In this work, near-infrared fluorescent silver nanoclusters
(Ag
NCs) were prepared based on the in situ formed poly methacrylic acid
(PMAA) as the template and stabilizer, which is synthesized by methacrylic
acid (MAA) and hydroxyl radical (·OH) that is generated by the
cascade nanoenzyme reaction of cupric oxide nanoparticles (CuO NPs).
CuO NPs possess the intrinsic glutathione-like (GPx-like) and peroxidase-like
(POD-like) activities, which can catalyze glutathione (GSH) and O2 to produce hydrogen peroxide (H2O2),
and then transform into ·OH. The fluorescence intensity of Ag
NCs decreases with the addition of GSH, because the −SH can
easily anchor on the surface, resulting in the PMAA leaving the Ag
NCs, and the coeffect of GSH and PMAA results in the aggregation to
form larger Ag NPs. A good linear relationship between the fluorescence
quenching rate and the GSH concentration was found in the range 0.01–40
μM with the detection limit 8.0 nM. The Ag NCs can be applied
in the detection of GSH in the serum, as well as bioimaging of endogenous
and exogenous GSH in cells with high sensitivity. Moreover, the normal
and cancer cells can be distinguished through bioimaging because of
the different GSH levels. The new method for the preparation of biocompatible
nanoprobe based on the nanozyme tandem catalysis and the in situ formed
template can avoid the direct usage of polymers or protein templates
that hinder preparation and separation, providing a reliable approach
for the synthesis, biosensing, and bioimaging of nanoclusters.