Cu(II)-coordinated GpG-duplex DNA as peroxidase mimetics and its application for label-free detection of Cu2+ ions

Herein a facile method is proposed to construct DNA-based peroxidase mimetics simply assembled by polymorphic DNA and Cu(2+) ions. The Cu(II)-catalyzed oxidation of TMB in the presence of H2O2 can be significantly accelerated through Cu(II)-coordination with DNA scaffolds, of which a colorimetric change can be discerned by naked-eye. The reaction rates of DNA-Cu(II) complexes are directly associated with sequence composition as well as the secondary structure of DNA scaffold, e.g., the reaction rate decreases in the following order: GpG-duplex ≈ G-rich coil > G-quadruplex > C-rich coil > i-motif. It is the first report to explore a colorimetric Cu(2+) sensing system on the basis of peroxidase mimicking activities of polymorphic DNA-Cu(II) complexes. One of our most intriguing results is that the GpG-duplex DNA demonstrates the ability to sense Cu(2+) ions in aqueous solution without significant interference from other metal ions. The Cu(2+) detection limit of 1.2 nM is achieved with a linear response range of 1.2-100 nM, and the developed sensing system is potentially applicable for quantitative determination of Cu(2+) in drinking water samples.