Colorimetric and Electrochemiluminescence Dual-Mode Sensing of Lead Ion Based on Integrated Lab-on-Paper Device

A highly selective two-point separation strategy was designed based on a cross-like all-in-one lab-on-paper analytical device. The stable and cleavable enzyme-coated reduced graphene oxide (rGO)-PdAu probe was fabricated as the signal reporter to enable the visualization and electrochemiluminescence (ECL) dual-mode sensing of Pb²⁺. Concretely, the experimental workflow consists of the following process: (i) fabrication of the lab-on-paper device and growth of Au nanoparticles on ECL detection zone, (ii) immobilization of Pb²⁺-specific DNAzyme, and (iii) hybridization between DNAzyme and rGO-PdAu-glucose oxidase (GOx) labeled oligonucleotide to form the double-stranded DNA. Upon addition of Pb²⁺ into the prepared system, the double-helix structure of the DNA was destroyed, resulting in the release of cleaved rGO-PdAu-GOx probe to visualization bar to promote the effective oxidation and color change of 3,3',5,5'-tetramethylbenzidine. As a consequence, the color change can be recognized by naked eye, meanwhile GOx on an uncleaved signal probe can oxidize glucose along with the H₂O₂ production. As a co-reaction reagent for luminol ECL system, the concentration of H₂O₂ is proportional to the ECL intensity, which constitutes a new mechanism for colorimetric and ECL dual mode to detect Pb²⁺. With the method developed here, the concentration of Pb²⁺ could be easily determined by the naked eye within a linear range from 5 to 2000 nM, as well as by monitoring the decreased ECL intensity of luminol in a linear range of 0.5-2000 nM. This work not only constructs a simple and versatile platform for on-site visible monitoring of Pb²⁺ in tap water and river water but also furnishes a strategy for designing a dual-mode sensing toward different heavy metal ions based on specific DNAzyme in the fields of environmental monitoring-related technologies.