Functionalized europium-porphyrin coordination polymer: Rational design of high performance electrochemiluminescence emitter for mucin 1 sensing

The excellent characteristics of porphyrins have inspired widespread interest in electrochemiluminescence (ECL). However, the limited ECL intensity and poor stability of porphyrins in aqueous solution are still severely restricted further biological application. Here, we subtly synthesized a functionalized europium and 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin (TCPP) coordination polymer (Eu-PCP) by a one-step solvothermal method. In sharp contrast to the pristine TCPP, Eu-PCP showed a higher and more stable ECL red-light emission (673 nm) at low potential (−1.1 V, vs Ag/AgCl), which was 7.7-fold higher ECL intensity and 4.6-fold efficiency. In view of the crucial role of mucin 1 (MUC1) in tumor overexpression, it was selected as the target molecule. Combined with exonuclease III (Exo III)-assisted recycling amplification strategy, a ternary ECL biosensor was constructed for the MUC1 detection based on Eu-PCP as a satisfied ECL emitter, gold nanoparticles capped CeO2 (CeO2@Au) as the coreactant accelerator and peroxydisulfate as coreactant. Meanwhile, gold nanoparticles capped MnO2 (MnO2@Au) was used as the quenching probe to achieve a highly sensitive detection of MUC1. The proposed biosensor exhibited a wide linear range from 1 fg mL−1 to 10 ng mL−1 with a low limit of detection (0.32 fg mL−1). By changing the corresponding target recognition DNA, this strategy could be expanded to detect other biomarkers.