Ratiometric determination of copper(II) using dually emitting Mn(II)-doped ZnS quantum dots as a fluorescent probe

A ratiometric probe is described for the fluorometric determination of Cu(II) ions based on their quenching effect on the luminescence of dually-emitting quantum dots (QDs). ZnS QDs were doped with Mn(II) and subsequently modified with mercaptopropionic acid to give the QD probe which consists of a  sole fluorophore but has two emission peaks (at 430 and 590 nm under 310 nm excitation, respectively). On addition of Cu(II) ions, the 590 nm band is quenched while the 430 nm band exhibits a little change. The changes in the intensity ratios of the yellow and the purple bands increases linearly in the 0 to 3.0 μM Cu(II) concentration range, and the detection limit reached 14 nM. The QD probe was validated and successfully applied to the determination of Cu(II) in spiked real water samples.