Optical Detection of Copper Ions via Structural Dissociation of Plasmonic Sugar Nanoprobes

Heavy metal ions are known to cause environmental pollution and several human diseases because of their inherent toxicity. Among them, Cu²⁺ is an essential element for the human body, but its continuous exposure and accumulation may cause adverse effects. Thus, copper ion levels in aquatic environments are strictly regulated by international standards. Herein, we demonstrate a simple optical method for detecting Cu²⁺ using plasmonic sugar nanoprobes (PSNs) composed of gold nanoparticles and polysaccharides. Gold precursors were reduced to nanoparticles and spontaneously embedded in the sugar-based polymeric network with the sulfated residues of carrageenan during the polymerization procedure. Owing to the abundant functional residues of PSNs and their affinity toward Cu²⁺, we observed the Cu²⁺-mediated preferential dissociation of the PSNs, resulting in absorbance spectral shifts and scattering shifts of the PSNs. Based on these plasmon band shifts, Cu²⁺ below the EPA regulation level of 20 μM can be easily detected by the optimized experimental condition. Additionally, the reaction mechanism between the PSNs and Cu²⁺ was elucidated by indepth spectroscopic analyses, which revealed that the increased binding of Cu²⁺ to the sulfate groups in the PSNs induces the eventual decomposition of the PSNs.