Silver nanocluster-based colorimetric/fluorimetric dual-mode sensor for the detection of bromide and sulfite in waters and wastewaters

Abstract

In this work, the development of a fluorimetric/colorimetric dual-mode nanosensor for the determination of sulfite and fluorimetric determination of bromide involving silver nanoclusters (AgNCs) is reported. SO2 and Br2 were found to significantly modify the optical properties of AgNCs. Particularly, both volatiles weakened the fluorescence of AgNCs, whereas a color change from nearly colorless to yellowish/brown upon exposure of AgNCs to SO2. Accordingly, three smartphone-based optical assays were devised for sulfite and bromide determination, involving in situ volatile generation and enrichment/trapping of the selectively formed volatiles by AgNCs confined in a droplet and exposed to the headspace above the sample. A hydrophobized cellulose substrate acting as drop holder enabled integrating both the enrichment and the subsequent smartphone-based optical detection in a straightforward manner. Smartphone-based digitization of the enriched AgNCs microdrops and subsequent image processing using a smartphone and its integrated App, respectively, were used for quantitative purposes. Under optimal conditions, limits of detection (LODs) of 1.1 µM and 1.5 µM were achieved for the fluorimetric determination of sulfite and bromide, respectively, whereas sulfite was alternatively determined by colorimetric readout, yielding a LOD of 37.0 µM. The repeatability, expressed as relative standard deviation, was found to be in the range of 5.1–5.9 % in all cases (N = 8). The applicability of the method was demonstrated in aqueous samples of increasing complexity, with recoveries in the range 91–109 %. In addition, the responsiveness of AgNCs to SO2 and Br2 rendered them suitable for the monitoring of bromide and sulfite in increasingly relevant advanced reduction processes such as the UV/sulfite system, as demonstrated in this work.