DNA-templated copper nanoclusters as a fluorescent probe for fluoride by using aluminum ions as a bridge

A selective fluorescent on-off-on probe has have designed for the detection of fluoride (F^-) ions based on DNA-templated copper nanocluster (CuNCs) and by using aluminum(III) ions as a bridge. A 40-mer polythymine acts as a template for the reduction of Cu(II) to Cu(0) by ascorbic acid. This result is the formation of red fluorescent CuNCs, with excitation/emission peaks at 340/640 nm. After addition of Al³⁺ ions, the fluorescence of CuNCs is quenched because the interaction of Al³⁺ and DNA disturbs the formation of DNA-templated CuNCs. Fluorescence is restored on addition of fluoride to the system. This is due to the desorption of Al³⁺ from the DNA and the formation of the Al(OH)₃F^- complex. This system displays a fast fluorometric response to fluoride, with high selectivity over other anions. Fluorescence increases linearly in the 2 to 150 μM F^- concentration range, and the detection limit is 1.0 μM. This probe has been successfully used for the detection of F^- ions in four brands of toothpaste. The method is rapid, cost-effective, selective, and does not require toxic solvents and reagents. Graphical abstract Schematic presentation of a method for fluorometric determination of fluoride by using DNA-templated copper nanoclusters (CuNCs) and using aluminum(III) as a bridge. The red fluorescence of the CuNCs is quenched in the presence of Al(III) ions but restored after addition of fluoride.