Dual-Mechanism Quenching of Electrochemiluminescence Immunosensor Based on a Novel ECL Emitter Polyoxomolybdate-Zirconia for 17β-Estradiol Detection.

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.