Whole Cell Biocatalysis of 5-Hydroxymethylfurfural for Sustainable Biorefineries

Abstract

The implementation of cost-effective and sustainable biorefineries to substitute the petroleum-based economy is dependent on coupling the production of bioenergy with high-value chemicals. For this purpose, the US Department of Energy identified a group of key target compounds to be produced from renewable biomass. Among them, 5-hydroxymethylfurfural (HMF) can be obtained by dehydration of the hexoses present in biomass and is an extremely versatile molecule that can be further converted into a wide range of higher value compounds. HMF derivatives include 2,5-bis(hydroxymethyl)furan (BHMF), 5-hydroxymethyl-furan-2-carboxylic acid (HMFCA), 2,5-diformylfuran (DFF), 5-formyl-2-furancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid (FDCA), all presenting valuable applications, in polymers, bioplastics and pharmaceuticals. Biocatalysis conversion of HMF into its derivatives emerges as a green alternative, taking into account the high selectivity of enzymes and the mild reaction conditions used. Considering these factors, this work reviews the use of microorganisms as whole-cell biocatalysts for the production of HMF derivatives. In the last years, a large number of whole-cell biocatalysts have been discovered and developed for HMF conversion into BHMF, FDCA and HMFCA, however there are no reports on microbial production of DFF and FFCA. While the production of BHMF and HMFCA mainly relies on wild type microorganisms, FDCA production, which requires multiple bioconversion steps from HMF, is strongly dependent on genetic engineering strategies. Together, the information gathered supports the possibility for the development of cell factories to produce high-value compounds, envisioning economical viable biorefineries.

Current Advances in the Sustainable Conversion of 5‐Hydroxymethylfurfural into 2,5‐Furandicarboxylic Acid

“…Aldehydes, such as HMF, are toxic molecules for living organisms; some microorganisms, like bacteria and fungi, developed detoxification mechanisms to convert toxic HMF to “non‐toxic” molecules, and this mechanism can be exploited for FDCA production. This biotransformation process has important advantages and is receiving increasing attention in recent years [101–110] . In fact, the whole‐cell catalysts are often robust, benefitting from a protective barrier, reactive substrates, endogenous cofactors, and enzymes that perpetuate catalytic pathways and inhibit by‐products [111,112] .…”

“…This biotransformation process has important advantages and is receiving increasing attention in recent years. [101][102][103][104][105][106][107][108][109][110] In fact, the whole-cell catalysts are often robust, benefitting from a protective barrier, reactive substrates, endogenous cofactors, and enzymes that perpetuate catalytic pathways and inhibit byproducts. [111,112] In the last years, several microorganisms involved in HMF conversion to FDCA have been studied.…”

Design and Synthesis of Porous Organic Polymers: Promising Catalysts for Lignocellulose Conversion to 5-Hydroxymethylfurfural and Derivates

“…The most possible method for large-scale production is to prepare FDCA by the catalytic reaction of HMF, which can be converted from biomass resources. For different oxidation methods, the catalytic methods for preparing FDCA from HMF can be divided into thermal catalysis [ 92 ], photocatalysis [ 93 ], electrocatalysis [ 94 ], and biocatalysis [ 95 ]. According to the current production level, thermal catalysis is the most compatible method in industry.…”

Effective Comprehensive Utilization Strategy for Upgrading Red Seaweed via Chemocatalysis and a Newly Isolated Pseudomonas rhodesiae in Tandem

“… − HMF can be reduced to generate 2,5-diformylfuran (BHMF) or selectively oxidized into 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), 5-formyl-2-furancarboxylic acid (FFCA), 2,5-diformylfuran (DFF), and 2,5-furandicarboxylic acid (FDCA) . Among these derivatives, HMFCA is generated by selectively oxidizing the aldehyde group of HMF and is a promising starting material for synthetic polyester. , Besides, HMFCA has been reported to have antitumor activity and can be used as an interleukin inhibitor. − …”