Selective Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Diformylfuran in Biphasic Media using Immobilized Galactose Oxidase: Proof of Concept and Limitations

verfasst von

Milica Milić, Emil Byström, Pablo Domínguez de María, Selin Kara

Abstract

The oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) is a key reaction in valorizing biomass. DFF is hardly soluble in water, while HMF is often obtained from biorefineries in crude wet organic fractions. Thus, the reaction is challenging for both biocatalysis performed in aqueous media, and for chemocatalysis where the presence of water often results in catalyst poisoning. Galactose oxidase (GalOx) can selectively oxidize HMF to DFF and displays promising activity in aqueous-organic media. In this study, GalOx was immobilized on ten carriers, assessing the immobilization yield, activity, and stability. Covalently immobilized GalOx catalyzed the oxidation of HMF to DFF in neat and water-saturated EtOAc, and in biphasic systems of various water contents. At 50 % v/v H

₂O, the reaction was conducted at a semi-preparative scale (50 mL) with no adverse effect on DFF yield. Some limitations arise, such as enzyme deactivation, and adsorption of DFF to the support, particularly in the aqueous fraction. Future options to upgrade the route may include designed stable enzymes under the presence of HMF/DFF, and the setup of microaqueous systems where DFF adsorption is minimized. The use of wet EtOAc media would be a promising approach in future biorefineries employing inexpensive crude wet organic fractions.

Organisationseinheit(en)

Institut für Technische Chemie

Externe Organisation(en)

Aarhus University
SpinChem AB
Sustainable Momentum SL

Typ

Artikel

Journal

CHEMCATCHEM

Band

ISSN

1867-3880

Publikationsdatum

22.02.2024

Publikationsstatus

Veröffentlicht

Peer-reviewed

ASJC Scopus Sachgebiete

Katalyse, Anorganische Chemie, Physikalische und Theoretische Chemie, Organische Chemie

Elektronische Version(en)

https://doi.org/10.1002/cctc.202301384 (Zugang: Offen)

BibTeX

@article{8a1f6defda2f4b54b57c30985ec95863,
title = "Selective Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Diformylfuran in Biphasic Media using Immobilized Galactose Oxidase: Proof of Concept and Limitations",
abstract = "The oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) is a key reaction in valorizing biomass. DFF is hardly soluble in water, while HMF is often obtained from biorefineries in crude wet organic fractions. Thus, the reaction is challenging for both biocatalysis performed in aqueous media, and for chemocatalysis where the presence of water often results in catalyst poisoning. Galactose oxidase (GalOx) can selectively oxidize HMF to DFF and displays promising activity in aqueous-organic media. In this study, GalOx was immobilized on ten carriers, assessing the immobilization yield, activity, and stability. Covalently immobilized GalOx catalyzed the oxidation of HMF to DFF in neat and water-saturated EtOAc, and in biphasic systems of various water contents. At 50 % v/v H 2O, the reaction was conducted at a semi-preparative scale (50 mL) with no adverse effect on DFF yield. Some limitations arise, such as enzyme deactivation, and adsorption of DFF to the support, particularly in the aqueous fraction. Future options to upgrade the route may include designed stable enzymes under the presence of HMF/DFF, and the setup of microaqueous systems where DFF adsorption is minimized. The use of wet EtOAc media would be a promising approach in future biorefineries employing inexpensive crude wet organic fractions.",
keywords = "5-hydroxymethylfurfural (HMF), biocatalysis, biphasic systems, enzyme immobilization, galactose oxidase",
author = "Milica Mili{\'c} and Emil Bystr{\"o}m and Mar{\'i}a, {Pablo Dom{\'i}nguez de} and Selin Kara",
note = "Funding Information: . This project has received funding from the European Union's Horizon 2020 research and innovation program under the Marie Sk{\l}odowska‐Curie grant agreement No. 860414. The authors thank Dr. Alessandra Basso and Dr. Simona Serban from Purolite Ltd. for providing the Lifetech carriers, Assoc. Prof. Thomas T{\o}rring and Thomas Dyekj{\ae}r from the Department of Biological and Chemical Engineering at Aarhus University for their kind help with HPLC analyses. Open Access funding enabled and organized by Projekt DEAL TM",
year = "2024",
month = feb,
day = "22",
doi = "10.1002/cctc.202301384",
language = "English",
volume = "16",
journal = "CHEMCATCHEM",
issn = "1867-3880",
publisher = "Wiley - VCH Verlag GmbH & CO. KGaA",
number = "4",
}