Polypyrrolic bipyridine bis(phenantrolinequinone) Ru(II) complex/carbon nanotube composites for NAD-dependent enzyme immobilization and wiring.

Abstract

We report the synthesis and electrochemical characterization of a novel electropolymerizable Ru(II) complex containing two phenanthrolinequinone ligands, Ru(II)(PhQ)2(bpy-pyrrole)(PF6)2. This complex was electropolymerized on glassy carbon (GC) and multiwalled carbon nanotube (MWCNT) electrodes. Higher apparent surface concentrations (80 nmol cm(-2)) were obtained on MWCNTs than on GC electrodes and correspond to ∼1000 equivalent compact monolayers of Ru complex. Moreover, the nanostructured metallopolymer exhibits efficient electrocatalytic properties toward oxidation of NADH. This metallopolymer can be electrogenerated in water from the adsorbed Ru(II) monomer. This property was applied to the immobilization of enzymes by coadsorption of Ru complex and enzyme and then electropolymerization of coatings. This two-step procedure leads to the entrapment of 70%-90% of the deposited amount of enzyme in poly-Ru(II)(PhQ)2(bpy-pyrrole) films. Glucose dehydrogenase (GDH) was thus efficiently immobilized in the electrogenerated polymer matrix. In presence of NAD(+) (10 mM), the resulting enzyme electrode exhibits high current densities for glucose oxidation of 1.04 mA cm(-2) at low overpotentials (-0.1 V) with a detection limit of 1 μM of glucose.