Abstract
Recently, highly efficient production of valuable furan-based chemicals from available and renewable lignocellulosic biomass has attracted more and more attention via a chemoenzymatic route in an environmentally friendly reaction system. In this work, the feasibility of chemoenzymatically catalyzing sugarcane bagasse into furfurylamine with heterogeneous catalyst and ω-transaminase biocatalyst was developed in the deep eutectic solvent (DES) ChCl:Gly–water. Sulfonated Al-Laubanite was firstly synthesized to catalyze sugarcane bagasse to furfural. SEM, BET, XRD, and FT-IR were used to characterize Al-Laubanite. Catalyst Al-Laubanite structure was significantly different from carrier laubanite. High furfural yield (60.9%) was achieved by catalyzing sugarcane bagasse in 20 min at 170 ℃ and pH 1.0 by Al-Laubanite (2.4 wt%) in the presence of ChCl:Gly (20 wt%). Potential catalytic mechanism was proposed under the optimized catalytic condition. In addition, one recombinant E. coli CV harboring ω-transaminase could completely transform biomass-derived furfural to furfurylamine at 40 °C and pH 7.5 using L-alanine as amine donor in ChCl:Gly–water (20:80, wt:wt). This established chemoenzymatic cascade reaction strategy was successfully utilized for valorization of biomass into furan-based chemicals in the benign ChCl:Gly–water system.
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References
Jiang, Y., Liu, K., Zhang, H., Wang, Y., Yuan, Q., Su, N., Bao, J., & Fang, X. (2017). Gluconic acid production from potato waste by Gluconobacter oxidans using sequential hydrolysis and fermentation. ACS Sustainable Chemistry & Engineering, 5(7), 6116–6123.
Li, Y. Y., Li, Q., Zhang, P. Q., Ma, C. L., Xu, J. H., & He, Y. C. (2021). Catalytic conversion of corncob to furfuryl alcohol in tandem reaction with tin-loaded sulfonated zeolite and NADPH-dependent reductase biocatalyst. Bioresource Technology, 320, 124267.
Zhang, P., Liao, X., Ma, C., Li, Q., & He, Y. (2019). Chemoenzymatic conversion of corncob to furfurylamine via tandem catalysis with tin-based solid acid and transaminase biocatalyst. ACS Sustainable Chemistry & Engineering, 7(21), 17636–17642.
Audemar, M., Ciotonea, C., De Oliveira Vigier, K., Royer, S., Ungureanu, A., Dragoi, B., Dumitriu, E., & Jerome, F. (2015). Selective hydrogenation of furfural to furfuryl alcohol in the presence of a recyclable Cobalt/SCBA-15 catalyst. Chemsuschem, 8(11), 1885–1891.
Hu, D. X., Xiao, L., Li, L. Z., Zhong, C., Ju, X., Yan, L. S., & Wu, T. Y. (2016). Effects of ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate ([Emim]DEP) on cellulase produced by Paenibacillus sp. LLZ1. ACS Sustainable Chemistry & Engineering, 4(9), 4922–4926.
Wang, Z. K., Shen, X. J., Chen, J. J., Jiang, Y. Q., Hu, Z. Y., Wang, X., & Liu, L. (2018). Lignocellulose fractionation into furfural and glucose by AlCl3-catalyzed DES/MIBK biphasic pretreatment. International Journal of Biological Macromolecules, 117, 721–726.
de Souza, P. M., Silvester, L., da Silva, A. G. M., Fernandes, C. G., Rodrigues, T. G., Paul, S., Camargo, P. H. C., & Wojcieszak, R. (2019). Exploiting the synergetic behavior of PtPd bimetallic catalysts in the selective hydrogenation of glucose and furfural. Catalysts, 9(2), 132.
He, Y. C., Ding, Y., Ma, C. L., Di, J., Jiang, C., & Li, A. (2017). One-pot conversion of biomass-derived xylose to furfuralcohol by a chemo-enzymatic sequential acid-catalyzed dehydration and bioreduction. Green Chemistry, 19, 3844–3850.
Gong, L., Xu, Z. Y., Dong, J. J., Li, H., Han, R. Z., Xu, G. C., & Ni, Y. (2019). Composite coal fly ash solid acid catalyst in synergy with chloride for biphasic preparation of furfural from corn stover hydrolysate. Bioresource Technology, 293, 122065.
