Abstract
It is expected that cellulose nanocrystals (CNCs) will be utilized for biomedical applications, especially hard tissue engineering, because of their low toxicity to the human body and exceptional physicochemical properties. In our group, CNC@HAp, composed of hydroxyapatite (HAp), a component of enamel, and CNC, with high mechanical strength and biocompatibility, was developed as a biocompatible dental restorative material. However, due to the high hydrophilicity of CNC@HAp, it cannot be used in the oral cavity and has limited the restorative function of HAp, called remineralization. In this work, we developed CNC@HAp/chitosan (CNC@HAp/CS) materials as novel dental biomaterials by mixing the organic‒inorganic CNC@HAp particles with a CS matrix. We confirmed that CNC@HAp and CS were successfully composited using FT-IR, XRD, and SEM–EDX. The hydrophobicity of the prepared samples was drastically improved and consequently protected the sample from deterioration in water. This was supported by the contact angle measurements of CNC@HAp (32.7°) and CNC@HAp/CS (72.1°). SEM–EDX analysis of the sample before and after the immersion of CNC@HAp/CS in artificial saliva confirmed that the HAp layer had formed by remineralization after immersion. Furthermore, the TGA measurements implied that the amount of HAp increased with increasing immersion time in artificial saliva. Therefore, it was confirmed that CNC@HAp/CS promoted remineralization. Based on these results, CNC@HAp/CS can be applied as a dental material with self-healing properties due to its ability to mediate remineralization.
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Abbreviations
- CNC:
-
Cellulose nanocrystal
- HAp:
-
Hydroxyapatite;
- CNC@HAp:
-
CNC and HAp composite;
- CS:
-
Chitosan
- CNC@HAp/CS:
-
CNC; HAp and chitosan composite
References
Araki J (2013) Electrostatic or steric?–preparations and characterizations of well-dispersed systems containing rod-like nanowhiskers of crystalline polysaccharides. Soft Matter 9:4125–4141. https://doi.org/10.1039/c3sm27514k
Barbero N, Marenchino M, Campos-Olivas R, Oliaro-Bosso S, Bonandini L, Boskovic J, Viscardi G, Visentin S (2016) Nanomaterial–protein interactions: the case of pristine and functionalized carbon nanotubes and porcine gastric mucin. J Nanopart Res 18:1–8. https://doi.org/10.1007/s11051-016-3388-z
Barros SC, da Silva AA, Costa DB, Costa CM, Lanceros-Méndez S, Maciavello MT, Ribelles JG, Sentanin F, Pawlicka A, Silva MM (2015) Thermal–mechanical behaviour of chitosan–cellulose derivative thermoreversible hydrogel films. Cellulose 22:1911–1929. https://doi.org/10.1007/s10570-015-0603-5
Cheng Z, Ye Z, Natan A, Ma Y, Li H, Chen Y, Wan L, Aparicio C, Zhu H (2019) Bone-inspired mineralization with highly aligned cellulose nanofibers as template. ACS Appl Mater Interfaces 11:42486–42495. https://doi.org/10.1021/acsami.9b15234
Chou C-T, Shi S-C, Chen T-H, Chen C-K (2023) Nanocellulose-reinforced, multilayered poly (vinyl alcohol)-based hydrophobic composites as an alternative sealing film. Sci Prog 106:00368504231157142. https://doi.org/10.1177/00368504231157142
Ditzel FI, Prestes E, Carvalho BM, Demiate IM, Pinheiro LA (2017) Nanocrystalline cellulose extracted from pine wood and corncob. Carbohyd Polym 157:1577–1585. https://doi.org/10.1016/j.carbpol.2016.11.036
Dong Y, Xie Y, Ma X, Yan L, Yu H-Y, Yang M, Abdalkarim SYH, Jia B (2023) Multi-functional nanocellulose based nanocomposites for biodegradable food packaging: hybridization, fabrication, key properties and application. Carbohyd Polym 321:121325. https://doi.org/10.1016/j.carbpol.2023.121325
