Molecular monolayers and interfacial electron transfer of Pseudomonas aeruginosa azurin on Au(111)

Qijin Chin, Jingdong Zhang, Jens U. Nielsen, Esben P. Friis, Ib Chorkendorff, Gerard W. Canters, Jens E.T. Andersen, Jens Ulstrup

Research output: Contribution to journalArticle

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Abstract

We provide a comprehensive approach to the formation and characterization of molecular monolayers of the blue copper protein Pseudomonas aeruginosa azurin on Au(111) in aqueous ammonium acetate solution. Main issues are adsorption patterns, reductive desorption, properties of the double layer, and long-range electrochemical electron transfer between the electrode and the copper center. Voltammetry, electrochemical impedance spectroscopy (EIS), in situ scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS) have been employed to disclose features of these issues. Zn-substituted azurin, cystine, and 1-butanethiol are investigated for comparison. Cyclic voltammetric and capacitance measurements show qualitatively that azurin is adsorbed at submicromolar concentrations over a broad potential range. The characteristics of reductive desorption suggest that azurin is adsorbed via its disulfide group to form a monolayer. The adsorption of this protein on Au(111) via a gold-sulfur binding mode is further supported by XPS measurements. In situ STM images with molecular resolution have been recorded and show a dense monolayer organization of adsorbed azurin molecules. Direct electron transfer (ET) between the copper atom of adsorbed azurin and the electrode has been revealed by differential pulse voltammetry. The rate constant is estimated from electrochemical impedance spectroscopy and shows that ET is compatible with a long-range ET mode such as that anticipated by theoretical frames. The results constitute the first case of an electrochemically functional redox protein monolayer at single-crystal metal electrodes.

Original languageEnglish
Pages (from-to)4047-4055
Number of pages9
JournalJournal of the American Chemical Society
Volume122
Issue number17
DOIs
Publication statusPublished - May 3 2000

Fingerprint

Azurin
Pseudomonas aeruginosa
Monolayers
Electrons
Scanning tunneling microscopy
Voltammetry
Scanning Tunnelling Microscopy
Proteins
Copper
Electrochemical impedance spectroscopy
Electrodes
Dielectric Spectroscopy
Photoelectron Spectroscopy
Desorption
X ray photoelectron spectroscopy
Cystines
Adsorption
Capacitance measurement
Rate constants
Cystine

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Chin, Q., Zhang, J., Nielsen, J. U., Friis, E. P., Chorkendorff, I., Canters, G. W., ... Ulstrup, J. (2000). Molecular monolayers and interfacial electron transfer of Pseudomonas aeruginosa azurin on Au(111). Journal of the American Chemical Society, 122(17), 4047-4055. https://doi.org/10.1021/ja993174t
Chin, Qijin ; Zhang, Jingdong ; Nielsen, Jens U. ; Friis, Esben P. ; Chorkendorff, Ib ; Canters, Gerard W. ; Andersen, Jens E.T. ; Ulstrup, Jens. / Molecular monolayers and interfacial electron transfer of Pseudomonas aeruginosa azurin on Au(111). In: Journal of the American Chemical Society. 2000 ; Vol. 122, No. 17. pp. 4047-4055.
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Chin, Q, Zhang, J, Nielsen, JU, Friis, EP, Chorkendorff, I, Canters, GW, Andersen, JET & Ulstrup, J 2000, 'Molecular monolayers and interfacial electron transfer of Pseudomonas aeruginosa azurin on Au(111)', Journal of the American Chemical Society, vol. 122, no. 17, pp. 4047-4055. https://doi.org/10.1021/ja993174t

Molecular monolayers and interfacial electron transfer of Pseudomonas aeruginosa azurin on Au(111). / Chin, Qijin; Zhang, Jingdong; Nielsen, Jens U.; Friis, Esben P.; Chorkendorff, Ib; Canters, Gerard W.; Andersen, Jens E.T.; Ulstrup, Jens.

In: Journal of the American Chemical Society, Vol. 122, No. 17, 03.05.2000, p. 4047-4055.

Research output: Contribution to journalArticle

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T1 - Molecular monolayers and interfacial electron transfer of Pseudomonas aeruginosa azurin on Au(111)

AU - Chin, Qijin

AU - Zhang, Jingdong

AU - Nielsen, Jens U.

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AU - Chorkendorff, Ib

AU - Canters, Gerard W.

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AU - Ulstrup, Jens

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AB - We provide a comprehensive approach to the formation and characterization of molecular monolayers of the blue copper protein Pseudomonas aeruginosa azurin on Au(111) in aqueous ammonium acetate solution. Main issues are adsorption patterns, reductive desorption, properties of the double layer, and long-range electrochemical electron transfer between the electrode and the copper center. Voltammetry, electrochemical impedance spectroscopy (EIS), in situ scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS) have been employed to disclose features of these issues. Zn-substituted azurin, cystine, and 1-butanethiol are investigated for comparison. Cyclic voltammetric and capacitance measurements show qualitatively that azurin is adsorbed at submicromolar concentrations over a broad potential range. The characteristics of reductive desorption suggest that azurin is adsorbed via its disulfide group to form a monolayer. The adsorption of this protein on Au(111) via a gold-sulfur binding mode is further supported by XPS measurements. In situ STM images with molecular resolution have been recorded and show a dense monolayer organization of adsorbed azurin molecules. Direct electron transfer (ET) between the copper atom of adsorbed azurin and the electrode has been revealed by differential pulse voltammetry. The rate constant is estimated from electrochemical impedance spectroscopy and shows that ET is compatible with a long-range ET mode such as that anticipated by theoretical frames. The results constitute the first case of an electrochemically functional redox protein monolayer at single-crystal metal electrodes.

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