A straightforward chemobiocatalytic route for one-pot valorization of glucose into 2,5-bis(hydroxymethyl)furan

Abstract

Direct conversion of inexpensive biomass into value-added chemicals via furanic platform molecules is highly attractive. In this work, we present a straightforward chemobiocatalytic route for glucose valorization into 2,5-bis(hydroxymethyl)furan (BHMF) in one pot, with no purification of the intermediate 5-hydroxymethylfurfural (HMF). Six candidate alcohol dehydrogenase (ADH) genes were located from Meyerozyma guilliermondii SC1103, based on comparative transcriptome analysis and real-time quantitative polymerase chain reaction. An ADH (MgADH1) was identified upon evaluation of catalytic performances of recombinant Saccharomyces cerevisiae harboring candidate ADHs in HMF reduction. Soluble expression of the enzyme in S. cerevisiae was greatly enhanced by its codon optimization, leading to improved HMF tolerance (up to 400 mM). In a fed-batch process, the desired product of approximately 473 mM (60.5 g/L) was produced within 30 h by recombinant S. cerevisiae_MgADH1. A chemobiocatalytic route toward BHMF was constructed by merging CaCl₂-mediated isomerization and dehydration with biocatalytic reduction with an overall yield of approximately 42%, starting from glucose. This work may pave the way for green manufacture of valuable biobased chemicals.

Keywords

Alcohol dehydrogenases / Biomass conversion / Biobased chemicals / Chemobiocatalysis / Furans

References

Antonucci V, Coleman J, Ferry JB, Johnson N, Mathe M, Scott JP, Xu J. Toxicological assessment of 2-methyltetrahydrofuran and cyclopentyl methyl ether in support of their use in pharmaceutical chemical process development. Org Process Res Dev, 2011, 15(4): 939-941.

Ask M, Bettiga M, Mapelli V, Olsson L (2013) The influence of HMF and furfural on redox-balance and energy-state of xylose-utilizing Saccharomyces cerevisiae. Biotechnol Biofuels 6(1):22. https://doi.org/10.1186/1754-6834-6-22

Bering L, Thompson J, Micklefield J. New reaction pathways by integrating chemo- and biocatalysis. Trends Chem, 2022, 4(5): 392-408.

Bijoy R, Agarwala P, Roy L, Thorat BN. Unconventional ethereal solvents in Organic Chemistry: a perspective on applications of 2-Methyltetrahydrofuran, Cyclopentyl Methyl Ether, and 4-Methyltetrahydropyran. Org Process Res Dev, 2022, 26(3): 480-492.

Birmingham WR, Toftgaard Pedersen A, Dias Gomes M, Bøje Madsen M, Breuer M, Woodley JM, Turner NJ. Toward scalable biocatalytic conversion of 5-hydroxymethylfurfural by galactose oxidase using coordinated reaction and enzyme engineering. Nat Commun, 2021, 12(1): 4946.

Chang S, He X, Li B, Pan X (2021) Improved bio-synthesis of 2,5-bis(hydroxymethyl)furan by Burkholderia contaminans NJPI-15 with co-substrate. Front Chem 9:635191. https://doi.org/10.3389/fchem.2021.635191

Cheng A-D, Shi S-S, Li Y, Zong M-H, Li N. Biocatalytic oxidation of biobased furan aldehydes: comparison of toxicity and inhibition of furans toward a whole-cell biocatalyst. ACS Sustainable Chem Eng, 2020, 8(3): 1437-1444.

Di J, Liao X, Li Q, He Y-C, Ma C. Significantly enhanced bioconversion of high titer biomass-derived furfural to furfuryl alcohol by robust endogenous aldehyde reductase in a sustainable way. Green Chem, 2023, 25(22): 9194-9202.

Du Z, Yang D, Cao Q, Dai J, Yang R, Gu X, Li F. Recent advances in catalytic synthesis of 2,5-furandimethanol from 5-hydroxymethylfurfural and carbohydrates. Bioresour Bioprocess, 2023, 10(1): 52.

Figueirêdo MB, Hita I, Deuss PJ, Venderbosch RH, Heeres HJ. Pyrolytic lignin: a promising biorefinery feedstock for the production of fuels and valuable chemicals. Green Chem, 2022, 24(12): 4680-4702.

Fu H, Liang Y, Zhong X, Pan Z, Huang L, Zhang H, Xu Y, Zhou W, Liu Z. Codon optimization with deep learning to enhance protein expression. Sci Rep, 2020, 10(1): 17617.

Fulignati S, Antonetti C, Licursi D, Pieraccioni M, Wilbers E, Heeres HJ, Raspolli Galletti AM (2019) Insight into the hydrogenation of pure and crude HMF to furan diols using Ru/C as catalyst. Appl Catal A: Gen 578:122–133. https://doi.org/10.1016/j.apcata.2019.04.007

Gao W-L, Li N, Zong M-H. Enzymatic regioselective acylation of nucleosides in biomass-derived 2-methyltetrahydrofuran: kinetic study and enzyme substrate recognition. J Biotechnol, 2013, 164(1): 91-96.