Du M, Chen J, Liu K, Xing H, Song C (2021) Recent advances in biomedical engineering of nano-hydroxyapatite including dentistry, cancer treatment and bone repair. Compos B Eng 215:108790. https://doi.org/10.1016/j.compositesb.2021.108790
Dufresne A (2017) Cellulose nanomaterial reinforced polymer nanocomposites. Curr Opin Colloid Interface Sci 29:1–8. https://doi.org/10.1016/j.cocis.2017.01.004
Emenike EC, Iwuozor KO, Saliu OD, Ramontja J, Adeniyi AG (2023) Advances in the extraction, classification, modification, emerging and advanced applications of crystalline cellulose: a review. Carbohydr Polym Technol Appl 6:100337. https://doi.org/10.1016/j.carpta.2023.100337
Ghorai SK, Roy T, Maji S, Ray PG, Sarkar K, Dutta A, De A, Bandyopadhyay S, Dhara S, Chattopadhyay S (2022) A judicious approach of exploiting polyurethane-urea based electrospun nanofibrous scaffold for stimulated bone tissue regeneration through functionally nobbled nanohydroxyapatite. Chem Eng J 429:132179. https://doi.org/10.1016/j.cej.2021.132179
Hollister SJ (2005) Porous scaffold design for tissue engineering. Nat Mater 4:518–524. https://doi.org/10.1038/nmat1421
Huang C, Yu H, Abdalkarim SYH, Li Y, Chen X, Yang X, Zhou Y, Zhang L (2022) A comprehensive investigation on cellulose nanocrystals with different crystal structures from cotton via an efficient route. Carbohyd Polym 276:118766. https://doi.org/10.1016/j.carbpol.2021.118766
Iwamoto S, Kai W, Isogai A, Iwata T (2009) Elastic modulus of single cellulose microfibrils from tunicate measured by atomic force microscopy. Biomacromol 10:2571–2576. https://doi.org/10.1021/bm900520n
Jiang H, Zuo Y, Cheng L, Wang H, Gu A, Li Y (2011) A homogenous CS/NaCMC/n-HA polyelectrolyte complex membrane prepared by gradual electrostatic assembling. J Mater Sci: Mater Med 22:289–297. https://doi.org/10.1007/s10856-010-4195-1
Kandori K, Yamaguchi Y (2017) Synthesis and characterization of Mn-doped calcium hydroxyapatite particles. Phosphorus Res Bull 33:26–34. https://doi.org/10.3363/prb.33.26
Kumar R, Prakash K, Cheang P, Gower L, Khor K (2008) Chitosan-mediated crystallization and assembly of hydroxyapatite nanoparticles into hybrid nanostructured films. J R Soc Interface 5:427–439. https://doi.org/10.1098/rsif.2007.1141
Lawrie G, Keen I, Drew B, Chandler-Temple A, Rintoul L, Fredericks P, Grøndahl L (2007) Interactions between alginate and chitosan biopolymers characterized using FTIR and XPS. Biomacromol 8:2533–2541. https://doi.org/10.1021/bm070014y
Li W, Guo R, Lan Y, Zhang Y, Xue W, Zhang Y (2014) Preparation and properties of cellulose nanocrystals reinforced collagen composite films. J Biomed Mater Res, Part A 102:1131–1139. https://doi.org/10.1002/jbm.a.34792
Maurer P, Pistner H, Schubert J (2006) Computer assisted chewing power in patients with segmental resection of the mandible. Mund Kiefer Gesichtschir 10:37–41. https://doi.org/10.1007/s10006-005-0656-y
Murizan NIS, Mustafa NS, Ngadiman NHA, Mohd Yusof N, Idris A (2020) Review on nanocrystalline cellulose in bone tissue engineering applications. Polymers 12:2818. https://doi.org/10.3390/polym12122818
Nohara T, Arita T, Tabata K, Saito T, Shimada R, Nakazaki H, Suzuki Y, Sato R, Masuhara A (2022) Novel filler-filled-type polymer electrolyte membrane for pefc employing poly (vinylphosphonic acid)-b-polystyrene-coated cellulose nanocrystals as a filler. ACS Appl Mater Interfaces 14:8353–8360. https://doi.org/10.1021/acsami.1c18695
