title: The oxidation of ascorbate at copolymeric sulfonated poly(aniline) coated on glassy carbon electrodes.
abstract: Self-doped poly(aniline)s as electrode coatings to catalyze ascorbate oxidation are revisited in this article. Sulfonated poly(aniline) (SPAN) was deposited on glassy carbon electrodes as a copolymer of aniline and its sulfonated derivative, 2-aminobenzenesulfonic acid (2-ABSA). The resulting deposits are reproducible and show good stability and electroactivity at pH>7, enabling studies at typical physiological pH values. Calibration curves were obtained using a rotating disc electrode at a sampling potential of 0.2V, displaying linear dependence in the region 0-20mM ascorbate. A kinetic model based on the Michaelis-Menten reaction mechanism, previously validated for poly(aniline) composites, was used to analyse the form of the calibration curve leading to values of the effective reaction constants K(ME) and k'(ME). New calibration curves constructed for different sampling potentials were used to elucidate the rate limiting step at saturated kinetics. Rotating disc voltammetry performed at increasing pH (from pH 2 to 9) showed a dramatic decrease in the limiting current, without any evidence for a change in the reaction mechanism.
authors.affiliation: Departamento de Química Física e Instituto de Materiales (IUMA), Universidad de Alicante, Ap. 99, E-03080 Alicante, Spain.
authors.forename: C
authors.initials: C
authors.lastname: Sanchis
authors.forename: M A
authors.initials: MA
authors.lastname: Ghanem
authors.forename: H J
authors.initials: HJ
authors.lastname: Salavagione
authors.forename: E
authors.initials: E
authors.lastname: Morallón
authors.forename: P N
authors.initials: PN
authors.lastname: Bartlett
mesh_terms: D000476:Alkanesulfonates / Q000737:chemistry*; D000814:Aniline Compounds / Q000737:chemistry*; D001205:Ascorbic Acid / Q000737:chemistry; D002138:Calibration; D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D004563:Electrochemistry / Q000379:methods; D004566:Electrodes; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D010084:Oxidation-Reduction; D011108:Polymers / Q000737:chemistry*
chemical_list: D000476:Alkanesulfonates; D000814:Aniline Compounds; D011108:Polymers; D002244:Carbon; D001205:Ascorbic Acid; C023650:aniline