A Hybrid Process for Valorization of <scp>d</scp>-Fructose to 2,5-Bis(hydroxymethyl)furan by Bridging Chemocatalysis and Biocatalysis in a Betaine:Benzenesulfonic Acid System

Yu, Peng; Jiang, Luyao; Di, Junhua; Ma, Cuiluan; Li, Qi; He, Yubin

doi:10.1021/acssuschemeng.2c02702

Cited by 16 publications

(6 citation statements)

References 65 publications

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“…On the other hand, costly HMF of high purity was used for the production of BHMF in most previous studies (Scheme ). Only few examples considered use of crude HMF as the starting material or direct conversion of inexpensive biomass to BHMF by sequential chemical dehydration and biocatalytic reduction. − It is also true in chemical hydrogenation of HMF over metals. , The reason may be the great poisoning effects of dehydration process-derived impurities such as solvents and byproducts on hydrogenation catalysts including chemical and biological ones.…”

Section: Introductionmentioning

confidence: 99%

One-Pot Chemobiocatalytic Production of 2,5-Bis(hydroxymethyl)furan and Its Diester from Biomass in Aqueous Media

Qian

Zong

2023

ACS Catal.

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Direct valorization of biomass into value-added chemicals is attractive yet challenging. Herein, we report a one-pot synthesis of 2,5-bis(hydroxymethyl)furan (BHMF) and its diacetate from inexpensive fructose and sugar syrup in the aqueous phase via sequential chemical dehydration, biocatalytic reduction, and esterification. A robust alcohol dehydrogenase from Escherichia coli (EcYjgB) was identified for HMF reduction, with high catalytic efficiencies toward 5hydroxymethylfurfural (HMF) (k cat /K m , 1300 s −1 mM −1 ) as well as NADPH (9700 s −1 mM −1 ). Recombinant E. coli harboring EcYjgB (E. coli_EcYjgB) showed high tolerance toward highly toxic and strongly inhibitory biobased furans, enabling smooth reduction of 1 M HMF and 0.5 M furfural. Its practicality was demonstrated by gram-scale synthesis of BHMF with a 79% isolated yield at approximately 126 g/L substrate loading. Biocatalytic process intensification was realized by improving cell membrane permeability using ethyl acetate, providing up to 15 g/L h BHMF productivity. A concurrent biocatalytic cascade for producing BHMF diacetate from HMF was constructed by combining E. coli_EcYjgB and Mycobacterium smegmatis acyltransferase (MsAcT) variant N94A, affording the desired product with a 93% yield in 1 h. Starting from crude HMF obtained via chemical dehydration and organic solvent evaporation, BHMF and its diacetate were produced with >99 and 88% yields, respectively. Finally, direct synthesis of these furan-based products from sugars was performed by chemobiocatalysis, without isolation of any intermediates, resulting in yields of up to 59% (relative to sugar). This work may pave the way for scalable production of furan-based chemicals from inexpensive renewable biomass.

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Section: Introductionmentioning

confidence: 99%

One-Pot Chemobiocatalytic Production of 2,5-Bis(hydroxymethyl)furan and Its Diester from Biomass in Aqueous Media

Qian

Zong

2023

ACS Catal.

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“…Moreover, the addition of methylated-β-cyclodextrin (MCD) permitted to further improve the yield of the process and to demonstrate the synergistic effect of DES and CDs in biocatalysis. Finally, Peng et al in 2022 [ 26 ] performed a dehydration of D-fructose in DES composed by betaine/benzenesulfonic acid (Bet/BSA, molar ratio 1:2) to produce 5-(hydroxymethyl)furan-2-carbaldehyde. This one was used as substrate by recombinant E. coli DCF (containing both the reductase and the formate dehydrogenase) to obtain furan-2,5-diyldimethanol ( Table 2 , entry 11).…”

Section: Reductionsmentioning

confidence: 99%

Combination of Enzymes and Deep Eutectic Solvents as Powerful Toolbox for Organic Synthesis

et al. 2023

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During the last decade, a wide spectrum of applications and advantages in the use of deep eutectic solvents for promoting organic reactions has been well established among the scientific community. Among these synthetic methodologies, in recent years, various examples of biocatalyzed processes have been reported, making use of eutectic mixtures as reaction media, as an improvement in terms of selectivity and sustainability. This review aims to show the newly reported protocols in the field, subdivided by reaction class as a ‘toolbox’ guide for organic synthesis.