Le, G. S., David, G., Claire, C., Frederic, D., & Christophe, L. (2016). Furfural production from D-xylose and xylan by using stable Nafion NR50 and NaCl in a microwave-assisted biphasic reaction. Molecules, 21(8), 1102.
Dedes, G., Karnaouri, A., & Topakas, E. (2020). Novel routes in transformation of lignocellulosic biomass to furan platform chemicals: From pretreatment to enzyme catalysis. Catalysts, 10(7), 74.
Hashim, L. H., Halilu, A., Sudarsanam, P., Umar, Y. B., & Bhargava, S. K. (2020). Bifunctional rice husk-derived SiO2-Cu-Al-Mg nanohybrid catalyst for one-pot conversion of biomass-derived furfural to furfuryl acetate. Fuel, 275, 117953.
Wang, Z. W., Gong, C. J., & He, Y. C. (2020). Improved biosynthesis of 5-hydroxymethyl-2-furancarboxylic acid and furoic acid from biomass-derived furans with high substrate tolerance of recombinant Escherichia coli HMFOMUT whole-cells. Bioresource Technology, 303, 122930.
Wen, M., Zhang, X. Y., Zong, M. H., & Li, N. (2020). Significantly improved oxidation of bio-based furans into furan carboxylic acids using substrate-adapted whole cells. Journal of Energy Chemistry, 41, 20–26.
Xue, X. X., Ma, C. L., Di, J. H., Huo, X. Y., & He, Y. C. (2018). One-pot chemo-enzymatic conversion of D-xylose to furfuralcohol by sequential dehydration with oxalic acid plus tin-based solid acid and bioreduction with whole-cells. Bioresource Technology, 268, 292–299.
Delbecq, F., Takahashi, Y., Kondo, T., Corbas, C. C., Ramos, E. R., & Len, C. (2018). Microwave assisted efficient furfural production using nano-sized surface-sulfonated diamond powder. Catalysis Communications, 110, 74–78.
Wang, Y., Delbecq, F., Kwapinski, W., & Len, C. (2017). Application of sulfonated carbon-based catalyst for the furfural production from D-xylose and xylan in a microwave-assisted biphasic reaction. Molecular Catalysis, 438, 167–172.
Ye, L., Han, Y., Bai, H., & Lu, X. (2020). HZ-ZrP catalysts with adjustable ratio of Brønsted and Lewis acids for the one-pot value-added conversion of biomass-derived furfural. ACS Sustainable Chemistry & Engineering, 8(19), 7403–7413.
Zhang, T. W., Li, W. Z., An, S. X., Huang, F., Li, X. Z., Liu, J. R., Pei, G., & Liu, Q. Y. (2018). Efficient transformation of corn stover to furfural using p-hydroxybenzene sulfonic acid-formaldehyde resin solid acid. Bioresource Technology, 264, 261–267.
Li, H. L., Ren, J. L., Zhong, L. J., Sun, R. C., & Liang, L. (2015). Production of furfural from xylose, water-insoluble hemicelluloses and water-soluble fraction of corncob via a tin-loaded montmorillonite solid acid catalyst. Bioresource Technology, 176, 242–248.
Qi, L., Mui, Y. F., Lo, S. W., Lui, M. Y., Akien, G. R., & Horváth, I. T. (2014). Catalytic conversion of fructose, glucose, and sucrose to 5-(Hydroxymethyl)furfural and levulinic and formic acids in γ-valerolactone as a green solvent. ACS Catalysis, 4(5), 1470–1477.
Espinode los Ángeles Fernández, M. M., Gomez, F. J. V., & Silva, M. F. (2016). Natural designer solvents for greening analytical chemistry. TrAC-Trends in Analytical Chemistry, 76, 126–136.
Morais, E., Freire, M., Freire, C., Coutinho, J., & Silvestre, A. (2020). Enhanced conversion of xylan into furfural using acidic deep eutectic solvents with dual solvent and catalyst behavior. Chemsuschem, 13(4), 784–790.
Hou, X. D., Li, N., & Zong, M. H. (2013). Facile and simple pretreatment of sugar cane bagasse without size reduction using renewable ionic liquids-water mixtures. ACS Sustainable Chemistry & Engineering, 1(5), 519–526.
Bystrzanowska, M., & Tobiszewski, M. (2021). Assessment and design of greener deep eutectic solvents – A multicriteria decision analysis. Journal of Molecular Liquids, 321, 114878.
