Biocatalytic transformation of 5-hydroxymethylfurfural into high-value

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Biocatalytic transformation of 5-hydroxymethylfurfural into high-value derivatives: recent advances and future aspects Lei Hu, Aiyong He, Xiaoyan Liu, Jun Xia, Jiaxing Xu, Shouyong Zhou, and Jiming Xu ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b04356 • Publication Date (Web): 23 Oct 2018 Downloaded from http://pubs.acs.org on October 23, 2018

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ACS Sustainable Chemistry & Engineering

Biocatalytic transformation of 5-hydroxymethylfurfural into highvalue derivatives: recent advances and future aspects

Lei Hu,* Aiyong He, Xiaoyan Liu, Jun Xia, Jiaxing Xu,* Shouyong Zhou, and Jiming Xu

Jiangsu Key Laboratory for Biomass-based Energy and Enzyme Technology, Jiangsu Collaborative Innovation Center of Regional Modern Agriculture & Environmental Protection, School of Chemistry and Chemical Engineering, Huaiyin Normal University, No. 111, Changjiang West Road, Huaian 223300, China

*Corresponding Author: [email protected], [email protected] Telephone/Fax: +86-0517-83526983

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ABSTRACT: Catalytic transformation of biomass-derived 5-hydroxymethylfurfural (HMF)

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into a series of high-value derivatives, such as 2,5-diformylfuran, 5-hydroxymethyl-2-

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furancarboxylic acid, 5-formyl-2-furancarboxylic acid, 2,5-furandicarboxylic acid, 2,5-

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dihydroxymethylfuran, 5-alkanoyloxymethylfurfural, 5,5-bis(hydroxymethyl)furoin and 5-

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hydroxymethylfurfurylamine, is a very important research field in biorefinery process. For

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a long time, chemocatalytic pathways are the main transformation methods of HMF, and

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so, they have been widely studied in recent years. However, considering some

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unavoidable issues of chemocatalytic pathways, biocatalytic pathways with many

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advantages, such as higher selectivity, gentler condition, lower investment and

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environmental friendliness, should be a promising alternative, and unfortunately, they

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have not yet attracted enough attention until now. To better understand the current

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research status, this review primarily retrospects and describes the discovery and

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development of biocatalytic transformation of HMF, and then systematically summarizes

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and discusses the latest studies and advancements on the biocatalytic transformation of

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HMF through oxidation, reduction, esterification, carboligation and amination in the

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presence of the corresponding enzymes or whole-cells. Furthermore, this review also

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proposes a few possible research trends in the future studies, aiming at providing a few

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helpful and feasible references and supports for the biocatalytic transformation of HMF

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in much more economical and effective ways.

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KEYWORDS: Biomass, 5-Hydroxymethylfurfural, Biotransformation, Enzymes, Whole-

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cells, High-value derivatives 2

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ABBREVIATIONS AA

acetic acid

FOA

furoic acid

AAD

aryl-alcohol dehydrogenase

GO

galactose oxidase

AAO

aryl-alcohol oxidase

HBA

4-hydroxybenzaldehyde

ADH

alcohol dehydrogenase

HFCA

5-hydroxymethyl-2-furancarboxylic acid

AF

2-acetylfuran

HLADH

horse liver alcohol dehydrogenase

ALD

aldehyde dehydrogenase

HMF

5-hydroxymethylfurfural

AMFCA

5-aminomethyl-2-furancarboxylic acid

HMFA

5-hydroxymethylfurfurylamine

AO

alcohol oxidase

HMFH

5-hydroxymethylfurfural oxidoreductase

AOMF

5-acetyloxymethylfurfural

HMFL

5-hydroxymethylfurfural levulinate

AOOMF

5-alkanoyloxymethylfurfural

HMFO

5-hydroxymethylfurfural oxidase

ARD

aldehyde reductase

HOMF

5-hexanoyloxymethylfurfural

BAL

benzaldehyde Lyase

IPA

isopropylamine

BHMF

5,5-bis(hydroxymethyl)furoin

LA

levulinic acid

CAL-B

Candida antarctica lipase B

LCA

laccase

CPME

cyclopentyl methyl ether

MB

2-methyl-2-butanol

CPO

chloroperoxidase

MBA

methylbenzylamine

CTL

catalase

MM

minimal medium

DA

dodecanoic acid

MnP

manganese peroxidase

DAMF

2,5-diaminomethylfuran

MOMF

5-methoxycarbonyloxymethylfurfural

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DCAD

dicarboxylic acid decarboxylase

MSM

mineral salt medium

DES

deep eutectic solvent

MTHF

2-methyltetrahydrofuran

DFF

2,5-diformylfuran

PAMO

phenylacetone monooxygenase

DHMF

2,5-dihydroxymethylfuran

PAO

periplasmic aldehyde oxidase

DMC

dimethylcarbonate

SA

syringaldehyde

DOMF

5-dodecanoyloxymethylfurfural

SCM

synthetic complete medium

EA

ethyl acetate

TAM

transaminase

EH

ethyl hexanoate

TCA

tricarboxylic acid

FA

formic acid

TEMPO

2,2,6,6-tetramethylpiperidine-1-oxyl

FDCA

2,5-furandicarboxylic acid

TPA

terephthalic acid

FEA

1-furan-2-ethylamine

UPO

unspecific peroxygenase

FF

furfural

VA

vanillin

FFA

furfurylamine

XDH

xanthine dehydrogenase

FFCA

5-formyl-2-furancarboxylic acid

XO

xanthine oxidase

INTRODUCTION

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In recent years, increasing development of global economy and rising emission of

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greenhouse gases have greatly stimulated the search for renewable resources to reduce the

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excessive reliance on nonrenewable fossil resources.1-5 Among various renewable resources

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in the nature, biomass is the most abundant carbonaceous feedstock,6-10 and it can be used

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to produce a wide variety of chemicals, fuels and materials in more sustainable ways. To

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make the utmost of biomass, biorefinery, which was firstly proposed by Bungay in 1982,11 4

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is considered to be a very effective approach.12-16 In biorefinery process, 5-

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hydroxymethylfurfural (HMF), which is produced by the dehydration of biomass-derived

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carbohydrates,17-32 such as glucose, fructose, sucrose, maltose, cellobiose, inulin, starch and

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cellulose, is listed as one of the “Top 10+4” value-added bio-based compounds by the

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United States Department of Energy.33-35 Due to the presence of three functional groups,

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including an aldehyde group, a hydroxyl group and a furan ring, it shows a very strong

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reactivity and can be further transformed into a lot of high-value derivatives (Figure 1), such

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as 2,5-diformylfuran (DFF),36-45 5-hydroxymethyl-2-furancarboxylic acid (HFCA),46 5-formyl-

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2-furancarboxylic

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dihydroxymethylfuran

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bis(hydroxymethyl)furoin (BHMF)72-76 and 5-hydroxymethylfurfurylamine (HMFA).77

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acid

(FFCA),47

(DHMF),57-66

2,5-furandicarboxylic

acid

5-alkanoyloxymethylfurfural

(FDCA),48-56

2,5-

(AOOMF),67-71

5,5-



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For a long time, chemocatalytic pathways have been the mainstream methods for the

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transformation of HMF.78-86 Although many important findings and breakthroughs were

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achieved, they still face a few unavoidable issues. On the one hand, chemocatalytic

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pathways generally employ metals, especially precious metals, such as gold, palladium,

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platinum, ruthenium, rhodium, rhenium and iridium, as catalysts, they are very expensive

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and then lack sufficient economical superiority.87 Besides, the selectivities of some metals

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are not very ideal in specific reactions, leading to the formation of various byproducts.88 On

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the other hand, chemocatalytic pathways usually require harsh reaction conditions, such as

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high temperatures, high pressures and corrosive reactants, to obtain the satisfactory 5

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results.89 In such situations, the special equipments bearing harsh reaction conditions can

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largely increase the initial investment. Additionally, the majority of chemocatalytic

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pathways also need organic solvents as reaction media, which are environmentally-

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unfriendly in the viewpoint of green chemistry.90 In light of the above-mentioned issues,

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biocatalytic pathways with many advantages, such as higher selectivity, gentler condition,

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lower investment and environmental friendliness, should be a promising alternative,87-91

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but unfortunately, they have not yet attracted enough attention until now. Considering the

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importance and potential of biocatalytic pathways, their current research status will be

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comprehensively reviewed in this work. First of all, the discovery and development of

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biocatalytic pathways for the transformation of HMF are retrospected and described. Then,

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the latest studies and advancements on biocatalytic pathways for the transformation of

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HMF through oxidation, reduction, esterification, carboligation and amination in the

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presence of the corresponding enzymes or whole-cells are systematically summarized and

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discussed. Moreover, some possible research trends are proposed to supply a few helpful

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and feasible references and supports for the future biocatalytic transformation of HMF.

