Abstract
Cellulose is lack of UV-blocking and antibacterial properties, which have limited its application. In this work, the nanoscale lignin with high content of hydroxyl groups and small particle size in prehydrolysate was isolated and used as a green reinforcement ingredient for fabrication of cellulose nanofibril (CNF) films with excellent mechanical properties, as well as UV protection and antibacterial capabilities. Cryogenic transmission electron microscopy (Cryo-TEM) and nuclear magnetic resonance analyses showed that the resulting lignin was in the form of nanoparticles (6–12 nm) with high phenolic hydroxyl contents (4.9 mmol/g). The optimum lignin inclusion rate of 5% allowed it to reinforce CNF composite film, increasing its tensile strength from 108.5 to 143.3 MPa. In addition, the film exhibited excellent UV protection capabilities. It blocked 91.5% of UV-A and 99.9% of UV-B light. Finally, the resulting lignin-based CNF films exhibited antibacterial activities against both Escherichia coli and Streptococcus hemolyticus. This work demonstrates the utility of nanoscale lignin from prehydrolysate can be used to produce cellulose-based composite films with valuable properties.
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References
Baurhoo B, Ruiz-Feria CA, Zhao X (2008) Purified lignin: nutritional and health impacts on farm animals—a review. Anim Feed Sci Technol 144:175–184. https://doi.org/10.1016/j.anifeedsci.2007.10.016
Bian H, Chen L, Gleisner R, Dai H, Zhu JY (2017) Producing wood-based nanomaterials by rapid fractionation of wood at 80 C using a recyclable acid hydrotrope. Green Chem 19:3370–3379. https://doi.org/10.1039/C7GC00669A
Bian H, Gao Y, Wang R, Liu Z, Wu W, Dai H (2018) Contribution of lignin to the surface structure and physical performance of cellulose nanofibrils film. Cellulose 25:1309–1318. https://doi.org/10.1007/s10570-018-1658-x
Bian H, Luo J, Wang R, Zhou X, Ni S, Shi R, Dai H (2019) Recyclable and reusable maleic acid for efficient production of cellulose nanofibrils with stable performance. ACS Sustain Chem Eng 7:20022–20031. https://doi.org/10.1021/acssuschemeng.9b05766
Chauhan PS (2019) Lignin nanoparticles: eco-friendly and versatile tool for new era. Bioresour Technol Rep 9:100374. https://doi.org/10.1016/j.biteb.2019.100374
Chen X, Cao X, Sun S, Yuan T, Wang S, Shi Q, Sun R (2019) Hydrothermal acid hydrolysis for highly efficient separation of lignin and xylose from pre-hydrolysis liquor of kraft pulping process. Sep Purif Technol 209:741–747. https://doi.org/10.1016/j.seppur.2018.09.032
Dai L, Zhu W, Lu J, Kong F, Si C, Ni Y (2019) A lignin-containing cellulose hydrogel for lignin fractionation. Green Chem 21:5222–5230. https://doi.org/10.1039/C9GC01975H
Dai L, Jiang W, Zhou X, Xu Y (2020) Enhancement in xylonate production from hemicellulose pre-hydrolysate by powdered activated carbon treatment. Bioresour Technol 316:123944. https://doi.org/10.1016/j.biortech.2020.123944
Dong H, Zheng L, Yu P, Jiang Q, Wu Y, Huang C, Yin B (2020) Characterization and application of lignin–carbohydrate complexes from lignocellulosic materials as antioxidants for scavenging in vitro and in vivo reactive oxygen species. ACS Sustain Chem Eng 8:256–266. https://doi.org/10.1021/acssuschemeng.9b05290
Du H, Liu W, Zhang M, Si C, Zhang X, Li B (2019) Cellulose nanocrystals and cellulose nanofibrils based hydrogels for biomedical applications. Carbohydr Polym 209:130–144. https://doi.org/10.1016/j.carbpol.2019.01.020
