Abstract
Cellulose nanocrystals (CNCs) have been widely used in the surface modification and construction of nanocomposites due to their excellent surface activity and high tensile strength. In this manuscript, nanocomposite hydrogels were prepared by implanting poly(glycidyl methacrylate)-modified CNCs (CNCs@PGMA) and biomass phytic acid (PA). After extracting CNCs from microcrystalline cellulose, PGMA was successfully grafted on the surface of CNCs by surface-initiated Activator Generated by Electron Transfer Atom Transfer Radical Polymerization (SI-AGET ATRP). With the assistance of PA, the reversible hydrogen bonding interaction between the internal structures of the matrix was promoted to construct the CNCs@PGMA/PA self-healing nanocomposite hydrogels. The obtained hydrogels by using CNCs@PGMA and PA as additives have excellent mechanical properties (tensile strength of 1.39 MPa) and self-healing ability (91.4% after 6 h). This study develops a facile method for the preparation of nanocomposite hydrogels with excellent self-healing properties.
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Bai L, Jiang X, Sun Z, Pei Z, Ma A, Wang W, Chen H, Yang H, Yang L, Wei D (2019) Self-healing nanocomposite hydrogels based on modified cellulose nanocrystals by surface-initiated photoinduced electron transfer ATRP. Cellulose 26:5305–5319. https://doi.org/10.1007/s10570-019-02449-2
Bettaieb F, Khiari R, Dufresne A, Mhenni MF, Belgacem MN (2015) Mechanical and thermal properties of Posidonia oceanica cellulose nanocrystal reinforced polymer. Carbohydr Polym 123:99–104. https://doi.org/10.1016/j.carbpol.2015.01.026
Bui HL, Huang CJ (2019) Tough polyelectrolyte hydrogels with antimicrobial property via incorporation of natural multivalent phytic acid. Polymers 17:1721. https://doi.org/10.3390/polym11101721
Cao L, Tian D, Lin B, Wang W, Bai L, Chen H, Yang L, Yang H, Wei D (2021) Fabrication of self-healing nanocomposite hydrogels with the cellulose nanocrystals-based Janus hybrid nanomaterials. Int J Biol Macromol 184:259–270. https://doi.org/10.1016/j.ijbiomac.2021.06.053
Chau M, France K, Kopera B, Machado V, Rosenfeldt S, Reyes L, Chan K, Forster S, Cranston E, Hoare T, Kumacheva E (2016) Composite hydrogels with tunable anisotropic morphologies and mechanical properties. Chem Mater 28:3406–3415. https://doi.org/10.1021/acs.chemmater.6b00792
Chen K, Zhang S, Li A, Tang X, Li L, Guo L (2018) Bioinspired interfacial chelating-like reinforcement strategy toward mechanically enhanced lamellar materials. ACS Nano 12:4269–4279. https://doi.org/10.1021/acsnano.7b08671
Chen A, Li Y, Shang J, Arai Y (2020) Ferrihydrite transformation impacted by coprecipitation of phytic acid. Environ Sci Technol 54:8837–8847. https://doi.org/10.1021/acs.est.0c02465
Choi J, Kim S, Yoo J, Choi S-H, Char K (2021) Self-healable antifreeze hydrogel based on dense quadruple hydrogen bonding. Macromolecules 54:6389–6399. https://doi.org/10.1021/acs.macromol.1c00295
Collazo-Bigliardi S, Ortega-Toro R, Chiralt Boix A (2018) Isolation and characterisation of microcrystalline cellulose and cellulose nanocrystals from coffee husk and comparative study with rice husk. Carbohydr Polym 191:205–215. https://doi.org/10.1016/j.carbpol.2018.03.022
