title: Electrochemically driven catalysis of Rhizobium sp. NT-26 arsenite oxidase with its native electron acceptor cytochrome c552.
abstract: We describe the catalytic voltammograms of the periplasmic arsenite oxidase (Aio) from the chemolithoautotrophic bacterium Rhizobium sp. str. NT-26 that oxidizes arsenite to arsenate. Electrochemistry of the enzyme was accomplished using its native electron transfer partner, cytochrome c552 (cyt c552), as a mediator. The protein cyt c552 adsorbed on a mercaptoundecanoic acid (MUA) modified Au electrode exhibited a stable, reversible one-electron voltammetric response at +275mV vs NHE (pH6). In the presence of arsenite and Aio the voltammetry of cyt c552 is transformed from a transient response to an amplified sigmoidal (steady state) wave consistent with an electro-catalytic system. Digital simulation was performed using a single set of parameters for all catalytic voltammetries obtained at different sweep rates and various substrate concentrations. The obtained kinetic constants from digital simulation provide new insight into the kinetics of the NT-26 Aio catalytic mechanism.
authors.affiliation: School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane 4072, Australia.
authors.forename: Palraj
authors.initials: P
authors.lastname: Kalimuthu
authors.forename: Matthew D
authors.initials: MD
authors.lastname: Heath
authors.forename: Joanne M
authors.initials: JM
authors.lastname: Santini
authors.forename: Ulrike
authors.initials: U
authors.lastname: Kappler
authors.forename: Paul V
authors.initials: PV
authors.lastname: Bernhardt
mesh_terms: D000327:Adsorption; D018053:Arsenites / Q000737:chemistry / Q000378:metabolism; D002384:Catalysis; D003574:Cytochrome c Group / Q000737:chemistry* / Q000378:metabolism; D004563:Electrochemistry; D004579:Electron Transport; D007700:Kinetics; D016877:Oxidants / Q000737:chemistry; D010084:Oxidation-Reduction; D010088:Oxidoreductases / Q000737:chemistry* / Q000378:metabolism; D012231:Rhizobium / Q000201:enzymology
chemical_list: D018053:Arsenites; D003574:Cytochrome c Group; D016877:Oxidants; C022302:cytochrome C-552; D010088:Oxidoreductases; C078179:arsenite oxidase; C015001:arsenite
keywords: Arsenite; Cytochrome; Enzyme; Molybdenum; Voltammetry