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“… 10 , 11 Recently, rheological and zwitterionic properties of betaine have initiated new possibilities for its use in novel chemical syntheses and other functionalities. 12 − 14 …”

Section: Introductionmentioning

confidence: 99%

“…Betaine is a modified version of the simplest amino acid, glycine, and has similar zwitterionic properties. , The ability of its methyl groups to serve as methyl donors in metabolism provides several advantages, for example, reduction of heart disease by remethylation of homocysteine. , In addition, it functions as an osmoprotectant in plants, bacteria, and mammals, and it can prevent protein destabilization caused by high salt concentrations. , Recently, rheological and zwitterionic properties of betaine have initiated new possibilities for its use in novel chemical syntheses and other functionalities. − …”

Section: Introductionmentioning

confidence: 99%

Reactive Extraction of Betaine from Sugarbeet Processing Byproducts

et al. 2023

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Betaine from natural sources is still preferred over its synthetic analogue in secondary industries. It is currently obtained by expensive separation means, which is one of the main reasons for its high cost. In this study, reactive extraction of betaine from sugarbeet industry byproducts, that is, molasses and vinasse, was investigated. Dinonylnaphthalenedisulfonic acid (DNNDSA) was used as the extraction agent, and the initial concentration of betaine in the aqueous solutions of byproducts was adjusted to 0.1 M. Although maximum efficiencies were obtained at unadjusted pH values (pH 6, 5, and 6 for aqueous betaine, molasses, and vinasse solutions, respectively), the effect of aqueous pH on betaine extraction was negligible in the range of 2–12. The possible reaction mechanisms between betaine and DNNDSA under acidic, neutral, and basic conditions were discussed. Increasing the extractant concentration significantly increased (especially in the range of 0.1–0.4 M) the yields, and temperature positively (but slightly) affected betaine extraction. The highest extraction efficiencies (∼71.5, 71, and 67.5% in a single step for aqueous betaine, vinasse, and molasses solutions, respectively) were obtained with toluene as an organic phase solvent, and it was followed by dimethyl phthalate, 1-octanol, or methyl isobutyl ketone, indicating that the efficiency increased with decreasing polarity. Recoveries from pure betaine solutions were higher (especially at higher pH values and [DNNDSA] < 0.5 M) than those from vinasse and molasses solutions, indicating the adverse influence of byproduct constituents; however, the lower yields were not due to sucrose. Stripping was affected by the type of organic phase solvent, and a significant amount (66–91% in single step) of betaine in the organic phase was transferred to the second aqueous phase using NaOH as the stripping agent. Reactive extraction has a great potential for use in betaine recovery due to its high efficiency, simplicity, low energy demand, and cost.

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A Hybrid Process for Valorization of d-Fructose to 2,5-Bis(hydroxymethyl)furan by Bridging Chemocatalysis and Biocatalysis in a Betaine:Benzenesulfonic Acid System

Cited by 16 publications

References 65 publications

One-Pot Chemobiocatalytic Production of 2,5-Bis(hydroxymethyl)furan and Its Diester from Biomass in Aqueous Media

One-Pot Chemobiocatalytic Production of 2,5-Bis(hydroxymethyl)furan and Its Diester from Biomass in Aqueous Media

Combination of Enzymes and Deep Eutectic Solvents as Powerful Toolbox for Organic Synthesis

Reactive Extraction of Betaine from Sugarbeet Processing Byproducts

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