydrolysis of AAP to AA is blocked, leading to the recovery of the catalytic TMB chromogenic reaction but the suppression of the fluorescence signal of CPNs(Ⅲ). According to this principle, by taking malathion as a pesticide model, dual-mode 'off-on-off' fluorescence and 'on-off-on' colorimetric detection of the pesticide with good sensitivity was realized. Excellent interference-tolerance and reliability were verified by applying it to analyze the target in real sample matrices. With good performance and practicability, the proposed dual-mode approach shows great potential in the facile and reliable monitoring of pesticide residues.