Two birds with one stone: An enzyme-regulated ratiometric fluorescent and photothermal dual-mode probe for organophosphorus pesticide detection

In this study, based on the oxidase activity and photothermal effect of manganese dioxide nanosheets (MnO2 NSs), with thiamine (TH) as the fluorescence response signal and tris (2,2'-bipyridyl) ruthenium (II) hexahydrate as the reference signal, an enzyme-regulated ratiometric fluorescence and photothermal dual-mode probe was constructed for the quantitative detection of organophosphorus pesticide (OPs) residues. OPs reduced the production of the reductive product thiocholine by inhibiting the activity of acetylcholinesterase, thereby regulating the residual amount of MnO2 NSs. With the increase of OPs concentration, the color of the probe solution gradually transitioned from red to blue, and the temperature gradually increased. Using dichlorvos and chlorpyrifos as pesticide models, the developed probes exhibited sensitive responses to OPs in a wide linear range of 0.1-8000 ng/mL. The detection limits of dichlorvos and chlorpyrifos in fluorescence mode were 1.13 × 10-3 ng/mL and 0.86 ng/mL, respectively. The corresponding detection limits in photothermal mode were 1.01 ng/mL and 1.02 ng/mL, respectively. The proposed probe displayed excellent anti-interference and reliability in the analysis of OPs residues in real samples. The dual-mode probe with self-verification function is expected to provide more accurate and robust detection results than the single-mode probe, and has a wider application prospect.