Citation: YANG Yang, HUO Wen-Shan, ZHOU Zheng, ZHANG Qi, ZENG Han. Direct Electrochemistry of Electrode Modified with Thin Film of Laccase Immobilized in Nano-Composite of Polyaniline-CoC2O4[J]. Chinese Journal of Inorganic Chemistry, ;2016, 32(12): 2117-2128. doi: 10.11862/CJIC.2016.277
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Electrochemical methods including cyclic voltammetry, differential pulse voltammetry, electrochemical impedance spectrometry and chronoamperometry, together with auxiliary means such as F-T infrared spectrometry, Ultra-violet visible spectrometry, atomic force microscopy, transmission electron microscopy and atomic adsorption spectrometry were used to characterize the chemical composition, structure and morphology of polyaniline-CoC2O4 nano-composite, to measure the change of conductivity in nano-composite before and after Laccase immobilization and to investigate the direct electrochemistry of redox protein molecules entrapped in the matrix. Its catalytic effect on oxygen reduction reaction and performance as electrochemical sensor for oxygen detection were evaluated subsequently. Results from tests indicated this Laccase-based electrode shuttled electrons from enzyme active site T2 as primary electron acceptor to dioxygen molecules attached chemically in the matrix, achieving the electro-reduction of O2 in the absence of any external mediator with its apparent electron transferring rate:0.017 s-1. This laccase-based electrode displayed favorable catalytic effect on oxygen reduction reaction (onset potential for catalysis:460 mV vs NHE, apparent turn-over frequency for oxygen reduction reaction:2.6×10-4 s-1). Enzymatic oxygen electro-reduction into water should be ascribed to the key process to promote the performance of biocathode. This Laccase based electrochemical sensor had such advantages as extremely low detection limit (0.20 μmol·L-1) to oxygen monitoring, wide linear responding range of concentration (0.4~7.5 μmol·L-1) and high affinity towards substrate (KM=122.4 μmol·L-1).
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