Das S, Martin P, Vasilyev G, Nandi R, Amdursky N, Zussman E (2020) Processable, ion-conducting hydrogel for flexible electronic devices with self-healing capability. Macromolecules 53:11130–11141. https://doi.org/10.1021/acs.macromol.0c02060
De France KJ, Hoare T, Cranston ED (2017) Review of hydrogels and aerogels containing nanocellulose. Chem Mater 29:4609–4631. https://doi.org/10.1021/acs.chemmater.7b00531
Delepierre G, Heise K, Malinen K, Koso T, Pitkanen L, Cranston ED, Kilpelainen I, Kostiainen MA, Kontturi E, Weder C, Zoppe JO, King A (2021) Challenges in synthesis and analysis of asymmetrically grafted cellulose nanocrystals via atom transfer radical polymerization. Biomacromol 22:2702–2717. https://doi.org/10.1021/acs.biomac.1c00392
Dhar P, Bhardwaj U, Kumar A, Katiyar V (2014) Cellulose nanocrystals: A potential nanofiller for food packaging applications. In: Food additives and packaging. ACS Symposium Series, pp 197–239. https://doi.org/10.1021/bk-2014-1162.ch017
Ding H, Liang X, Xu J, Tang Z, Li Z, Liang R, Sun G (2021) Hydrolyzed hydrogels with super stretchability, high strength, and fast self-recovery for flexible sensors. ACS Appl Mater Interfaces 13:22774–22784. https://doi.org/10.1021/acsami.1c04781
Dong XM, Kimura T, Revol J-F, Gray DG (1996) Effects of ionic strength on the isotropic−chiral nematic phase transition of suspensions of cellulose crystallites. Langmuir 12:2076–2082. https://doi.org/10.1021/la950133b
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
Fan Q, Jiang C, Wang W, Bai L, Chen H, Yang H, Wei D, Yang L (2020) Eco-friendly extraction of cellulose nanocrystals from grape pomace and construction of self-healing nanocomposite hydrogels. Cellulose 27:2541–2553. https://doi.org/10.1007/s10570-020-02977-2
Franke D, Gerlach G (2020) Swelling studies of porous and nonporous semi-IPN hydrogels for sensor and actuator applications. Micromachines 11:425. https://doi.org/10.3390/mi11040425
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. https://doi.org/10.1007/s10570-013-0030-4
Gabrielli V, Baretta R, Pilot R, Ferrarini A, Frasconi M (2022) Insights into the gelation mechanism of metal-coordinated hydrogels by paramagnetic NMR spectroscopy and molecular dynamics. Macromolecules 55:450–461. https://doi.org/10.1021/acs.macromol.1c01756
Gao Y, Peng X, Wu Q, Yang D, Wang W, Peng Q, Wang T, Wang J, Liu J, Zhang H, Zeng H (2022) Hydrogen-bonding-driven multifunctional polymer hydrogel networks based on tannic acid. ACS Appl Polym Mater 4:1836–1845. https://doi.org/10.1021/acsapm.1c01724
Geleta GS, Zhao Z, Wang Z (2018) A sensitive electrochemical aptasensor for detection of Aflatoxin B2 based on a polyacrylamide/phytic acid/polydopamine hydrogel modified screen printed carbon electrode. Anal Methods 10:4689–4694. https://doi.org/10.1039/c8ay01675e
Grishkewich N, Akhlaghi SP, Zhaoling Y, Berry R, Tam KC (2016) Cellulose nanocrystal-poly(oligo(ethylene glycol) methacrylate) brushes with tunable LCSTs. Carbohydr Polym 144:215–222. https://doi.org/10.1016/j.carbpol.2016.02.044
