Ag(I) Ion-Concentration-Dependent Dynamic Mechanism of Thiolactic-Acid-Capped Gold Nanoclusters Revealed by Fluorescence Spectra and Two-Dimensional Correlation Spectroscopy.

Based on fluorescence spectroscopy, being combined with several spectral analysis techniques including principal component analysis (PCA), two-dimensional correlation spectroscopy (2D-COS), and moving window 2D-COS, the study disclosed the structural variations of gold nanoclusters capped by thiolactic acid (AuNCs@TLA) induced by Ag(I) ions. Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) were applied to monitor the morphology evolution of the surface and composition of the nanoclusters induced by Ag(I) ions. Several spectral components, centered at (790, 607) nm, (670, 590) nm, and (740, 670) nm were revealed by 2D-COS analysis, suggesting new luminescent species or groups were generated with the introduction of Ag(I) ions. A two-stage mechanism was revealed for the photoluminescence variations of AuNCs@TLA induced by Ag(I) ion. The first stage was characterized by the emission quench of 790 nm followed by the emerging emission of 607 nm, which was attributed to the anti-galvanic reaction; and the second stage featured by the noticeable growth of the emission's intensity around 670 nm as result of the AuNCs' size effect. The present study will attract more focuses on near-infrared (NIR)-emitted metal nanoclusters and promote their synthesis and utilities.