Integration of the All-in-One electrode in an electrochemical flow cell for in situ hydrogen peroxide supply in hydroxylation mediated by immobilized unspecific peroxygenase

Hydrogen peroxide (H₂O₂) is a strong oxidizing agent that is commonly employed in chemical synthesis. Nevertheless, its utilization as a cosubstrate in biocatalytic reactions remains limited due to the deactivating effect on biocatalysts at an elevated concentration. An electrochemical synthesis of...

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Main Authors: Giovanni V. Sayoga, Victoria S. Bueschler, Hubert Beisch, Bodo Fiedler, Daniel Ohde, Andreas Liese
Format: Article
Language:English
Published: Elsevier 2025-08-01
Series:Electrochemistry Communications
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Online Access:http://www.sciencedirect.com/science/article/pii/S1388248125000888
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author Giovanni V. Sayoga
Victoria S. Bueschler
Hubert Beisch
Bodo Fiedler
Daniel Ohde
Andreas Liese
author_facet Giovanni V. Sayoga
Victoria S. Bueschler
Hubert Beisch
Bodo Fiedler
Daniel Ohde
Andreas Liese
author_sort Giovanni V. Sayoga
collection DOAJ
description Hydrogen peroxide (H₂O₂) is a strong oxidizing agent that is commonly employed in chemical synthesis. Nevertheless, its utilization as a cosubstrate in biocatalytic reactions remains limited due to the deactivating effect on biocatalysts at an elevated concentration. An electrochemical synthesis of H₂O₂ represents an attractive approach, offering a controllable in situ generation of H₂O₂ without producing complex by-products. The objective of this study is to demonstrate the feasibility of the in situ electrogeneration of H₂O₂ using the All-in-One (AiO) electrode within a flow reactor technology. Integrating a bioelectrochemical system (BES) into a flow reactor technology, such as a flow cell, presents an alternative strategy for scale-up. In this study, the in situ generation of H₂O₂ is coupled with the hydroxylation of 4-ethylbenzoic acid catalyzed by the immobilized recombinant unspecific peroxygenase from Agrocybe aegerita (rAaeUPO) within a complete BES under batch and fed-batch operation modes. The electrochemical flow cell facilitates a controllable H₂O₂ generation by adjusting experimental parameters such as current density, aeration rate and residence time. The flow cell BES equipped with the AiO electrode yielded a catalytic productivity as high as 1.24 ± 0.02 mM h−1 (4.95 ± 0.1 g L−1 d−1), a total turnover number of rAaeUPO up to 3.38 · 105 ± 702 mol mol−1 and a turnover frequency up to 8.34 ± 0.14 s−1.
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spelling doaj-art-463b27a577674a18a3b21f154e02ff372025-08-20T02:48:39ZengElsevierElectrochemistry Communications1388-24812025-08-0117710794910.1016/j.elecom.2025.107949Integration of the All-in-One electrode in an electrochemical flow cell for in situ hydrogen peroxide supply in hydroxylation mediated by immobilized unspecific peroxygenaseGiovanni V. Sayoga0Victoria S. Bueschler1Hubert Beisch2Bodo Fiedler3Daniel Ohde4Andreas Liese5Institute of Technical Biocatalysis, Hamburg University of Technology, Denickestraße 15, 21073 Hamburg, Germany; Corresponding authors at: Institute of Technical Biocatalysis, Hamburg University of Technology, Denickestraße 15, 21073 Hamburg, Germany.Institute of Technical Biocatalysis, Hamburg University of Technology, Denickestraße 15, 21073 Hamburg, GermanyInstitute of Polymers and Composites, Hamburg University of Technology, Denickestraße 15, 21073 Hamburg, GermanyInstitute of Polymers and Composites, Hamburg University of Technology, Denickestraße 15, 21073 Hamburg, GermanyInstitute of Technical Biocatalysis, Hamburg University of Technology, Denickestraße 15, 21073 Hamburg, GermanyInstitute of Technical Biocatalysis, Hamburg University of Technology, Denickestraße 15, 21073 Hamburg, Germany; Corresponding authors at: Institute of Technical Biocatalysis, Hamburg University of Technology, Denickestraße 15, 21073 Hamburg, Germany.Hydrogen peroxide (H₂O₂) is a strong oxidizing agent that is commonly employed in chemical synthesis. Nevertheless, its utilization as a cosubstrate in biocatalytic reactions remains limited due to the deactivating effect on biocatalysts at an elevated concentration. An electrochemical synthesis of H₂O₂ represents an attractive approach, offering a controllable in situ generation of H₂O₂ without producing complex by-products. The objective of this study is to demonstrate the feasibility of the in situ electrogeneration of H₂O₂ using the All-in-One (AiO) electrode within a flow reactor technology. Integrating a bioelectrochemical system (BES) into a flow reactor technology, such as a flow cell, presents an alternative strategy for scale-up. In this study, the in situ generation of H₂O₂ is coupled with the hydroxylation of 4-ethylbenzoic acid catalyzed by the immobilized recombinant unspecific peroxygenase from Agrocybe aegerita (rAaeUPO) within a complete BES under batch and fed-batch operation modes. The electrochemical flow cell facilitates a controllable H₂O₂ generation by adjusting experimental parameters such as current density, aeration rate and residence time. The flow cell BES equipped with the AiO electrode yielded a catalytic productivity as high as 1.24 ± 0.02 mM h−1 (4.95 ± 0.1 g L−1 d−1), a total turnover number of rAaeUPO up to 3.38 · 105 ± 702 mol mol−1 and a turnover frequency up to 8.34 ± 0.14 s−1.http://www.sciencedirect.com/science/article/pii/S1388248125000888BiocatalysisBioelectrochemical systemElectrosynthesisFlow reactorHydroxylationUnspecific peroxygenase
spellingShingle Giovanni V. Sayoga
Victoria S. Bueschler
Hubert Beisch
Bodo Fiedler
Daniel Ohde
Andreas Liese
Integration of the All-in-One electrode in an electrochemical flow cell for in situ hydrogen peroxide supply in hydroxylation mediated by immobilized unspecific peroxygenase
Electrochemistry Communications
Biocatalysis
Bioelectrochemical system
Electrosynthesis
Flow reactor
Hydroxylation
Unspecific peroxygenase
title Integration of the All-in-One electrode in an electrochemical flow cell for in situ hydrogen peroxide supply in hydroxylation mediated by immobilized unspecific peroxygenase
title_full Integration of the All-in-One electrode in an electrochemical flow cell for in situ hydrogen peroxide supply in hydroxylation mediated by immobilized unspecific peroxygenase
title_fullStr Integration of the All-in-One electrode in an electrochemical flow cell for in situ hydrogen peroxide supply in hydroxylation mediated by immobilized unspecific peroxygenase
title_full_unstemmed Integration of the All-in-One electrode in an electrochemical flow cell for in situ hydrogen peroxide supply in hydroxylation mediated by immobilized unspecific peroxygenase
title_short Integration of the All-in-One electrode in an electrochemical flow cell for in situ hydrogen peroxide supply in hydroxylation mediated by immobilized unspecific peroxygenase
title_sort integration of the all in one electrode in an electrochemical flow cell for in situ hydrogen peroxide supply in hydroxylation mediated by immobilized unspecific peroxygenase
topic Biocatalysis
Bioelectrochemical system
Electrosynthesis
Flow reactor
Hydroxylation
Unspecific peroxygenase
url http://www.sciencedirect.com/science/article/pii/S1388248125000888
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