Abstract
In this study, a green and effective stepwise catalytic system for cellulose conversion to 5-hydroxymethylfurfural (HMF) is reported. In a pretreatment process, very fast (15 min) dissolution of cellulose was achieved at a low temperature of 70 °C, utilizing ZnBr2·4H2O as the best dissolution solvent, which to improve the reactivity of cellulase for raw cellulose and increase efficiency of cellulose degradation. Enzyme-inorganic hybrid nanoflowers (Cellulase@β-glucosidase/Zn3(PO4)2-NF and Glucose isomerase@Zn3(PO4)2-NF) with different morphological structures were prepared to act as biocatalyst in the sequential conversion of pretreated cellulose to glucose and glucose to fructose. HCl was applied catalyst for dehydration of fructose to 5-HMF in a water/tert-butanol biphasic system. Under optimal reaction conditions, the yield of 5-HMF for the overall reaction from cellulose was about 21.6%. A feasibility route for green conversion of cellulose to 5-HMF is reported.
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The authors declare that [the/all other] data supporting the findings of this study are available within the article [and its supplementary information files] Competing interests. Additional data available upon request.
References
Alfred DF (2017) Glucose, not cellobiose, is the repeating unit of cellulose and why that is important. Cellulose 24:4605–4609. https://doi.org/10.1007/s10570-017-1450-3
Amatto IVD, Rosa-Garzon NG, Simoes FAD, Santiago F, Leite NPD, Martins JR, Cabral H (2022) Enzyme engineering and its industrial applications. Biotechnol Appl Biochem 69:389–409. https://doi.org/10.1002/bab.2117
Awosusi AA, Ayeni A, Adeleke R, Daramola MO (2017) Effect of water of crystallization on the dissolution efficiency of molten zinc chloride hydrate salts during the pre-treatment of corncob biomass. J Chem Technol Biotechnol 92:2468–2476. https://doi.org/10.1002/jctb.5266
Bohre A, Modak A, Chourasia V, Jadhao PR, Sharma K, Pant KK (2022) Recent advances in supported ionic liquid catalysts for sustainable biomass valorisation to high-value chemicals and fuels. Chem Eng J 450:138032. https://doi.org/10.1016/j.cej.2022.138032
Bornscheuer UT, Huisman GW, Kazlauskas RJ, Lutz S, Moore JC, Robins K (2012) Engineering the third wave of biocatalysis. Nature 485:185–194. https://doi.org/10.1038/nature11117
Cai X, Wang ZC, Ye YY, Wang D, Zhang ZX, Zheng ZF, Liu YQ, Li SR (2021) Conversion of chitin biomass into 5-hydroxymethylfurfural: A review. Renew Sustain Energy Rev 150:111452. https://doi.org/10.1016/j.rser.2021.111452
Fischer S, Leipner H, Thümmler K, Brendler E, Peters J (2003) Inorganic molten salts as solvents for cellulose. Cellulose 10:227–236. https://doi.org/10.1023/A:1025128028462
Gao J, Kong W, Zhou L, He Y, Ma L, Wang Y, Yin LY, Jiang YJ (2017) Monodisperse core-shell magnetic organosilica nanoflowers with radial wrinkle for lipase immobilization. Chem Eng J 309:70–79. https://doi.org/10.1016/j.cej.2016.10.021
Ge J, Lei JD, Zare RN (2012) Protein-inorganic hybrid nanoflowers. Nat Nanotechnol 7:428–432. https://doi.org/10.1038/nnano.2012.80
Gschwend FJV, Malaret F, Shinde S, Brandt-Talbot A, Hallett JP (2018) Rapid pretreatment of Miscanthus using the low-cost ionic liquid triethylammonium hydrogen sulfate at elevated temperatures. Green Chem 20:3486–3498. https://doi.org/10.1039/C8GC00837J
Han J, Luo P, Wang L, Wu JC, Li CM, Wang Y (2020) Construction of a Multienzymatic Cascade Reaction System of Coimmobilized Hybrid Nanoflowers for Efficient Conversion of Starch into Gluconic Acid. ACS Appl Mater Interfaces 12:15023–15033
Huang RL, Qi W, Su R, He ZM (2010) Integrating enzymatic and acid catalysis to convert glucose into 5-hydroxymethylfurfural. Chem Commun 46:1115–1117. https://doi.org/10.1039/B921306F
