Dual enhanced electrochemiluminescence using aggregation induction and coraction accelerator strategies for trace determination of acetamiprid

Developing electrochemiluminescence (ECL) systems with excellent analytical performance for sensitive detection of trace analytes is highly challenging. Herein, a high-performance ECL system for sensitive detection of trace acetamiprid was developed using a combination of aggregation induction and coreactant accelerator strategy with zinc ions-induced 3,4,9,10-perylenetetracarboxylic (Zn−PTC) as luminophore, potassium persulfate (K₂S₂O₈) as coreactant and Au@MnCo₂O₄ as coreaction accelerator. In the presence of K₂S₂O₈, PTC fail to exhibited an obvious ECL signal, while Zn−PTC showed a significant ECL signal around −1.6 V. Au@MnCo₂O₄ nanomaterial as the coreaction accelerator could be enhanced the ECL signal of Zn−PTC by 4 times, which is mainly due to the following three aspects: i) Zn−PTC with Zn^2 +-induced PTC aggregation not only eliminates the aggregation-induced quenching effect between PTC molecules, but also has a new metal-to-ligand charge-transfer effect, which could transfer the energy of Zn²⁺ to the PTC ligand, thereby enhancing the ECL signal. ii) Au@MnCo₂O₄ could accelerate the electrochemical reduction of S₂O₈²⁻ and H₂O to generate a large amount of active free radicals for enhancing ECL signal because the excellent reversible redox properties of Mn²⁺/Mn³⁺ and Co²⁺/Co³⁺ in Au@MnCo₂O₄. iii) Au@MnCo₂O₄ acted as a satisfying nanocarrier to immobilize more Zn−PTC thereby further enhancing ECL signal. Benefitting from the fabulous performance of the developed ECL system from Zn−PTC/S₂O₈²⁻/Au@MnCo₂O₄, the developed ECL aptasensor for detecting acetamiprid exhibits a wide linear range from 5 to 100 nM as well as a low detection limit of 1.22 fM. As expected, the proposed ECL aptasensor was triumphantly applied to detect acetamiprid in actual samples with desirable results. This work integrated dual signal amplification strategies to effectively enhance ECL, which provided a novel perspectives and approaches to constructing sensors for trace detection of complex matrix species targets.