Li Chuanping, Hang Tianxiang, Jin Yongdong
State Key Laboratory of Electroanalytical Chemistry Changchun Institute of Applied Chemistry Chinese Academy of Sciences Changchun People's Republic of China.
Anhui Laboratory of Functional Coordinated Complexes for Materials Chemistry and Application Anhui Polytechnic University Wuhu People's Republic of China.
Exploration (Beijing). 2023 Jul 7;3(4):20220151. doi: 10.1002/EXP.20220151. eCollection 2023 Aug.
The successful application of electrochemiluminescence (ECL) in immunoassays for clinical diagnosis requires stable electrodes and high-efficient ECL signal amplification strategies. Herein, the authors discovered a new class of atomically dispersed peroxidase-like nanozymes with multiple active sites (CoNi-MOF@PCN-224/Fe), which significantly improved the catalytic performance and uncovered the underlying mechanism. Experimental studies and theoretical calculation results revealed that the nanozyme introduced a Fenton-like reaction into the catalytic system and the crucial synergistic effects of definite active moieties endow CoNi-MOF@PCN-224/Fe strong electron-withdrawing effect and low thermodynamic activation energy toward HO. Benefiting from the high peroxidase-like activity of the hybrid system, the resultant ECL electrode exhibited superior catalytic activity in the luminol-HO system and resulted in an ≈17-fold increase in the ECL intensity. In addition, plasmonic Ag/Au core-satellite nanocubes (Ag/AuNCs) were designed as high-efficient co-reactant quenchers to improve the performance of the ECL immunoassay. On the basis of the differential signal amplification strategy (DSAS) proposed, the immunoassay displayed superior detection ability, with a low limit of detection (LOD) of 0.13 pg mL for prostate-specific antigen (PSA). The designed atomically anchored MOF-on-MOF nanozyme and DSAS strategy provides more possibilities for the ultrasensitive detection of disease markers in clinical diagnosis.
电化学发光（ECL）在临床诊断免疫分析中的成功应用需要稳定的电极和高效的ECL信号放大策略。在此，作者发现了一类具有多个活性位点的新型原子分散的类过氧化物酶纳米酶（CoNi-MOF@PCN-224/Fe），其显著提高了催化性能并揭示了潜在机制。实验研究和理论计算结果表明，该纳米酶将类芬顿反应引入催化体系，特定活性部分的关键协同效应赋予CoNi-MOF@PCN-224/Fe对HO具有强吸电子效应和低热力学活化能。受益于混合体系的高类过氧化物酶活性，所得的ECL电极在鲁米诺-HO体系中表现出优异的催化活性，使ECL强度提高了约17倍。此外，等离子体Ag/Au核-卫星纳米立方体（Ag/AuNCs）被设计为高效的共反应淬灭剂，以提高ECL免疫分析的性能。基于所提出的差分信号放大策略（DSAS），该免疫分析显示出优异的检测能力，前列腺特异性抗原（PSA）的检测限低至0.13 pg mL。所设计的原子锚定的MOF-on-MOF纳米酶和DSAS策略为临床诊断中疾病标志物的超灵敏检测提供了更多可能性。
