Functional ZnS:Mn(II) quantum dot modified with L-cysteine and 6-mercaptonicotinic acid as a fluorometric probe for copper(II)

Manganese-doped ZnS quantum dots (ZnS:Mn(II) QDs) were synthesized and modified with L-cysteine (L-Cys) and 6-mercaptonicotinic acid (MNA). This prevents the aggregation of the QDs and makes them available for the interaction with Cu(II) ions via Cu(II)-S interaction. As a result, the fluorescence of the QDs is quenched by Cu(II) due to an electron transfer mechanism. The QDs display two emission peaks under 325 nm excitation, one (being red) peaking at 593 nm, the other (blue) at 412 nm. The red fluorescence is strongly quenched, while the blue fluorescence is not affected. An easily distinguishable color change from orange red to purple can be observed in fluorescence as the concentration of Cu(II) is increased. The probe is selective over commonly encountered other ions. The ratio of fluorescence intensities at 593 and 412 nm increases linearly in the 5 to 500 nM Cu(II) concentration range, and the detection limit is 1.2 nM. Schematic of the preparation of manganese-doped quantum dots functionalized with L-cysteine and 6-mercaptonicotinic acid for selective and sensitive visual detection of copper ions.