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DISCOVERY AND DEVELOPMENT OF BIOTRANSFORMATION OF HMF

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As is known to all, pretreatment is an essential and crucial step to overcome the

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inherent recalcitrance of biomass for its effective depolymerization and conversion into

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various valuable products by microbial fermentation and other reactions.92-94 Owing to high

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efficiencies and low costs, acid-catalyzed and thermal-mediated hydrolysis are two of the

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most widely applied pretreatment methods.95-98 However, in addition to generating the 6

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desired fermentable sugars during these processes, numerous undesired compounds,

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including phenolic compounds, such as vanillin (VA), syringaldehyde (SA) and 4-

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hydroxybenzaldehyde (HBA), furan compounds, such as HMF and furfural (FF), and organic

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acids, such as formic acid (FA), acetic acid (AA) and levulinic acid (LA), are also formed

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because of severe conditions.99-102 More unfortunately, these compounds have strong

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suppression to microbial growth, which will lead to low product concentration and

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productivity.103 Among them, HMF, possessing a relatively higher abundance in

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hydrolysates, is regarded as the most potent inhibitor,104-107 because it can violently attack

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microorganisms, and then, interfere their metabolic processes by damaging cell wall and

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membrane, reducing enzymatic and biological activity, breaking down deoxyribonucleic

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acid and inhibiting ribonucleic acid and protein synthesis,103 which are very similar with the

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inhibition of FF. To remove HMF and facilitate microbial fermentation, additional

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remediation treatments or detoxification procedures are definitely required. In the past few

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decades, a lot of physical and chemical pathways, such as water washing, over-liming,

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activated charcoal or ion exchange adsorption, organic solvent extraction, ammonia

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neutralization and alkaline precipitation, have been widely investigated and employed.108-

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110

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commercialization due to their high processing costs that are caused by the excessive

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consumption of fresh water and reagents, the massive generation of waste water and

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residues and the substantial loss of fermentable sugars.107 In this context, if HMF can be in

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situ metabolized by microorganisms via the biotransformation or biodetoxification

However, these pathways are hardly acceptable from the viewpoint of

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processes, some momentous improvements in microbial fermentation will be readily

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achieved.

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Gratifyingly, Boopathy et al. in 1993 found for the first time that several enteric

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bacterial strains, such as Citrobacter, Edwardsiella, Escherichia, Enterobacter, Klebsiella and

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Proteus, could not only grow in the presence of HMF but also degrade approximately 95%

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HMF in 24 h, suggesting that they displayed a good ability to metabolize HMF,111 which was

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evidently proved by ultraviolet-visible spectroscopy (Figure 2). Following this study, other

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types of bacteria,112-124 yeasts125-132 and fungi,133-136 which can metabolize HMF into the less

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toxic products, such as DFF, HFCA, FFCA, FDCA and DHMF, or fully degrade it, have been

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gradually discovered in recent years (Table 1). The corresponding experimental results

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indicated that some special oxidoreductases and decarboxylases, such as the generically

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reported 5-hydroxymethylfurfural oxidoreductase (HMFH),137-139 5-hydroxymethylfurfural

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oxidase (HMFO),140-144 chloroperoxidase (CPO),145 aryl-alcohol oxidase (AAO),146-148

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unspecific peroxygenase (UPO),146-148 galactose oxidase (GO),147-149 periplasmic aldehyde

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oxidase (PAO),148-150 laccase (LCA),151-153 alcohol oxidase (AO),151 phenylacetone

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monooxygenase (PAMO),154 xanthine oxidase (XO),151 catalase (CTL),151 manganese

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peroxidase (MnP),155 aryl-alcohol dehydrogenase (AAD),135 xanthine dehydrogenase

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(XDH),149 aldehyde dehydrogenase (ALD),137 alcohol dehydrogenase (ADH),156-159 aldehyde

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reductase (ARD)160-163 and dicarboxylic acid decarboxylase (DCAD),122 were confirmed to

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play an important role in the metabolism of HMF (Table 1). Moreover, it should be

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emphatically noted that genera and enzymes may be different, but the metabolic pathways 8

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of HMF in the corresponding microorganisms were verified to be very similar by Zhang et

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al.,114 Liu et al.,104 Ran et al.,133 Wang et al.134 and Koopman et al.137 As shown in Figure 3,

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HMF is generally reduced into DHMF under aerobic conditions, and then, reoxidized into

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HMF at a much lower and harmless concentration, which does not affect the microbial

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growth and metabolism. Subsequently, HMF is oxidized into FDCA via FFCA over various

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oxidases or dehydrogenases, and then, decarboxylated into furoic acid (FOA) via a

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decarbonylation reaction. Finally, FOA joins the metabolism of FF, and through six steps, it

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is converted into 2-oxo-glutaric acid, which enters the cycle of tricarboxylic acid (TCA) to

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accomplish the entire metabolic process. However, under anaerobic conditions, HMF is

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merely reduced into DHMF and it can not be reoxidized into FDCA, meaning that the

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presence of oxygen is the prerequisite for the thorough metabolism of HMF.

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BIOTRANSFORMATION OF HMF INTO HIGH-VALUE DERIVATIVES

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Through Oxidation. Biocatalytic oxidation is an attractive and important method for

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the biotransformation of HMF. By means of different enzymes or whole-cells, various high-

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value derivatives, such as DFF, HFCA, FFCA and FDCA, can be selectively produced according

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to the position and degree of HMF oxidation. In the following section, we will summarize

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their respective studies and advancements in a comprehensive manner (Table 2), and we

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also discuss the effects of related reaction parameters, including catalysts, oxidants, buffers, 9

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cofactors and cosubstrates, on the biocatalytic oxidation of HMF.


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DFF. DFF contains two symmetrical aldehyde groups, and so, it is a very crucial

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precursor in the synthesis of pharmaceuticals, fungicides and functional polymers.164-167 The

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biocatalytic oxidation of HMF into DFF was firstly reported in 1997 by Sheldon and co-

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workers,145 where CPO, an extracellular enzyme that was isolated from Caldariomyces

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fumago, was used as a catalyst. In the presence of hydrogen peroxide (H2O2) that served as

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an oxidant, the yield and selectivity of DFF could be achieved to 53% and 59% in citrate

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buffer at room temperature (RT) for 2.5 h, respectively. However, it should be noted that

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HMF was hard to be completely oxidized by CPO, and its maximum conversion was only 92%

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under the above reaction conditions. Additionally, during the CPO-catalyzed oxidation of

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HMF, the formed oxoiron(V)porphyrin intermediate of CPO could competitively abstract

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hydrogen from the hydroxy and aldehyde moieties of HMF, which would lead to the

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generation of other byproducts, such as HFCA and FFCA, via the further direct oxygen

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transfer. Hence, CPO is not very applicable for the biocatalytic oxidation of HMF into the

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sole product.

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Following this study, Li and co-workers in 2015 also investigated the biocatalytic

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oxidation of HMF by using air as an oxidant.151 Fortunately, three AOs were found to have

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the ability to promote the formation of DFF as the sole product with the assistance of CTL.

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Note that CTL could convert the produced H2O2 into H2O and O2, which would remove the

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harmful effect of H2O2 on AOs. More interestingly, the formed O2 could again act as a 10

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substrate of AOs (Figure 4). Among the tested AOs, AO from Candida boidinii displayed the

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highest activity for the biocatalytic oxidation of HMF, leading to 41% yield of DFF in

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phosphate buffer at 25 C for 72 h. Furthermore, compared with AO, GO from Dactylium

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dendroides was a better catalyst for the synthesis of DFF from HMF when the reaction

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conditions were carefully optimized. Due to the strong activation effect of HRP towards GO

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and the excellent removal effect of CTL towards H2O2, the introduction of HRP and CTL could

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significantly increase the activity of GO, and then improve the yield of DFF,151 which was in

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accordance with the results of Carnell and co-workers.148 In addition, it should be

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particularly pointed out that the buffer types could also influence the activity of GO in the

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presence of HRP and CTL. For example, when the biocatalytic oxidation of HMF was

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performed in deionized water, the yield of DFF was 56% at 25 C for 72 h. However, under

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the same reaction conditions, DFF yield was drastically decreased to 28% in phosphate

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buffer, this might be attributed to the formation of copper phosphate precipitate (Cu3(PO4)2)

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when the copper-dependent GO was incubated in phosphate buffer, thus resulting in a

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lower activity. Although GO performed poorly in phosphate buffer, Carnell and co-workers

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found that the M3-5 variant of GO performed better, even at a much higher substrate

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concentration.148 Besides, they also found that when the pH value of phosphate buffer was

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6.5, the M3-5 variant of GO gave 77% yield of DFF at 37 C for 1 h. If the pH value was turned

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into 7.5, DFF yield would be achieved to 88% under the same reaction conditions, clearly

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indicating that the pH values of buffers were another crucial factor to influence the activity

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of GO. Based on the above findings, after careful optimization of reaction conditions, the 11

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yield of DFF could be further improved to 91%148 and 92%.151

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HFCA. HFCA is the oxidation product of aldehyde group in HMF, it is a promising

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versatile intermediate for the preparation of polyesters.168 Moreover, it is reported that

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HFCA is also an antitumor agent169 as well as an interleukin inhibitor.170 To the best of our

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knowledge, there are only a few studies on the biocatalytic synthesis of HFCA from HMF. In

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2013, Krystof et al. developed an interesting reaction system for the oxidation of HMF with

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the stepwise addition of H2O2 via the Baeyer-Villiger-type reaction mechanism (Figure 5), in

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which the commercially available immobilized lipase B from Candida antarctica (CALB) and

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ethyl acetate (EtOAc) or ethyl butyrate (EtOBu) were used as a catalyst and an acyl donor,

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respectively, and the in situ generated peracid would act as a direct oxidant.171 The results

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demonstrated that this biocatalytic system could successfully lead to the formation of HFCA

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with the yield of 76% in t-butanol (tBuOH) at 40 C for 24 h, and the usage of different acyl

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donors did not remarkably change the yield and distribution of products,171 suggesting that

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the lipase-mediated and peracid-assisted oxidation of HMF was highly favourable for the

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synthesis of challenging “semi-oxidized” products, such as HFCA. Furthermore, it is worth

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noting that the over-oxidation products, such as FFCA and FDCA, were not observed,

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however, more than 20% esters of HFCA were simultaneously formed as the byproducts in

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the above process.171 In order to further improve the yield and selectivity of HFCA, Li and

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co-workers in 2015 employed XO, a molybdenum-dependent enzyme from Escherichia coli,

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as a catalyst for the biocatalytic oxidation of HMF,151 affording 94% yield and 99% selectivity 12

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of HFCA in the presence of phosphate buffer and air at 37 C for 7 h, this remarkable

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reaction rate might be related to the formation of highly active superoxide anion radicals

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by XO.172 Compared with the lipase-mediated and peracid-assisted oxidation of HMF, the

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XO-catalyzed process showed many advantages: (1) much higher product yield and

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selectivity; (2) much shorter reaction time; (3) using air as the oxidant; (4) avoiding the

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addition of H2O2, the generation of peracid and the usage of organic solvents. More recently,

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Li and co-workers also designed an effectively coupled reaction system (Figure 6), in which

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the biocatalytic oxidation of HMF into HFCA over horse liver alcohol dehydrogenase (HLADH)

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was well compatible with the enzymatic regeneration of NAD(P)+ over hemoglobin (Hb) and

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H2O2.159 Specifically, under the catalytic action of HLADH, HMF was firstly oxidized into HFCA

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by NAD(P)+ in phosphate buffer, in which the oxidant NAD(P)+ was reduced into NAD(P)H.

