A versatile and ultrasensitive molecularly imprinted electrochemiluminescence sensor with HRP-encapsulated liposome labeled by light-triggered click reaction for pesticide residues.

A novel approach for trace detection of fipronil with a molecularly imprinted electrochemiluminescence sensor (MIECLS) is proposed. The sensitivity is significantly improved via signal amplification of the enzymatic reaction of horseradish peroxidase (HRP) released from encapsulated liposomes which linked onto the template molecules after rebinding. The molecularly imprinted polymer membrane was prepared through the electropolymerization of monomers with fipronil as a template. After the elution of the template molecules, the analyte fipronil was reabsorbed into the cavities. HRP-encapsulated liposomes were linked to the target molecules by light-triggered click reaction. The higher the concentration of the target was, the more HRP-encapsulated liposomes were present on the molecularly imprinted polymer (MIP) sensor. Then, HRP was liberated from liposomes, and the catalytic degradation of hydrogen peroxide (H2O2) by HRP occurs, which changed the electrochemiluminescence intensity of luminol significantly. The change of the ∆ECL intensity was linearly proportional to the logarithm of the fipronil concentration ranging from 1.00 × 10-14 to 1.00 × 10-9 mol/L, and the detection limit was 7.77 × 10-16 mol/L. The recoveries obtained ranged from 95.7 to 105.8% with RSD < 5%. The sensitivity of the detection was significantly improved, and the analysis process was simplified in that the incubation step required in the conventional method was avoided. The sensor proposed provides a feasible platform for ultra-trace amount determination.