Ishizawa CI, Davis MF, Schell DF, Johnson DK (2007) Porosity and its effect on the digestibility of dilute sulfuric acid pretreated corn stover. J Agric Food Chem 55:2575–2581. https://doi.org/10.1021/jf062131a
Lara-Serrano M, Morales-delaRosa S, Campos-Martin JM, Fierro JLG (2022) High enhancement of the hydrolysis rate of cellulose after pretreatment with inorganic salt hydrates. Green Chem 12:3860–3866. https://doi.org/10.1039/D0GC01066A
Li CM, Chen G, Sun JX, Feng YJ, Liu JJ, Dong HJ (2015) Ultrathin nanoflakes constructed erythrocyte-like Bi2WO6 hierarchical architecture via anionic self-regulation strategy for improving photocatalytic activity and gas-sensing property. Appl Catal B 163:415–423. https://doi.org/10.1016/j.apcatb.2014.07.060
Mascal M (2015) 5-(chloromethyl) furfural is the new HMF: functionally equivalent but more practical in terms of its production from biomass. Chemsuschem 8:3391–3395. https://doi.org/10.1002/cssc.201500940
Mascal M, Dutta S (2011) Synthesis of the natural herbicide δ-aminolevulinic acid from cellulose-derived 5-(chloromethyl) furfural. Green Chem 13:40–41. https://doi.org/10.1039/C0GC00548G
McNeff CV, Nowlan DT, McNeff LC, Yan BW, Fedie RL (2010) Continuous production of 5-hydroxymethylfurfural from simple and complex carbohydrates. Appl Catal A 384:65–69. https://doi.org/10.1016/j.apcata.2010.06.008
Moreau C, Durand R, Razigade S, Duhamet J, Faugeras P, Rivalier P, Ros P, Avignon G (1996) Dehydration of fructose to 5-hydroxymethylfurfural over H-mordenites. Appl Catal A 145:211–224. https://doi.org/10.1016/0926-860X(96)00136-6
Moreau C, Belgacem MN, Gandini A (2004) Recent catalytic advances in the chemistry of substituted furans from carbohydrates and in the ensuing polymers. Top Catal 27:11–30. https://doi.org/10.1002/chin.200431251
Nakamura E, Ozaki N, Oaki Y, Imai H (2021) Cellulose intrafibrillar mineralization of biological silica in a rice plant. Sci Rep 11:1–7. https://doi.org/10.1038/s41598-021-87144-8
Pena CA, Soto A, King AWT, Rodriguez H (2019) Improved reactivity of cellulose via its crystallinity reduction by nondissolving pretreatment with an ionic liquid. Acs Sustain Chem Eng 7:9164–9171. https://doi.org/10.1021/acssuschemeng.8b06357
Rollin JA, Tam TK, Zhang YHP (2013) New biotechnology paradigm: cell-free biosystems for biomanufacturing. Green Chem 15:1708–1719. https://doi.org/10.1039/C3GC40625C
Román-Leshkov Y, Barrett CJ, Liu ZY, Dusemic JA (2007) Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates. Nature 447:982–985. https://doi.org/10.1038/nature05923
Saikia K, Rathankumar AK, Kumar PS, Varjani S, Nizar M, Lenin R, Georgea J, Vaidyanathan VK (2022) Recent advances in biotransformation of 5-hydroxymethylfurfural: challenges and future aspects. J Chem Technol Biotechnol 97:409–419. https://doi.org/10.1002/jctb.6670
Sailer-Kronlachner W, Thoma C, Böhmdorfer S, Bacher M, Konnerth J, Rosenau T, Potthast A, Solt P, van Herwijnen H (2021) Sulfuric acid-catalyzed dehydratization of carbohydrates for the production of adhesive precursors. ACS Omega 25:16641–16648
Sen S, Losey BP, Gordon EE, Argyropoulos DS, Martin JD (2016) Ionic Liquid Character of Zinc Chloride Hydrates Define Solvent Characteristics that Afford the Solubility of Cellulose. J Phys Chem B 120:1134–1141. https://doi.org/10.1021/acs.jpcb.5b11400
Shen Y, Sun JK, Yi YY, Li MF, Wang B, Xu F, Sun RC (2014) InCl3-catalyzed conversion of carbohydrates into 5-hydroxymethylfurfural in biphasic system. Biores Technol 172:457–460. https://doi.org/10.1016/j.biortech.2014.09.077
Solanki P, Putatunda C, Kumar A, Bhatia R, Walia A (2021) Microbial proteases: ubiquitous enzymes with innumerable uses. 3 Biotech 11:428. https://doi.org/10.1007/s13205-021-02928-z
Sun LY, Han J, Wu JC, Huang WR, Li YY, Mao YL, Wang L, Wang Y (2022) Cellulose pretreatment with inorganic salt hydrate: dissolution, regeneration, structure and morphology. Cellulose 180:114722. https://doi.org/10.1016/j.indcrop.2022.114722
