Dual Physically Cross-Linked Nanocomposite Hydrogels Reinforced by Tunicate Cellulose Nanocrystals with High Toughness and Good Self-Recoverability
05 Jul 2017-ACS Applied Materials & Interfaces (American Chemical Society)-Vol. 9, Iss: 28, pp 24230-24237
TL;DR: This work provided a universal strategy for construction of tough nanocomposite hydrogel reinforced with cellulose nanocrystals and exhibited excellent self-recoverability after treating the stretched samples in FeCl3 aqueous solution.
Abstract: The weak mechanical properties of hydrogels usually limited their application in biomedical and industrial fields. Herein, we reported a nanocomposite network of poly(acrylic acid-co-acrylamide) (PAAAM) sequentially cross-linked by quaternized tunicate cellulose nanocrystals (Q-TCNCs) and Fe3+. Q-TCNCs acted as both interfacial compatible reinforcements and cross-linkers in the nanocomposite hydrogels to form loose cross-linking, whereas compact cross-linking was built by ionic coordination between Fe3+ and −COO– of PAAAM. The toughness of dual cross-linked hydrogel (D-Gel) was 340 times that of mono-cross-linked hydrogel (m-Gel), which was 10 times that of PAAAM hydrogel. Moreover, the nanocomposite hydrogels exhibited excellent self-recoverability after treating the stretched samples in FeCl3 aqueous solution. This work provided a universal strategy for construction of tough nanocomposite hydrogel reinforced with cellulose nanocrystals.
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TL;DR: This work opens a novel pathway to fabricate on-demand dissolvable self-healing hydrogels to speed deep partial thickness burn wound healing and eliminate pain at wound dressing changes and prevent scar formation.
Abstract: Deep partial thickness burn wounds present big challenges due to the long healing time, large size and irregular shape, pain and reinjury at wound dressing changes, as well as scarring. The clinically effective therapy to alleviate pain at wound dressing changes, and the scar left on the skin after the healing of wound is still unavailable. To combat this, we develop a nanocomposite self-healing hydrogel that can be injected into irregular and deep burn wound beds and subsequently rapidly self-heal to reform into an integrated piece of hydrogel that thoroughly fills the wound area and protects the wound site from external environment, finally being painlessly removed by on-demand dissolving using amino acid solution at wound dressing changes, which accelerates deep partial thickness burn wound healing and prevents scarring. The hydrogel is made out of naturally occurring polymers, namely, water-soluble carboxymethyl chitosan (CMC) and rigid rod-like dialdehyde-modified cellulose nanocrystal (DACNC). They are cross-linked by dynamic Schiff-base linkages between amines from CMC and aldehydes from DACNC. The large aspect ratio and specific surface area of DACNC raise massive active junctions within the hydrogel, which can be readily broken and reformed, allowing hydrogel to rapidly self-heal. Moreover, DACNC serves as nanoreinforcing fillers to improve the hydrogel strength, which also restricts the "soft" CMC chains' motion when soaked in aqueous system, endowing high fluid uptake capacity (350%) to hydrogel while maintaining integrity. Cytotoxicity assay and three-dimensional cell culture demonstrate excellent biocompatibility of the hydrogel and capacity as extracellular matrix to support cell growth. This work opens a novel pathway to fabricate on-demand dissolvable self-healing hydrogels to speed deep partial thickness burn wound healing and eliminate pain at wound dressing changes and prevent scar formation.
289 citations
TL;DR: In this article, the authors demonstrate a facile and universal strategy in the fabrication of dual-cross-linked (DC) single network hydrogels with high toughness, nonswellability, rapid self-healing, and versatile adhesiveness based on polymer-tannic acid (TA) multiple hydrogen bonds.
Abstract: We demonstrate a facile and universal strategy in the fabrication of dual-cross-linked (DC) single network hydrogels with high toughness, “nonswellability”, rapid self-healing, and versatile adhesiveness based on polymer–tannic acid (TA) multiple hydrogen bonds. Two widely used hydrogels, physically cross-linked poly(vinyl alcohol) and chemically cross-linked polyacrylamide, have been transformed to TA-based DC hydrogels by dipping the corresponding aerogels into TA solution. The second cross-link via multiple polymer–TA hydrogen bonds effectively suppresses the crack propagation, resulting in both DC gels with high mechanical strength. But these two TA-based DC hydrogels go through different deformation mechanisms during the stretching based on analyzing their stress–strain curves using the Mooney–Rivlin equation. Moreover, these DC hydrogels are swelling-resistant, with strong toughness, good self-recoverability, rapid self-healing, and versatile adhesiveness. This work provides a simple route to fabric...
246 citations
TL;DR: In this paper, the authors discuss the current progress of naturally-derived bionanocomposites that has advanced our understanding of the biological/synthetic interfaces and present an outlook on the current trends in providing structural and interfacial enhancement as well as emerging applications which will employ new optical, sensing, structural, and actuating functionalities and properties.