Grishkewich N, Mohammed N, Tang J, Tam KC (2017) Recent advances in the application of cellulose nanocrystals. Curr Opin Colloid Interface Sci 29:32–45. https://doi.org/10.1016/j.cocis.2017.01.005
Guo Y, Zhou X, Zhao F, Bae J, Rosenberger B, Yu G (2019) Synergistic energy nanoconfinement and water activation in hydrogels for efficient solar water desalination. ACS Nano 13:7913–7919. https://doi.org/10.1021/acsnano.9b02301
Guo J, Li Y, Zhang Y, Ren J, Yu X, Cao X (2021) Switchable supramolecular configurations of Al3+/LysTPY coordination polymers in a hydrogel network controlled by ultrasound and heat. ACS Appl Mater Interfaces 13:40079–40087. https://doi.org/10.1021/acsami.1c10150
Hayase G, Yoshino D (2020) CNC-Milled superhydrophobic macroporous monoliths for 3D cell culture. ACS Appl Bio Mater 3:4747–4750. https://doi.org/10.1021/acsabm.0c00719
Huang G, Tang Z, Peng S, Zhang P, Sun T, Wei W, Zeng L, Gou H, Guo H, Meng G (2022) Modification of hydrophobic hydrogels into a strongly adhesive and tough hydrogel by electrostatic interaction. Macromolecules 55:156–165. https://doi.org/10.1021/acs.macromol.1c01115
Jian Y, Handschuh-Wang S, Zhang J, Lu W, Zhou X, Chen T (2021) Biomimetic anti-freezing polymeric hydrogels: keeping soft-wet materials active in cold environments. Mater Horiz 8:351–369. https://doi.org/10.1039/d0mh01029d
Kiriakou MV, Pakdel AS, Berry RM, Hoare T, Dubé MA, Cranston ED (2022) Incorporation of polymer-grafted cellulose nanocrystals into latex-based pressure-sensitive adhesives. ACS Mater Au 2:176–189. https://doi.org/10.1021/acsmaterialsau.1c00052
Lam E, Male KB, Chong JH, Leung AC, Luong JH (2012) Applications of functionalized and nanoparticle-modified nanocrystalline cellulose. Trends Biotechnol 30:283–290. https://doi.org/10.1016/j.tibtech.2012.02.001
Le Gars M, Bras J, Salmi-Mani H, Ji M, Dragoe D, Faraj H, Domenek S, Belgacem N, Roger P (2020) Polymerization of glycidyl methacrylate from the surface of cellulose nanocrystals for the elaboration of PLA-based nanocomposites. Carbohydr Polym 234:115899. https://doi.org/10.1016/j.carbpol.2020.115899
Lee Y, Choi H, Zhang H, Wu Y, Lee D, Wong W, Tang X, Park J, Yu H, Tam K (2021) Sensitive, stretchable, and sustainable conductive cellulose nanocrystal composite for human motion detection. ACS Sustain Chem Eng 9:17351–17361. https://doi.org/10.1021/acssuschemeng.1c06741
Li QL, Wang L, Qiu LX, Sun YL, Wang PX, Liu Y, Li F, Qi AD, Gao H, Yang YW (2014) Stimuli-responsive biocompatible nanovalves based on β-cyclodextrin modified poly(glycidyl methacrylate). Polym Chem 5:3389–3395. https://doi.org/10.1039/c4py00041b
Li B, Zhang Y, Han Y, Guo B, Luo Z (2019) Tough and self-healable nanocomposite hydrogels from poly(acrylic acid) and polyacrylamide grafted cellulose nanocrystal crosslinked by coordination bonds and hydrogen bonds. Cellulose 26:6701–6711. https://doi.org/10.1007/s10570-019-02581-z
Li R, Fan T, Chen G, Xie H, Su B, He M (2020) Highly transparent, self-healing conductive elastomers enabled by synergistic hydrogen bonding interactions. Chem Eng J 393:124685. https://doi.org/10.1016/j.cej.2020.124685
Lin N, Dufresne A (2013) Physical and/or chemical compatibilization of extruded cellulose nanocrystal reinforced polystyrene nanocomposites. Macromolecules 46:5570–5583. https://doi.org/10.1021/ma4010154