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Subsequently, NAD(P)H was reoxidized into NAD(P)+ by Hb and H2O2, and then, the

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regenerated NAD(P)+ would again act as an oxidant for the oxidation of HMF into HFCA. By

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optimizing reaction conditions, the conversion of HMF and the yield of HFCA could be

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achieved to 100% and 81% at 30 C for 60 h,159 respectively. As far as we know, this is the

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first time that Hb-mediated regeneration route of NAD(P)+ was developed and applied for

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the HLADH-catalyzed oxidation of HMF into HFCA, which may open up a novel opportunity

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for the biotransformation of HMF. Following this study, another novel coupled reaction

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system, consisting of PAMO and phosphite dehydrogenase (PTDH), was also developed in

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2017 for the biocatalytic oxidation of HMF.154 After 16 h at 25 C in the presence of

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phosphate buffer, phosphite and O2, FFCA was detected as the major product with the 13

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almost complete conversion of HMF.

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In contrast to the isolated enzymes, the whole-cells should be more preferable for the

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biotransformation of HMF in theory, because they are not only inexpensive and stable but

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also do not require complex procedures that are necessary for the separation and

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purification of enzymes.88 However, the whole-cell-catalyzed biotransformation of HMF

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remains challenging, because HMF is a well-known inhibitor and toxic compound to

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microorganisms.124 Additionally, many side reactions may easily occur in the whole-cell-

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catalyzed biotransformation of HMF, which is due to the existence of various enzymes in

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microbial cells.123 Hence, screening for a highly selective microbial strain with a high

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tolerance to HMF is crucial for the biotransformation of HMF into high-value derivatives. In

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this respect, the biocatalytic oxidation of HMF into HFCA is no exception. As early as 2004,

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Mitsukura et al. surveyed three kinds of bacteria, including Acetobacter rancens IFO3297,

233

Serratia liquefaciens LF14 and Acetobacter pasteurianus IFO13753, the results

234

demonstrated that the first two strains showed a very strong aldehyde-oxidizing activity

235

without hydroxy-oxidizing activity.124 Hence, when HMF was used as a substrate, the

236

aldehyde group of HMF was selectively oxidized and the oxidation of hydroxy group of HMF

237

was not observed. Furthermore, it is noteworthy that compared with A. rancens IFO3297,

238

S. liquefaciens LF14 was more active for the oxidation of HMF, gaving 97% yield of HFCA at

239

20 C for 26 h.124 Inspired by this encouraging study, Zhang et al. in 2017 isolated a new 14

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bacterial strain Comamonas testosteroni SC1588 from soil samples, which not only showed

241

a high tolerance to HMF, but also displayed a good selectivity to the aldehyde group of

242

HMF.123 Interestingly, its catalytic activity was largely influenced by the cultivation status of

243

cells. Compared with the growing cells, the resting cells were observed to be much more

244

effective for the synthesis of HFCA,123 this might be ascribed to that the oxidized cofactors,

245

such as NAD(P)+, could be efficiently regenerated in the absence of nutrients (especially

246

carbon sources), thus facilitating the formation of the oxidized product, which is in

247

agreement with the metabolic pathways of HMF in Figure 3. In addition, it should be

248

specifically pointed out that the acidity of HFCA and the pH value of reaction system also

249

had a large effect on the catalytic activity of C. testosteroni SC1588.123 Based on its

250

physiological and biochemical properties, the combination of histidine addition and pH

251

tuning was found to be an available approach, which could not only significantly enhance

252

the tolerance to HMF, but also further improve the yield of HFCA. With the addition of 20

253

mM histidine into phosphate buffer, HMF-tolerance level and HFCA yield could be up to 180

254

mM and 98% when the pH value was adjusted to 7.0,123 respectively. More importantly, C.

255

testosteroni SC1588 could not use glucose and xylose as carbon sources, thus avoiding the

256

loss of sugars during the biotransformation and biodetoxification of microorganisms.

257

FFCA. FFCA is another product in the partial oxidation of HMF, and it bears an aldehyde

258

group and a carboxyl group, which make it attractive for the further applications in the

259

preparation of surfactants and resins.173 However, FFCA is challenging to be selectively

260

synthesized from HMF, which is due to its highly oxidized and yet uncompleted state. 15

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Fortunately, an organocatalytic-enzymatic method was developed in 2013 by Dominguez

262

de Maria and co-workers,171 in which 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and

263

CALB were applied as catalysts for the primary oxidation of HMF into DFF and the further

264

oxidation of DFF into FFCA, respectively. After 24 h at 40 C in tBuOH, 52% yield of FFCA

265

could be obtained.171 Enlightened by this study, Qin et al. reported a similar method, the

266

main difference was that the oxidation of HMF were performed in the presence of acetate

267

buffer and air over the combination of TEMPO and LCA.151 Analogously, DFF was firstly

268

formed as the dominant intermediate at the initial stage, and then, it was further

269

transformed into FFCA. Moreover, the results demonstrated that among three tested LCAs,

270

LCA from P. conchatus provided the highest yield of FFCA with 82% at 25 C for 96 h.151

271

In the subsequent studies, to circumvent the usage of TEMPO, the specific enzymes

272

were explored for the oxidation of HMF into FFCA. For instance, AAO is a secreted

273

flavoenzyme, which is generally present in several basidiomycetes for the degradation of

274

lignin.174 Excitingly, Carro et al. in 2014 found for the first time that AAO possessed a strong

275

ability to selectively oxidize HMF into FFCA via DFF. When AAO from Pleurotus eryngii was

276

employed as a catalyst, the yield of FFCA could be up to 98% in a shorter time of 4 h at 25

277

C,146 which was an important scientific finding, expanding our knowledge about the

278

substrates of AAO. However, it should be noted that AAO was not able to further oxidize

279

the aldehyde group of FFCA. In the same year, HMFO from Methylovorus sp. MP688, which

280

is a flavin adenine dinucleotide-containing oxidase and belongs to the glucose-methanol-

281

choline-type flavoprotein oxidase family, was also found to be very effective for the 16

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oxidation of HMF. After 5 h at 25 C, 92% yield of FFCA was obtained in phosphate buffer.140

283

More gratifyingly, the activity of HMFO was not restricted to HMF, and it was still active on

284

FF and many aromatic and aliphatic primary alcohols and aldehydes. In addition, HMFO

285

showed excellent thermal stability and catalytic stability over a wide range of pH. Based on

286

these results, HMFO is considered as a suitable and robust catalyst for the industrial

287

applications. Subsequently, in order to get more insights into the catalytic performance of

288

HMFO, its crystal structure was solved by Mattevi and co-workers in 2015,142 indicating that

289

H467 was the active site (Figure 7), which provided an essential hydrogen-bonding point

290

that could activate substrates and position their α-carbon in direct and proper contact with

291

the flavin. Besides, the mutational V367R and W466F were also identified as the sites for

292

further improving the activities on the aldehyde- and carboxyl-containing substrates (Figure

293

8). All these findings will guide more systematic and thorough investigations on the catalytic

294

performance of HMFO.

