Electrochemiluminescence of Hot Exciton Nanomaterial Featuring Aggregation-Induced Emission for “Signal-on” Detection of Alkaline Phosphatase
摘要
Traditional fluorescent emitters cannot effectively utilize triplet excitons owing to the spin statistical limitation, thus their electrochemiluminescence (ECL) efficiency (ΦECL) is relatively low. Improving the utilization efficiency of triplet excitons is of great significance for developing efficient luminescent materials. Here we designed a hot exciton molecule (NZ2TPA) containing highly efficient chromophore naphthothiadiazole as an electron acceptor and triphenylamine (TPA) with aggregation induced emission (AIE) property as the strong electron donor to synthesize an ECL nanoemitter-NZ2TPA nanoparticles (NT NPs). The hybridized local and charge-transfer (HLCT) excited state of NZ2TPA achieved a high exciton utilization through the reverse intersystem crossing from higher triplet states (hRISC). The combination of HLCT and AIE characteristics endowed NT NPs with superior ΦECL over other nanoemitters, which provided an excellent material for the design of highly sensitive ECL biosensors. Using alkaline phosphatase (ALP) as an analyte model, a “signal-on” ECL biosensing approach was constructed by combining the quenching of manganese dioxide nanosheets (MnO2 NSs) on ECL emission of NT NPs and the reduction of MnO2 by ascorbic acid produced from ALP-catalyzed dephosphorylation, which showed a detectable range of 0.004 − 400 U/L with a detection limit of 0.57 mU/L. The excellent performance demonstrated the immense potential of organic nanomaterials through combining HLCT and AIE properties to improve ΦECL.