Bifunctional single-labelled oligonucleotide probe for detection of trace Ag(I) and Pb(II) based on cytosine-Ag(I)-cytosine mismatches and G-quadruplex

A novel bifunctional oligonucleotide (OND) probe with single fluorescent group HEX labelled at 5′-end was designed for detecting trace Ag(I) and Pb(II) in real samples. In the presence of Ag(I), the hairpin structure originating from Ag(I) induced cytosine-Ag(I)-cytosine mismatches causes the proximity of the HEX to the consecutive guanine bases (G)4 at 3′-terminal, resulting in the fluorescence quenching of the HEX. While in the presence of Pb(II), the G-quadruplex structure originating from two G-quartet planes by the intramolecular hydrogen bond with Pb(II) also causes the HEX approaching the (G)4 terminal and consequently the fluorescence quenching. The results showed the quantitative detection of trace Ag(I) and Pb(II) both in the linear response ranges of 1.0–20.0 × 10−9 mol L−1 with no visible interferences of other 11 metal ions observed. And the detection limits were 82 × 10−12 mol L−1 for Ag(I), 92 × 10−12 mol L−1 for Pb(II), respectively. The fluorescence quenching mechanism of the (G)4 to HEX was verified to be the photoinduced electron transfer in the aspect of thermodynamics. This method provided a feasible application for sensitive and selective detection of Pb(II) and Ag(I) in water and Chinese traditional herbs with convenient operation. [Display omitted] •A novel OND probe was designed for dual-function of Ag(I) and Pb(II) detection.•The LODs of detection were picomole-quantities.•The deviation was less than 5% between the results in this method with AAS.•The verified quenching mechanism of (G)4-HEX was photoinduced electron transfer.