295



296



297

FDCA. FDCA, the complete oxidation product of HMF, has two symmetrical carboxyl

298

groups, so it is thought to be an environmental-friendly substitute for the replacement of

299

terephthalic acid (TPA),175-177 which can be extensively applied for the production of various

300

polyesters.178-194 In addition, FDCA can also be used as a renewable biochemical building

301

block to synthesize a series of medicines,122 polyamides195-197 and coordination

302

compounds.198 In general, the oxidation of HMF into FDCA can proceed by two routes 17

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303

(Figure 9). In the first route (Route A), the aldehyde group of HMF is firstly oxidized into the

304

carboxylic group, thus yielding HFCA, which is further oxidized into FDCA via FFCA. In the

305

second route (Route B), the hydroxy group of HMF is firstly oxidized into the aldehyde group,

306

thus yielding DFF, which is further oxidized into FDCA via FFCA. From the above routes, it

307

can be seen that the synthesis of FDCA from HMF involves three consecutive steps. Because

308

most enzymes are limited to either aldehyde oxidation or hydroxy oxidation, hence, the

309

mixed enzymes are usually employed as catalysts for the biocatalytic oxidation of HMF into

310

FDCA. For instance, Li and co-workers in 2015 designed a tandem oxidation system, in which

311

HMF was ultimately transformed into FDCA by the combination of GO and CALB via a

312

sequential stepwise process in the presence of deionized water and tBuOH (Figure 10),

313

resulting in 88% product yield,151 which was approximately equal to that by the combination

314

of TEMPO and CALB.171 In the same year, a similar oxidation system consisting of M3-5

315

variant of GO and PAO was developed by Carnell and co-workers,149 in which M3-5 variant

316

of GO was primarily added into the reaction system prior to the addition of PAO. After 8 h

317

at 37 C, HMF could be completely transformed, and more gratifyingly, FDCA as the only

318

oxidation product was produced in nearly quantitative yield. Following these studies, other

319

multi-enzyme reaction systems, such as AAO/UPO,146 AO/AAO/UPO,136 GO/AAO/UPO147

320

and GO/PAO/CTL/HRP,148 have also been investigated for the complete oxidation of HMF

321

(or 5-methoxymethylfurfural, MMF) in recent years. As expected, they displayed excellent

322

catalytic activities, leading to more than 80% yield of FDCA. In contrast to multi-enzyme

323

reaction systems, the complete oxidation of HMF into FDCA by a single enzyme is very 18

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challenging. In this respect, Fraaije and co-workers reported a ground-breaking work, they

325

found that HMFO was not restricted to aldehyde oxidation or hydroxyl oxidation, and it had

326

a catalytic activity to both aldehyde and hydroxyl oxidations.141 Therefore, when HMFO was

327

used as a single enzyme for the complete oxidation of HMF, FDCA was successfully formed.

328

By optimizing various reaction parameters, such as buffer, pH value, reaction temperature,

329

reaction time, substrate concentration and enzyme amount, FDCA yield could be achieved

330

to 95%,141 which was a very satisfactory result. Additionally, it should be particularly pointed

331

out that FDCA can be synthesized by two routes in theory, however, Route B in Figure 9 was

332

proved to be the preferred and main pathway, and Route A was hardly or not involved when

333

HMFO was adopted for the complete oxidation of HMF. By means of reaction kinetics,

334

isotope labeling and atmospheric pressure chemical ionization mass spectrometry, the

335

reasons for this interesting phenomenon should be due to that HMFO was a true alcohol

336

oxidase and its actual substrate was the hydrated aldehyde (gem-diol).141 Specifically, the

337

aldehyde group of HMF was not directly oxidized, but the hydroxyl group of HMF and the

338

hydrated form (gem-diol) of DFF could be oxidized by HMFO. Moreover, the hydrated

339

degree of aldehyde group was strongly dependent on the substituents on the furan ring.

340

When an electron-withdrawing substituent (such as formyl) was present, the aldehyde

341

group was more easily hydrated. However, when the substituent was a carboxylic acid, the

342

hydrated degree of aldehyde group would be reduced. Based on these results, during the

343

complete oxidation of HMF into FDCA over HMFO, the reaction rates for the formation of

344

DFF and FDCA were relatively slow and the reaction rate for the formation of FFCA was 19

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345 346 347

more faster in route B (Figure 9).

348

Apart from the enzymatic approaches, the whole-cell-catalyzed approaches have also

349

gained a series of interesting results in the complete oxidation of HMF into FDCA. For

350

example, Yang and Huang in 2016120 and 2017121 isolated six bacterial strains from soil

351

samples. After screening and acclimatizing, five strains (H-1, H-2, H-3, G-1 and G-2) were

352

found to be capable of growing in the presence of HMF as the sole carbon source. Among

353

them, H-2 and G-2, which were identified as Burkholderia cepacia and Methylobacterium

354

radiotolerans by 16S rDNA gene sequencing method, respectively, could commendably

355

biotransform HMF into FDCA.120 In addition, because the produced FDCA could be further

356

consumed by M. radiotolerans G-2, so its yield with 42% was lower than 51% that was

357

obtained by B. cepacia H-2.121 However, both two results were not ideal. To further improve

358

the yield of FDCA, some metabolic engineering techniques were applied for the complete

359

oxidation of HMF through the whole-cell-catalyzed approaches. For instance, Raoultella

360

ornithinolytica BF60, containing aldR that encodes ARD, dcaD that encodes DCAD and aldH

361

that encodes ALD, was isolated by Hossain et al. in 2017.122 When the wild-type strain was

362

used for the complete oxidation of HMF, the yield of FDCA was only 51% under the optimal

363

conditions. When aldR and dcaD were mutated by an intron gene insertional mutagenesis

364

system to prevent the formation of DHMF and the degradation of FDCA (Figure 11),

365

respectively, FDCA yield could be significantly increased to 72%.122 If aldH was 20

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overexpressed in the above mutant to promote the formation of FDCA (Figure 11), its yield

367

would be further improved to 89%.122 In addition to mutation and overexpression,

368

transgenosis was also proved to be a practicable and valid method by Koopman et al. in

369

2010119 and Yuan et al. in 2018.143 To be specific, by means of standard molecular cloning

370

procedures, two genes, one encoding HMFH from Cupriavidus basilensis HMF14137 and

371

another encoding HMFO from Methylovorus sp. MP688,140 were introduced into

372

Pseudomonas putida S12 (possessing aldH) and R. ornithinolytica BF60, respectively, and

373

the results indicated that the recombinational strains exhibited much better catalytic

374

performance for the complete oxidation of HMF, leading to 97% and 94% yields of FDCA at

375

30 C for 144 h119 and 120 h,143 respectively, which is very conductive to the high-efficiency

376

and industrial production of FDCA. More interestingly, FDCA was found to have a small

377

solubility (0.4 g/L) at low pH (0.5) and a high solubility (18 g/L) in tetrahydrofuran. Hence,

378

when FDCA was formed, it could be separated and recovered from the reaction mixture by

379

the combination of acid precipitation and tetrahydrofuran extraction. After measuring by

380

gas chromatography mass spectrometry, elemental analysis and nuclear magnetic

381

resonance, the purity of FDCA was proved to be up to more than 99%.119

382



383

Through Reduction. In the biotransformation of HMF, biocatalytic reduction is also a

384

typical method for the production of high-value derivatives. In 1993, Boopathy et al.111 for

385

the first time found that HMF could be reduced by many types of bacteria into its alcohol

386

with a maximum absorbance of 222 nm (Figure 2). Unfortunately, it was not authentically 21

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387

studied and analyzed due to the lack of internal control and commercial source at that time.

388

Until 2004, Liu et al. isolated and purified the reduction product of HMF from the yeast-

389

based conversion mixtures, and identified it as DHMF, which is a highly attractive platform

390

compound with wide applications in the synthesis of ethers,199-201 ketones202 and

391

polymers,203-213 with a molecular weight of 128 and a composition of C6H8O3 by means of

392

ultraviolet spectrum, high performance liquid chromatography, gas chromatographic mass

393

spectrometry and nuclear magnetic resonance spectrum,125 which largely accelerated the

394

studies on the biocatalytic reduction of HMF. Furthermore, it can be seen from the above

395

results that the whole-cell-catalyzed approaches showed many advantages and

396

tremendous potentials in the biotransformation of HMF, hence, they have been widely used

397

for the production of DHMF in recent years (Table 3).

398



399

For instance, Liu et al. in 2005 reported two strains of yeasts (Saccharomyces cerevisiae

400

307-12H60 and 307-12H120) for the reduction of HMF. Surprisingly, they could not only

401

tolerate 60 mM HMF but also reduce it into DHMF with the yield of 100% at 30 C for 48

402

h.126 Subsequently, Li et al. in 2017 isolated a new yeast strain (Meyerozyma guilliermondi

403

SC1103), which was proved to be more active for the reduction of HMF.132 Using 100 mM

404

HMF, 86% DHMF yield could be achieved at 35 C for 12 h. On this basis, the authors in 2018

405

further improved the tolerance and catalytic activity of M. guilliermondi SC1103 by

406

acclimatization and immobilization on calcium alginate.214 By using the modified strain, 86%

407

and 82% yields of DHMF were obtained when the concentration of HMF was up to 200 mM 22

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and 300 mM at 35 C for 7 h and 24 h, respectively. More satisfactorily, He et al. found that

409

E. coli CCZU-K14, a recombinational strain with high activity of carbonyl reductase,215 also

410

exhibited an amazing performance.118 Under the optimum reaction conditions, its tolerance

411

to HMF could be achieved to 400 mM, which did not seriously suppress the reduction of

412

HMF (Figure 12). After 72 h at 30 C, a moderate yield of DHMF with 70% could still be

413

obtained. If the concentration of HMF was decreased to 100 mM and 200 mM, DHMF yield

414

could even be as high as 100% and 91% in 24 h and 72 h, respectively, obviously

415

demonstrating excellent prospect of industrialization. Additionally, it is worth noting that

416

NAD(P)H as a cofactor was very important for the reduction of HMF into DHMF (Figure 3),

417

and its effective regeneration was strongly associated with the types of cosubstrates and

418

their concentrations. Among various available cosubstrates, glucose is very cheap and

419

abundant, so it with the appropriate concentration was commonly used to promote the

420

reduction of HMF into DHMF via the whole-cell-catalyzed approaches.118, 125, 132, 214

421 422

Through Other Reactions. In addition to oxidation and reduction reactions, other

423

reactions, such as (trans)esterification, carboligation and amination, have been gradually

424

employed for the biotransformation of HMF into the corresponding high-value derivatives

425

in recent years (Table 4).

