Damage-free remote SF₆ plasma-treated CNTs for facile fabrication of electrochemical enzyme biosensors

Remote SF₆ plasma treatment of CNTs is performed to graft hydrophobic fluorine on the surface of CNTs. Fluorinated CNTs (F-CNTs) allow for the facile adsorption of enzyme molecules via hydrophobic interaction between F-CNTs and the hydrophobic patches of enzyme molecules. The loading of glucose oxidase (GOx) on F-CNTs correlates well with plasma treatment time. Interestingly, the Rct value of GOx/F-CNTs decreases when CNTs are treated with plasma for a short time such as 1 and 5 min, which is due to weakly-bound chemisorbed fluorine molecules on F-CNTs (semi-ionic C-F). As an example, the Rct value of GOx/F-CNT electrode with 1 min plasma treatment is 0.57 times lower than that of GOx/CNTs, while increasing its sensitivity by 2.5 times. Upon extending the treatment time such as 30, 45 and 60 min, the XPS results reveal the dominance of covalently-attached fluorine, leading to marginally-increased resistance and sensitivity. It is worthy of noting this work is the first report of simple enzyme adsorption on remote-plasma treated CNT surfaces together with its detailed mechanism studies, especially for the binding of enzyme molecules semi-ionic fluorine.