Tandem Biocatalysis by CotA-TJ102@UIO-66-NH₂ and Novozym 435 for Highly Selective Transformation of HMF into FDCA

Abstract

2,5-Furandicarboxylic acid (FDCA) is a potential biorenewable chemical for applications including plastics, polyamides, drugs, etc. The selective biosynthesis of FDCA from 5-hydroxymethylfurfural (HMF) by a specific enzyme poses a great challenge. In this study, we reported an efficient strategy to produce FDCA from HMF by the tandem biocatalysis of laccase (CotA-TJ102@UIO-66-NH₂) and Novozym 435. For the first step, a nanoparticle metal–organic framework was synthesized as a carrier to immobilize CotA-TJ102@UIO-66-NH₂, which was assigned for the production of 5-formyl-2-furancarboxylic acid (FFCA) and featured an enzyme loading of 255.54 mg/g, specific activity of 135.90 U/mg, and solid loading ratio of 99.65%. Under optimal conditions, an ideal FFCA yield of 98.5% was achieved, and the CotA-TJ102@UIO-66-NH₂ presented a high recycling capacity after 10 cycles. For the second step, Novozym 435 was applied for the further conversion of FFCA into FDCA, presenting a high FDCA yield of 95.5% under the optimized conditions. Novozym 435 also exhibited a high recyclability after eight cycles. As a result, the tandem biocatalysis strategy provided a 94.2% FDCA yield from HMF, indicating its excellence as a method for FDCA production.

Keywords

CotA-TJ102@UIO-66-NH₂ / Novozym 435 / Tandem biocatalysis / 5-Hydroxymethylfurfural / 2, 5-Furandicarboxylic acid

References

[1] Liu DJ, Chen EYX. Integrated catalytic process for biomass conversion and upgrading to C12 furoin and alkane fuel. ACS Catal, 2014, 4(5): 1302-1310.

[2] Casoni AI, Hoch PM, Volpe MA, et al. Catalytic conversion of furfural from pyrolysis of sunflower seed hulls for producing bio-based furfuryl alcohol. J Clean Prod, 2018, 178: 237-246.

[3] Jaafari L, Ibrahim H, Jaffary B, et al. Catalytic production of furfural by pressurized liquid water liquefaction of flax straw. Renew Energy, 2019, 130: 1176-1184.

[4] Li HL, Deng AJ, Ren JL, et al. Catalytic hydrothermal pretreatment of corncob into xylose and furfural via solid acid catalyst. Bioresour Technol, 2014, 158: 313-320.

[5] Ren SJ, Lei HW, Wang L, et al. Microwave torrefaction of Douglas fir sawdust pellets. Energy Fuels, 2012, 26(9): 5936-5943.

[6] Wang Q, Hou W, Li S, et al. Hydrophilic mesoporous poly(ionic liquid)-supported Au–Pd alloy nanoparticles towards aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid under mild conditions. Green Chem, 2017, 19(16): 3820-3830.

[7] Qin YZ, Li YM, Zong MH, et al. Enzyme-catalyzed selective oxidation of 5-hydroxymethylfurfural (HMF) and separation of HMF and 2,5-diformylfuran using deep eutectic solvents. Green Chem, 2015, 17(7): 3718-3722.

[8] Buonerba A, Impemba S, Litta AD, et al. Aerobic oxidation and oxidative esterification of 5-hydroxymethylfurfural by gold nanoparticles supported on nanoporous polymer host matrix. Chemsuschem, 2018, 11(18): 3139-3149.

[9] Nguyen CV, Liao YT, Kang TC, et al. A metal-free, high nitrogen-doped nanoporous graphitic carbon catalyst for an effective aerobic HMF-to-FDCA conversion. Green Chem, 2016, 18(22): 5957-5961.

[10] Dick GR, Frankhouser AD, Banerjee A, et al. A scalable carboxylation route to furan-2,5-dicarboxylic acid. Green Chem, 2017, 19(13): 2966-2972.

[11] Wang F, Zhang ZH. Cs-substituted tungstophosphate-supported ruthenium nanoparticles: an effective catalyst for the aerobic oxidation of 5-hydroxymethylfurfural into 5-hydroxymethyl-2-furancarboxylic acid. J Taiwan Inst Chem Eng, 2017, 70: 1-6.

[12] Moreau C, Belgacem MN, Gandini A. Recent catalytic advances in the chemistry of substituted furans from carbohydrates and in the ensuing polymers. Top Catal, 2004, 27(1–4): 11-30.

[13] Gandini A, Silvestre AJD, Neto CP, et al. The furan counterpart of poly(ethylene terephthalate): an alternative material based on renewable resources. J Polym Sci A Polym Chem, 2009, 47(1): 295-298.