426



427

AOOMF. AOOMF is a new-type ester, which is well known for its diverse applications

428

as fuel additives,67 surfactants,68 plasticizers,88 fungicides216 and monomers,217 and it is 23

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429

generally prepared by the chemocatalytic pathways via the (trans)esterification of HMF

430

with various acyl donors, including carboxylic acids, natural oils, alkyl esters and carbonates,

431

in the presence of homogeneous and heterogeneous catalysts, such as sulfuric acid, metal

432

chlorides and transition metals.67, 68, 218 Although the biocatalytic (trans)esterification of

433

HMF into AOOMF can be traced back to 1993,219 where lipase and vinyl ester were used in

434

tetrahydrofuran, this field has hitherto attracted very little interest, which should be due to

435

the poorer stabilities and recyclabilities of enzymes and high costs of substrates.

436

Recently, Qin et al. reported a more promising catalytic system for the

437

(trans)esterification of HMF by using Novozym 435 and levulinic acid (LA) as a immobilized

438

lipase and a renewable acyl donor in the commercially available biomass-based solvent 2-

439

methyltetrahydrofuran (MTHF) (Figure 13), respectively, leading to 94% conversion of HMF

440

at 40 C for 12 h.220 In addition to the excellent thermostability of Novozym 435 and its high

441

tolerance to LA, this high conversion should also be ascribed to the usage of MTHF, because

442

it not only had much better enzyme-compatibility, but also could increase substrate affinity

443

of enzyme.220 More interestingly, Krystof et al. in 2013 established a solvent-free catalytic

444

system, and the results indicated that high yields of various AOOMF, such as 5-

445

methoxycarbonyloxymethylfurfural (MOMF), 5-acetyloxymethylfurfural (AOMF), 5-

446

hexanoyloxymethylfurfural (HOMF) and 5-dodecanoyloxymethylfurfural (DOMF), could be

447

obtained in the presence of CALB by the (trans)esterification of HMF with

448

dimethylcarbonate (DMC), ethyl acetate (EA), ethyl hexanoate (EH) and dodecanoic acid

449

(DA),216 respectively. Although this solvent-free catalytic system avoided the usage of 24

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external solvents and then lowered the corresponding production costs, the separation of

451

the formed AOOMF from the unreacted HMF would be still needed. Because HMF is highly

452

reactive, especially at high temperature, so the traditional procedures, such as distillation,

453

might not be recommended for this specific case. Considering the above situations, the

454

authors developed a biphasic system by using deep eutectic solvents (DES) as separation

455

agents.216 DES, as an kind of emerging solvents that are commonly formed by hydrogen-

456

bond donors (such as alcohols, amines and organic acids) and hydrogen-bond acceptors

457

(such as choline chloride), were able to dissolve the hydrogen-bond-containing HMF, but

458

tended to form a second phase with the non-hydrogen-bond-containing AOOMF (Figure 14).

459

Hence, by means of DES, AOOMF could be successfully separated in high purity of 99% with

460

satisfactory recovery efficiency of 93%.216

461



462



463

BHMF. BHMF, possessing one carbonyl group, two furan rings and three hydroxyl

464

groups, is a multifunctional compound, which can be employed for the production of

465

oxygen-containing diesels,72 long-chain alkanes221 and linear or branched polyurethanes.222

466

In terms of theory, BHMF can not be directly formed by the self-aldol condensation of HMF

467

due to the absence of -hydrogen atom.222-224 However, Chen and co-workers in 2012-2016

468

found that two molecules of HMF could readily connect together to produce BHMF over 1-

469

ethyl-3-methylimidazolin-2-ylidene, 1,3-dimesitylbutyl-imidazolin-2-ylidene, 3-benzyl-5-(2-

470

hydroxyethyl)-4-methylthiazolin- 5-ylidene or 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol25

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471

5-ylidene, a kind of N-heterocyclic carbenes that are present in the corresponding ionic

472

liquids, via the umpolung carboligation,73-76 which was verified to be related to the change

473

of electrophilic carbonyl carbon into the nucleophilic center as an acyl anion equivalent

474

(Figure 15). Gratifyingly, Donnelly et al. in 2015 confirmed that the umpolung carboligation

475

of HMF could also be accomplished by means of an enzymatic system, in which thiamine-

476

diphosphate dependent benzaldehyde lyase (BAL) from Pseudomonas fluorescens was used

477

as a catalyst in phosphate buffer, leading to 70% yield of BHMF at RT for 18 h.224 To the best

478

of our knowledge, this is by far the only one report on the biocatalytic umpolung

479

carboligation of HMF into BHMF. Note that if the reaction time was prolonged, the

480

produced BHMF would be further oxidized into its diketone (Figure 16). More excitingly,

481

due to the presence of three hydroxyl groups in BHMF, it was also proved to be an effective

482

hydrogen-bond donor to create a new DES by mixing with choline chloride (Figure 17),

483

which should be a neoteric biomass-derived solvent.

484



485



486



487

HMFA. HMFA, which is similar to furfurylamine with many potential applications in the

488

preparation of diuretics, antihypertensives, antiseptic agents and curing agents,77 is a very

489

important intermediate that can be produced by the reductive amination of HMF. Due to

490

the sensitivity of furan ring to reductive conditions and the tendency to form secondary and

491

tertiary amines,225-228 the conventional chemocatalytic pathways are not desirable for the 26

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492

synthesis of HMFA. For this reason, biocatalytic pathways should be a promising alternative.

493

Fortunately, Dunbabin et al. in 2017 confirmed this speculation (Figure 18), in which three

494

transaminases

495

Arthrobacter sp. ArRMut11 (AS-TAM) and Mycobacterium vanbaalenii (MV-TAM) were

496

employed for the reductive amination of HMF in the presence of isopropylamine (IPA) or α-

497

methylbenzylamine (MBA) as an amine donor, resulting in HMFA with 66%-89% yield.77

498

Note that when the amine donor was IPA, the large-scale production and isolation of HMFA

499

would be more facile, because IPA and its corresponding product (acetone) are very volatile.

500

Furthermore, it should be particularly pointed out that TAM was also applicable for the

501

reductive amination of other furan-based aldehydes, such as FF, DFF, FFCA and 2-

502

acetylfuran (AF), into the corresponding primary amines with excellent yields, which

503

provides a high-efficiency method to produce the valuable nitrogen-implanted chemicals.

504



505

(TAM)

from

Chromobacterium

violaceum

DSM30191

(CV-TAM),

CONCLUSIONS AND PERSPECTIVES

506

Currently, the high-value utilization of HMF is a hot topic in biorefinery process. As a

507

typical kind of alternatives to chemocatalytic pathways, some biocatalytic pathways with a

508

series of well-known advantages have been gradually reported in recent years for the

509

synthesis of various valuable derivatives, such as DFF, HFCA, FFCA, FDCA, DHMF, AOOMF,

510

BHMF and HMFA. Although several interesting and promising results were obtained, their

511

practical applications still have a lot of problems and challenges, especially under

512

industrially-sound conditions. Among many possible bottlenecks, the first and foremost one 27

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513

should be the strong toxicity and inhibitory effect of HMF on biocatalysts, including enzymes

514

and whole-cells. Thus, developing the more robust biocatalysts with high tolerance and

515

selectivity is urgently needed in this research field. Besides, in order to further promote the

516

biocatalytic transformation of HMF into high-value derivatives on an industrial scale, the

517

following issues should also be emphatically strengthened in the future studies: (1)

518

Thoroughly investigating the metabolic mechanisms and rate-limiting steps of HMF

519

biotransformation to supply some meritorious references for the exploration and

520

modification of novel transformation pathways in the corresponding microorganisms. (2)

521

Intensively analyzing the stereochemical structures and active sites of enzymes to provide

522

a few theoretical directions for their subsequent design and usage. (3) Systematically

523

constructing the effective mutation and expression technologies of enzymes to improve

524

their yields and activities and then accomplish the selective synthesis of specific products.

525

(4) Creatively establishing the effective and inexpensive immobilization methods of

526

enzymes and whole-cells to realize their recovery and reuse and then lower the relevant

527

costs. (5) Comprehensively building high-efficiency and energy-efficient separation and

528

purification of target products on basis of their respective physicochemical properties to

529

push them into the actual application processes. (6) Innovatively exploring other possible

530

biocatalytic pathways to synthesize new high-value derivatives except the above-

531

mentioned derivatives and then expand the application range of HMF. Last but not at least,

532

considerable efforts should also be consecutively concentrated on the economical

533

production of HMF due to its high and unacceptable price. If the biocatalytic transformation 28

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of HMF can be in situ combined with its economical production, a much greater

535

breakthrough in the synthesis of HMF-based high-value derivatives may be achieved in the

536

near future. Despite facing many difficulties, we still believe that this is predictable and

537

realizable with the deepening of researches and the progressing of technologies.

538

ACKNOWLEDGEMENTS

539

This work was financially supported by the National Natural Science Foundation of

540

China (21506071), the Natural Science Foundation of Jiangsu Province (BK20150413) and

541

the Special Foundation for Young Talents of Jiangsu Collaborative Innovation Center of

542

Regional Modern Agriculture & Environmental Protection (HSXT2-316).

543

AUTHOR INFORMATION

544

Corresponding Author

545

*Lei

546

*Jiaxing

547 548

Hu. E-mail: [email protected]. Telephone/Fax: +86-0517-83526983. Xu. E-mail: [email protected]. Telephone/Fax: +86-0517-83526983.

Notes The authors declare no competing financial interest.

549

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1214

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furfuryl alcohol with aqueous formaldehyde in the presence of dealuminated

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(215) He, Y. C.; Tao, Z. C.; Zhang, X.; Yang, Z. X.; Xu, J. H. Highly efficient synthesis of ethyl

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unsubstituted 3-heteroaromatic pyridine analogues of nicotine as selective inhibitors

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1308

Commun. 2018, 114, 15-18, DOI 10.1016/j.catcom.2018.05.011.