Abstract: Naturally derived materials with hierarchical organization are attractive candidates for high-performance and functional bionanocomposites because of their renewability, biocompatibility, biodegradability, flexibility, and the availability of multiple reactive sites for introducing novel functionalities. Complementary to these inherent properties, the synergistic combination of biological and synthetic components facilitated by strong interfacial interactions, can substantially enhance the structural performance and facilitate added functionalities of these bio-enabled nanocomposites. In this review, we discuss the current progress of naturally-derived bionanocomposites that has advanced our understanding of the biological/synthetic interfaces. In these bionanocomposites, various novel synthetic nanomaterials (e.g., graphene, carbon nanotube, mineral nanoparticles and metallic nanoparticles) are efficiently integrated with biological components to achieve novel properties such as superior electrical and thermal conductivity, controlled gas barrier properties, complex actuation, and unique optical properties. Two popular biocomponents, nanocellulose and silk, are mainly discussed in this review as representatives of classes of polysaccharides and polypeptides with some other biopolymers briefly discussed as well. The structures and morphologies, processing strategies, tailored functionalities and emerging applications of these bionanocomposites are analyzed and summarized. Finally, we present an outlook on the current trends in providing structural and interfacial enhancement as well as emerging applications which will employ new optical, sensing, structural, and actuating functionalities and properties.
159 citations
TL;DR: This review focuses on state-of-the-art progress in cellulose-based hydrogels, which covers from their preparation methods and physicochemical properties to their biomedical applications, including drug delivery, tissue engineering, wound dressing, bioimaging, wearable sensors and so on.
Abstract: In recent decades, cellulose has been extensively investigated due to its favourable properties, such as hydrophilicity, low-cost, biodegradability, biocompatibility, and non-toxicity, which makes it a good feedstock for the synthesis of biocompatible hydrogels. The plentiful hydrophilic functional groups (such as hydroxyl, carboxyl, and aldehyde groups) in the backbone of cellulose and its derivatives can be used to prepare hydrogels easily with fascinating structures and properties, leading to burgeoning research interest in biomedical applications. This review focuses on state-of-the-art progress in cellulose-based hydrogels, which covers from their preparation methods (including chemical methods and physical methods) and physicochemical properties (such as stimuli-responsive properties, mechanical properties, and self-healing properties) to their biomedical applications, including drug delivery, tissue engineering, wound dressing, bioimaging, wearable sensors and so on. Moreover, the current challenges and future prospects for cellulose-based hydrogels in regard to their biomedical applications are also discussed at the end.
156 citations
TL;DR: In this article, a review describes the recent advances in the production and application of cellulose nanomaterials (CNMs) and their applications in various fields such as medical, sensors, in wastewater treatment, paper and board/packaging industry.
Abstract: This review describes the recent advances in the production and application of cellulose nanomaterials. Cellulose nanomaterials (CNMs), especially cellulose nanocrystals and cellulose nanofibers, can be produced using different preparation processes resulting in materials with unique structures and physicochemical properties that are exploited in different fields such as, biomedical, sensors, in wastewater treatment, paper and board/packaging industry. These materials possess attractive properties such as large surface area, high tensile strength and stiffness, surface tailor-ability via hydroxyl groups and are renewable. This has been a driving force to produce these materials in industrial scale with several companies producing CNMs at tons-per-day scale. The recent developments in their production rate and their applications in various fields such as medical sector, environmental protection, energy harvesting/storage are comprehensively discussed in this review. We emphasize on the current trends and future remarks based on the production and applications of cellulose nanomaterials.
134 citations
Cites background from "Dual Physically Cross-Linked Nanoco..."
...Tunicates and algal cellulose (AC)Cellulose can be synthesized by different microorganisms such as algae and fungi (Zhang et al. 2017a, b; Keshk 2014)....
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...…78 8 10 – 2 1 Hardwood 43–47 25–35 – – – – Spence et al. (2011) Softwood 40–44 25–29 – – – – case, mantle consists of tunic cellulose which aggregates to form microfibrils composed of a nearly pure cellulose Ib allomorph which varies depending on the species (Zhao et al. 2015; Zhang et al.…...
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...The resulting particle are mainly composed of Ib allomorph which vary depending on the specie under investigation (Zhao et al. 2015; Zhang et al. 2017a, b)....
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...…5–20 5–30 50–80 Sharma et al. (2018) Tunicate-CNCs (t-CNCs) Whiskers, nanowhiskers, nanocrystalline cellulose Tunicates 100–4000 5–20 70–100 85–100 Zhao et al. (2015), Zhang et al. (2017) Algal cellulose – Algae 200- [ 1000 5–25 25–70 Chen et al. (2016b) El Achaby, et al.…...
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TL;DR: Measurements of the elastic modulus of tunicate cellulose using a Raman spectroscopic technique show that the tunicate sample is a two-dimensional in-plane random network of fibers, and the modulus is very high, at about 143 GPa.
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