Upconversion Nanoparticles Encapsulated with Amorphous Silica and Their Emission Quenching by FRET: A Nanosensor Excited by NIR for Mercury Detection

Abstract

Near-infrared (NIR) region has been considered as a diagnostic window since it avoids sample autofluorescence and light scattering. Upconversion nanoparticles (UCNPs) convert NIR light into high energy excitation light, making them a suitable excitation source for nanoprobes with deep penetration depth and high signal-to-noise ratio. The current work reported a rhodamine-derived probe for the detection of Hg(II). Corresponding absorption and emission responses for Hg(II) and detailed recognizing mechanism were discussed. An absorption titration experiment was performed. It was found that Hg(II) directly bonded with probe with chemical stoichiometry of 1:1, its association constant was calculated as 2.59 × 105 M−1. Such a high value indicated a direct coordination affinity between Hg(II) and this rhodamine-derived probe. Most metal cations exerted no increasing effect on the probe emission or absorption, exhibiting good sensing selectivity of probe towards Hg(II). Upconversion nanoparticles (UCNPs) were firstly encapsulated with silica (SiO2) and then bonded with the probe via a covalent bond. Given a near-infrared (NIR) laser excitation with wavelength of 980 nm, this probe, (E)-2-((3′,6′-bis(diethylamino)-2′,7′-dimethyl-3-oxospiro[isoindoline-1,9′-xanthen]-2-yl)imino)acetaldehyde (denoted as RHO), captured the energy of UCNPs via a FRET (fluorescence resonance energy transfer) path, resulting in the emission quenching of UCNPs. This composite system showed linear sensing behavior towards Hg(II) with high selectivity, which was similar to the case of pure probe. No probe emission, however, was observed from the composite system, which was different from the case of most literature reports. The self-quenching between probe molecules was claimed responsible for the probe emission, which was confirmed by experiment result and analysis. To the best of our knowledge, this is the first demonstration of covalently integrating SiO2-coated UCNPs with a rhodamine-derived probe for Hg(II) sensing.