Probing How Various Metal Ions Interact with the Surface of QDs: Implication of the Interaction Event on the Photophysics of QDs.

Abstract

With an aim to understand the mechanism of interaction between quantum dots (QDs) and various metal ions, fluorescence response of less-toxic and water-soluble glutathione-capped Zn-Ag-In-S (GSH@ZAIS) QDs in the presence of different metal ions has been investigated at both ensemble and single-molecule level. Fourier transform infrared (FT-IR) spectroscopy has also been performed to obtain a molecular level understanding of the interaction event. The steady-state data reveal no significant change in QD emission for alkali and alkaline earth metal ions, while there is a decrease in fluorescence intensity for transition metal (TM) and some heavy transition metal (HTM) ions. Interestingly, a significant fluorescent enhancement (FE) (19-96%) of QDs is found for Cd2+ ions. Time-resolved fluorescence studies reveal that all the three decay components of QDs decrease in the presence of first-row TM ions. However, in the case of Cd2+, the shorter component is found to increase while the longer one decreases. The analysis of data reveals that photoinduced electron transfer is responsible for fluorescence quenching of QDs in the presence of first-row TM ions and destruction/removal of trap/defect states in the case of Cd2+ causes the FE. In FT-IR experiments, a prominent peak at 670 cm-1, corresponding to Cd-S stretching vibrations, indicates strong ground-state interactions between the -SH of GSH and Cd2+ ions. Moreover, a decrease in the diffusion coefficient of QDs in the presence of Cd2+ ions during fluorescence correlation spectroscopy (FCS) studies further substantiates the removal of GSH by Cd2+ from the surface of QDs. The optical output of this study demonstrates that ZAIS can be used for fluorescence signaling of various metal ions and in particular selective detection of Cd2+. More importantly, these results also suggest that Cd2+ can effectively be used for enhancing the fluorescence quantum yield of thiol-capped QDs such as GSH@ZAIS.