Detection of arsenate in colored grains using an interference-free dual-signal ratiometric HEC sensor

The design of novel homogeneous electrochemical (HEC) sensors with dual-signal ratiometric response holds great potential for highly sensitive and reliable detection of arsenic in food matrices. Herein, COF-based hybrids were prepared by integrating methylene blue (MB) signals and MnO₂ nanozyme coatings, possessing the advantages of high signal loading, oxidase-mimicking activity, and ascorbic acid (AA)-specific recognition to realize ratiometric HEC detection of arsenate. The hydrolysate AA, produced from ALP-catalyzed AAP hydrolysis, could decompose MnO₂ coatings into Mn²⁺, and regulate MB release and o-phenylenediamine oxidation to 2,3-diaminophenazine (DAP). Furthermore, arsenate specifically inhibited ALP, subsequently restraining AA formation and MnO₂ decomposition. Consequently, a decreased MB current and an increased DAP current with opposite responses were regulated by arsenate compared with those without arsenate. Thus, this dual-signal ratiometric HEC sensor achieved sensitive detection of arsenate, with a LOD of 0.509 ppb. It was successfully applied to reliable detection of arsenate in complex food matrices.