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OH O

O HO

HO HO

OH

HO O

O

OH

OH O OH

O H OH OHOH

O

OH

OH

Cellulose

OH

O

O

O OH HO

O HO

Sucrose

n

OH

OH H

OH O n

Starch

Hydrolysis

Hydrolysis

Hydrolysis

OH

O

OH

Hydrolysis

HO

OH OH

H

H

Hydrolysis

O

HO H Fructose

O

HO

ro ge

O

n tio

O

H

te

OH

rif

lig a

OH

O

O Es

FFCA

n

C ar

tio

bo

a ic

O OH BHMF

OH

HFCA

O

O

O

O

Oxidation

O

O

OH

O

O

HMF

OH

O HO

n

n

O FDCA

1310

tio

HO

OH

Oxidation

OH

NH2

O

O

1309

a in Am

tio

H

DFF

HO

O

O

HMFA

na

O

HO

HO HO

HO

O

O

OH OH

OH

DHMF

H

OH

Dehydration

HO

O

Maltose

HO

OH

HO HO

OHOH Glucose Isomerization

O

Cellobiose

OH HO

O

HO HO

d Hy

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 66 of 105

R

OH

O

O

H

AOOMF

Figure 1. Catalytic transformation of biomass-derived HMF into high-value derivatives.

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ACS Sustainable Chemistry & Engineering

1311 1312

Figure 2. Ultraviolet-visible spectrum of the 0 and 24 h samples of K. pneumoniae in the

1313

presence of 10 mM of FF or HMF. Adapted with permission from ref 111. Copyright 1993

1314

Springer Nature.

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O

Page 68 of 105

O

HO

OH

DHMF

FFA NAD(P)

+

NAD(P)

ARD

+

NAD(P)

+

O

NAD(P)

O2/H2O

H2O2

NAD(P)H

O

Acyl-CoA syntherase

O

HO

CO2

Oxidase

OH

FDCA

H2O2

O

O2/H2O

H2O2

O

COOH

FFCA

TCA cycle

ADP

O O

O S CoA

Furoyl-CoA ACCOX

ACCred

HOOC

HOOC

H 2O

Dehydrogenase

1315

Oxidase

ATP

CoASH

HO

O2/H2O

NAD(P)H

O

O

COOH Decarboxylase

FOA

+

Dehydrogenase

Oxidase

Dehydrogenase

O

HMF

FF NAD(P)

NAD(P)H

HO

O

+

ADH

NAD(P)H

NAD(P)H

O

NAD(P)+

ARD

ADH

NAD(P)H

OH

COOH

O 2-Oxoglutaric acid

O O

CoASH

H 2O

O S CoA

5-Hydroxy-2-furoyl-CoA

O

O

S CoA O H2O 2-Oxoglutaryl-CoA

rase este

Thio

S CoA

Lactonase

5-Oxo-2-furoyl-CoA

O HOOC

S CoA OH 2-Hydroxyglutaryl-CoA

1316

Figure 3. Metabolic pathways of HMF in microorganisms. Note: NADH, reduced form of

1317

nicotinamide adenine dinucleotide; NADPH, reduced form of nicotinamide adenine

1318

dinucleotide phosphate; NAD+, oxidized form of nicotinamide adenine dinucleotide;

1319

NADP+, oxidized form of nicotinamide adenine dinucleotide phosphate; ACC, acceptor,

1320

which is reduced (red) or oxidized (ox); CoA: coenzyme-A; ATP, adenosine triphosphate;

1321

ADP, adenosine diphosphate. Adapted with permission from ref 134. Copyright 2015 68

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1322

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BioMed Central.

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AO

O HO

O

H

+

O2

Phosphate buffer

1324

O

O H2O2

+

H

O DFF

HMF

1323

Page 70 of 105

CTL

Figure 4. Oxidation of HMF into DFF over AO and CTL.151

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H

Page 71 of 105 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

O R

O

O O

Lipase (CAL-B)

H2O2

R

OOH

HO

O

OH

HFCA

OH

O O R

1325

HO OH

O

H

HMF

1326

Figure 5. Lipase-catalyzed oxidation of HMF into HFCA via the Baeyer-Villiger-type

1327

reaction in the presence of H2O2. Adapted with permission from ref 171. Copyright 2013

1328

John Wiley and Sons.

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Page 72 of 105

O

O HO

O

H

HLADH

NAD+

H 2O

OH

HFCA

HMF

1329

O

HO

NADH

Hb

H 2O 2

1330

Figure 6. HLADH-catalyzed and Hb-mediated oxidation of HMF into HFCA. Adapted with

1331

permission from ref 159. Copyright 2017 John Wiley and Sons.

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ACS Sustainable Chemistry & Engineering

1332 1333

Figure 7. Stereoview of the active site of HMFO. Residues surrounding the space in front

1334

of the flavin ring are shown, including three water molecules (red spheres) that are

1335

conserved in all determined crystal structures. Carbon, oxygen, nitrogen, sulfur and

1336

phosphorus atoms are expressed by yellow, red, blue, green and magenta, respectively.

1337

Hydrogen bonds are represented as the dashed lines. Adapted with permission from ref

1338

142. Copyright 2015 ACS Publications.

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1339 1340

Figure 8. Modeling of substrate binding in the active site of HMFO. (A) Proposed model

1341

for the binding of HMF. The furan ring orientation is constrained by the narrow shape of

1342

the cleft, and the α-carbon is in the proper position to be oxidized by the flavin. The

1343

protein atom closest to the hydroxyl group is N of H467, which is perfectly positioned to

1344

form a hydrogen bond with HMF. The arginine side chain of V367R mutant is modeled to

1345

show the possible interaction with HMF, which will provide an explanation for the

1346

increased activity of this mutant with FFCA. (B) Similarly to HMF, the secondary alcohol

1347

(S)-1-phenylethanol is modeled in the active site of HMFO with the assistance of W466F. 74

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Page 74 of 105

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Adapted with permission from ref 142. Copyright 2015 ACS Publications.

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Page 76 of 105

O Route A

HO

O

O OH

Route A

O

O

HFCA HO

O

FFCA

O

ute Ro

HMF

1349 1350

B

O

O Route B

O

O

OH

O

DFF

HO

O FDCA

Figure 9. Pathways for the complete oxidation of HMF into FDCA.

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OH

Page 77 of 105 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

HO

1351

O HMF

O

GO, Air Water

O

O

O

O

O

CALB,H2O2 EtOAc-tBuOH

DFF

HO

O

OH

FDCA

1352

Figure 10. Tandem oxidation of HMF into FDCA over GO and CALB. Adapted with

1353

permission from ref 151. Copyright 2015 Royal Society of Chemistry.

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ACS Sustainable Chemistry & Engineering

HO

HMF

ALD (aldH)

H

NADP+

HO

1354

NADPH

O

FFCA

OH

ALD (aldH)

NADP+

NADPH

Gene overexpression O

OH

O

O

O O

Insertional mutation

O

HO

OH

FDCA DCAD (dcaD)

O O

ARD (aldR)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 78 of 105

O O

OH

FOA

DHMF

1355

Figure 11. Metabolic pathways of HMF and FDCA in R. ornithinolytica BF60. Adapted with

1356

permission from ref 122. Copyright 2017 American Society for Microbiology.

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ACS Sustainable Chemistry & Engineering

HO

1357

O HMF (50~400 mM)

O

E. coli CCZU-K14

HO

Phosphate buffer, Glucose, 30 C

O

OH

DHMF (Yield: 70~100%)

1358

Figure 12. Biocatalytic reduction of HMF into DHMF by E. coli CCZU-K14. Adapted with

1359

permission from ref 118. Copyright 2018 Elsevier.

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Page 80 of 105

O

O

1360

O HMF

O

OH OH

O

O

Novozym 435, MTHF

O HMFL

O O

+

H 2O

1361

Figure 13. Biocatalytic esterification of HMF into HMFL over Novozym 435. Adapted with

1362

permission from ref 220. Copyright 2016 ACS Publications.

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ACS Sustainable Chemistry & Engineering

O R

AOOMF

O

O

O O

AOOMF + DES

HO

R

O

O HO

HMF

O

O O

DES

1363

O

O HMF

DEEP-EUTECTIC SOLVENTS (DES) OH O OH N N N OH OH OH HO OH H2N NH2 OH HO Cl Cl Cl OH OH Choline Chloride : Glycerol Choline Chloride : Urea Choline Chloride : Xylitol

1364

Figure 14. Separation of AOOMF and HMF by using DES. Adapted with permission from

1365

ref 216. Copyright 2013 John Wiley and Sons.

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N

O

N OAc

N +HOAc

HOAc

OH

O

O

O

O

OH BHMF

OH

HO

N OH

O

Page 82 of 105

HMF

N N

OH O N N

O

N

H

N

O

OH

OH O

N N

OH

O O H

O OH

N HMF

1366

OH

OH O

N

1367

Figure 15. Umpolung carboligation of HMF into BHMF over EMIY. Adapted with

1368

permission from ref 73. Copyright 2012 Royal Society of Chemistry.

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HO

1369

HMF

O Umpolung carboligation BAL

O

OH

O

OH O

O

O OH BHMF

Oxidation

OH

BAL

O

O O Diketone

OH

1370

Figure 16. BAL-catalyzed umpolung carboligation of HMF into BHMF and its spontaneous

1371

oxidation. Adapted with permission from ref 224. Copyright 2015 Royal Society of

1372

Chemistry.

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1373 1374

Figure 17. Formation of a new DES by combining BHMF and choline chloride. Adapted

1375

with permission from ref 224. Copyright 2015 Royal Society of Chemistry.

