Electrocatalytic Aldehyde Oxidation by a Tungsten Dependent Aldehyde Oxidoreductase from Aromatoleum Aromaticum.


Journal

Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783

Informations de publication

Date de publication:
06 Apr 2023
Historique:
received: 01 10 2022
medline: 7 4 2023
pubmed: 18 1 2023
entrez: 17 1 2023
Statut: ppublish

Résumé

In contrast to their molybdenum dependent relatives, tungsten enzymes operate at significantly lower redox potentials, and in some cases they can carry out reversible redox transformations of their substrates and products. Still, the electrochemical properties of W enzymes have received much less attention than their Mo relatives. Herein we analyse the tungsten enzyme aldehyde oxidoreductase (AOR) from the mesophilic bacterium Aromatoleum aromaticum which has been immobilised on a glassy carbon working electrode. This generates a functional system that electrochemically oxidises a wide variety of aromatic and aliphatic aldehydes in the presence of the electron transfer mediators benzyl viologen, methylene blue or dichlorophenol indophenol. Simulation of the cyclic voltammetry has enabled a thorough kinetic analysis of the system, which reveals that methylene blue acts as a two-electron acceptor. In contrast, the other two mediators act as single electron oxidants. The different electrochemical driving forces imparted by these mediators also lead to significantly different outer sphere electron transfer rates with AOR. This work shows that electrocatalytic aldehyde oxidation can be achieved at a low applied electrochemical potential leading to an extremely energy efficient catalytic process.

Identifiants

pubmed: 36648073
doi: 10.1002/chem.202203072
doi:

Substances chimiques

Aldehyde Oxidoreductases EC 1.2.-
Aldehydes 0
Tungsten V9306CXO6G
Methylene Blue T42P99266K
Aldehyde Dehydrogenase EC 1.2.1.3

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

e202203072

Subventions

Organisme : Australian Research Council
ID : DP220103268
Organisme : Deutsche Forschungsgemeinschaft
ID : He2190/11-1
Organisme : EU Project POWR
ID : 03.02.00-00-I004/16

Informations de copyright

© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

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Auteurs

Palraj Kalimuthu (P)

School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane, 4072, Australia.

Dominik Hege (D)

Laboratory for Microbial Biochemistry, and, Center for Synthetic Microbiology, Philipps University Marburg, 35043, Marburg, Germany.

Agnieszka Winiarska (A)

Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezapominajek Kraków, 8, 30 239, Cracow, Poland.

Yvonne Gemmecker (Y)

Laboratory for Microbial Biochemistry, and, Center for Synthetic Microbiology, Philipps University Marburg, 35043, Marburg, Germany.

Maciej Szaleniec (M)

Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezapominajek Kraków, 8, 30 239, Cracow, Poland.

Johann Heider (J)

Laboratory for Microbial Biochemistry, and, Center for Synthetic Microbiology, Philipps University Marburg, 35043, Marburg, Germany.

Paul V Bernhardt (PV)

School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane, 4072, Australia.

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Classifications MeSH