A Self-Healing Cellulose Nanocrystal-Poly(ethylene glycol) Nanocomposite Hydrogel via Diels–Alder Click Reaction

Self-healing hydrogels are particularly desirable for increased safety and functional lifetimes because of stress-induced deformation and propagation of cracks. In this paper, we report a tough, highly resilient, fast self-recoverable, and self-healing nanocomposite hydrogel, which builds an interpenetrated network encapsulating rod-like cellulose nanocrystals (CNCs) by flexible polymer chains of poly(ethylene glycol) (PEG). A thermally reversible covalent Diels–Alder click reaction between furyl-modified CNCs and maleimide-end-functionalized PEG was confirmed by Fourier transform infrared spectroscopy. Uniaxial tensile tests and unconfined compression tests displayed outstanding mechanical properties of the hydrogels with a high fracture elongation up to 690% and a fracture strength up to 0.3 MPa at a strain of 90%. Cyclic loading–unloading tests showed excellent self-recovery and antifatigue properties of the nanocomposite hydrogels. The self-healing capability of nanocomposite hydrogels assessed by ten...

[1]  N. Gabilondo,et al.  Maleimide-grafted cellulose nanocrystals as cross-linkers for bionanocomposite hydrogels. , 2016, Carbohydrate polymers.

[2]  E. Cranston,et al.  Injectable polysaccharide hydrogels reinforced with cellulose nanocrystals: morphology, rheology, degradation, and cytotoxicity. , 2013, Biomacromolecules.

[3]  Akira Harada,et al.  Preorganized Hydrogel: Self‐Healing Properties of Supramolecular Hydrogels Formed by Polymerization of Host–Guest‐Monomers that Contain Cyclodextrins and Hydrophobic Guest Groups , 2013, Advanced materials.

[4]  Jiaxi Cui,et al.  Multivalent H-bonds for self-healing hydrogels. , 2012, Chemical communications.

[5]  Masaru Yoshida,et al.  High-water-content mouldable hydrogels by mixing clay and a dendritic molecular binder , 2010, Nature.

[6]  Amy M. Peterson,et al.  Room temperature self-healing thermoset based on the Diels-Alder reaction. , 2013, ACS applied materials & interfaces.

[7]  Mpf Mark Pepels,et al.  Self-healing systems based on disulfide–thiol exchange reactions , 2013 .

[8]  Yan-Min Shen,et al.  Thermosensitive hydrogels synthesized by fast Diels–Alder reaction in water , 2009 .

[9]  A. Dufresne,et al.  TEMPO-oxidized nanocellulose participating as crosslinking aid for alginate-based sponges. , 2012, ACS applied materials & interfaces.

[10]  Jiazhi Yang,et al.  Rapid Fabrication of Composite Hydrogel Microfibers for Weavable and Sustainable Antibacterial Applications , 2016 .

[11]  Jay C. Sy,et al.  Maleimide Cross‐Linked Bioactive PEG Hydrogel Exhibits Improved Reaction Kinetics and Cross‐Linking for Cell Encapsulation and In Situ Delivery , 2012, Advanced materials.

[12]  David J. Pine,et al.  Rapidly recovering hydrogel scaffolds from self-assembling diblock copolypeptide amphiphiles , 2002, Nature.

[13]  D. McGrath,et al.  Thermally reversible dendronized linear ab step-polymers via "click" chemistry , 2011 .

[14]  Marek W. Urban,et al.  Chemical and physical aspects of self-healing materials , 2015 .

[15]  Lina Zhang,et al.  Reinforced Mechanical Properties and Tunable Biodegradability in Nanoporous Cellulose Gels: Poly(L-lactide-co-caprolactone) Nanocomposites. , 2016, Biomacromolecules.

[16]  Y. Amemiya,et al.  Dependence of the swelling behavior of a pH-responsive PEG-modified nanogel on the cross-link density , 2012 .

[17]  Cheng-Chih Hsu,et al.  Rapid self-healing hydrogels , 2012, Proceedings of the National Academy of Sciences.

[18]  V. Khutoryanskiy,et al.  Biomedical applications of hydrogels: A review of patents and commercial products , 2015 .

[19]  M. in het Panhuis,et al.  Self‐Healing Hydrogels , 2016, Advanced materials.

[20]  A. Gandini,et al.  Reversible polymerization of novel monomers bearing furan and plant oil moieties: a double click exploitation of renewable resources , 2012 .

