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-ZrO₂) were discovered for the first time and their luminescence mechanism was initially explored. Virgulate POM-ZrO₂ 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-ZrO₂ (energy donor), while the appropriate energy level can be regarded as the condition for electron transfer to quench the ECL intensity of POM-ZrO₂. 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.

中文翻译：

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基于新型 ECL 发射体多氧钼酸盐-氧化锆的电化学发光免疫传感器的双机制猝灭用于 17β-雌二醇检测

新型电化学发光（ECL）试剂的探索一直是ECL免疫分析的突破性工作。本工作首次发现了聚氧钼酸盐-氧化锆（POM-ZrO _{2 ）的ECL特性，并初步探讨了其发光机理。}Virgulate POM-ZrO ₂以磷钼酸水合物和氯氧化锆为原料，采用溶剂热法合成，在负电位下实现了强而稳定的阴极 ECL 发射。使用聚苯胺@Au 纳米晶体 (PANI@AuNPs) 作为双机制猝灭策略的执行者来降低输出信号。ECL能量转移和电子转移的双重机制显着提高了猝灭效率。具体而言，PANI@AuNPs可以作为能量受体吸收POM-ZrO ₂（能量供体）发出的能量，而适当的能级可以作为电子转移的条件，以猝灭POM-ZrO _{2的ECL强度。}. 在此，通过构建竞争性免疫传感器，将所提出的双机制猝灭策略应用于 17β-雌二醇的免疫测定。正如预期的那样，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 的宽传感范围。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。