Au_xAg_1–x Nanocomposites with 40-Fold Emission Enhancement Formed by the Electrostatic Assembly of Gold Nanoclusters and Silver Nanoclusters for Bioimaging and Bioanalysis

Noble metal nanoclusters (NCs) have been widely used in bioimaging and bioanalysis due to their unique molecular-like structures and good biocompatibility. Bright nanomaterials with high quantum yields are in need for widespread applications. Unfortunately, the weak photoluminescence (PL) of metal NCs hampers their biomedical applications, and thus it is urgent to develop effective routes to enhance their brightness, especially in aqueous solutions. In this work, we reported a facile strategy to prepare highly luminescent AuxAg1–x nanocomposites (x: molar ratio of Au) by electrostatic-induced assembly of nonluminescent glutathione (GSH) stabilized silver NCs (GSH-Ag NCs) and weak orange-emitting GSH stabilized gold NCs (GSH-Au NCs) in aqueous solutions. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), fluorescence spectroscopy, inductively coupled plasma mass spectrometry (ICP-MS), UV–vis absorption spectroscopy, and dynamic light scattering (DLS) shed light on the mechanism of PL enhancement. It was found that the positively charged gold nanoclusters and the negatively charged silver nanoclusters formed aggregates by electrostatic force, leading to a 40-fold fluorescence intensity enhancement compared with GSH-Au NCs. This was a novel method to strengthen the fluorescence of nanoclusters with such large enhancement in aqueous solutions. With the molar ratio of Au and Ag changing from 80:1 to 2:3, the emission maximum of the AuxAg1–x nanocomposites could be tuned from 590 to 548 nm. The electrostatic force of the Au0.50Ag0.50 nanocomposites enabled them to respond to pH. The Au0.50Ag0.50 nanocomposites were fluorescent turn-on and turn-off at pH 2.6 and pH 7.5, respectively. In this respect, they can be used as a fluorescent switch and be further used as a general recyclable pH probe in the range of 2.6–7.5. This work will inspire even better strategies to further improve the brightness of noble metal NCs.