Label-free fluorescence detection of mercury ions based on the regulation of the Ag autocatalytic reaction

In this work, a novel facile nanoparticle autocatalytic sensor based on the inhibition of the Ag autocatalytic reaction for the determination of Hg2+ was developed. o-Phenylenediamine (OPD) tended to be oxidized into 2,3-diaminophenazine (OPDox) by silver ions (Ag+) followed by the formation of silver nanoparticles (AgNPs). Employed as a catalyst, the thus-formed AgNPs would further promote the reaction between OPD and Ag+. When Hg2+ was introduced, Hg2+ adsorbed on the surface of the AgNPs, thus inhibiting the oxidation process mentioned above and achieving weakened fluorescence intensity. A linear relationship between fluorescence intensity and Hg2+ concentration (within the range from 10 nM to 2500 nM) was obtained and the detection limit reached as low as 8.2 nM. The proposed method was also applied for the determination of Hg2+ in real water samples with satisfactory results. The protocol showed excellent advantages of sensitivity and selectivity for Hg2+ over various metal ions and anions. Meanwhile, this method was simpler and more cost-effective compared with many reported nanomaterial- and DNA-based approaches. Furthermore, an “INHIBIT” logic gate based on the Ag+–Hg2+–OPD system has also been designed.