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HO

O

O

TAM, Phosphate buffer

HO

HMF

1376

Coproduct

Amine donor

O

NH2

HMFA

1377

Figure 18. Reductive amination of HMF into HMFA over TAM. Adapted with permission

1378

from ref 77. Copyright 2017 Royal Society of Chemistry.

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Table 1. Various types of microorganisms and oxidoreductases for metabolizing HMF

1379

Category

Microorganism

Strain

Enzyme

Ref

Bacterium

Acetobacter rancens

IFO3297



124

Bacterium

Acetobacter pasteurianus

FO13753



124

Bacterium

Burkholderia cepacia

H-1



120

Bacterium

B. cepacia

H-2



120

Bacterium

B. cepacia

H-3



120

Bacterium

Citrobacter freundii

Quinn



111

Bacterium

Clostridium cetobutylicum

ATCC 824

ARD

113

Bacterium

Cupriavidus basilensis

HMF14

HMFH

137

Bacterium

Caldariomyces fumago



CPO

145

Bacterium

Comamonas testosteroni

SC1588



123

Bacterium

Escherichia coli

ATCC 1175



111

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Bacterium

E. coli

LS5218



112

Bacterium

E. coli

055 B5



111

Bacterium

E. coli

B5 Cas



111

Bacterium

E. coli

Snyder



111

Bacterium

E. coli

MC4100



116

Bacterium

E. coli

CCZU-K14

ADH

118

Bacterium

E. coli

TP1000

PAO

149

Bacterium

E. coli



XO

151

Bacterium

Enterobacter cloacae

ATCC 13047



111

Bacterium

Enterobacter aerogenes

ATCC 13048



111

Bacterium

Enterobacter sp.

FDS8



114

Bacterium

Klebsiella pneumoniae

UI 495



111

Bacterium

Proteus mirabilis

H



111

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Bacterium

Pseudomonas putida

KT2440



117

Bacterium

P. putida

S12

ALD

137

Bacterium

Raoultella ornithinolytica

BF60

ARD

122

Bacterium

Rhodococcus capsulatus

E232V

XDH

149

Bacterium

Serratia liquefaciens

LF14



124

Bacterium

Methylobacterium radiotolerans

G-2



121

Bacterium

Methylovorus sp.

MP688

HMFO

140

Yeast

Saccharomyces cerevisiae

ATCC 211239

ADH

125

Yeast

S. cerevisiae

NRRL Y-12632

ARD

125

Yeast

S. cerevisiae

NRRL Y-50049

ARD

104

Yeast

S. cerevisiae

BY4742

ARD

162

Yeast

S. cerevisiae

307-12H60



126

Yeast

S. cerevisiae

307-12H120



126

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Yeast

S. cerevisiae

P6H9

ADH

131

Yeast

S. cerevisiae

TMB3000

ADH

157

Yeast

S. cerevisiae

TMB3400

ADH

158

Yeast

Scheffersomyces stipitis

KCTC 7228



130

Yeast

Pichia stipitis

NRRL Y-7124

ADH

125

Yeast

P. stipitis

307 10H60



126

Yeast

P. stipitis

αMnP1-1

MnP

155

Yeast

P. pastoris



AO

136

Yeast

Candida boidinii



AO

151

Yeast

Meyerozyma guilliermondii

SC1103



132

Fungus

Amorphotheca resinae

ZN1

ARD

133

Fungus

Agrocybe aegerita



UPO

146

Fungus

Bjerkandera adusta



AAO

147

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Fungus

Trametes versicolor



LCA

151

Fungus

Pleurotus ostreatus

PC9

AAO

135

Fungus

P. ostreatus

PC9

AAD

135

Fungus

Pleurotus eryngii



AAO

146

Fungus

Panus conchatus



LCA

151

Fungus

Fusarium graminearum



GO

149

Fungus

Flammulina velutipes



LCA

151

Fungus

Dactylium dendroides



AO

151

Fungus

D. dendroides



GO

151

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Table 2. Biocatalytic oxidation of HMF into high-value derivatives

1381

HMF Product

Catalyst

Oxidant

Buffer

pH

concentration (mM)

Temperature

Time

(C)

(h)

Conversion Yield (%)

(%)

Ref

DFF

CPO

H2O2

Citrate

5.0

50

RT

5/2

89

53

145

DFF

CPO

H2O2

Citrate

6.0

50

RT

5/2

83

50

145

DFF

AO/CTL

Air

Phosphate

7.5

30

25

72



41

151

DFF

GO/CTL/HRP

Air

Phosphate

7.0

30

25

72



28

151

DFF

GO/CTL/HRP

Air

Water



30

25

72



56

151

DFF

GO/CTL/HRP

Air

Water



30

25

96



92

151

DFF

GO/CTL/HRPa

Air

Phosphate

7.5

50

37

1



88

148

DFF

GO/CTL/HRPa

Air

Phosphate

7.0

50

37

1



91

148

DFF

GO/CTL/HRPa

Air

Phosphate

6.5

50

37

1



77

148

DFF

GO/CTL/HRPa

Air

Phosphate

7.0

100

37

1



80

148

HFCA

CALB

H2O2

tBuOHb



50

40

24



76

171

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Page 92 of 105

HFCA

XO

Air

Phosphate

7.5

26

37

7

95

94

151

HFCA

UPO

H2O2

Phosphate

7.0

3

25

24



97

146

HFCA

HLADH

NAD(P)+

Phosphate

7.0

10

30

60

100

81

159

HFCA

PAMO

O2

Phosphate

7.5

5

25

16

85



154

HFCA

S. liquefaciens LF14

Air

Phosphate

7.0

300c

20

26

97

97

124

HFCA

C. testosteroni SC1588

Air

Phosphate

8.0

40

30

11

100

92

123

HFCA

C. testosteroni SC1588

Air

Phosphate

7.0

40

35

11

100

94

123

HFCA

C. testosteroni SC1588

Air

Phosphate

7.0

90

30

24

100

99

123

HFCA

C. testosteroni SC1588

Air

Phosphate

7.0

100

30

42

100

98

123

HFCA

C. testosteroni SC1588

Air

Phosphate

7.0

110

30

48

100

96

123

HFCA

C. testosteroni SC1588

Air

Phosphate

7.0

130

30

60

100

88

123

HFCA

C. testosteroni SC1588

Air

Phosphate

7.0

150

30

60

100

70

123

HFCA

C. testosteroni SC1588

Air

Phosphate

7.0

180

30

120

100

52d

123

HFCA

C. testosteroni SC1588

Air

Phosphate

7.0

130

30

60

100

91d

123

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HFCA

C. testosteroni SC1588

Air

Phosphate

7.0

160

30

60

100

90d

123

HFCA

C. testosteroni SC1588

Air

Phosphate

7.0

160

30

36

100

98e

123

FFCA

CALB

H2O2

tBuOHb



50

40

24



52f

171

FFCA

TEMPO/LCA

Air

Acetate

4.5

30

25

48



68

151

FFCA

TEMPO/LCA

Air

Acetate

4.5

30

25

72



70

151

FFCA

TEMPO/LCA

Air

Acetate

4.5

30

25

96



82

151

FFCA

AAO

O2

Phosphate

6.0

3

25

4

100

98

146

FFCA

AAO

O2

Phosphate

6.0

3

25

2



90g

146

FFCA

HMFO

O2

Phosphate

8.0

2

25

5

100

92

140

FDCA

CALB

H2O2

tBuOHb



50

40

24



93f

171

FDCA

CALB

H2O2

tBuOHb



50

40

24



100g

171

FDCA

CALB

H2O2

tBuOHb



30

40

24



88h

151

FDCA

GO/PAOa

Air

Phosphate

7.0

50

37

8

100

100

149

FDCA

GO/PAOa

Air

Phosphate

7.0

100

37

10



74

149

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FDCA

AAO/UPO

O2

Phosphate

7.0

3

25

120

100

91

146

FDCA

AO/AAO/UPO

O2

Phosphate

7.0

3/2i

25

120

100

98j

136

FDCA

GO/AAO/UPO

O2

Phosphate

7.5

10

25

24

95

80

147

FDCA

PAO/CTL

Air

Phosphate

7.0

50

37

3/2

100

91g

148

FDCA

GO/PAO/CTL/HRPa

Air

Phosphate

7.0

50

37

3

100

100

148

FDCA

GO/PAO/CTL/HRPa

Air

Phosphate

7.0

100

37

6

100

100

148

FDCA

HMFO

O2

Phosphate

7.0

4

25

15

100

95

141

FDCA

B. cepacia H-2

Air

MSMk

7.0

16

26

24

100

48

120

FDCA

B. cepacia H-2

Air

MSMk

7.0

16

28

24

100

51

120

FDCA

M. radiotolerans G-2

Air

MSMk

7.0

8

26

24

100

42

121

FDCA

M. radiotolerans G-2

Air

MSMk

7.0

8

28

24

100

40

121

FDCA

R. ornithinolytica BF60l

Air

Phosphate

7.0

100

30

168

100

51

122

FDCA

R. ornithinolytica BF60m

Air

Phosphate

8.0

100

30

168

100

59

122

FDCA

R. ornithinolytica BF60n

Air

Phosphate

8.0

100

30

168

100

72

122

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FDCA

R. ornithinolytica BF60o

Air

Phosphate

8.0

100

30

168

100

89

122

FDCA

R. ornithinolytica BF60p

Air

Phosphate

8.0

100

30

120

100

94

143

FDCA

P. putida S12q

O2

MMr

7.0

25

30

144

100

97

119

The used GO is the M3-5 variant of GO. b EtOAc was added as the acyl donor. c HMF was added at 26 times into the reaction mixture

1382

a

1383

to reduce its inhibitory effect. d HFCA was synthesized in the presence of 20 mM histidine. e HFCA was synthesized by furfuryl alcohol-

1384

induced cells in the presence of 20 mM histidine. f The product yield is based on the isolated DFF that was synthesized from HMF by

1385

TEMPO. g The product yield is based on the pure DFF. h The product yield is based on the isolated DFF that was synthesized from HMF

1386

by GO. i Methanol was added as the cosubstrate to promote the formation of FDCA. j MMF was used as the substrate. k MSM is

1387

representative of mineral salt medium. l R. ornithinolytica BF60 is the wild-type strain. m R. ornithinolytica BF60 is the dcaD mutant. n

1388

R. ornithinolytica BF60 is the aldR and dcaD double mutant.

1389

ornithinolytica BF60 is the hmfH and hmfO transgenic strain. q P. putida S12 is the hmfH transgenic strain. r MM is representative of

1390

minimal medium.

o

R. ornithinolytica BF60 is the aldH overexpressing strain.

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p

R.

