Spectroelectrochemical investigation of a flavoprotein with a flavin-modified gold electrode

Gilbert Nöll, Erika Kozma, Rita Grandori, Jannette Carey, Thomas Schödl, Günter Hauska, Jörg Daub

Research output: Contribution to journalArticlepeer-review

29 Scopus citations


A flavin-modified gold electrode was developed in order to catalyze the electrochemical oxidoreduction of flavoproteins. Surface modification was carried out by a two-step procedure. In the first step a mixed self-assembled monolayer obtained by adsorption of activated and nonactivated 3,3′-dithiopropionic acid (free acid and N-succinimidyl ester) was formed, followed by the covalent attachment of a N(10)-hexylamino-alkylated flavin derivative via an amide bond in the second step. The electrochemical properties of the flavin-modified electrode are presented and discussed. The redox potential of the attached flavin was measured at various pH values and the electron-transfer rate constant between electrode and flavin was determined as K 0 = 5 s -1 independent of pH. The flavin-modified electrode was successfully applied to the electrochemical and spectroelectrochemical investigation of the flavoprotein WrbA from Escherichia coli that shows some structural similarities to flavodoxins. It is concluded that the electron transfer "electrode -flavin → flavoprotein" occurs by a two-step hopping mechanism where the first step is rate determining. Kinetic details are discussed. Furthermore, it turned out that, in contrast to flavodoxins, where the semiquinone state is stabilized, WrbA rapidly takes up two electrons, directly leading to the fully reduced form. The presented electrode surface modification may generally lend itself for spectroelectrochemical investigations of flavoproteins.

Original languageEnglish (US)
Pages (from-to)2378-2383
Number of pages6
Issue number5
StatePublished - Feb 28 2006

All Science Journal Classification (ASJC) codes

  • Condensed Matter Physics
  • Spectroscopy
  • General Materials Science
  • Surfaces and Interfaces
  • Electrochemistry


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