Farooq M, Zou T, Riviere G, Sipponen MH, Österberg M (2018) Strong ductile and waterproof cellulose nanofibril composite films with colloidal lignin particles. Biomacromolecules 20:693–704. https://doi.org/10.1021/acs.biomac.8b01364
Frangville C, Rutkevičius M, Richter AP, Velev OD, Stoyanov SD, Paunov VN (2012) Fabrication of environmentally biodegradable lignin nanoparticles. ChemPhysChem 13:4235–4243. https://doi.org/10.1002/cphc.201200537
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. https://doi.org/10.1007/s10570-013-0030-4
French AD, Cintrón MS (2013) Cellulose polymorphy, crystallite size, and the Segal crystallinity index. Cellulose 20:583–588. https://doi.org/10.1007/s10570-012-9833-y
Fu H, Gao W, Wang B, Zeng J, Cheng Z, Xu J, Chen K (2019) Effect of lignin content on the microstructural characteristics of lignocellulose nanofibrils. Cellulose 27:1–14. https://doi.org/10.1007/s10570-019-02859-2
Gellerstedt G, Pettersson FL (1977) Light-induced oxidation of lignin: part 2. The oxidative degradation of aromatic rings. Svensk papperstidning 80:15–21
Giummarella N, Zhang L, Henriksson G, Lawoko M (2016) Structural features of mildly fractionated lignin carbohydrate complexes (LCC) from spruce. RSC Adv 6:42120–42131. https://doi.org/10.1039/C6RA02399A
Guo Y, Chen JQ, Su M, Hong JG (2018) Bio-based plastics with highly efficient esterification of lignocellulosic biomass in 1-methylimidazole under mild conditions. J Wood Chem Technol 38:338–349. https://doi.org/10.1080/02773813.2018.1488876
Han J, Wang H, Yue Y, Mei C, Chen J, Huang C (2019) A self-healable and highly flexible supercapacitor integrated by dynamically cross-linked electro-conductive hydrogels based on nanocellulose-templated carbon nanotubes embedded in a viscoelastic polymer network. Carbon 149:1–18. https://doi.org/10.1016/j.carbon.2019.04.029
Henriksson M, Isaksson BP (2008) Cellulose nanopaper structures of high toughness. Biomacromolecules 9:1579–1585. https://doi.org/10.1021/bm800038n
Huang C, He J, Narron R, Wang Y, Yong Q (2017) Characterization of kraft lignin fractions obtained by sequential ultrafiltration and their potential application as a biobased component in blends with polyethylene. ACS Sustain Chem Eng 5:11770–11779. https://doi.org/10.1021/acssuschemeng.7b03415
Huang C, Wang X, Liang C, Jiang X, Yang G, Xu J, Yong Q (2019) A sustainable process for procuring biologically active fractions of high-purity xylooligosaccharides and water-soluble lignin from Moso bamboo prehydrolyzate. Biotechnol Biofuels 12:189. https://doi.org/10.1186/s13068-019-1527-3
Iglesias MC, Gomez-Maldonado D, Via BK, Jiang Z, Peresin MS (2020) Pulping processes and their effects on cellulose fibers and nanofibrillated cellulose properties: a review. For Prod J 70:10–21. https://doi.org/10.13073/FPJ-D-19-00038
Imani M, Ghasemian A, Dehghani-Firouzabadi MR, Afra E, Borghei M, Johansson L, Rojas OJ (2019) Coupling nanofibril lateral size and residual lignin to tailor the properties of lignocellulose films. Adv Mater Interfaces 6:1900770. https://doi.org/10.1002/admi.201900770
Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85. https://doi.org/10.1039/C0NR00583E
Lanzalunga O, Bietti MJ (2000) Photo- and radiation chemical induced degradation of lignin model compounds. J Photochem Photobiol B 56:85–108. https://doi.org/10.1016/S1011-1344(00)00054-3
Lavoine N, Bras J, Saito T, Isogai A (2016) Improvement of the thermal stability of tempo-oxidized cellulose nanofibrils by heat-induced conversion of ionic bonds to amide bonds. Macromol Rapid Commun 37:1033–1039. https://doi.org/10.1002/marc.201600186
