Carbaryl as an important insecticide is always used in agricultures to achieve higher yields. So, rapid detection of carbaryl residues in agricultural products is very necessary due to its potential harm to human beings. Herein, a hollow covalent-organic frameworks (HCOFTFPB-DBD) gold nanoparticles (AuNPs) nanospheres was used to construct a sensitive electrochemical carbaryl biosensor. The surface of electrode modified by HCOFTFPB-DBD-AuNPs nanospheres was negatively charged and repelled the [Fe(CN)6]3-/4-. The acetylcholinesterase (AChE) immobilized on HCOFTFPB-DBD-AuNPs nanospheres catalyzed the hydrolysis of acetylcholine chloride to thiocholine (TCh). The obtained positively charged TCh was adsorbed on the electrode surface by Au-S, which made the electrode surface positively charged to adsorb the negatively charged [Fe(CN)6]3-/4-, showing enhanced oxidation current of [Fe(CN)6]3-/4-. After carbaryl was added, the oxidation current of [Fe(CN)6]3-/4- deceased because ChE activity were inhibited by carbaryl. So, the sensitive detection of carbaryl was achieved at a low potential, which resulted in a high selectivity. The biosensor had a detection limit of 0.38 μM, a linear range of 1.10 μM-40.0 μM, a sensitivity of 0.00863 mA μM−1 and better performance in actual sample.
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