Xu, G. C., DingJ, C., & Han, R. Z. (2016). Biobutanol production from corn stover hydrolysate pretreated with recycled inoic liquid by Clostridium saccharobutylicum DSM 13864. Bioresource Technology, 203, 364–369.
Li, A., Hou, X., Lin, K., Zhang, X., & Fu, M. (2018). Rice straw pretreatment using deep eutectic solvents with different constituents molar ratios: Biomass fractionation, polysaccharides enzymatic digestion and solvent reuse. Journal of Bioscience and Bioengineering, 126(3), 346–354.
Chen, Z., Reznicek, W. D., & Wan, C. (2018). Aqueous choline chloride: A novel solvent for switchgrass fractionation and subsequent hemicellulose conversion into furfural. ACS Sustainable Chemistry & Engineering, 6(5), 6910–6919.
Dong, C. L., Wang, H. T., Du, H. C., Peng, J. B., Cai, Y., Guo, S., Zhang, J. L., Smart, C., & Ding, M. Y. (2020). Ru/HZSM-5 as an efficient and recyclable catalyst for reductive amination of furfural to furfurylamine. Molecular Catalysis, 482, 110755.
Chatterjee, M., Ishizaka, T., & Kawanami, H. (2016). Reductive amination of furfural to furfurylamine using aqueous ammonia solution and molecular hydrogen: An environmentally friendly approach. Green Chemistry, 18, 487–496.
Nishimura, S., Mizuhori, K., & Ebitani, K. (2016). Reductive amination of furfural toward furfurylamine with aqueous ammonia under hydrogen over Ru-supported catalyst. Reserach on Chemical Intermediates, 42, 19–30.
Liu, X. X., Wang, Y. X., Jin, S. W., Li, X., & Zhang, Z. H. (2020). High performance of nitrogen-doped carbon-supported cobalt catalyst for the mild and selective synthesis of primary amines. Arabian Journal of Chemistry, 13(4), 4916–4925.
Jin, M. J., Sousa, L. D., Schwartz, C., He, Y. X., Sarks, C., Gunawan, C., Balan, V., & Dale, B. E. (2016). Toward lower cost cellulosic biofuel production using ammonia based pretreatment technologies. Green Chemistry, 18, 957–966.
Chong, G. G., He, Y. C., Liu, Q. X., Kou, X. Q., Huang, X. J., Di, J. H., & Ma, C. L. (2017). Effective enzymatic in situ saccharification of bamboo shoot shell pretreated by dilute alkalic salts sodium hypochlorite/sodium sulfide pretreatment under the autoclave system. Bioresource Technology, 241, 726–734.
He, Y. C., Liu, F., Di, J. H., Ding, Y., Gao, D. Z., Zhang, D. P., Tao, Z. C., Chong, G. G., Huang, M. Z., & Ma, C. L. (2016). Effective pretreatment of dilute NaOH-soaked chestnut shell with glycerol–HClO4–water media: Structural characterization, enzymatic saccharification, and ethanol fermentation. Bioprocess and Biosystems Engineering, 39, 533–543.
Loow, Y. L., New, E. K., Yang, G. H., Ang, L. Y., Foo, L. Y. W., & Wu, T. Y. (2017). Potential use of deep eutectic solvents to facilitate lignocellulosic biomass utilization and conversion. Cellulose, 24, 3591–3618.
Bu, C., Yan, Y., Zou, L., Ouyang, S., Zheng, Z., & Ouyang, J. (2021). Comprehensive utilization of corncob for furfuryl alcohol production by chemo-enzymatic sequential catalysis in a biphasic system. Bioresource Technology, 319, 124156.
He, Y. C., Jiang, C. X., Chong, G. G., Di, J. H., & Ma, C. L. (2018). Biological synthesis of 2,5-bis(hydroxymethyl)furan from biomass-derived 5-hydroxymethylfurfural by E. coli CCZU-K14 whole cells. Bioresource Technology, 247, 121–1220.
Xu, J. X., Zhou, S. Y., Zhao, Y. J., Xia, J., Liu, X. Y., Xu, J. M., He, B. F., Wu, B., & Zhang, J. F. (2017). Asymmetric whole-cell bioreduction of sterically bulky 2-benzoylpyridine derivatives in aqueous hydrophilic ionic liquid media. Chemical Engineering Journal, 316, 919–927.
Ni, Y., Zhou, J. Y., & Sun, Z. H. (2012). Production of a key chiral intermediate of Betahistine with a newly isolated Kluyveromyces sp. in an aqueous two-phase system. Process Biochemistry, 47, 1042–1048.