Li D, Wang Y, Xia Y (2004) Electrospinning nanofibers as uniaxially aligned arrays and layer-by-layer stacked films. Adv Mater 16:361–366. https://doi.org/10.1002/adma.200306226
Lin W, Chen D, Yong Q, Huang C, Huang S (2019) Improving enzymatic hydrolysis of acid-pretreated bamboo residues using amphiphilic surfactant derived from dehydroabietic acid. Bioresour Technol 293:122055. https://doi.org/10.1016/j.biortech.2019.122055
Liu C, Gelius E, Liu G, Steiner H, Dziarski R (2000) Mammalian peptidoglycan recognition protein binds peptidoglycan with high affinity is expressed in neutrophils and inhibits bacterial growth. J Biol Chem 275:24490–24499. https://doi.org/10.1074/jbc.M001239200
Narron RH, Chang HM, Jameel H, Park S (2017) Soluble lignin recovered from biorefinery pretreatment hydrolyzate characterized by lignin–carbohydrate complexes. ACS Sustain Chem Eng 5:10763–10771. https://doi.org/10.1021/acssuschemeng.7b02716
Nie S, Hao N, Zhang K, Xing C, Wang S (2020) Cellulose nanofibrils-based thermally conductive composites for flexible electronics: a mini review. Cellulose 27:4173–4187. https://doi.org/10.1007/s10570-020-03103-y
Pei W, Shang W, Liang C, Jiang X, Huang C, Yong Q (2020) Using lignin as the precursor to synthesize Fe3O4@ lignin composite for preparing electromagnetic wave absorbing lignin–phenol–formaldehyde adhesive. Ind Crop Prod 154:112638. https://doi.org/10.1016/j.indcrop.2020.112638
Rahouti M, Steiman R, Seigle-Murandi F, Christov LP (1999) Growth of 1044 strains and species of fungi on 7 phenolic lignin model compounds. Chemosphere 38:2549–2559. https://doi.org/10.1016/S0045-6535(98)00462-7
Rojo E, Peresin MS, Sampson WW, Hoeger IC, Vartiainen J, Laine J (2015) Comprehensive elucidation of the effect of residual lignin on the physical barrier mechanical and surface properties of nanocellulose films. Green Chem 17:1853–1866. https://doi.org/10.1039/C4GC02398F
Sadeghifar H, Venditti R, Jur J, Gorga RE, Pawlak JJ (2017b) Cellulose-lignin biodegradable and flexible UV protection film. ACS Sustain Chem Eng 5:625–631. https://doi.org/10.1021/acssuschemeng.6b02003
Sadeghifar H, Wells T, Le RK, Sadeghifar F, Yuan JS. Jonas Ragauskas A (2017a) Fractionation of organosolv lignin using acetone: water and properties of the obtained fractions. ACS Sustain Chem Eng 5:580–587. https://doi.org/10.1021/acssuschemeng.6b01955
Segal LGJMA, Creely JJ, Martin JAE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794. https://doi.org/10.1177/004051755902901003
Seki Y, Altinisik A, Demircioğlu B, Tetik C (2014) Carboxymethylcellulose (CMC)–filmshydroxyethylcellulose (HEC) based hydrogels: synthesis and characterization. Cellulose 21:1689–1698. https://doi.org/10.1007/s10570-014-0204-8
Shen XJ, Chen T, Wang HM, Mei Q, Yue F, Sun S (2020) Structural and morphological transformations of lignin macromolecules during bio-based deep eutectic solvent (DES) pretreatment. ACS Sustain Chem Eng 8:2130–2137. https://doi.org/10.1021/acssuschemeng.9b05106
Sipponen MH, Lange H, Crestini C, Henn A, Österberg M (2019) Lignin for nano-and microscaled carrier systems: applications trends and challenges. ChemSusChem 12:2039–2054. https://doi.org/10.1002/cssc.201900480
Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D, Crocker DL (2011) Determination of structural carbohydrates and lignin in biomass, laboratory analytical procedure (LAP). Technical report NREL/TP-510-42618, National Renewable Energy Laboratory (NREL), U.S. Dept. of Energy, Golden
Wang RH, Xin JH, Tao XM (2005) UV-blocking property of dumbbell-shaped ZnO crystallites on cotton fabrics. Inorg Chem 44:3926. https://doi.org/10.1021/ic0503176
