A simple strategy for the visual detection and discrimination of Hg2+ and CH3Hg+ species using fluorescent nanoaggregates

Abstract

Fluorescent nanoaggregates (FNAs) based on phenanthroline-based amphiphiles show changes in solution color from colorless to yellow upon addition of both Hg²⁺ (LOD ∼4 ppb) and CH₃Hg⁺ (LOD ∼18 ppb). However, the extent of fluorescence quenching is more prominent with Hg²⁺ (∼12 fold) than with CH₃Hg⁺ (∼4 fold). Also, unlike Hg²⁺, the interaction of CH₃Hg⁺ needs more time, ∼10 min at room temperature. Experimental evidence indicates that both mercury species coordinate with the phenanthroline unit and facilitate the charge transfer interaction while destabilizing the nanoassembly. The lower charge density on CH₃Hg⁺ along with its large size compared to Hg²⁺ may be the reason for such observations. Interestingly, FNAs show a selective response towards CH₃Hg⁺ when pre-treated with EDTA. Further, analysis of heavy metal pollutants in drinking water and biological samples was performed. High recovery values ranging from 96% to 103.0% were estimated along with relatively small standard deviations (<3%). Low-cost, reusable test strips were designed for rapid, on-site detection of mercury species. Further, the in situ formed metal complexes are allowed to interact with thiol-containing amino acids. As expected, CH₃Hg⁺, being less thiophillic, endures less interaction with cysteine. Mechanistic investigations indicate that thiolated amino acids can bind with the metal ion center and form a tertiary complex (cooperative interaction).