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Laccase-mediated synthesis of lignin-core hyperbranched copolymers

  • Biotechnological products and process engineering
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Abstract

Lignin, one of the major chemical constituents of woody biomass, is the second most abundant biopolymer found in nature. The pulp and paper industry has long produced lignin on the scale of millions of tons annually as a by-product of the pulping process, and the dawn of cellulosic ethanol production has further contributed to this amount. Historically, lignin has been perceived as a waste material and burned as a fuel for the pulping process. However, recent research has been geared toward developing cost-effective technologies to convert lignin into valuable commodities. Attributing to the polyphenolic structure of lignin, enzymatic modification of its surface using laccases (benzenediol:oxygen oxidoreductases, EC 1.10.3.2) has demonstrated to be highly successful. The current study aims at developing lignin-core hyperbranched copolymers via the laccase-assisted copolymerization of kraft lignin with methylhydroquinone and a trithiol. Based on the physical properties of the resulting material, it is likely that crosslinking reactions have taken place during the drying process to produce a copolymeric network rather than discrete hyperbranched copolymers, with NMR data providing evidence of covalent bonding between monomers. Preliminary thermal analysis data reveals that the copolymeric material possesses a moderate glass transition temperature and exhibits good thermostability, thus may have potential application as a lignin-based thermoplastic. Scanning electron microscopy images confirm the smooth, glossy surface of the material and that it is densely packed. The presented results are a sustainable, ecofriendly, economic method to create an exciting novel biomaterial from a renewable feedstock while further enhancing lignin valorization.

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References

  • Aracri E, Diaz Blanco C, Tzanov T (2014) An enzymatic approach to develop a lignin-based adhesive for wool floor coverings. Green Chem 16(5):2597–2603

    Article  CAS  Google Scholar 

  • Barbaro P, Bianchini C, Scapacci G, Masi D, Zanello P (1994) Dioxomolybdenum (VI) complexes stabilized by polydentate ligands with NO3, N2O2, and NS2 donor-atom sets. Inorg Chem 33(14):3180–3186

    Article  CAS  Google Scholar 

  • Cannatelli MD, Ragauskas AJ (2015a) Value added biomaterials via laccase-mediated surface functionalization. J Biotechnol Biomater 5(1):1–2

    Article  Google Scholar 

  • Cannatelli MD, Ragauskas AJ (2015b) Laccase-catalyzed synthesis of 2,3-ethylenedithio-1,4-quinones. J Mol Catal B Enzym 119:85–89

    Article  CAS  Google Scholar 

  • Cannatelli MD, Ragauskas AJ (2016) Conversion of lignin into value-added materials and chemicals via laccase-assisted copolymerization. Appl Microbiol Biotechnol 100(20):8685–8691

    Article  CAS  PubMed  Google Scholar 

  • Cannatelli MD, Ragauskas AJ (2017) Two decades of laccases: advancing sustainability in the chemical industry. Chem Rec 17(1):122–140

    Article  CAS  PubMed  Google Scholar 

  • Cateto CA, Barreiro MF, Rodrigues AE, Brochier-Salon MC, Thielemans W, Belgacem MN (2008) Lignins as macromonomers for polyurethane synthesis: a comparative study on hydroxyl group determination. J Appl Polym Sci 109(5):3008–3017

    Article  CAS  Google Scholar 

  • Froass PM (1996) Structural changes in lignin during kraft pulping and chlorine dioxide bleaching. Dissertation, Institute of Paper Science and Technology, Atlanta, USA

  • Granata A, Argyropoulos DS (1995) 2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, a reagent for the accurate determination of the uncondensed and condensed phenolic moieties in lignins. J Agric Food Chem 43(6):1538–1544

    Article  CAS  Google Scholar 

  • Hüttermann A, Mai C, Kharazipour A (2001) Modification of lignin for the production of new compounded materials. Appl Microbiol Biotechnol 55(4):387–394

    Article  PubMed  Google Scholar 

  • Ibrahim V, Mamo G, Gustafsson PJ, Hatti-Kaul R (2013) Production and properties of adhesives formulated from laccase modified kraft lignin. Ind Crop Prod 45:343–348

    Article  CAS  Google Scholar 

  • Kai D, Low ZW, Liow SS, Karim AA, Ye H, Jin G, Li K, Loh XJ (2016) Development of lignin supramolecular hydrogels with mechanically responsive and self-healing properties. ACS Sustain Chem Eng 3(9):2160–2169

    Article  Google Scholar 

  • Kalia S, Thakur K, Kumar A, Celli A (2014) Laccase-assisted surface functionalization of lignocellulosics. J Mol Catal B Enzym 102:48–58

    Article  CAS  Google Scholar 

  • Kosa M (2012) Direct and multistep conversion of lignin to biofuels. Dissertation, Georgia Institute of Technology, Atlanta, USA

