Polyfluorene and its derivatives (PFs) are extremely appealing electrochemiluminescence (ECL) illuminants thanks to their easy modification, high quantum yield, excellent photostability, and nontoxicity, exhibiting great application potential in ECL sensing and imaging. Unfortunately, most reported PFs-based ECL bioanalysis generally exhibited high triggering potential (>1.0 V vs Ag/AgCl), which introduced undesirable electrochemical interference to adversely affect the sensitivity and accuracy of biological analysis. This work innovatively exploited poly(3,4-ethylenedioxythiophene) (PEDOT) as an interfacial conductor to modulate the low ECL triggering potential of poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1',3}-thiadazole)] (PFBT) nanoparticles (NPs). The unique conductivity of in situ electrodeposited PEDOT promoted electron transfer between PFBT NPs and coreactant tripropylamine (TPrA), negatively shifting the ECL triggering potential of PFBT NPs from +1.22 to +0.78 V. The PFBT NPs/PEDOT coupled the localized hybridization chain reaction (LHCR) circuits to achieve a specific and sensitive ECL detection of malathion (MAL), and a low limit of detection (LOD) of 22 fg/mL was obtained. The interfacial conductor provides inspiration for creating the low ECL triggering potential. PFBT NPs-coupled PEDOT builds a low ECL triggering potential of the PFs-based platform for pesticide residue analysis with low interference and high sensitivity.
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