Analyte-triggered cyclic autocatalytic oxidation amplification combined with an upconversion nanoparticle probe for fluorometric detection of copper(II)

Abstract

The authors describe an upconversion nanoparticle-based (UCNP–based) fluorometric method for ultrasensitive and selective detection of Cu²⁺. The UCNPs show a strong emission band at 550 nm under near-infrared excitation at 980 nm. The principle of the strategy is that gold nanoparticles (AuNP) can quench the fluorescence of UCNP. In contrast, the addition of L-cysteine (Cys) can induce the aggregation of AuNP, resulting in a fluorescence recovery of the UCNPs. On addition of Cu²⁺, it oxidizes Cys to cystine and is reduced to Cu⁺. The Cu⁺ thusformed can be oxidized cyclically to Cu²⁺ by dissolved O₂, which catalyzes and recycles the whole reaction. Thus, the aggregation of AuNP is inhibited and the fluorescence recovered by Cys is quenched. Under the optimal condition, the quenching efficiency shows a good linear response to the concentrations of Cu²⁺ in the 0.4–40 nM range. The limit of detection is 0.16 nM, which is 5 orders of magnitude lower than the U.S. Environmental Protection Agency limit for Cu²⁺ in drinking water (20 μM). The method has been further applied to monitor Cu²⁺ levels in real samples. The results of detection are well consistent with those obtained by atomic absorption spectroscopy.