Luminescent silver nanoclusters acting as a label-free photoswitch in metal ion sensing

In this work, we report the application of protein-templated Ag nanoclusters as a luminescent photoswitch for the detection of metal ions. Ag nanoclusters were synthesized using the circulatory protein human serum albumin (HSA) as a template, whose synthetic procedure can be tuned to make them toggle between blue-emitting (Ag9:HSA) and red-emitting (Ag14:HSA) nanoclusters. The photoluminescence (PL) intensity of Ag9:HSA was quenched significantly in the presence of 1 mM Co(II) ions. However, the PL of these quenched nanoclusters was completely restored in the presence of 3 mM Zn(II) ions. This enables them to be used as dual sensors and can serve as luminescent turn "on" and "off" metal switches. In contrast, the Ag14:HSA did not exhibit any photoswitchable properties but was able to detect Hg(II) selectively and to a high detection limit (10 nM). The luminescent-based sensing properties of these Ag:NCs were further supported by our time-resolved studies. The present study exhibits a promising step toward the application of luminescent metal nanoclusters as potential metal sensors since by tuning their luminescent properties we were able to detect and quantify metal ions selectively and simultaneously switch their sensing behaviors.