Aptamer-Target Recognition-Promoted Ratiometric Electrochemical Strategy for Evaluating the Microcystin-LR Residue in Fish without Interferences.

Given the significance of food safety, it is highly urgent to develop a sensitive yet reliable sensor for the practical analysis of algal toxins. As most of the developed sensors are disturbed by interfering substances and the target toxin is detected in a single-signal manner based on the immunoassay technology. Herein, we developed an aptamer-based dual-signal ratiometric electrochemical sensor for the sensitive and accurate analysis of microcystin-LR (MC-LR), using it as a proof-of-concept analyte. Methylene blue-tagged ssDNA (MB-ssDNA) was immobilized at the gold electrode surface accompanied with the absence of ferrocene-tagged ssDNA (Fc-ssDNA), resulting in a high differential pulse voltammetry (DPV) current of MB and a low DPV current of Fc. The recognition of MB-ssDNA by MC-LR stimulated the formation of MC-LR@MB-ssDNA, which induced the removal of MB-ssDNA from the electrode and the exposure of SH-ssDNA, enabling Fc-ssDNA to be captured at the electrode surface via nucleic acid hybridization. In comparison with MC-LR deficiency, the DPV signal of MB dropped along with an improved DPV signal of Fc, contributing to the ratiometric detection of MC-LR, with the limit of detection down to 0.0015 nM. Furthermore, this ratiometric electrochemical sensor was successfully explored to assess the bioaccumulated amount of MC-LR in the liver and meat of fish. The aptamer-based ratiometric strategy to develop an electrochemical MC-LR assay will offer a promising avenue to develop high-performance sensors, and the sensor will find more useful application in MC-LR-related aquatic product safety studies.