Electrochemiluminescence solid-state imprinted sensor based on graphene/CdTe@ZnS quantum dots as luminescent probes for low-cost ultrasensing of diethylstilbestrol

摘要

A novel molecularly imprinted electrochemiluminescence (MIP-ECL) sensor was fabricated for diethylstilbestrol (DES), which exploited the strategy of specific identification by molecularly imprinted polymers (MIPs) instead of expensive biomolecules. Core-shell quantum-dots (QDs) of CdTe@ZnS were utilized to enhance ECL emission. The sensor was assembled as a solid-state electrode by immobilizing CdTe@ZnS/reduced-graphene oxide (r-GO) composite on a glassy carbon electrode (GCE) surface, and then being covered with MIPs film with specific cavities. The fabricated sensor (denoted as MIP/CdTe@ZnS/r-GO/GCE) was based on the obstruction of ECL signals by DES molecules enriched on MIP film. The ECL intensity of the QDs-K_2S_2O_8 system was reduced when the DES molecules were selectively rebound onto the MIP film by molecularly imprinted solid phase extraction (MISPE). Accordingly, the logarithm of the quenched ECL intensity versus the logarithm of the DES concentration was in a good linear relationship over a wide range from 1.8 × 10~(-3) to 25.0 nmol/L with the limit of detection (LOD) of 0.25 pmol/L (S/N = 3). The sensor also exhibits excellent selectivity with fast response and good accuracy. Lake water and milk samples were assayed by this sensor, and the recoveries ranging from 92.2%-108.3% were obtained.