Collaborative Innovation Center for Green Chemical Manufacturing and Accurate Detection, Key Laboratory of Interfacial Reaction & Sensing Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, Shandong, China.
State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
Anal Chem. 2022 Sep 20;94(37):12742-12749. doi: 10.1021/acs.analchem.2c02350. Epub 2022 Sep 2.
The exploration of novel electrochemiluminescence (ECL) reagents has been a breakthrough work in ECL immunoassay. In this work, the ECL properties of polyoxomolybdate-zirconia (POM-ZrO) were discovered for the first time and their luminescence mechanism was initially explored. Virgulate POM-ZrO was synthesized from phosphomolybdic acid hydrate and zirconium oxychloride by solvothermal method, which achieved intense and stabilized cathode ECL emission at a negative potential. Polyaniline@Au nanocrystals (PANI@AuNPs) as the executor of the dual-mechanism quenching strategy were used to reduce the output signal. The quenching efficiency was significantly enhanced by the dual mechanisms of ECL energy transfer and electron transfer. Specifically, PANI@AuNPs can serve as an energy receptor to absorb the energy emitted by POM-ZrO (energy donor), while the appropriate energy level can be regarded as the condition for electron transfer to quench the ECL intensity of POM-ZrO. Herein, the proposed dual-mechanism quenching strategy was applied to the immunoassay of 17β-estradiol by constructing a competitive immunosensor. As expected, the immunosensor demonstrated favorable analytical performance and a wide sensing range from 0.01 pg/mL to 200 ng/mL. Hence, it provides a novel method for the sensitive analysis of other biomolecules, such as disease markers and environmental estrogens.
新型电化学发光（ECL）试剂的探索是 ECL 免疫分析中的一项突破工作。在这项工作中，首次发现了多酸-氧化锆（POM-ZrO）的 ECL 性质，并初步探索了其发光机制。采用溶剂热法从磷钼酸水合物和氧氯化锆合成了螺旋多酸-ZrO，在负电势下实现了强烈稳定的阴极 ECL 发射。聚邻苯二胺@金纳米晶（PANI@AuNPs）作为双机制猝灭策略的执行者，用于降低输出信号。双机制 ECL 能量转移和电子转移显著增强了猝灭效率。具体而言，PANI@AuNPs 可以作为吸收 POM-ZrO 发射能量的能量受体（能量供体），而适当的能级可以被视为电子转移以猝灭 POM-ZrO 的 ECL 强度的条件。在此，提出的双机制猝灭策略被应用于构建竞争性免疫传感器以用于 17β-雌二醇的免疫分析。正如预期的那样，该免疫传感器表现出良好的分析性能和从 0.01 pg/mL 到 200 ng/mL 的宽检测范围。因此，它为其他生物分子（如疾病标志物和环境雌激素）的灵敏分析提供了一种新方法。
