Electrochemical immunosensor for ultrasensitive detection of microcystin-LR based on graphene-gold nanocomposite/functional conducting polymer/gold nanoparticle/ionic liquid composite film with electrodeposition
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文摘
The study developed an electrochemical immunosensor for ultrasensitive detection of microcystin-LR in water. Graphene oxide and chloroauric acid were alternately electrodeposited on the surface of glassy carbon electrode for 20 cycles to fabricate graphene-gold nanocomposite. The composite was characterized and its apparent heterogeneous electron transfer rate constant (37.28¡À0.16 cm s?1) was estimated by Laviron's model. To immobilize microcystin-LR antibody and improve the electrical conductivity, 2,5-di-(2-thienyl)-1-pyrrole-1-(p-benzoic acid) and chloroauric acid were electrodeposited on the modified electrode in sequence. The ionic liquid was then dropped on the electrode surface and finally microcystin-LR antibody was covalently connected to the conducting polymer film. Experiment showed the electrochemical technique offers control over reaction parameters and excellent repeatability. The graphene-gold nanocomposite and gold nanoparticles enhance electron transfer of Fe(CN)63?/4? to the electrode. The ionic liquid, 1-isobutyl-3-methylimidazolium bis(trifluoromethane-sulfonyl)imide, improves stability of the antibody. The sensor displays good repeatability (RSD=1.2 % ), sensitive electrochemical response to microcystin-LR in the range of 1.0¡Á10-16-8.0¡Á10?15 M and detection limit of 3.7¡Á10?17 M (S/N=3). The peak current change of the sensor after and before incubation with 2.0¡Á10?15 M of microcystin-LR can retain 95 % over a 20-weeks storage period. Proposed method presents remarkable improvement of sensitivity, repeatability and stability when compared to present microcystin-LR sensors. It has been successfully applied to the microcystin-LR determination in water samples with a spiked recovery in the range of 96.3-105.8 % .

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