Redox-Switchable Biocatalyst for Controllable Oxidation or Reduction of 5-Hydroxymethylfurfural into High-Value Derivatives

Abstract

Biocatalytic upgrading of biomass-derived 5-hydroxymethylfurfural (HMF) into high-value derivatives is of great significance in green chemistry. In this study, we disclosed the successful utilization of whole-cell Paraburkholderia azotifigens F18 for its switchable catalytic performance in the on-demand catalysis of HMF to different value-added derivatives, namely, selective reduction to 2,5-bis(hydroxymethyl)furan (BHMF) or oxidation to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). Based on the fine-tuning of biochemical properties, the biocatalyst can proceed an efficient hydrogenation reaction toward HMF with a good selectivity of 97.6% to yield the BHMF at 92.2%. Noteworthily, BHMF could be further oxidized to HMFCA and 2,5-furandicarboxylic acid (FDCA) by the whole cell. To realize the on-demand syntheses of HMFCA, the genes encoding HMF oxidoreductase/oxidase of whole-cell F18 were then deleted to prevent the further conversion of HMFCA to FDCA, which led to a 10-fold decrease of FDCA. Thus, an HMF conversion of 100% with an HMFCA yield of 98.3% was finally achieved by the engineered whole cell at a substrate concentration of 150 mM. Moreover, HMFCA synthesis was efficiently prepared with an excellent selectivity of 96.3% and a yield of 85.1% even at a high substrate concentration of up to 200 mM.

Advances in Electrochemical Modification Strategies of 5‐Hydroxymethylfurfural

“…Recently reviewed, a wide variety of bacteria have been shown capable of HMF transformation including oxidation to high‐value products, such as DFF, 5‐hydroxymethyl‐2‐furancarboxylic acid (HFCA), FFCA, and FDCA, and HMF reduction to DHMF with the product yield and composition dependent on the utilized bacterial species [80] . Some bacterial strains investigated for HMF transformation into value‐added chemicals include Comamonas testosteroni SC1588 for the production of HFCA, [91] Methylobacterium radiotolerans G‐2 for the production of FDCA, [92] Paraburkholderia azotifigens F18 for the production of DHMF, HFCA, and FDCA, [93] Meyerozyma guilliermondii SC1103 for the production of DHMF, [94] and recombinant Escherichia coli CCZU‐K14 for the production of DHMF, [95] among others reviewed recently [80,96] . With the advances of microbial synthesis from HMF, the pairing of these studies with microbial electrochemistry offers exciting opportunities to control the selectivity and production by using an electrical current to influence the metabolisms of the bacterial cells [89] .…”

Improved Bio-Synthesis of 2,5-bis(hydroxymethyl)furan by Burkholderia contaminans NJPI-15 With Co-substrate

“…etc.) have been reported to be directly/indirectly involved in regenerating the reduced cofactors ( He et al, 2015 ; Xu et al, 2020 ). Glutamine plays a pleiotropic role in cell function, contributing to processes such as energy synthesis, macromolecular synthesis, mTOR activation, and reactive oxygen balance ( Sayed et al, 2019 ).…”

Whole Cell Biocatalysis of 5-Hydroxymethylfurfural for Sustainable Biorefineries

“…More recently, fungi, yeast and bacteria strains have been described as biocatalysts for its production from HMF (Table 1). The bacteria Paraburkholderia azotifigens F18 was found to produce 36.9 mM of BHMF from HMF, with a 92% yield, under anaerobic conditions [22]. The yeast Meyerozyma guilliermondii SC1103 was identified as a BHMF producer [23], and its conversion abilities were further improved by cell acclimatization and immobilization in calcium alginate beads, reaching BHMF titers of 181 mM, with 85% and a productivity of 25.8 mM/h [24].…”

“…Surprisingly, in that work the authors did not explore the potential of the E. coli modified with the original hmfo for FDCA production, which presented yields of ~80%. The Paraburkholderia azotifigens F18 strain, capable of producing BHMF under anaerobic conditions, was found to accumulate HMFCA in more aerobic conditions, and with deletion of genes encoding HMF oxidoreductase/oxidase (to prevent oxidation of HMFCA to FDCA) it produced 147.5 mM of HMFCA with 98% yield [22].…”