Ghose TK. Measurement of cellulase activities. Pure Appl Chem, 1987, 59(2): 257-268.

Gröger H, Gallou F, Lipshutz BH. Where Chemocatalysis meets Biocatalysis. Water Chem Rev, 2023, 123(9): 5262-5296.

Gundekari S, Karmee SK. Catalytic Conversion of Levulinic Acid into 2-Methyltetrahydrofuran: a review. Molecules, 2024, 29(1): 242.

Hao Y-C, Zong M-H, Chen Q, Li N (2023) Engineering carbonyl reductase for one-pot chemobiocatalytic enantioselective synthesis of value-added N-containing chiral alcohol from N-acetyl-D-glucosamine. Green Chem 25:5051–5058. https://doi.org/10.1039/D2GC04878G

He Y-C, Jiang C-X, Chong G-G, Di J-H, Wu Y-F, Wang B-Q, Xue X-X, Ma C-L (2017) Chemical-enzymatic conversion of corncob-derived xylose to furfuralcohol by the tandem catalysis with SO₄ ^2–/SnO₂-kaoline and E. coli CCZU-T15 cells in toluene–water media. Bioresour Technol 245:841-849. https://doi.org/10.1016/j.biortech.2017.08.219

He YC, Jiang CX, Chong GG, Di JH, Ma CL (2018) Biological synthesis of 2,5-bis(hydroxymethyl)furan from biomass-derived 5-hydroxymethylfurfural by E. coli CCZU-K14 whole cells. Bioresour Technol 247:1215-1220. https://doi.org/10.1016/j.biortech.2017.09.071

Hoyos P, Quezada MA, Sinisterra JV, Alcantara AR. Optimised dynamic kinetic resolution of benzoin by a chemoenzymatic approach in 2-MeTHF. J Mol Catal B: Enzym, 2011, 72(1–2): 20-24.

Hu Y-D, Zong M-H, Li N. Enzymatic synthesis and anti-oxidative activities of plant oil-based ascorbyl esters in 2-methyltetrahydrofuran-containing mixtures. Biocatal Biotransform, 2016, 34(4): 181-188.

Hu L, Xu J, Zhou S, He A, Tang X, Lin L, Xu J, Zhao Y. Catalytic advances in the production and application of biomass-derived 2,5-dihydroxymethylfuran. ACS Catal 82959 – 2980, 2018

Huang L, Wang L, Zhang Z, Guo X, Zhang X, Chabu JM, Liu P, Tang F (2022a) Understanding the promotional effects of trace doped Zn in Co/NC for efficient one-pot catalytic conversion of furfural to 2-methyl-tetrahydrofuran. J Energy Chem 71:225–233. https://doi.org/10.1016/j.jechem.2022.03.031

Huang ZX, Wang JH, Lei J, Zhao WG, Chen H, Yang YJ, Xu Q, Liu XX (2022b) Recent advances in the Catalytic Hydroconversion of 5-Hydroxymethylfurfural to Valuable Diols. Front Chem 10:925603. https://doi.org/10.3389/fchem.2022.925603

Klausli T. AVA Biochem: commercialising renewable platform chemical 5-HMF. Green Process Synth, 2014, 3(3): 235-236.

Lanza AM, Curran KA, Rey LG, Alper HS (2014) A condition-specific codon optimization approach for improved heterologous gene expression in Saccharomyces cerevisiae. BMC Syst Biol 8(1):33. https://doi.org/10.1186/1752-0509-8-33

Li N, Zong M-H. Chemo)biocatalytic upgrading of biobased furanic platforms to chemicals, fuels, and materials: a comprehensive review. ACS Catal, 2022, 12(16): 10080-10114.

Li Y-M, Zhang X-Y, Li N, Xu P, Lou W-Y, Zong M-H. Biocatalytic reduction of HMF to 2,5-bis(hydroxymethyl)furan by HMF-tolerant whole cells. Chemsuschem, 2017, 10(2): 372-378.

Lin C, Chai C, Li Y, Chen J, Lu Y, Wu H, Zhao L, Cao F, Chen K, Wei P, . CaCl₂ molten salt hydrate-promoted conversion of carbohydrates to 5-hydroxymethylfurfural: an experimental and theoretical study. Green Chem, 2021, 23(5): 2058-2068.

Liu B, Zhang Z. One-Pot Conversion of carbohydrates into Furan derivatives via Furfural and 5-Hydroxylmethylfurfural as intermediates. Chemsuschem, 2016, 9(16): 2015-2036.

Modig T, Liden G, Taherzadeh MJ (2002) Inhibition effects of furfural on alcohol dehydrogenase, aldehyde dehydrogenase and pyruvate dehydrogenase. Biochem J 363(3):769–776. https://doi.org/10.1042/0264-6021:3630769

Pace V, Hoyos P, Castoldi L, María PD, Alcántara AR. 2-Methyl-tetrahydrofuran (2-MeTHF): a biomass-derived solvent with broad application in organic chemistry. Chemsuschem, 2012, 5(8): 1369-1379.

