A dual-emitting fluoroprobe fabricated by aloe leaf-based N-doped carbon quantum dots and copper nanoclusters for nitenpyram detection in waters by virtue of inner filter effect and static quenching principles

Abstract

Fluorescence sensing technique has been used in environmental analysis due to its simplicity, low cost, and visualization. Although the fruit pulp-based biomass carbon quantum dots (CQDs) have excellent luminescent properties, aloe leaves possess the superiority of being easily accessible in all seasons compared to fruit pulp. Thus, we fabricated Aloe carazo leaf-based nitrogen doping-CQDs (N-CQDs) using a facile hydrothermal approach, which emitted bright blue fluorescence with a quantum yield of 21.4 %. By comparison, the glutathione-encapsulated copper nanoclusters (GSH-CuNCs) displayed strong red fluorescence. A blue/red dual emission based on the N-CQDs/CuNCs mixture was established for nitenpyram detection.At the 350-nm excitation, the N-CQD/CuNCs system produced dual-wavelength emitting peaks at 440 and 660 nm, respectively. Moreover, when nitenpyram was introduced into the system, the fluorescence intensities (FIs) of N-CQDs significantly decreased, whereas the FIs of GSH-CuNCs varied slightly; simultaneously, the solution color changed from bright blue to dark red. Both the spectral overlapping between nitenpyram's UV–Vis absorption and N-CQDs’ excitation and almost unchanged fluorescence lifetimes indicated the occurrence of inner-filtering effect (IFE) in the dual-emitting fluoroprobe. In addition, the Stern-Volmer constant (Ksv = 6.92 × 103 M−1), temperature effect, as well as UV–Vis absorption of N-CQD/CuNCs before and after the addition of nitenpyram corroborated the static-quenching behavior. Consequently, the fluorescence-quenching of N-CQDs by nitenpyram was attributable to the joint IFE and static-quenching principles. A good linearity existed between the F660/F440 values and nitenpyram concentrations (0.5–200 μM) with a method detection limit of 0.15 μM.The dual-emitting fluoroprobe provided the satisfactory recoveries (95.0%–107.0 %) for nitenpyram detection in real-world waters, which were comparable with the results of traditional liquid chromatography coupled to tandem mass spectrometry method. Owing to its simple operations, low-cost, and adaptability for on-site outdoor monitoring, the newly developed dual-emitting fluoroprobe possesses great potential applications in routine monitoring of nitenpyram under field conditions.