Lin Y, Dong S, Zhao W, Hu K, Liu J, Wang S, Tu M, Du B, Zhang D (2020) Application of hydrogel-based delivery system in endometrial repair. ACS Appl Bio Mater 3:7278–7290. https://doi.org/10.1021/acsabm.0c00971
Ling Z, Wang T, Makarem M, Cintron M, Cheng H, Kang X, Bacher M, Potthast A, Rosenau T, King H, Delhom C, Nam S, Edwards J, Kim S, Xu F, Franch A (2019) Effects of ball milling on the structure of cotton cellulose. Cellulose 26:305–328. https://doi.org/10.1007/s10570-018-02230-x
Liu Y, Wang W, Gu K, Yao J, Shao Z, Chen X (2021) Poly(vinyl alcohol) hydrogels with integrated toughness, conductivity, and freezing tolerance based on ionic liquid/water binary solvent systems. ACS Appl Mater Interfaces 13:29008–29020. https://doi.org/10.1021/acsami.1c09006
Lu P, Hsieh Y-L (2010) Preparation and properties of cellulose nanocrystals: rods, spheres, and network. Carbohydr Polym 82:329–336. https://doi.org/10.1016/j.carbpol.2010.04.073
Meng L, Shao C, Cui C, Xu F, Lei J, Yang J (2020) Autonomous self-healing silk fibroin injectable hydrogels formed via surfactant-free hydrophobic association. ACS Appl Mater Interfaces 12:1628–1639. https://doi.org/10.1021/acsami.9b19415
Nie Y, Yue D, Xiao W, Wang W, Chen H, Bai L, Yang L, Yang H, Wei D (2022) Anti-freezing and self-healing nanocomposite hydrogels based on poly (vinyl alcohol) for highly sensitive and durable flexible sensors. Chem Eng J 436:135243. https://doi.org/10.1016/j.cej.2022.135243
Pei Z, Yu Z, Li M, Bai L, Wang W, Chen H, Yang H, Wei D, Yang L (2021) Self-healing and toughness cellulose nanocrystals nanocomposite hydrogels for strain-sensitive wearable flexible sensor. Int J Biol Macromol 179:324–332. https://doi.org/10.1016/j.ijbiomac.2021.03.023
Peng Y, Yan B, Li Y, Lan J, Shi L, Ran R (2019) Antifreeze and moisturizing high conductivity PEDOT/PVA hydrogels for wearable motion sensor. J Mater Sci 55:1280–1291. https://doi.org/10.1007/s10853-019-04101-7
Salajková M, Berglund LA, Zhou Q (2012) Hydrophobic cellulose nanocrystals modified with quaternary ammonium salts. J Mater Chem 22:19798–19805. https://doi.org/10.1039/c2jm34355j
Schneider EL, Henise J, Reid R, Ashley GW, Santi DV (2016) Hydrogel drug delivery system using self-cleaving covalent linkers for once-a-week administration of exenatide. Bioconjug Chem 27:1210–1215. https://doi.org/10.1021/acs.bioconjchem.5b00690
Shang Q, Liu C, Hu Y, Jia P, Hu L, Zhou Y (2018) Bio-inspired hydrophobic modification of cellulose nanocrystals with castor oil. Carbohydr Polym 191:168–175. https://doi.org/10.1016/j.carbpol.2018.03.012
Shao C, Wang M, Chang H, Xu F, Yang J (2017) A self-healing cellulose nanocrystal-poly(ethylene glycol) nanocomposite hydrogel via diels-alder click reaction. ACS Sustain Chem Eng 5:6167–6174. https://doi.org/10.1021/acssuschemeng.7b01060
Shao L, Li Y, Ma Z, Bai Y, Wang J, Zeng P, Gong P, Shi F, Ji Z, Qiao Y, Xu R, Xu J, Zhang G, Wang C, Ma J (2020) Highly sensitive strain sensor based on a stretchable and conductive poly(vinyl alcohol)/phytic acid/NH2-POSS hydrogel with a 3D microporous structure. ACS Appl Mater Interfaces 12:26496–26508. https://doi.org/10.1021/acsami.0c07717
