Direct electrochemistry and intramolecular electron transfer of ascorbate oxidase confined on l-cysteine self-assembled gold electrode

Bhushan Patil, Yoshiki Kobayashi, Shigenori Fujikawa, Takeyoshi Okajima, Lanqun Mao, Takeo Ohsaka

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

A direct electrochemistry and intramolecular electron transfer of multicopper oxidases are of a great importance for the fabrication of these enzyme-based bioelectrochemical-devices. Ascorbate oxidase from Acremonium sp. (ASOM) has been successfully immobilized via a chemisorptive interaction on the l-cysteine self-assembled monolayer modified gold electrode (cys-SAM/AuE). Thermodynamics and kinetics of adsorption of ASOM on the cys-SAM/AuE were studied using cyclic voltammetry.A well-defined redox wave centered at 166±3mV (vs. AgAgClKCl(sat.)) was observed in 5.0mM phosphate buffer solution (pH7.0) at the fabricated ASOM electrode, abbreviated as ASOM/cys-SAM/AuE, confirming a direct electrochemistry, i.e., a direct electron transfer (DET) between ASOM and cys-SAM/AuE. The direct electrochemistry of ASOM was further confirmed by taking into account the chemical oxidation of ascorbic acid (AA) by O2 via an intramolecular electron transfer in the ASOM as well as the electrocatalytic oxidation of AA at the ASOM/cys-SAM/AuE.Thermodynamics and kinetics of the adsorption of ASOM on the cys-SAM/AuE have been elaborated along with its direct electron transfer at the modified electrodes on the basis of its intramolecular electron transfer and electrocatalytic activity towards ascorbic acid oxidation and O2 reduction. ASOM saturated surface area was obtained as 2.41×10-11molcm-2 with the apparent adsorption coefficient of 1.63×106Lmol-1. The ASOM confined on the cys-SAM/AuE possesses its essential enzymatic function.

Original languageEnglish
Pages (from-to)15-22
Number of pages8
JournalBioelectrochemistry
Volume95
DOIs
Publication statusPublished - Feb 1 2014

Fingerprint

Ascorbate Oxidase
Electrochemistry
oxidase
cysteine
electrochemistry
Gold
Cysteine
electron transfer
Electrodes
Electrons
gold
ascorbic acid
Ascorbic acid
electrodes
Ascorbic Acid
Adsorption
Thermodynamics
Oxidation
oxidation
adsorption

All Science Journal Classification (ASJC) codes

  • Biophysics
  • Physical and Theoretical Chemistry
  • Electrochemistry

Cite this

Direct electrochemistry and intramolecular electron transfer of ascorbate oxidase confined on l-cysteine self-assembled gold electrode. / Patil, Bhushan; Kobayashi, Yoshiki; Fujikawa, Shigenori; Okajima, Takeyoshi; Mao, Lanqun; Ohsaka, Takeo.

In: Bioelectrochemistry, Vol. 95, 01.02.2014, p. 15-22.

Research output: Contribution to journalArticle

Patil, Bhushan ; Kobayashi, Yoshiki ; Fujikawa, Shigenori ; Okajima, Takeyoshi ; Mao, Lanqun ; Ohsaka, Takeo. / Direct electrochemistry and intramolecular electron transfer of ascorbate oxidase confined on l-cysteine self-assembled gold electrode. In: Bioelectrochemistry. 2014 ; Vol. 95. pp. 15-22.
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AB - A direct electrochemistry and intramolecular electron transfer of multicopper oxidases are of a great importance for the fabrication of these enzyme-based bioelectrochemical-devices. Ascorbate oxidase from Acremonium sp. (ASOM) has been successfully immobilized via a chemisorptive interaction on the l-cysteine self-assembled monolayer modified gold electrode (cys-SAM/AuE). Thermodynamics and kinetics of adsorption of ASOM on the cys-SAM/AuE were studied using cyclic voltammetry.A well-defined redox wave centered at 166±3mV (vs. AgAgClKCl(sat.)) was observed in 5.0mM phosphate buffer solution (pH7.0) at the fabricated ASOM electrode, abbreviated as ASOM/cys-SAM/AuE, confirming a direct electrochemistry, i.e., a direct electron transfer (DET) between ASOM and cys-SAM/AuE. The direct electrochemistry of ASOM was further confirmed by taking into account the chemical oxidation of ascorbic acid (AA) by O2 via an intramolecular electron transfer in the ASOM as well as the electrocatalytic oxidation of AA at the ASOM/cys-SAM/AuE.Thermodynamics and kinetics of the adsorption of ASOM on the cys-SAM/AuE have been elaborated along with its direct electron transfer at the modified electrodes on the basis of its intramolecular electron transfer and electrocatalytic activity towards ascorbic acid oxidation and O2 reduction. ASOM saturated surface area was obtained as 2.41×10-11molcm-2 with the apparent adsorption coefficient of 1.63×106Lmol-1. The ASOM confined on the cys-SAM/AuE possesses its essential enzymatic function.

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