Highly sensitive and selective ratiometric fluorescent and visual detection of Cu2+ based on the hydroxytyrosol–naphthoresorcin–quantum dots sensing platform

Abstract

Fluorescence-based visual analysis has attracted considerable attention in on-site detection owing to their distinct color gradient changes, easy operation and high sensitivity. In this work, we construct an exceptionally simple dual-emission ratio fluorescence sensor through the synergy of hydroxytyrosol (HYT), naphthoresorcin (NR) and ZnCdSe/ZnS quantum dots (QDs), namely HYT–NR–QD, for the fluorescent and visual detection of Cu2+. The design of ratiometric nanosensor is based on our new finding that Cu2+ can catalyze the reaction between HYT and NR to produce a cyan-emitting fluorophore (emission: 480 nm), and the copper species existed in the form of Cu+ and Cu2+ in reaction system. After adding QDs (emission: 605 nm), the free Cu+, Cu2+ and the resulting fluorophore in this system caused a great reduction in the FL intensity of QDs, due to the rapid cation exchange reaction between QDs and Cu2+/Cu+ as well as the inner filter effect between QDs and the resulting fluorophore. Overall, Cu2+ induced emission intensity changes at 480 and 605 nm leads to a distinct color change from red to cyan. A ratiometric fluorescence Cu2+ sensor with a lowest concentration of 3.42 nM was developed. Furthermore, the concentration of Cu2+ can be conveniently reflected with a smartphone application by identifying the RGB value. Moreover, the method proposed by us can be explored for Cu2+ determination in environmental water samples with a satisfying result, providing a novel, simple-operating and on-site detection of Cu2+ in water samples.