A molecularly imprinted sensor for single-molecule detection of pesticide metabolite at the amol/L level sensitized by water-soluble luminol derivative encapsulated liposome via click reaction

A novel luminol derivative, 4-[(1,4-dioxo-1,2,3,4-tetrahydrophthalazin-5-yl)amino]-4-oxobut-2-enoic acid (ALD) with electrochemiluminescence intensity and stability characteristics similar to luminol, but higher solubility in near neutral solution, was designed and synthesized in this study. Using this derivative, a molecular imprinted electrochemiluminescence sensor (MIECLS) was prepared for the sensitive and selective determination of 2-amino-5-mercapto-1,3,4-thiadiazole (AMT), a metabolite of bismerthiazol, thiediazole copper, thiazole zinc, and other pesticides. The ALD probes encapsulated in liposomes are immobilized on the molecularly imprinted film by light-triggered click reaction, and the concurrent release of multiple probes allows for highly sensitive detection. In the AMT concentration range of 1.00 × 10-18 - 5.00 × 10-13 mol/L, the relation between ECL response and log AMT concentration is linear. With a detection limit of 5.25 × 10-19 mol/L (about 4 - 6 molecules in 10 μL of the sample), the sensor allows for high sensitivity analysis of ultra-trace amounts of small organic compounds. In general, the ECL-based single-molecule detection technique proposed herein might be a promising alternative to fluorescence single-molecule detection.