Cu nanoclusters-based ratiometric fluorescence probe for ratiometric and visualization detection of copper ions

Copper is a highly toxic environmental pollutant with bioaccumulative properties. Therefore, sensitive detection of Cu²⁺ is very important to prevent over-ingestion, and visual detection is preferred for practical applications. In this work, we developed a simple and environmental friendly approach to synthesize hyperbranched polyethyleneimine-protected copper nanoclusters (hPEI-Cu NCs) with great stability against extreme pH, high ionic strength, thiols etching and light illumination, which were then conjugated to the surface of silica coated CdSe quantum dots (QDs) to design a ratiometric fluorescence probe. In the presence of different amounts of Cu²⁺ ions, the fluorescence of Cu NCs can be drastically quenched, while the emission from QDs stayed constant to serve as a reference signal and the color of the probe changed from yellow-green to red, resulting in ratiometric and visualization detection of Cu²⁺ ion with high accuracy. The detection limit for Cu²⁺ was estimated to be 8.9 nM, much lower than the allowable level of Cu²⁺ in drinking water (~20 μM) set by U.S. Environmental Protection Agency. Additionally, this probe can be also applied for the determination of Cu²⁺ ion in complex real water samples.