Song Y, Ye G, Lu Y, Chen J, Wang J, Matyjaszewski K (2016) Surface-initiated ARGET ATRP of poly(glycidyl methacrylate) from carbon nanotubes via bioinspired catechol chemistry for efficient adsorption of uranium ions. ACS Macro Lett 5:382–386. https://doi.org/10.1021/acsmacrolett.6b00099
Teodoro KBR, Sanfelice RC, Migliorini FL, Pavinatto A, Facure MHM, Correa DS (2021) A review on the role and performance of cellulose nanomaterials in sensors. ACS Sens 6:2473–2496. https://doi.org/10.1021/acssensors.1c00473
Wang C, Zhao S, Wei Y (2012) Hydrophilic modification of microporous polysulfone membrane via surface-initiated atom transfer radical polymerization and hydrolysis of poly(glycidylmethacrylate). Chin J Chem 30:2473–2482. https://doi.org/10.1002/cjoc.201200443
Wang J, Zhang W, Zheng Y, Zhang N, Zhang C (2019) Multi-functionalization of magnetic graphene by surface-initiated ICAR ATRP mediated by polydopamine chemistry for adsorption and speciation of arsenic. Chin J Chem 478:15–25. https://doi.org/10.1016/j.apsusc.2019.01.188
Wang W, Xiang L, Diaz-Dussan D, Zhang J, Yang W, Gong L, Chen J, Narain R, Zeng H (2020a) Dynamic flexible hydrogel network with biological tissue-like self-protective functions. Chem Mater 32:10545–10555. https://doi.org/10.1021/acs.chemmater.0c03526
Wang Y, Garcia CR, Ding Z, Gabrilska R, Rumbaugh KP, Wu J, Liu Q, Li W (2020b) Adhesive, self-healing, and antibacterial chitosan hydrogels with tunable two-layer structures. ACS Sustain Chem Eng 8:18006–18014. https://doi.org/10.1021/acssuschemeng.0c05730
Xu G, Nigmatullin R, Koev TT, Khimyak YZ, Bond IP, Eichhorn SJ (2022) Octylamine-modified cellulose nanocrystal-enhanced stabilization of pickering emulsions for self-healing composite coatings. ACS Appl Mater Interfaces 14:12722–12733. https://doi.org/10.1021/acsami.2c01324
Yan Q, Zhou M, Fu H (2020) Study on mussel-inspired tough TA/PANI@CNCs nanocomposite hydrogels with superior selfhealing and self-adhesive properties for strain sensors.COMPOS PART B-ENG 201:108356. https://doi.org/10.1016/j.compositesb.2020.108356
Yu H, Rouelle N, Qiu A, Oh J, Kempaiah D, Whittle J, Aakyiir M, Xing W, Ma J (2020) Hydrogen bonding-reinforced hydrogel electrolyte for flexible, robust, and all-in-one supercapacitor with excellent low-temperature tolerance. ACS Appl Mater Interfaces 12:37977–37985. https://doi.org/10.1021/acsami.0c05454
Yuan W, Wang C, Lei S, Chen J, Lei S, Li Z (2018) Ultraviolet light-, temperature- and pH-responsive fluorescent sensors based on cellulose nanocrystals. Polym Chem 9:3098–3107. https://doi.org/10.1039/c8py00613j
Zhang Z, Tam KC, Sebe G, Wang X (2018) Convenient characterization of polymers grafted on cellulose nanocrystals via SI-ATRP without chain cleavage. Carbohydr Polym 199:603–609. https://doi.org/10.1016/j.carbpol.2018.07.060
Zhang S, Zhang Y, Li B, Zhang P, Kan L, Wang G, Wei H, Zhang X, Ma N (2019a) One-step preparation of a highly stretchable, conductive, and transparent poly(vinyl alcohol)-phytic acid hydrogel for casual writing circuits. ACS Appl Mater Interfaces 11:32441–32448. https://doi.org/10.1021/acsami.9b12626