Velvizhi G, Balakumar K, Shetti NP, Ahmad E, Pant KK, Aminabhavi TM (2022) Integrated biorefinery processes for conversion of lignocellulosic biomass to value added materials: paving a path towards circular economy. Biores Technol 343:126151. https://doi.org/10.1016/j.biortech.2021.126151
Wang YP, Wang G, Cheng HT, Tian GL, Liu Z, Xiao QF, Zhou XQ, Han XJ, Gao XS (2010) Structures of bamboo fiber for textiles. Text Res J 80(4):334–343. https://doi.org/10.1177/0040517509337633
Wang L, Lan HL, Guan WM, Han J, Liu YH, Wang Y, Mao YL, Wang Y (2023) One-step purification of target enzymes using interaction- and structure-based design of aptamer-affinity responsive polymers: Selective immobilization and enhanced stability. Sep Purif Technol 307:122758. https://doi.org/10.1016/j.seppur.2022.122758
Wei WQ, Wu SB (2017) Depolymerization of cellulose into high-value chemicals by using synergy of zinc chloride hydrate and sulfate ion promoted titania catalyst. Biores Technol 241:760–766. https://doi.org/10.1016/j.biortech.2017.06.004
Wong JX, Ogura K, Chen SX, Rehm BHA (2020) Bioengineered polyhydroxyalkanoates as immobilized enzyme scaffolds for industrial applications. Front Bioeng Biotechnol 8:156. https://doi.org/10.3389/fbioe.2020.00156
Yan LS, Ma RS, Wei HX, Li LZ, Zou B, Xu YW (2019) Ruthenium trichloride catalyzed conversion of cellulose into 5-hydroxymethylfurfural in biphasic system. Biores Technol 279:84–91. https://doi.org/10.1016/j.biortech.2019.01.120
Yang YJ, Shin JM, Kang TH, Kimura S, Wada M, Kim UJ (2014) Cellulose dissolution in aqueous lithium bromide solutions. Cellulose 21:1175–1181. https://doi.org/10.1007/s10570-014-0183-9
Yu XX, Wang MM, Huang XR (2016) Spectroscopy and kinetics evidence for the hydrogen-bond activating effect of anion/cation of [Bmim] OAc on the hydrolysis of esters. J Mol Liq 216:354–359. https://doi.org/10.1016/j.molliq.2016.01.049
Zhang LL, Tian Y, Wang YY, Dai LY (2021a) Enhanced conversion of α-cellulose to 5-HMF in aqueous biphasic system catalyzed by FeCl3-CuCl2. Chin Chem Lett 32:2233–2238. https://doi.org/10.1016/j.cclet.2020.12.030
Zhang MR, Zhang Y, Yang CK, Ma CY, Tang JG (2021b) Enzyme-inorganic hybrid nanoflowers: classification, synthesis, functionalization and potential applications. Chem Eng J 415:129075. https://doi.org/10.1016/j.cej.2021.129075
Acknowledgments
Thank the National Natural Science Foundation of China (Nos. 22078133 and 22278191) for their help with this study.
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This work was supported by the National Natural Science Foundation of China (Nos. 22078133 and 22278191).
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TW: Methodology, Investigation, Formal analysis, Writing-Original Draft, Software, Validation, Investigation. CZ: Methodology, Investigation, Formal analysis, Writing-Original Draft, Data Curation, Software, Validation. HF: Validation, Formal analysis, Investigation, Methodology, Software. QZ: Methodology, Data Curation, Investigation, Project administration. WH: Investigation, Software, Methodology, Validation, Data Curation. JW: Methodology, Investigation, Data Curation, Software, Validation. JH: Conceptualization, Resources, Investigation, Methodology, Writing-Original Draft, Project administration, Data Curation, Funding acquisition. YW: Conceptualization, Resources, Project administration, Supervision, Funding acquisition, Investigation, Writing-Review & Editing.
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Wang, T., Zhang, C., Feng, H. et al. A novel strategy for highly efficient conversion of cellulose into 5-hydroxymethylfurfural using green and effective stepwise catalytic systems. Cellulose 30, 7575–7589 (2023). https://doi.org/10.1007/s10570-023-05378-3
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DOI: https://doi.org/10.1007/s10570-023-05378-3