Okabe Y, Kurihara S, Yajima T, Seki Y, Nakamura I, Takano I (2005) Formation of super-hydrophilic surface of hydroxyapatite by ion implantation and plasma treatment. Surf Coat Technol 196:303–306. https://doi.org/10.1016/j.surfcoat.2004.08.190
Pallela R, Venkatesan J, Janapala VR, Kim SK (2012) Biophysicochemical evaluation of chitosan-hydroxyapatite-marine sponge collagen composite for bone tissue engineering. J Biomed Mater Res, Part A 100:486–495. https://doi.org/10.1002/jbm.a.33292
Pighinelli L, Kucharska M (2013) Chitosan–hydroxyapatite composites. Carbohyd Polym 93:256–262. https://doi.org/10.1016/j.carbpol.2012.06.004
Pillai CK, Paul W, Sharma CP (2009) Chitin and chitosan polymers: chemistry, solubility and fiber formation. Prog Polym Sci 34:641–678. https://doi.org/10.1016/j.progpolymsci.2009.04.001
Qi Y, Cheng Z, Ye Z, Zhu H, Aparicio C (2019) Bioinspired mineralization with hydroxyapatite and hierarchical naturally aligned nanofibrillar cellulose. ACS Appl Mater Interfaces 11:27598–27604. https://doi.org/10.1021/acsami.9b09443
Rasool A, Ata S, Islam A (2019) Stimuli responsive biopolymer (chitosan) based blend hydrogels for wound healing application. Carbohyd Polym 203:423–429. https://doi.org/10.1016/j.carbpol.2018.09.083
Sabir M, Ali A, Siddiqui U, Muhammad N, Khan AS, Sharif F, Iqbal F, Shah AT, Rahim A, Rehman IU (2020) Synthesis and characterization of cellulose/hydroxyapatite based dental restorative composites. J Biomater Sci Polym Ed 31:1806–1819. https://doi.org/10.1080/09205063.2020.1777827
Sachlos E, Czernuszka J (2003) Making tissue engineering scaffolds work. Review: the application of solid freeform fabrication technology to the production of tissue engineering scaffolds. Eur Cell Mater 5:39–40. https://doi.org/10.22203/ecm.v005a03
Saha A, Ben Halima H, Saini A, Gallardo-Gonzalez J, Zine N, Viñas C, Elaissari A, Errachid A, Teixidor F (2020) Magnetic nanoparticles fishing for biomarkers in artificial saliva. Molecules 25:3968. https://doi.org/10.3390/molecules25173968
Saito T, Nohara T, Tabata K, Nakazaki H, Makino T, Matsuo Y, Sato K, Abadie C, Masuhara A (2022) Relationship between the proton conductive performance and water uptake ratio on a filler-filled polymer electrolyte membrane. Energy Fuels 36:13924–13929. https://doi.org/10.1021/acs.energyfuels.2c02527
Sato R, Arita T, Shimada R, Nohara T, Tabata K, Koseki K, Umemoto K, Masuhara A (2021) Biocompatible composite of cellulose nanocrystal and hydroxyapatite with large mechanical strength. Cellulose 28:871–879. https://doi.org/10.1007/s10570-020-03550-7
Shadjou N, Hasanzadeh M (2015) Bone tissue engineering using silica-based mesoporous nanobiomaterials: recent progress. Mater Sci Eng, C 55:401–409. https://doi.org/10.1016/j.msec.2015.05.027
Shaheen TI, Montaser A, Li S (2019) Effect of cellulose nanocrystals on scaffolds comprising chitosan, alginate and hydroxyapatite for bone tissue engineering. Int J Biol Macromol 121:814–821. https://doi.org/10.1016/j.ijbiomac.2018.10.081
Sharma V, Srinivasan A, Nikolajeff F, Kumar S (2021) Biomineralization process in hard tissues: the interaction complexity within protein and inorganic counterparts. Acta Biomater 120:20–37. https://doi.org/10.1016/j.actbio.2020.04.049
Sorlier P, Denuzière A, Viton C, Domard A (2001) Relation between the degree of acetylation and the electrostatic properties of chitin and chitosan. Biomacromol 2:765–772. https://doi.org/10.1021/bm015531+