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Page 96 of 105

Table 3. Biocatalytic reduction of HMF into DHMF

1391

HMF concentration

Temperature

Time

Conversion

Yield

(mM)

(C)

(h)

(%)

(%)



30

30

48

100



125

SCMa



30

30

48

100

100

126

S. cerevisiae 307-12H60

SCMa



60

30

48

100

100

126

S. cerevisiae 307-12H120

SCMa



30

30

48

100

100

126

S. cerevisiae 307-12H120

SCMa



60

30

48

100

100

126

M. guilliermondi SC1103

Phosphate

7.2

40

30

24



55

132

M. guilliermondi SC1103

Phosphateb

7.2

40

30

7



91

132

M. guilliermondi SC1103

Phosphateb

7.2

100

35

12



86

132

M. guilliermondi SC1103

Phosphateb

7.2

110

35

36



87

132

M. guilliermondi SC1103c

Tris-HClb

8.0

50

35

5

100

100

214

M. guilliermondi SC1103c

Tris-HClb

8.0

75

35

10



98

214

Catalyst

Buffer

pH

S. cerevisiae NRRL Y-12632

SCMa

S. cerevisiae 307-12H60

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Ref

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M. guilliermondi SC1103c

Tris-HClb

8.0

200

35

7



86

214

M. guilliermondi SC1103c

Tris-HClb

8.0

300

35

24



82

214

M. guilliermondi SC1103c

Tris-HClb

8.0

300

35

36



61

214

E. coli CCZU-K14d

Phosphateb

6.5

50

30

10



96

118

E. coli CCZU-K14d

Phosphateb

6.5

100

30

10



85

118

E. coli CCZU-K14d

Phosphateb

6.5

100

30

24

100

100

118

E. coli CCZU-K14d

Phosphateb

6.5

200

30

72



91

118

E. coli CCZU-K14d

Phosphateb

6.5

400

30

72



70

118

SCM is representative of synthetic complete medium.

b

Glucose was added as a cosubstrate.

a

1393

acclimatized and immobilized strain. d E. coli CCZU-K14 is a recombinational strain with high activity of carbonyl reductase.

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c

M. guilliermondi SC113 is an

1392

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Page 98 of 105

Table 4. Biocatalytic transformation of HMF into high-value derivatives via (trans)esterification, carboligation and amination

1394

Product

Catalyst

Cosubstrate

Buffer

pH

HMF concentration (mM)

HMFLa

Novozym 435

LA

MTHF



50

40

12

95



220

HMFLa

Novozym 435

LA

tBuOH



50

40

12

94



220

HMFLa

Novozym 435

LA

CPMEb



50

40

12

92



220

HMFLa

Novozym 435

LA

MBc



50

40

24

92



220

MOMF

CALB

DMC





50

40

24



91

216

AOMF

CALB

EA





50

RT

24



90

216

HOMF

CALB

EH





50

40

24



81

216

DOMF

CALB

DA





50

60

24



85

216

BHMF

BAL



Phosphate

8.0

20

RT

18



70

224

HMFA

CV-TAM

MBA

Phosphate

7.5

20

30

24



75

77

HMFA

CV-TAM

IPA

Phosphate

7.5

20

35

24



89

77

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Temperature (C)

Time (h)

Conversion (%)

Yield (%)

Ref

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HMFA

ASTAM

MBA

Phosphate

7.5

20

30

24



69

77

HMFA

AS-TAM

IPA

Phosphate

7.5

20

35

24



44

77

HMFA

MV-TAM

MBA

Phosphate

7.5

20

30

24



53

77

HMFA

MV-TAM

IPA

Phosphate

7.5

20

35

24



66

77

FFAd

CV-TAM

MBA

Phosphate

7.5

20e

30

24



80

77

FFAd

CV-TAM

IPA

Phosphate

7.5

20e

35

24



92

77

AMFCAf

CV-TAM

IPA

Phosphate

7.5

20g

35

24



88

77

AMFCAf

MV-TAM

IPA

Phosphate

7.5

20g

35

24



59

77

DAMFh

CV-TAM

MBA

Phosphate

7.5

20i

30

24



70

77

FEAj

MV-TAM

MBA

Phosphate

7.5

20k

30

24



54

77

1395

a HMFL is

representative of HMF levulinate. b CPME is representative of cyclopentyl methyl ether. c MB is representative of 2-methyl-

1396

2-butanol.

1397

furancarboxylic acid. g FFCA was used as a substrate. h DAMF is representative of 2,5-diaminomethylfuran. i DFF was used as a substrate.

1398

j FEA

d

FFA is representative of furfurylamine.

e

FF was used as a substrate. f AMFCA is representative of 5-aminomethyl-2-

is representative of 1-furan-2-ethylamine. k AF was used as a substrate.

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1399

Graphical abstract

1400 1401 1402

Recent studies and advancements on the biotransformation of HMF over the corresponding enzymes or whole-cells are comprehensively summarized and discussed.

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ACS Sustainable Chemistry & Engineering

Biographies and Photographs

1404 1405

Lei Hu was born in Shandong, China. He received his M.S. and Ph.D. degrees in

1406

microbiology and energy chemistry from Fujian Agriculture and Forestry University and

1407

Xiamen University in 2010 and 2013, respectively. Since 2013, he joined the School of

1408

Chemistry and Chemical Engineering at Huaiyin Normal University. In 2016, he was

1409

promoted to associate professor, and his current research interests are mainly focused

1410

on biomass conversion, material synthesis and green chemistry.

1411 1412

Aiyong He was born in Jiangsu, China. He received his B.S. and Ph.D. degrees in

1413

Biological Engineering and Biochemical Engineering from Nanjing Tech University in 2010

1414

and 2016, respectively. Since 2017, he joined the School of Chemistry and Chemical 101

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1415

Engineering at Huaiyin Normal University, and his current research fields are mainly

1416

focused on the production of biobutanol from biomass and the biodetoxification of 5-

1417

hydroxymethylfurfural and other inhibitors.

1418 1419

Xiaoyan Liu was born in Shandong, China. She received her B.S. and Ph.D. degrees in

1420

Marine Biology and Microbiology from Ocean University of China in 2009 and 2012,

1421

respectively. Since 2012, she joined the School of Chemistry and Chemical Engineering at

1422

Huaiyin Normal University. In 2017, she was promoted to associate professor, and her

1423

current research areas are mainly focused on the biocatalytic synthesis of high value-

1424

added chemicals from biomass.

1425 1426

Jun Xia was born in Jiangsu, China. He received his B.S. and Ph.D. degrees in Biological 102

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Engineering from Nanjing Tech University in 2009 and 2014, respectively. Since 2014, he

1428

joined the School of Chemistry and Chemical Engineering at Huaiyin Normal University. In

1429

2018, he was promoted to associate professor, and his current research interests are

1430

mainly focused on the biocatalytic synthesis of high value-added chemicals from biomass.

1431 1432

Jiaxing Xu was born in Shandong, China. He received his M.S. and Ph.D. degrees in

1433

biochemical engineering from Nanjing Tech University in 2010 and 2012, respectively.

1434

During his Doctor’s thesis, he worked with Prof. Bingfang He at the Extremophiles Lab of

1435

Jiangsu Province. Since 2012, he joined the School of Chemistry and Chemical Engineering

1436

at Huaiyin Normal University. In 2016, he was promoted to associate professor, and his

1437

current research fields are mainly focused on biomass conversion and enzymatic catalysis.

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1438 1439

Shouyong Zhou was born in Jiangsu, China. He received his M.S. and Ph.D. degrees

1440

in applied chemistry and material chemical engineering from Nanjing Normal University

1441

and Nanjing Tech University in 2002 and 2009, respectively. From 2013 to 2014, he served

1442

as a senior visiting scholar in the Department of Chemical Engineering at Imperial College

1443

London and worked with Prof. Kang Li. In 2016, he was promoted to professor in the

1444

School of Chemistry and Chemical Engineering at Huaiyin Normal University, and his

1445

current research areas are mainly focused on membrane material synthesis and biomass

1446

conversion.

1447 1448

Jiming Xu was born in Jiangsu, China. He received his M.S. and Ph.D. degrees in

1449

organic chemistry and analytical chemistry from East China Normal University in 1998 and 104

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1450

2003, respectively. From 2011 to 2012, he served as a senior visiting scholar at Sam

1451

Houston State University. Today, he is professor and dean of School of Chemistry and

1452

Chemical Engineering at Huaiyin Normal University, and his current research interests are

1453

mainly focused on electrochemistry and biomass conversion.

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