Untangling the Effects of Doping Carbon with Diverse Heteroatoms on the Bioelectrochemistry of Glucose Oxidase.

Great enthusiasm for doping carbon materials with nonmetallic heteroatoms for promoting electrical contact of redox enzymes with electrodes in bioelectronics has been aroused. However, systematic studies of different heteroatoms on enzyme activities are still lacking. Herein, choosing glucose oxidase (GOD) as a model enzyme, carbon nanotubes (CNTs) are used as electron carriers to evaluate the effects of heteroatoms' species on the direct electron transfer and catalytic activities of GOD. Experimental data demonstrate that phosphorus (P)-doped CNTs provide the most intimate electrical contact with GOD compared to other elements (B, N, and S) doping, delivering a 3-fold increase in rate constant ( k s , 2.1 s -1 ) and an enhanced turnover rate ( k cat , 2.74 × 10 -9 M cm -2 s -1 ) in comparison with CNTs. Meanwhile, theoretical modeling clarifies that the active center of GOD interacts more strongly with P-doped CNTs and maintains their conformation well compared to other CNTs. This study will help to understand the mechanism of heteroatom doping of carbon on the enzymatic electron transfer and shed light on the design of efficient bioelectrocatalytic interfaces.