Positive Impact of Natural Deep Eutectic Solvents on the Biocatalytic Performance of 5-Hydroxymethyl-Furfural Oxidase

Caterina Martin,Gonzalo De Gonzalo,Marco W Fraaije

doi:10.3390/catal10040447

Caterina Martin, Gonzalo De Gonzalo + Show 1 more

Open Access

https://doi.org/10.3390/catal10040447

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Journal: Catalysts	Publication Date: Apr 22, 2020
Citations: 22	License type: CC BY 4.0

Affiliation: University of Groningen, Universidad de Sevilla

Abstract

Deep eutectic solvents (DESs) have been applied as cosolvents in various biocatalytic processes during recent years. However, their use in combination with redox enzymes has been limited. In this study, we have explored the beneficial effects of several DES as cosolvents on the performance of 5-hydroxymethylfurfural oxidase (HMFO), a valuable oxidative enzyme for the preparation of furan-2,5-dicarboxylic acid (FDCA), and other compounds, such as carbonyl compounds and carboxylic acids. The use of natural DESs, based on glucose and fructose, was found to have a positive effect. Higher conversions are obtained for the synthesis of several oxidized compounds, including FDCA. Depending on the type of DES, the stability of HMFO could be significantly improved. As the use of DES increases the solubility of many substrates while they only mildly affect dioxygen solubility, this study demonstrates that biocatalysis based on HMFO and other redox biocatalysts can benefit from a carefully selected DES.

Highlights

Deep eutectic solvents (DESs) have been applied as cosolvents in various biocatalytic processes during recent years
As can be observed in Entries 4 and 6, electron-withdrawing groups seem to have a positive effect on hydroxymethylfurfural oxidase (HMFO), as both 4-bromo- (4a) and 4-nitrobenzyl alcohol (6a) are oxidized with good conversions into the corresponding aldehydes (78.2% and 93.0% after 14 h, respectively)
DES has a negative effect on the performance of HMFO. These results show that the use of this DES up show that the use of this DES up to 60% v/v can improve the efficiency of oxidase-based biocatalytic to 60% v/v can improve the efficiency of oxidase-based biocatalytic processes

Summary

Introduction

5-Hydroxymethylfurfural oxidase (HMFO, EC 1.1.3.47) from Methylovorus sp. strain MP688 is a flavin-containing oxidase that only requires molecular oxygen as a mild oxidant to catalyze various oxidation reactions which include selective oxidations of alcohols, aldehydes and even thiols [1,2,3]. In order to increase the number of DES and their applications, natural products such as amino acids, organic acids and urea or sugars have been employed for the preparation of DES, forming the so-called natural DESs (NADESs) [20,21] These compounds show high diversity, are biodegradable and present very low toxicology, making them attractive for pharmaceutical purposes. Until recently, no examples of the application of DESs as cosolvents in reactions catalyzed by flavin-containing oxidases have been reported For this reason, we have analyzed the effect of different (NA)DESs in the oxidation of a variety of alcohols catalyzed by HMFO

Results and Discussion

Kinetic resolution of racemic

Experiments regarding the

Methods

Biocatalyzed Oxidation of 4-Chlorobenzyl Alcohol at Multimilligram Scale

Conclusions