Immobilization of Enzymes by Electrochemical and Chemical Oxidative Polymerization of L-DOPA to Fabricate Amperometric Biosensors and Biofuel Cells

Electrochemical/chemical oxidative synthesis and biosensing/biofuel cell applications of poly(L-DOPA) (PD) are studied versus polydopamine (PDA) as a recent hotspot biomaterial. The enzyme electrode developed by coelectrodeposition of PD and glucose oxidase (GOx), uricase, or tyrosinase shows biosensing performance superior to that of the corresponding PDA-based enzyme electrode. The chemical oxidative polymerization of L-DOPA (PDC) by NaAuCl4 in GOx-containing neutral aqueous solution is used to immobilize GOx and gold nanoparticles (AuNPs). The thus-prepared chitosan (CS)/GOx-PDC-AuNPs/Au(plate)/Au electrode working in the first-generation biosensing mode responds linearly to glucose concentration with a sensitivity of 152 μA mM(-1) cm(-2), which is larger than those of the CS/GOx-PDAC-AuNPs/Au(plate)/Au electrode, the CS/GOx-poly(3-anilineboronic acid) (PABA)-AuNPs/Au(plate)/Au electrode, and the most reported GOx-based enzyme electrodes. This PDC-based enzyme electrode also works well in the second-generation biosensing mode and as an excellent bioanode in biofuel cell construction, probably because PD as an amino acid polymer has the higher biocompatibility and the more favorable affinity to the enzyme than PDA. The PD material of great convenience in synthesis, outstanding biocompatibility for preparing high-performance bionanocomposites, and strong capability of multifunctional coatings on many surfaces may find wide applications in diversified fields including biotechnology and surface-coating.