Sultankulov B, Berillo D, Sultankulova K, Tokay T, Saparov A (2019) Progress in the development of chitosan-based biomaterials for tissue engineering and regenerative medicine. Biomolecules 9:470. https://doi.org/10.3390/biom9090470
Tang E, Huang M, Lim LY (2003) Ultrasonication of chitosan and chitosan nanoparticles. Int J Pharm 265:103–114. https://doi.org/10.1016/S0378-5173(03)00408-3
Valentin R, Bonelli B, Garrone E, Di Renzo F, Quignard F (2007) Accessibility of the functional groups of chitosan aerogel probed by FT-IR-monitored deuteration. Biomacromol 8:3646–3650. https://doi.org/10.1021/bm070391a
Venkatesan J, Kim SK (2010) Effect of temperature on isolation and characterization of hydroxyapatite from tuna (Thunnus obesus) bone. Materials 3:4761–4772. https://doi.org/10.3390/ma3104761
Venkatesan J, Pallela R, Bhatnagar I, Kim S-K (2012) Chitosan–amylopectin/hydroxyapatite and chitosan–chondroitin sulphate/hydroxyapatite composite scaffolds for bone tissue engineering. Int J Biol Macromol 51:1033–1042. https://doi.org/10.1016/j.ijbiomac.2012.08.020
Weiss AM, Macke N, Zhang Y, Calvino C, Esser-Kahn AP, Rowan SJ (2021) In vitro and in vivo analyses of the effects of source, length, and charge on the cytotoxicity and immunocompatibility of cellulose nanocrystals. ACS Biomater Sci Eng 7:1450–1461. https://doi.org/10.1021/acsbiomaterials.0c01618
Xu X, Chen X, Li J (2020) Natural protein bioinspired materials for regeneration of hard tissues. J Mater Chem B 8:2199–2215. https://doi.org/10.1039/D0TB00139B
Yadav S, Mehrotra G, Dutta P (2021) Chitosan based ZnO nanoparticles loaded gallic-acid films for active food packaging. Food Chem 334:127605. https://doi.org/10.1016/j.foodchem.2020.127605
Zaharia A, Muşat V, Anghel EM, Atkinson I, Mocioiu O-C, Buşilă M, Pleşcan VG (2017) Biomimetic chitosan-hydroxyapatite hybrid biocoatings for enamel remineralization. Ceram Int 43:11390–11402. https://doi.org/10.1016/j.ceramint.2017.05.346
Zhang Y, Zhu Y, Habibovic P, Wang H (2023) Advanced synthetic scaffolds based on one-dimensional inorganic micro-/nanomaterials for bone regeneration. Adv Healthcare Mater. https://doi.org/10.1002/adhm.202302664
Acknowledgments
This work was supported by the “Network Joint Research Center for Materials and Devices (Grant Number 20221071)” cooperative research program and a Grant-in-Aid for Challenging Exploratory Research (Grant Number JP21K19132).
Funding
This work was supported by the “Network Joint Research Center for Materials and Devices (Grant Number 20221071)” cooperative research program and a Grant-in-Aid for Challenging Exploratory Research (Grant Number JP21K19132).
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YM, TA and AM contributed to the study conception and design. Material preparation was performed by YM, RS and KT. Data collection and analysis were performed by YM, RS, KT, TM, TS and KS. YM wrote the first draft of the manuscript. RS, TA and AM commented on previous versions of the manuscript. Funding was acquired by TA and AM. All the authors have read and approved the final manuscript.
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Matsuo, Y., Sato, R., Tabata, K. et al. Hybrid composite cellulose nanocrystal, hydroxyapatite, and chitosan material with controlled hydrophilic/hydrophobic properties as a remineralizable dental material. Cellulose 31, 2267–2279 (2024). https://doi.org/10.1007/s10570-024-05763-6
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DOI: https://doi.org/10.1007/s10570-024-05763-6