[14] Zhu JH, Cai JL, Xie WC, et al. Poly(butylene 2,5-furan dicarboxylate), a biobased alternative to PBT: synthesis, physical properties, and crystal structure. Macromolecules, 2013, 46(3): 796-804.

[15] Vilela C, Sousa AF, Fonseca AC, et al. The quest for sustainable polyesters—insights into the future. Polym Chem, 2014, 5(9): 3119-3141.

[16] Yang ZZ, Qi W, Su RX, et al. Selective synthesis of 2,5-diformylfuran and 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural and fructose catalyzed by magnetically separable catalysts. Energy Fuels, 2017, 31(1): 533-541.

[17] Antonyraj CA, Huynh NTT, Park SK, et al. Basic anion-exchange resin (AER)-supported Au-Pd alloy nanoparticles for the oxidation of 5-hydroxymethyl-2-furfural (HMF) into 2, 5-furan dicarboxylic acid (FDCA). Appl Catal A Gen, 2017, 547: 230-236.

[18] Xia HA, An JH, Hong M, et al. Aerobic oxidation of 5-hydroxymethylfurfural to 2, 5-difurancarboxylic acid over Pd-Au nanoparticles supported on Mg-Al hydrotalcite. Catal Today, 2019, 319: 113-120.

[19] Saha B, Dutta S, Abu-Omar MM. Aerobic oxidation of 5-hydroxylmethylfurfural with homogeneous and nanoparticulate catalysts. Catal Sci Technol, 2012, 2(1): 79-81.

[20] Mei N, Liu B, Zheng JD, et al. A novel magnetic palladium catalyst for the mild aerobic oxidation of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid in water. Catal Sci Technol, 2015, 5(6): 3194-3202.

[21] Han XW, Li CQ, Liu XH, et al. Selective oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid over MnOx–CeO₂ composite catalysts. Green Chem, 2017, 19(4): 996-1004.

[22] Gao TY, Yin YX, Fang WH, et al. Highly dispersed ruthenium nanoparticles on hydroxyapatite as selective and reusable catalyst for aerobic oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid under base-free conditions. Mol Catal, 2018, 450: 55-64.

[23] Gao TY, Chen J, Fang WH, et al. Ru/Mn _XCe₁O _Y catalysts with enhanced oxygen mobility and strong metal-support interaction: exceptional performances in 5-hydroxymethylfurfural base-free aerobic oxidation. J Catal, 2018, 368: 53-68.

[24] Braun M, Antonietti M. A continuous flow process for the production of 2, 5-dimethylfuran from fructose using (non-noble metal based) heterogeneous catalysis. Green Chem, 2017, 19(16): 3813-3819.

[25] Insyani R, Verma D, Kim SM, et al. Direct one-pot conversion of monosaccharides into high-yield 2,5-dimethylfuran over a multifunctional Pd/Zr-based metal–organic framework@sulfonated graphene oxide catalyst. Green Chem, 2017, 19(11): 2482-2490.

[26] D’Acunzo F, Baiocco P, Fabbrini M, et al. A mechanistic survey of the oxidation of alcohols and ethers with the enzyme laccase and its mediation by TEMPO. Eur J Org Chem, 2002, 24: 4195-4201.

[27] McKenna SM, Mines P, Law P, et al. The continuous oxidation of HMF to FDCA and the immobilisation and stabilisation of periplasmic aldehyde oxidase (PaoABC). Green Chem, 2017, 19(19): 4660-4665.

[28] Koopman F, Wierckx N, de Winde JH, et al. Identification and characterization of the furfural and 5-(hydroxymethyl)furfural degradation pathways of Cupriavidus basilensis HMF₁₄. Proc Natl Acad Sci, 2010, 107(11): 4919-4924.

[29] Dijkman WP, Groothuis DE, Fraaije MW. Enzyme-catalyzed oxidation of 5-hydroxymethylfurfural to furan-2,5-dicarboxylic acid. Angew Chem Int Ed, 2014, 53(25): 6515-6518.

[30] Wang KF, Liu CL, Sui KY, et al. Efficient catalytic oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid by magnetic laccase catalyst. ChemBioChem, 2018, 19(7): 654-659.

[31] Fan LL, Wang Y, Zhao M, et al. Magnetic Ganoderma lucidum spore microspheres: a novel material to immobilize CotA multicopper oxidase for dye decolorization. J Hazard Mater, 2016, 313: 122-129.

[32] Wang TN, Lu L, Wang JY, et al. Enhanced expression of an industry applicable CotA laccase from Bacillus subtilis in Pichia pastoris by non-repressing carbon sources together with pH adjustment: recombinant enzyme characterization and dye decolorization. Process Biochem, 2015, 50(1): 97-103.

