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 Au
x
Ag1–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 Au
x
Ag1–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.