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.