[33] Chiplunkar PP, Zhao XM, Tomke PD, et al. Ultrasound-assisted lipase catalyzed hydrolysis of aspirin methyl ester. Ultrason Sonochemistry, 2018, 40: 587-593.

[34] Jahangiri A, Møller AH, Danielsen M, et al. Hydrophilization of bixin by lipase-catalyzed transesterification with sorbitol. Food Chem, 2018, 268: 203-209.

[35] Arcens D, Grau E, Grelier S, et al. 6-O-glucose palmitate synthesis with lipase: investigation of some key parameters. Mol Catal, 2018, 460: 63-68.

[36] Chen Y, Cheong LZ, Zhao JH, et al. Lipase-catalyzed selective enrichment of omega-3 polyunsaturated fatty acids in acylglycerols of cod liver and linseed oils: modeling the binding affinity of lipases and fatty acids. Int J Biol Macromol, 2019, 123: 261-268.

[37] Patil HS, Jadhav DD, Paul A, et al. Lipase catalyzed synthesis of antimicrobial andrographolide derivatives. Data Brief, 2018, 18: 1134-1141.

[38] Park S, Doan TTN, Koo YM, et al. Ionic liquids as cosolvents for the lipase-catalyzed kinetic resolution of ketoprofen. Mol Catal, 2018, 459: 113-118.

[39] Bhushan I, Saraswat R, Gupta P, et al. Enantioselective resolution of 2-arylpropionic acid derivatives employing immobilization of lipase from Bacillussubtilis strain Kakrayal_1 (BSK-L). Bioresour Technol, 2018, 269: 581-585.

[40] Zeng ZM, Tian LJ, Li Z, et al. Whole-cell method for phenol detection based on the color reaction of phenol with 4-aminoantipyrine catalyzed by CotA laccase on endospore surfaces. Biosens Bioelectron, 2015, 69: 162-166.

[41] Zhang CY, Chang X, Zhu L, et al. Highly efficient and selective production of FFCA from CotA-TJ102 laccase-catalyzed oxidation of 5-HMF. Int J Biol Macromol, 2019, 128: 132-139.

[42] Cao SL, Yue DM, Li XH, et al. Novel nano/micro-biocatalyst: soybean epoxide hydrolase immobilized on UiO-66-NH₂ MOF for efficient biosynthesis of enantipure (R)-1, 2-octanediol in deep eutectic solvents. ACS Sustain Chem Eng, 2016, 4(6): 3586-3595.

[43] Huo J, Aguilera-Sigalat J, El-Hankari S, et al. Magnetic MOF microreactors for recyclable size-selective biocatalysis. Chem Sci, 2015, 6(3): 1938-1943.

[44] Liu X, Qi W, Wang YF, et al. A facile strategy for enzyme immobilization with highly stable hierarchically porous metal–organic frameworks. Nanoscale, 2017, 9(44): 17561-17570.

[45] Hu JP, Yuan BN, Zhang YM, et al. Immobilization of laccase on magnetic silica nanoparticles and its application in the oxidation of guaiacol, a phenolic lignin model compound. RSC Adv, 2015, 5(120): 99439-99447.

[46] Krystof M, Pérez-Sánchez M, Domínguez de María P. Lipase-mediated selective oxidation of furfural and 5-hydroxymethylfurfural. ChemSusChem, 2013, 6(5): 826-830.

[47] Carboni-Oerlemans C, Domínguez de María P, Tuin B, et al. Hydrolase-catalysed synthesis of peroxycarboxylic acids: biocatalytic promiscuity for practical applications. J Biotechnol, 2006, 126(2): 140-151.

[48] Berkessel A, Andreae MRM. Efficient catalytic methods for the Baeyer–Villiger oxidation and epoxidation with hydrogen peroxide. Tetrahedron Lett, 2001, 42(12): 2293-2295.

[49] Hu YL, Dai LM, Liu DH, et al. Rationally designing hydrophobic UiO-66 support for the enhanced enzymatic performance of immobilized lipase. Green Chem, 2018, 20(19): 4500-4506.

[50] Gascón V, Carucci C, Jiménez MB, et al. Rapid in situ immobilization of enzymes in metal-organic framework supports under mild conditions. ChemCatChem, 2017, 9(7): 1182-1186.

[51] Xia GH, Cao SL, Xu P, et al. Inside cover: preparation of a nanobiocatalyst by efficiently immobilizing aspergillus Niger lipase onto magnetic metal-biomolecule frameworks (BioMOF). ChemCatChem, 2017, 9(10): 1719