Wang Q, Du H, Zhang F, Zhang Y, Wu M, Yu G (2018) Flexible cellulose nanopaper with high wet tensile strength high toughness and tunable ultraviolet blocking ability fabricated from tobacco stalk via a sustainable method. J Mater Chem A 6:13021–13030. https://doi.org/10.1039/c8ta01986j
Wang HM, Ma CY, Li HY, Chen TY, Wen JL, Cao XF (2020a) Structural variations of lignin macromolecules from early growth stages of poplar cell walls. ACS Sustain Chem Eng 8:1813–1822. https://doi.org/10.1021/acssuschemeng.9b05845
Wang P, Yin B, Dong H, Zhang Y, Zhang Y, Chen R, Yang Z, Huang C, Jiang Q (2020b) Coupling biocompatible Au nanoclusters and cellulose nanofibrils to prepare the antibacterial nanocomposite films. Front Bioeng Biotechnol 18:986. https://doi.org/10.3389/fbioe.2020.00986
Wei DW, Wei H, Gauthier AC, Song J, Jin Y, Xiao H (2020) Superhydrophobic modification of cellulose and cotton textiles: method-ologies and applications. J Bioresour Bioprod 5:1–16. https://doi.org/10.1016/j.jobab.2020.03.001
Wu Y, Tang Q, Yang F, Xu L, Wang X, Zhang J (2019) Mechanical and thermal properties of rice straw cellulose nanofibrils-enhanced polyvinyl alcohol films using freezing-and-thawing cycle method. Cellulose 26:3193–3204. https://doi.org/10.1007/s10570-019-02310-6
Yang W, Fortunati E, Gao D, Balestra GM, Giovanale G, He X (2018) Valorization of acid isolated high yield lignin nanoparticles as innovative antioxidant/antimicrobial organic materials. ACS Sustain Chem Eng 6:3502–3514. https://doi.org/10.1021/acssuschemeng.7b03782
Yu HY, Yao JM (2016) Reinforcing properties of bacterial polyester with different cellulose nanocrystals via modulating hydrogen bonds. Compos Sci Technol 136:53–60. https://doi.org/10.1016/j.compscitech.2016.10.004
Yu J, Zhu Y, Ma H, Liu L, Hu Y, Xu J, Fan Y (2019) Contribution of hemicellulose to cellulose nanofiber-based nanocomposite films with enhanced strength flexibility and UV-blocking properties. Cellulose 26:6023–6034. https://doi.org/10.1007/s10570-019-02518-6
Zhang X, Yang M, Yuan Q, Cheng G (2019) Controlled preparation of corncob lignin nanoparticles and their size-dependent antioxidant properties: toward high value utilization of lignin. ACS Sustain Chem Eng 7:17166–17174. https://doi.org/10.1021/acssuschemeng.9b03535
Zhao Y, Zhang Y, Lindström ME, Li J (2015) Tunicate cellulose nanocrystals: preparation neat films and nanocomposite films with glucomannans. Carbohydr Polym 117:286–296. https://doi.org/10.1016/j.carbpol.2014.09.020
Zhao Z, Hayashi S, Xu W, Wu Z, Tanaka S, Sun S (2019) A novel eco-friendly wood adhesive composed by sucrose and ammonium dihydrogen phosphate. Polymers 10:1251. https://doi.org/10.3390/polym10111251
Zhu M, Wang Y, Zhu S, Xu L, Jia C, Dai J, Song J, Yao Y, Wang Y, Li Y, Henderson D (2017) Anisotropic, transparent films with aligned cellulose nanofibers. Adv Mater 29:1606284. https://doi.org/10.1002/adma.201606284
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This work was supported by the Natural Science Foundation of Jiangsu Province (BK20180772) and National Natural Science Foundation of China (31800501).
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Huang, C., Dong, H., Zhang, Z. et al. Procuring the nano-scale lignin in prehydrolyzate as ingredient to prepare cellulose nanofibril composite film with multiple functions. Cellulose 27, 9355–9370 (2020). https://doi.org/10.1007/s10570-020-03427-9
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DOI: https://doi.org/10.1007/s10570-020-03427-9