[21]  Lina Zhang,et al.  High‐Strength and High‐Toughness Double‐Cross‐Linked Cellulose Hydrogels: A New Strategy Using Sequential Chemical and Physical Cross‐Linking , 2016 .

[22]  Yaling Zhang,et al.  Synthesis of multiresponsive and dynamic chitosan-based hydrogels for controlled release of bioactive molecules. , 2011, Biomacromolecules.

[23]  Krzysztof Matyjaszewski,et al.  Self‐Healing of Covalently Cross‐Linked Polymers by Reshuffling Thiuram Disulfide Moieties in Air under Visible Light , 2012, Advanced materials.

[24]  Todd Hoare,et al.  Review of Hydrogels and Aerogels Containing Nanocellulose , 2017 .

[25]  Jessica J. Cash,et al.  Room-Temperature Self-Healing Polymers Based on Dynamic-Covalent Boronic Esters , 2015 .

[26]  Florian Herbst,et al.  Self-healing polymers via supramolecular forces. , 2013, Macromolecular rapid communications.

[27]  Biao Huang,et al.  Synthesis of pH-Sensitive Fluorescein Grafted Cellulose Nanocrystals with an Amino Acid Spacer , 2016 .

[28]  Hisashi Tanimoto,et al.  Self-healing in nanocomposite hydrogels. , 2011, Macromolecular rapid communications.

[29]  Eric D. Pressly,et al.  Rapid Synthesis of Block and Cyclic Copolymers via Click Chemistry in the Presence of Copper Nanoparticles. , 2011, Journal of polymer science. Part A, Polymer chemistry.

[30]  O. Altintas,et al.  Synthesis of terpolymers by click reactions. , 2011, Chemistry, an Asian journal.

[31]  D. Tuncaboylu,et al.  Self-healing hydrogels formed in catanionic surfactant solutions , 2013 .

[32]  Zhenda Lu,et al.  Colloidal nanoparticle clusters: functional materials by design. , 2012, Chemical Society reviews.

[33]  O. Scherman,et al.  Supramolecular polymeric hydrogels. , 2012, Chemical Society reviews.

[34]  Yoshihito Osada,et al.  Novel Biocompatible Polysaccharide‐Based Self‐Healing Hydrogel , 2015 .

[35]  B. Sumerlin,et al.  Dynamic-covalent macromolecular stars with boronic ester linkages. , 2011, Journal of the American Chemical Society.

[36]  Akira Harada,et al.  Redox-responsive self-healing materials formed from host–guest polymers , 2011, Nature communications.

[37]  D. Tuncaboylu,et al.  Dynamics and Large Strain Behavior of Self-Healing Hydrogels with and without Surfactants , 2012 .

[38]  James R. McElhanon,et al.  Thermally Reversible Dendronized Step-Polymers Based on Sequential Huisgen 1,3-Dipolar Cycloaddition and Diels-Alder ``Click'' Reactions , 2010 .

[39]  Yaling Zhang,et al.  Facilely prepared inexpensive and biocompatible self-healing hydrogel: a new injectable cell therapy carrier , 2012 .

[40]  Lifeng Yan,et al.  Supramolecular Hydrogel of Chitosan in the Presence of Graphene Oxide Nanosheets as 2D Cross-Linkers , 2014 .

[41]  D. Mooney,et al.  Hydrogels for tissue engineering. , 2001, Chemical Reviews.

[42]  Hui Li,et al.  An Eco-Friendly Scheme for the Cross-Linked Polybutadiene Elastomer via Thiol–Ene and Diels–Alder Click Chemistry , 2015 .

[43]  Yoshihito Osada,et al.  Self-healing gels based on constitutional dynamic chemistry and their potential applications. , 2014, Chemical Society reviews.

[44]  J. Lehn,et al.  Room temperature dynamic polymers based on Diels-Alder chemistry. , 2009, Chemistry.

[45]  Jinrong Yao,et al.  Robust Protein Hydrogels from Silkworm Silk , 2016 .

[46]  Xueming Zhang,et al.  Elucidating Dynamics of Precoordinated Ionic Bridges as Sacrificial Bonds in Interpenetrating Network Hydrogels , 2016 .

[47]  Xiaodong Cao,et al.  Diels-Alder Click-Based Hydrogels for Direct Spatiotemporal Postpatterning via Photoclick Chemistry. , 2015, ACS macro letters.

[48]  Zhibin Guan,et al.  Malleable and Self-Healing Covalent Polymer Networks through Tunable Dynamic Boronic Ester Bonds. , 2015, Journal of the American Chemical Society.