Novel Enhanced Lanthanide Electrochemiluminescence Luminophores: Ce3+-Doped TbPO4 Facile Synthesis and Detection for Mucin1.

ABSTRACT

Despite the upsurging interest in electrochemiluminescence (ECL) of lanthanides, the research in this field is still in its infancy due to the low intensity. In this work, a series of Ce3+-doped terbium orthophosphates (TbPO4Ce) in different proportions have been synthesized through the co-precipitation method at room temperature. Meanwhile, through the investigation of morphologies and ECL properties of these TbPO4Ce, it is concluded that the ECL intensity reaches the maximum when the molar ratio of Tb/Ce is 91 and the material is nanorod-shaped. The ECL intensity of TbPO4Ce is significantly improved by doping with Ce3+ due to the dual sensitization strategy of the antenna effect from PO43- to Tb3+ and the energy transfer from Ce3+ to Tb3+. Interestingly, doping with Ce3+ can not only adjust morphology of TbPO4Ce but also improve the ECL intensity. In addition, to verify the application of TbPO4Ce, two single mucin1 (MUC1) aptamers are linked together to form a dual MUC1 aptamer chain. Then, a simple and sensitive ECL biosensor is constructed for the detection of MUC1, which can recognize the double amount of MUC1 and quench the ECL signal. As expected, the proposed biosensor shows good stability and acceptable selectivity and achieves sensitive detection of MUC1 with a dynamic range from 1 fg·mL-1 to 10 ng·mL-1 and a limit of detection of 0.5 fg·mL-1. This work may pave a new avenue for the study of direct ECL emission of lanthanides and prove to be ideal for the research of new ECL luminophores in electrochemical analysis.