  • Langholtz M, Downing M, Graham R, Baker F, Compere A, Griffith W, Boeman R, Keller M (2014) Lignin-derived carbon fiber as a co-product of refining cellulosic biomass. SAE Int J Mater Manf 7(1):115–121

    Article  Google Scholar 

  • Li H, Sivasankarapillai G, McDonald AG (2014) Lignin valorization by forming thermally stimulated shape memory copolymeric elastomers—partially crystalline hyperbranched polymer as crosslinks. J Appl Polym Sci 131(22):41103/1–41103/10

    CAS  Google Scholar 

  • Lora JH, Glasser WG (2002) Recent industrial applications of lignin: a sustainable alternative to nonrenewable materials. J Polym Environ 10(1):39–48

    Article  CAS  Google Scholar 

  • Messerschmidt A (1997) Multi-copper oxidases. World Scientific, Singapore

    Book  Google Scholar 

  • Milstein O, Hüttermann A, Fründ R, Lüdemann HD (1994) Enzymatic co-polymerization of lignin with low-molecular mass compounds. Appl Microbiol Biotechnol 40(5):760–767

    Article  CAS  Google Scholar 

  • Ragauskas AJ, Williams CK, Davison BH, Britovsek G, Cairney J, Eckert CA, Frederick WJ Jr, Hallett JP, Leak DJ, Liotta CL, Mielenz JR, Murphy R, Templer R, Tschaplinski T (2006) The path forward for biofuels and biomaterials. Science 311(5760):484–489

    Article  CAS  PubMed  Google Scholar 

  • Ragauskas AJ, Beckham GT, Biddy MJ, Chandra R, Chen F, Davis MF, Davison BH, Dixon RA, Gilna P, Keller M, Langan P, Naskar AK, Saddler JN, Tschaplinski TJ, Tuskan GA, Wyman CE (2014) Lignin valorization: improving lignin processing in the biorefinery. Science 344(6185):1246843

    Article  PubMed  Google Scholar 

  • Saito T, Brown RH, Hunt MA, Pickel DL, Pickel JM, Messman JM, Baker FS, Keller M, Naskar AK (2012) Turning renewable resources into value-added polymer: development of lignin-based thermoplastic. Green Chem 14(12):3295–3303

    Article  CAS  Google Scholar 

  • Sealey J, Ragauskas AJ (1998) Residual lignin studies of laccase-delignified kraft pulps. Enzym Microb Technol 23(7–8):422–426

    Article  CAS  Google Scholar 

  • Sivasankarapillai G, McDonald AG, Li H (2012) Lignin valorization by forming toughened lignin-co-polymers: development of hyperbranched prepolymers for cross-linking. Biomass Bioenergy 47:99–108

    Article  CAS  Google Scholar 

  • Solomon EI, Augustine AJ, Yoon J (2008) O2 reduction to H2O by the multicopper oxidases. Dalton Trans 30:3921–3932

    Article  Google Scholar 

  • Stahel WR (2016) Circular economy. Nature 531(7595):435–438

    Article  CAS  PubMed  Google Scholar 

  • Sun M, Hong CY, Pan CY (2012) A unique aliphatic tertiary amine chromophore: fluorescence, polymer structure, and application in cell imaging. J Am Chem Soc 134(51):20581–20584

    Article  CAS  PubMed  Google Scholar 

  • Thurston CF (1994) The structure and function of fungal laccases. Microbiology 140(1):19–26

    Article  CAS  Google Scholar 

  • Vanholme R, Demedts B, Morreel K, Ralph J, Boerjan W (2010) Lignin biosynthesis and structure. Plant Physiol 153(3):895–905

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Wolfenden BS, Willson RL (1982) Radical-cations as reference chromogens in kinetic studies of one electron transfer reactions: pulse radiolysis studies of 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulphonate). J Chem Soc Perkin Trans II 7:805–812

  • Zawadzki M, Ragauskas AJ (2001) N-hydroxy compounds as new internal standards for the 31P-NMR determination of lignin hydroxy functional groups. Holzforschung 55(3):283–285

    Article  CAS  Google Scholar 

  • Zheng Y, Li S, Weng Z, Gao C (2015) Hyperbranched polymers: advances from synthesis to applications. Chem Soc Rev 44(12):4091–4130

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgments

The authors are thankful for a student fellowship supported by the Renewable Bioproducts Institute at Georgia Institute of Technology. The authors would also like to thank Dr. Y. Berta for her assistance in gathering SEM images and Brett Hester for his help with TGA experiments.

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Correspondence to Arthur J. Ragauskas.

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This article does not contain any studies with human participants or animals performed by any of the authors.

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This study was funded by a student fellowship supported by the Renewable Bioproducts Institute at Georgia Institute of Technology.

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The authors declare that they have no conflict of interest.

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Cannatelli, M.D., Ragauskas, A.J. Laccase-mediated synthesis of lignin-core hyperbranched copolymers. Appl Microbiol Biotechnol 101, 6343–6353 (2017). https://doi.org/10.1007/s00253-017-8325-2

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