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Voltammetry and Electrocatalysis of Achromobacter Xylosoxidans Copper Nitrite Reductase on Functionalized Au(111)-Electrode Surfaces

  • Anna C. Welinder , Jingdong Zhang , Allan G. Hansen , Kasper Moth-Poulsen , Hans E. M. Christensen , Alexander M. Kuznetsov , Thomas Bjørnholm and Jens Ulstrup
Published/Copyright: September 25, 2009
Zeitschrift für Physikalische Chemie
From the journal Zeitschrift für Physikalische Chemie Volume 221 Issue 9-10

A long-standing issue in protein film voltammetry (PFV), particularly electrocatalytic voltammetry of redox enzyme monolayers, is the variability of protein adsorption modes, reflected in distributions of catalytic activity of the adsorbed protein/enzyme molecules. Use of well-defined, atomically planar electrode surfaces is a step towards the resolution of this central issue.

We report here the voltammetry of copper nitrite reductase (CNiR, Achromobacter xylosoxidans) on Au(111)-electrode surfaces modified by monolayers of a broad variety of thiol-based linker molecules. These represent positively charged and electrostatically neutral, hydrophobic and hydrophilic, aliphatic and aromatic, and variable-length micro-environments, as well as their combinations. Optimal conditions for enzyme function seems to be a combination of hydrophobic and hydrophilic surface linker properties, which can lead to close to complete non-catalytic monolayer interfacial electron transfer function and electrocatalysis with activity approaching enzyme activity in homogeneous solution. Thiophenol (combined hydrophobic stacking and interdispersed water molecules), 4-methyl-thiophenol (hydrophobic and water molecules), and 3- and 4-aminothiophenol (hydrophilic, hydrophobic) offer the overall most efficient micro-environments. Subtle differences with even small structural linker differences, however, lead to widely different electrocatalytic properties, strikingly illuminated by the ω-mercaptoamines. CuNiR thus shows highly efficient, close to ideal reversible electrocatalytic voltammetry on cysteamine-covered Au(111)-electrode surfaces, most likely due to two cysteamine orientations previously disclosed by in situ scanning tunnelling microscopy. Such a dual orientation exposes both a hydrophobic and a positively charged, hydrophilic surface feature. In contrast, the higher cysteamine homologues expose only the hydrophilic component with no electrocatalytic activity on these surfaces. These results offer a basis for rational surface design in forthcoming biological electrocatalysis useful both fundamentally and in novel biosensor technology.

Keywords: Nitrite Reductase; Functionalized Au(111)-Electrodes; Non-Catalytic and Catalytic Protein Film Voltammetry; Electrocatalytic Mechanism
Received: 2007-7-22
Accepted: 2007-7-23
Published Online: 2009-9-25
Published in Print: 2007-10-1