Liu, Z. Q., Dong, S. C., Yin, H. H., Xue, Y. P., Tang, X. X., Zhang, X. J., He, J. Y., & Zheng, Y. G. (2017). Enzymatic synthesis of an ezetimibe intermediate using carbonyl reductase coupled with glucose dehydrogenase in an aqueous-organic solvent system. Bioresource Technology, 229, 26–32.
He, Y. C., Tao, Z. C., Ding, Y., Zhang, D. P., Wu, Y. Q., Liu, F., Xue, Y. F., Wang, C., & Xu, J. H. (2015). Journal of Biotechnology, 203, 62–67.
Liu, Y., Liu, P., Gao, S., Wang, Z., Luan, P., González-Sabín, J., & Jiang, Y. (2021). Construction of chemoenzymatic cascade reactions for bridging chemocatalysis and Biocatalysis: Principles, strategies and prospective. Chemical Engineering Journal, 420, 127659.
Xu, P., Du, P. X., Zong, M. H., Li, N., & Lou, W. Y. (2016). Combination of deep eutectic solvent and ionic liquid to improve biocatalytic reduction of 2-octanone with Acetobacter pasteurianus GIM1.158 cell. Scientific Reports, 6, 26518.
Szőllősi, G. (2018). Asymmetric one-pot reactions using heterogeneous chemical catalysis: Recent steps towards sustainable processes. Catalysis Science and Technology, 8(2), 389–422.
Xing, W. R., Xu, G. C., Dong, J. J., Han, R. Z., & Ni, Y. (2018). Novel dihydrogen-bonding deep eutectic solvents: Pretreatment of rice straw for butanol fermentation featuring enzyme recycling and high solvent yield. Chemical Engineering Journal, 333, 712–720.
Cai, R. F., Liu, L., Chen, F. F., Li, A., Xu, J. H., & Zheng, G. W. (2020). Reductive amination of biobased levulinic acid to unnatural chiral γ-amino acid using an engineered amine dehydrogenase. ACS Sustainable Chemistry & Engineering, 8(46), 17054–17061.
Xu, G. C., Dai, W., Wang, Y., Zhang, L., Sun, Z. W., Zhou, J. Y., & Ni, Y. (2020). Molecular switch manipulating Prelog priority of an alcohol dehydrogenase toward bulky-bulky ketones. Molecular Catalysis, 484, 110741.
Zhang, J. D., Zhao, J. W., Gao, L. L., Chang, H. H., Wei, W. L., & Xu, J. H. (2019). Enantioselective synthesis of enantiopure β-amino alcohols via kinetic resolution and asymmetric reductive amination by a robust transaminase from Mycobacterium vanbaalenii. Journal of Biotechnology, 290, 24–32.
Negro, M. J., Manzanares, P., Ballesteros, I., Oliva, J. M., Cabanas, A., & Ballesteros, M. (2003). Hydrothermal pretreatment conditions to enhance ethanol production from poplar biomass. Applied Biochemistry & Biotechnology, 105, 87–100.
Cotana, F., Cavalaglio, G., Gelosia, M., Coccia, V., Petrozzi, A., & Nicolini, A. (2014). Effect of double-step steam explosion pretreatment in bioethanol production from softwood. Applied Biochemistry & Biotechnology, 174(1), 156–167.
Funding
The authors gratefully acknowledge the National Natural Science Foundation of China (No. 21978072), Natural Science Foundation of the Jiangsu Higher Education Institutions of China (No. 20KJB350003), Open Funding Project of the State Key Laboratory of Biocatalysis and Enzyme Engineering (Hubei University), and Open Project of Jiangsu Key Laboratory for Biomass-based Energy and Enzyme Technology (No. BEETKB1902).
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Conceptualization and methodology: J. Di. Data analysis: Nana Zhao. Software: B. Fan. Writing original manuscript: J. Di. Review and revising manuscript: Y. He. Funding acquisition: Y. He, B. Fan, C. Ma. All authors reviewed and approved the final manuscript.
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Di, J., Zhao, N., Fan, B. et al. Efficient Valorization of Sugarcane Bagasse into Furfurylamine in Benign Deep Eutectic Solvent ChCl:Gly–Water. Appl Biochem Biotechnol 194, 2204–2218 (2022). https://doi.org/10.1007/s12010-021-03784-6
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DOI: https://doi.org/10.1007/s12010-021-03784-6