A dual colorimetric probe for rapid environmental monitoring of Hg2+ and As3+ using gold nanoparticles functionalized with d-penicillamine

Abstract

A highly sensitive and selective colorimetric assay for the dual detection of Hg²⁺ and As³⁺ using gold nanoparticles (AuNPs) conjugated with d-penicillamine (DPL) was developed. When Hg²⁺ and As³⁺ ions coordinate with AuNP-bound DPLs, the interparticle distance decreases, inducing aggregation; this results in a significant color change from wine red to dark midnight blue. The Hg4f and As3d signals in the X-ray photoelectron spectra of Hg²⁺ (As³⁺)-DPL-AuNPs presented binding energies indicative of Hg²⁺-N(O) and As³⁺-N(O) bonds, and the molecular fragment observed in time-of-flight secondary ion mass spectra confirmed that Hg²⁺ and As³⁺ coordinated with two oxygen and two nitrogen atoms in DPL. The detection of Hg²⁺ and As³⁺ can be accomplished by observing the color change with the naked eye or by photometric methods, and this was optimized to provide optimal probe sensitivity. The assay method can be applied for environmental monitoring by first selectively quantifying Hg²⁺ in water samples at pH 6, then estimating the As³⁺ concentration at pH 4.5. The efficiency of the DPL-AuNP probe was evaluated for the sequential quantification of Hg²⁺ and As³⁺ in tap, pond, waste, and river water samples, and absorbance ratios (A ₇₃₀/A ₅₂₅) were correlated with Hg²⁺ and As³⁺ concentrations in the linear range of 0-1.4 μM. The limits of detection in water samples were found to be 0.5 and 0.7 nM for Hg²⁺ and As³⁺, respectively. This novel probe can be utilized for the dual determination of Hg²⁺ and As³⁺, even in the presence of interfering substances in environmental samples.