Zhang Z-X, Liow SS, Xue K, Zhang X, Li Z, Loh XJ (2019b) Autonomous chitosan-based self-healing hydrogel formed through noncovalent interactions. ACS Appl Polym Mater 1:1769–1777. https://doi.org/10.1021/acsapm.9b00317
Zhang X, Peng Y, Shi L, Ran R (2020) Highly efficient solar evaporator based on a hydrophobic association hydrogel. ACS Sustain Chem Eng 8:18114–18125. https://doi.org/10.1021/acssuschemeng.0c06462
Zhang Q, Liu X, Zhang JW, Duan LJ, Gao GH (2021a) A highly conductive hydrogel driven by phytic acid towards a wearable sensor with freezing and dehydration resistance. J Mater Chem A 9:22615–22625. https://doi.org/10.1039/d1ta06408h
Zhang S, He J, Xiong S, Xiao Q, Xiao Y, Ding F, Ji H, Yang Z, Li Z (2021b) Construction and nanostructure of chitosan/nanocellulose hybrid aerogels. Biomacromol 22:3216–3222. https://doi.org/10.1021/acs.biomac.1c00266
Zhang X, Peng Y, Wang X, Ran R (2021c) Melanin-inspired conductive hydrogel sensors with ultrahigh stretchable, self-healing, and photothermal capacities. ACS Appl Polym Mater 3:1899–1911. https://doi.org/10.1021/acsapm.0c01430
Zhang Y, Duvigneau J, Sui X, Vancso GJ (2022) Foaming of polylactic acid/cellulose nanocrystal composites: pickering emulsion templating for high-homogeneity filler dispersions. ACS Appl Polym Mater 4:111–120. https://doi.org/10.1021/acsapm.1c01046
Zhao L, Li X, Li Y, Wang X, Yang W, Ren J (2021) Polypyrrole-doped conductive self-healing composite hydrogels with high toughness and stretchability. Biomacromol 22:1273–1281. https://doi.org/10.1021/acs.biomac.0c01777
Zheng T, Pilla S (2020) Melt processing of cellulose nanocrystal-filled composites: toward reinforcement and foam nucleation. Ind Eng Chem Res 59:8511–8531. https://doi.org/10.1021/acs.iecr.0c00170
Zhou C, Wu Q (2011) A novel polyacrylamide nanocomposite hydrogel reinforced with natural chitosan nanofibers. Colloids Surf, B 84:155–162. https://doi.org/10.1016/j.colsurfb.2010.12.030
Zhou C, Wu Q, Yue Y, Zhang Q (2011) Application of rod-shaped cellulose nanocrystals in polyacrylamide hydrogels. J Colloid Interface Sci 353:116–123. https://doi.org/10.1016/j.jcis.2010.09.035
Zhou C, Chen Z, Yang H, Hou K, Zeng X, Zheng Y, Cheng J (2017) Nature-inspired strategy toward superhydrophobic fabrics for versatile oil/water separation. ACS Appl Mater Interfaces 9:9184–9194. https://doi.org/10.1021/acsami.7b00412
Zhu F, Lin J, Wu ZL, Qu S, Yin J, Qian J, Zheng Q (2018) Tough and conductive hybrid hydrogels enabling facile patterning. ACS Appl Mater Interfaces 10:13685–13692. https://doi.org/10.1021/acsami.8b01873
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The research was financial supported by the National Natural Science Foundation of China (No. 51973086), the Project of Shandong Province Higher Educational Science (No. 2019KJA011) and the Natural Science Foundation of Shandong Province (No. ZR2021MB124).
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Li, C., Hou, Z., Li, P. et al. Phytic acid-assist for self-healing nanocomposite hydrogels with surface functionalization of cellulose nanocrystals via SI-AGET ATRP. Cellulose 30, 1087–1102 (2023). https://doi.org/10.1007/s10570-022-04936-5
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DOI: https://doi.org/10.1007/s10570-022-04936-5