Metal-Enhanced Hg²⁺-Responsive Fluorescent Nanoprobes: From Morphological Design to Application to Natural Waters

Metal-enhanced fluorescence (MEF) is a powerful tool in the design of sensitive chemical sensors by improving brightness and photostability of target-responsive fluorophores. Compounding these advantages with the modest hardware requirements of fluorescence sensing compared to that of centralized elemental analysis instruments, thus expanding the use of MEF to the detection of low-level inorganic pollutants, is a compelling aspiration. Among the latter, monitoring mercury in the environment, where some of its species disseminate through the food chain and, in time, to humans, has elicited a broad research effort toward the development of Hg²⁺-responsive fluorescent sensors. Herein, a Hg²⁺-sensitive MEF-enabled probe was conceived by grafting a Hg²⁺-responsive fluorescein derivative to concentric Ag@SiO₂ NPs, where the metallic core enhances fluorescence emission of molecular probes embedded in a surrounding silica shell. Time-resolved fluorescence measurements showed that the fluorophore's excited-state lifetime decreases from 3.9 ns in a solid, coreless silica sphere to 0.4 ns in the core-shell nanoprobe, granting the dye a better resistance to photobleaching. The Ag-core system showed a sizable improvement in the limit of detection at 2 nM (0.4 ppb) compared to 50 nM (10 ppb) in silica-only colloids, and its effectiveness for natural water analysis was demonstrated. Overall, the reported nanoarchitecture hints at the potential of MEF for heavy metal detection by fluorescence detection.