Ultralow Potential Cathodic Electrochemiluminescence Aptasensor for Detection of Kanamycin Using Copper Nanoribbons as Coreaction Accelerator

Abstract

An ultralow cathodic potential electrochemiluminescence (ECL) aptasensor was designed, employing DNA nanoribbon template self-assembly copper nanoclusters (DNR-CuNCs) as a novel coreaction accelerator within the luminol-H₂O₂ system for the sensitive detection of kanamycin (KANA). Mechanistic investigations revealed that the DNR-CuNCs preferred to generate highly active hydroxyl radicals by facilitating the reduction of the coreactant H₂O₂ under neutral pH conditions, consequently enhancing cathodic luminescence. By the strong π-π stacking effect of KANA aptamer and graphene as a signal modulation switch, DNR-CuNCs were displaced from the electrode surface due to the affinity of KANA and its aptamer, resulting in the inhibition of the luminol-H₂O₂ system and a decrease in the ECL signal. Under optimal experiments, the aptasensor demonstrated exceptional sensitivity in detecting KANA within the concentration range from 1 × 10^-2 to 5 × 10⁵ pg/mL, with the detection limit as low as 0.18 fg/mL. This innovative strategy provided a novel approach to designing effective ECL emitters for monitoring food safety.