© Oldenbourg Wissenschaftsverlag

Articles in the same Issue

  1. Preface: Dieter Kolb zum 65. Geburtstag
  2. Precursor Adsorption of SbBr3 on Au(111) and Au(100) for Antimony Underpotential Deposition in a BMIBF4 Ionic Liquid – A Comparison with SbCl3
  3. Electroreduction of Nitrate at Copper Electrodes and Copper-PANI Composite Layers
  4. Potential Program Invariant Representation of Diffusion–Adsorption Related Voltammograms
  5. A Way for Determining the Effective Three Phase Boundary Width of Solid State Electrochemical Reactions from the Primary and Secondary Current Distribution at Microelectrodes
  6. Carbon Nanotubes and Electrochemistry
  7. Pd3Fe and Pt Monolayer-Modified Pd3Fe Electrocatalysts for Oxygen Reduction
  8. Electrochemical Nucleation and Growth Kinetics of Nanostructured Gold on Rotating Disc and Stationary Electrodes
  9. Theoretical Trends in Particle Size Effects for the Oxygen Reduction Reaction
  10. Metal Deposition by Inducing a Microgalvanic Cell with the Scanning Electrochemical Microscope (SECM)
  11. Formation of a Molecular Glue Based on the Electrochemical Reduction of 4-Hydroxyphenyldiazonium for the Attachment of Thin Sol–Gel Film on Glassy Carbon
  12. Confined Spatio-Temporal Chaos During Metal Electrodissolution: Simulations
  13. Comparative Study of Thymine Adsorption on Cu- and Ag-Adlayers on Au(111) Electrodes
  14. The Adsorption and Growth of Copper on As-Terminated GaAs(001): Physical Vapour versus Electrochemical Deposition
  15. Monte Carlo Simulation of Kinetically Limited Electrodeposition on a Surface with Metal Seed Clusters
  16. Normalized Differential Reflectance Spectroscopy at Polycrystalline Platinum Electrodes in Aqueous Acidic Electrolytes: Quantitative Aspects
  17. Hydrogen Adsorption on Activated Platinum Electrodes – An Electrochemical Impedance Spectroscopy Study
  18. Voltammetry and Electrocatalysis of Achromobacter Xylosoxidans Copper Nitrite Reductase on Functionalized Au(111)-Electrode Surfaces
  19. Electrocatalytic Trends on IB Group Metals: The Oxygen Reduction Reaction
  20. DFT Studies on the Nature of Coadsorbates on SO42-/Au(111)
  21. In Situ Scanning Tunnelling Microscopy in Ionic Liquids: Prospects and Challenges
https://doi.org/10.1524/zpch.2007.221.9-10.1343
Keywords for this article
Nitrite Reductase; Functionalized Au(111)-Electrodes; Non-Catalytic and Catalytic Protein Film Voltammetry; Electrocatalytic Mechanism

Articles in the same Issue

  1. Preface: Dieter Kolb zum 65. Geburtstag
  2. Precursor Adsorption of SbBr3 on Au(111) and Au(100) for Antimony Underpotential Deposition in a BMIBF4 Ionic Liquid – A Comparison with SbCl3
  3. Electroreduction of Nitrate at Copper Electrodes and Copper-PANI Composite Layers
  4. Potential Program Invariant Representation of Diffusion–Adsorption Related Voltammograms
  5. A Way for Determining the Effective Three Phase Boundary Width of Solid State Electrochemical Reactions from the Primary and Secondary Current Distribution at Microelectrodes
  6. Carbon Nanotubes and Electrochemistry
  7. Pd3Fe and Pt Monolayer-Modified Pd3Fe Electrocatalysts for Oxygen Reduction
  8. Electrochemical Nucleation and Growth Kinetics of Nanostructured Gold on Rotating Disc and Stationary Electrodes
  9. Theoretical Trends in Particle Size Effects for the Oxygen Reduction Reaction
  10. Metal Deposition by Inducing a Microgalvanic Cell with the Scanning Electrochemical Microscope (SECM)
  11. Formation of a Molecular Glue Based on the Electrochemical Reduction of 4-Hydroxyphenyldiazonium for the Attachment of Thin Sol–Gel Film on Glassy Carbon
  12. Confined Spatio-Temporal Chaos During Metal Electrodissolution: Simulations
  13. Comparative Study of Thymine Adsorption on Cu- and Ag-Adlayers on Au(111) Electrodes
  14. The Adsorption and Growth of Copper on As-Terminated GaAs(001): Physical Vapour versus Electrochemical Deposition
  15. Monte Carlo Simulation of Kinetically Limited Electrodeposition on a Surface with Metal Seed Clusters
  16. Normalized Differential Reflectance Spectroscopy at Polycrystalline Platinum Electrodes in Aqueous Acidic Electrolytes: Quantitative Aspects
  17. Hydrogen Adsorption on Activated Platinum Electrodes – An Electrochemical Impedance Spectroscopy Study
  18. Voltammetry and Electrocatalysis of Achromobacter Xylosoxidans Copper Nitrite Reductase on Functionalized Au(111)-Electrode Surfaces
  19. Electrocatalytic Trends on IB Group Metals: The Oxygen Reduction Reaction
  20. DFT Studies on the Nature of Coadsorbates on SO42-/Au(111)
  21. In Situ Scanning Tunnelling Microscopy in Ionic Liquids: Prospects and Challenges
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