Efficient reduction of 5-hydroxymethylfurfural to 2, 5-bis (hydroxymethyl) furan by a fungal whole-cell biocatalyst
Graphical abstract
Introduction
Lignocellulose-derived 5-Hydroxymethylfurfural (HMF) is one of versatile bio-based platform chemicals [1,2]. HMF could be transformed into a number of synthetically valuable chemicals via chemical transformations [[3], [4], [5]]. The structure of the compound that contains a hydroxymethyl group and aldehyde group confers it high reactivity, enabling it to undergo various reactions, such as oxidation, reduction, and esterification. Selective reduction of the aldehyde group in HMF would afford 2, 5-Bis(hydroxymethyl)furan (BHMF) which is an interesting diol and widely used for the synthesis of polymers, therapeutic drugs, crown ethers, biologically active compounds [6,7].
Currently, catalytic hydrogenation of HMF for BHMF synthesis with chemical catalysts remains dominant, and great progress has been achieved [[8], [9], [10], [11], [12]]. Biocatalytic reduction of HMF for production of BHMF offers an important alternative to chemical approaches by virtue of its high catalytic efficiency, and often excellent selectivity as well as mild environmentally friendly reaction conditions [13,14]. In addition, compared with using isolated enzyme employing microbial whole cell biocatalysts for BHMF synthesis circumvents the enzyme isolation and reduces cost [15]. However, biocatalytic synthesis of BHMF with microbial cells remains challenging due to the well-known cell toxicity of HMF [17]. Although several microbial cells were reported on HMF reduction in biological detoxification of lignocellulosic hydrolysates [[17], [18], [19]], they are not suitable catalysts for the purpose of BHMF production because of low substrate concentration and poor selectivity. To date, there are only a few reports on selective microbial production of BHMF from HMF, in which process engineering methods were also used to improve the conversion [4,6,20,21]. Discovery of new biocatalysts for HMF conversion to BHMF will accelerate the utilization of biomass based HMF. Thus, it is essential to explore the microbes with high HMF-tolerance and excellent catalytic activity for HMF conversion.
Recently, a black yeast-like fungus, Aureobasidium subglaciale F134 was isolated from extreme environments [22,23]. Its cells exhibit high tolerance to metal ions, radiations, and low temperature. In addition, A. subglaciale F134 can produce extracellular polysaccharide pullulan and melanin as secondary metabolites, implying remarkable diversity of metabolic pathway inside cells [24]. Considering the unique biological properties, we surmised that it would be of great interest to explore the potential applications of A. subglaciale F134 for biocatalysis. In fact, A. subglaciale F134 was found as a whole-cell bifunctional biocatalyst for Baeyer-Villiger oxidation or carbonyl reduction in our previous study [25].
In this study, we report that A. subglaciale F134 can be used as an efficient biocatalyst in BHMF synthesis by selective reduction of HMF (Scheme 1). The catalytic properties of this strain and the effects of some key reaction factors on BHMF synthesis were further investigated. Besides, the fed-batch strategy was adopted to accumulate a high concentration of BHMF.
Section snippets
Biological and chemical materials
The A. subglaciale F134 strain was preserved in our lab and was subsequently deposited at China Center for Type Culture Collection (CCTCC) with the access number of CCTCC No. M2019476. The culture medium was purchased from Shanghai Macklin Biochemical Co., Ltd (Shanghai, China). All chemicals were analytical grade, obtained from commercial sources, and used without further purification. High-performance liquid chromatography (HPLC) grade acetonitrile was purchased from Macklin Biochemical Co.,
Whole A. subglaciale F134 cells as catalysts in HMF reduction with selective formation of BHMF
In contrast to isolated enzyme that shows high specificity, transformations catalyzed by whole cells usually result in the formation of multiple products from single substrate due to inevitable side-reaction occurred inside cells [26,27]. Based on this, discovery of new microorganism for selective production of value-added product from HMF is not a trivial task. In this work, microbial reduction of HMF for BHMF production was carried out using growing and resting A. subglaciale F134 cells
Conclusions
An efficient biocatalytic approach for the synthesis of BHMF from HMF was successfully established with black yeast-like A. subglaciale F134 fungus. At 180 mM of HMF, BHMF product was obtained with a yield of 82 % and selectivity of 97 % under optimized conditions. Up to 430 mM BHMF was synthesized within 15 h by employing fed-batch strategy, leading to a productivity of 3.7 g/L/h. Glucose that are commonly used as co-substrate for cofactor regeneration is not necessary in this new developed
CRediT authorship contribution statement
Dong Chen: Investigation. Ran Cang: Investigation. Zhi-Dong Zhang: Investigation. He Huang: Resources, Writing - original draft. Zhi-Gang Zhang: Conceptualization, Funding acquisition, Resources, Writing - original draft, Writing - review & editing. Xiao-Jun Ji: Conceptualization, Funding acquisition, Writing - review & editing.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (21646014, 21776134, and 21922806), the National Key Research and Development Program of China (2018YFA0903700), the program of Jiangsu Synergetic Innovation Center for Advanced Bio-Manufacture (XTE1851).
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These authors contributed equally to this work.