2024年5月7日，Elsevier 旗下top期刊《Analytica Chimica Acta》在线发表了云南师范大学能源与环境科学学院徐锐教授课题组最新研究成果《Multiple signal-enhanced electrochemiluminescence aptamer sensors based on carboxylated ruthenium (II) complexes for acetamiprid detection》。云南师范大学能源与环境科学学院徐锐教授和张勇教授为通讯作者。

https://www.sciencedirect.com/science/article/pii/S0003267024004781

AbstractBackground

Rapid and sensitive detection for acetamiprid, a kind of widely used neonicotinoid insecticide, is very meaningful for the development of modern agriculture and the protection of human health. Highly stable electrochemiluminescence (ECL) materials are one of the key factors in ECL sensing technology. ECL materials prepared by porous materials (e.g., MOFs) coated with chromophores have been used for ECL sensing detection, but these materials have poor stability because the chromophores escape when they are in aqueous solution. Therefore, the development of highly stable ECL materials is of great significance to improve the sensitivity of ECL sensing technology.

Results

In this work, by combining etched metal-organic frameworks (E-UIO-66-NH2) as carrier with Tris(4,4′-dicarboxylic acid-2,2′-bipyridine)Ru(II) chloride (Ru(dcbpy)32+) as signal probe via amide bonds, highly stable nanocomposites (E-UIO-66-NH2-Ru) with excellent ECL performance were firstly prepared. Then, using MoS2 loaded with AuNPs as substrate material and co-reactant promoter, a signal off-on-off ECL aptamer sensor was prepared for sensitive detection of acetamiprid. Due to the excellent catalytic activity of E-UIO-66-NH2-Ru and MoS2@Au towards K2S2O8, the ECL signals can be enhanced by multiple signal enhancement pathways, the prepared ECL aptamer sensor could achieve sensitive detection of acetamiprid in the linear range of 10−13 to10−7 mol L−1, with the limit of detection (LOD) of 2.78ⅹ10−15 mol L−1 (S/N = 3). After the evaluation of actual sample testing, this sensing platform was proven to be an effective method for the detection of acetamiprid in food and agricultural products.

Significance and novelty

The E-UIO-66-NH2-Ru prepared by linking Ru(dcbpy)32+ to E-UIO-66-NH2 via amide bonding has very high stability. The synergistic catalytic effect of MoS2 and AuNPs enhanced the ECL signal. By exploring the sensing mechanism and evaluating the actual sample tests, the proposed signal "on-off" ECL sensing strategy was proved to be an effective and excellent ECL sensing method for sensitive and stable detection of acetamiprid.

Graphical abstract

The conventional cathodic ECL response uses K2S2O8 as co-reactant. Generally, K2S2O8 can only be activated by participating in redox reactions on the electrode surface, and then the reactive intermediate SO4•− is produced to participate in the subsequent luminescence process (Route 1). However, since the amount of the active intermediate SO4•− limits the luminescence efficiency of the luminophore, increasing the production rate of the active intermediate SO4•− is an effective way to improve the efficiency of ECL. In this study we used MOFs material (E-UIO-66-NH2) etched by thermal treatment as the carrier of the luminophore Ru(dcbpy)32+, and the etched E-UIO-66-NH2 exposed more amino groups, which can effectively catalyze the activation process of K2S2O8 and produce more SO4•− (Route 4). Not only that, the Mo4+/Mo6+ active sites produced by 3D MoS2 nanoflowers involved in the redox reaction on the electrode surface can also effectively catalyze the activation process of K2S2O8 (Route 2). AuNPs grown in situ on the MoS2 surface can also effectively catalyze the activation process of K2S2O8 (Route 3). Therefore, we constructed a sandwich-type ECL sensor based on multiple signal enhancement strategy to achieve efficient and sensitive detection of acetamiprid in the range of 10−13 to 10−7 mol L−1 with a detection limit of 2.78ⅹ10−15 mol L−1. This provides an effective method for the sensitive detection of acetamiprid in food and agricultural products.

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张勇教授入职云南师范大学