Pan X, Wang X, Wu S, Xu L, Zhang L, Zhang Z, Li B, He X, Chang S. Insights into the molecular mechanism of a new efficient whole-cell biocatalyst Enterobacter ludwigii YYP3 in 5-hydroxymethylfurfural reduction. Green Chem, 2022, 24(22): 8691-8704.

Peng Y, Jiang L-Y, Di J-H, Ma C-L, Li Q, He Y-C. 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. ACS Sustainable Chem Eng, 2022, 10(37): 12165-12176.

Post C, Maniar D, Voet VSD, Folkersma R, Loos K. Biobased 2,5-Bis(hydroxymethyl)furan as a versatile building block for sustainable polymeric materials. ACS Omega, 2023, 8(10): 8991-9003.

Ren H, Zong M-H, Wu H, Li N. Efficient pretreatment of wheat straw using novel renewable cholinium ionic liquids to improve enzymatic saccharification. Ind Eng Chem Res, 2016, 55(6): 1788-1795.

Rudroff F, Mihovilovic MD, Gröger H, Snajdrova R, Iding H, Bornscheuer UT. Opportunities and challenges for combining chemo- and biocatalysis. Nat Catal, 2018, 1(1): 12-22.

Schmidt S, Castiglione K, Kourist R. Overcoming the incompatibility challenge in Chemoenzymatic and Multi-catalytic Cascade reactions. Chem Eur J, 2018, 24(8): 1755-1768.

Shanmuganathan S, Natalia D, van den Wittenboer A, Kohlmann C, Greiner L, Dominguez de Maria P. Enzyme-catalyzed C-C bond formation using 2-methyltetrahydrofuran (2-MTHF) as (co)solvent: efficient and bio-based alternative to DMSO and MTBE. Green Chem, 2010, 12(12): 2240-2245.

Sheldon RA (2018) Chemicals from renewable biomass: a renaissance in carbohydrate chemistry. Curr Opin Green Sustainable Chem 14:89–95. https://doi.org/10.1016/j.cogsc.2018.08.003

Sultan M, Amstislavskiy V, Risch T, Schuette M, Dökel S, Ralser M, Balzereit D, Lehrach H, Yaspo M-L. Influence of RNA extraction methods and library selection schemes on RNA-seq data. BMC Genomics, 2014, 15(1): 675.

Turkin AA, Makshina EV, Sels BF. Catalytic Hydroconversion of 5-HMF to Value-added chemicals: insights into the role of Catalyst properties and Feedstock Purity. Chemsuschem, 2022, 15(13): e202200412.

van Putten R-J, van der Waal JC, de Jong E, Rasrendra CB, Heeres HJ, de Vries JG. Hydroxymethylfurfural, a versatile platform chemical made from renewable resources. Chem Rev, 2013, 113(3): 1499-1597.

Wang J-P, Zong M-H, Li N. Photobiocatalysis: a promising tool for sustainable synthesis. Chem Catal, 2024

Wrigstedt P, Keskiväli J, Perea-Buceta JE, Repo T. One-Pot Transformation of carbohydrates into Valuable Furan derivatives via 5-Hydroxymethylfurfural. ChemCatChem, 2017, 9(22): 4244-4255.

Wu Q, Zong M-H, Li N (2023) One-Pot Chemobiocatalytic production of 2,5-Bis(hydroxymethyl)furan and its Diester from Biomass in Aqueous Media. ACS Catal 13:9404–9414. https://doi.org/10.1021/acscatal.3c01216

Xia Z-H, Zong M-H, Li N (2020) Catalytic synthesis of 2,5-bis(hydroxymethyl)furan from 5-hydroxymethylfurfual by recombinant Saccharomyces cerevisiae. Enzyme Microb Technol 134:109491. https://doi.org/10.1016/j.enzmictec.2019.109491

Xia J, Jiang S, Liu J, Yang W, Qiu Z, Liu X, He A, Li D, Xu J (2023) Efficient reduction of 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan by Bacillus subtilis HA70 whole cells. Mol Catal 542:113122. https://doi.org/10.1016/j.mcat.2023.113122

Xu Z-H, Cheng A-D, Xing XP, Zong M-H, Bai Y-P, Li N (2018) Improved synthesis of 2,5-bis(hydroxymethyl)furan from 5-hydroxymethylfurfural using acclimatized whole cells entrapped in calcium alginate. Bioresour Technol 262:177–183. https://doi.org/10.1016/j.biortech.2018.04.077

Xu C, Paone E, Rodríguez-Padrón D, Luque R, Mauriello F. Recent catalytic routes for the preparation and the upgrading of biomass derived furfural and 5-hydroxymethylfurfural. Chem Soc Rev, 2020, 49(13): 4273-4306.

Zhao W, Wang F, Zhao K, Liu X, Zhu X, Yan L, Yin Y, Xu Q, Yin D. Recent advances in the catalytic production of bio-based diol 2,5-bis(hydroxymethyl)furan. Carbon Resour Conv, 2023, 6(2): 116-131.

Funding

National Natural Science Foundation of China(22078110); National Key Research and Development Program of China(2021YFC2102700)