Abstract
Stimuli-responsive hydrogels have become one of the most popular artificial soft materials due to their excellent adaption to complex environments. Thermoresponsive hydrogels triggered by temperature change can be efficiently utilized in many applications. However, these thermoresponsive hydrogels mostly cannot recover their mechanical states under large strain during the process. Herein, we utilize the heterogeneous comb-type polymer network with semicrystalline hydrophobic side chains to design self-recovery semi-crystalline hydrogels. Based on hydrophilic/hydrophobic cooperative complementary interaction and heterogeneous polymer network, hydrogels can be endowed with excellent thermosensitive properties and mechanical performance. The hydrogels exhibit high compressive strength (7.57 MPa) and compressive modulus (1.76 MPa) due to the semi-crystalline domains formed by association of the hydrophobic poly (ε-caprolactone) PCL. The melting-crystalline transition of PCL and elastic polymer network provide the hydrogels excellent thermomechanical performance and self-recovery property. Furthermore, the hydrogels exhibit shape memory behavior, which can be realized by simple process and smart surface patterning. With these excellent properties, our hydrogels can be applied in sensors, flexible devices and scaffolds for tissue engineering.
摘要
热响应性水凝胶在组织工程、 药物运输和柔性器件等领域有着广泛应用. 但传统的热响应性水凝胶在大形变下回复性能差, 而且一般需要复杂的化学合成. 亲疏水二元协同作用可以使水凝胶网络具备优异的响应性和力学性能. 基于此, 我们制备了具有异质梳状网络的半结晶水凝胶. 这种半结晶水凝胶以亲水的DMA和MEA作为网络框架, 疏水的PCL聚集形成结晶微区作为热响应单元, 表现出优异的力学性质、 自恢复特性、 热响应性机械性能和形状记忆的能力.
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Zhao ZG, Xu YC, Fang RC, et al. Bioinspired adaptive gel materials with synergistic heterostructures. Chin J Polym Sci, 2018, 36: 683–696
Zhao Z, Fang R, Rong Q, et al. Bioinspired nanocomposite hydrogels with highly ordered structures. Adv Mater, 2017, 29: 1703045
Chen L, Yin Y, Liu Y, et al. Design and fabrication of functional hydrogels through interfacial engineering. Chin J Polym Sci, 2017, 35: 1181–1193
Zhang Y, Liao J, Wang T, et al. Polyampholyte hydrogels with pH modulated shape memory and spontaneous actuation. Adv Funct Mater, 2018, 28: 1707245
Kim YS, Liu M, Ishida Y, et al. Thermoresponsive actuation enabled by permittivity switching in an electrostatically anisotropic hydrogel. Nat Mater, 2015, 14: 1002–1007
Lu W, Le X, Zhang J, et al. Supramolecular shape memory hydrogels: a new bridge between stimuli-responsive polymers and supramolecular chemistry. Chem Soc Rev, 2017, 46: 1284–1294
Le X, Lu W, Zheng J, et al. Stretchable supramolecular hydrogels with triple shape memory effect. Chem Sci, 2016, 7: 6715–6720
Li Z, Lu W, Ngai T, et al. Mussel-inspired multifunctional supramolecular hydrogels with self-healing, shape memory and adhesive properties. Polym Chem, 2016, 7: 5343–5346
Wang W, Fan X, Li F, et al. Magnetochromic photonic hydrogel for an alternating magnetic field-responsive color display. Adv Opt Mater, 2018, 6: 1701093
Shim TS, Kim SH, Sim JY, et al. Dynamic modulation of photonic bandgaps in crystalline colloidal arrays under electric field. Adv Mater, 2010, 22: 4494–4498
Klouda L, Mikos AG. Thermoresponsive hydrogels in biomedical applications. Eur J Pharm BioPharm, 2008, 68: 34–45
Gao F, Zhang Y, Li Y, et al. Sea cucumber-inspired autolytic hydrogels exhibiting tunable high mechanical performances, repairability, and reusability. ACS Appl Mater Interfaces, 2016, 8: 8956–8966
Hu Y, Kahn JS, Guo W, et al. Reversible modulation of DNA-based hydrogel shapes by internal stress interactions. J Am Chem Soc, 2016, 138: 16112–16119
Dong LC, Yan Q, Hoffman AS. Controlled release of amylase from a thermal and pH-sensitive, macroporous hydrogel. J Control Release, 1992, 19: 171–177
Zhang XZ, Yang YY, Chung TS, et al. Preparation and characterization of fast response macroporous poly(N-isopropylacrylamide) hydrogels. Langmuir, 2001, 17: 6094–6099
Rong Q, Lei W, Chen L, et al. Anti-freezing, conductive selfhealing organohydrogels with stable strain-sensitivity at subzero temperatures. Angew Chem Int Ed, 2017, 56: 14159–14163
Luo F, Sun TL, Nakajima T, et al. Oppositely charged polyelectrolytes form tough, self-healing, and rebuildable hydrogels. Adv Mater, 2015, 27: 2722–2727
Zhang HJ, Sun TL, Zhang AK, et al. Tough physical double-network hydrogels based on amphiphilic triblock copolymers. Adv Mater, 2016, 28: 4884–4890
Zhao Z, Zhang K, Liu Y, et al. Highly stretchable, shape memory organohydrogels using phase-transition microinclusions. Adv Mater, 2017, 29: 1701695
Dai X, Zhang Y, Gao L, et al. A mechanically strong, highly stable, thermoplastic, and self-healable supramolecular polymer hydrogel. Adv Mater, 2015, 27: 3566–3571
Zhang Y, Li Y, Liu W. Dipole-dipole and H-bonding interactions significantly enhance the multifaceted mechanical properties of thermoresponsive shape memory hydrogels. Adv Funct Mater, 2015, 25: 471–480
Liu M, Jiang L. Dialectics of nature in materials science: binary cooperative complementary materials. Sci China Mater, 2016, 59: 239–246
Zhao Z, Liu Y, Zhang K, et al. Biphasic synergistic gel materials with switchable mechanics and self-healing capacity. Angew Chem, 2017, 129: 13649–13654
Gao H, Zhao Z, Cai Y, et al. Adaptive and freeze-tolerant heteronetwork organohydrogels with enhanced mechanical stability over a wide temperature range. Nat Commun, 2017, 8: 15911
Abdurrahmanoglu S, Can V, Okay O. Design of high-toughness polyacrylamide hydrogels by hydrophobic modification. Polymer, 2009, 50: 5449–5455
Tuncaboylu DC, Argun Ai, Sahin M, et al. Structure optimization of self-healing hydrogels formed via hydrophobic interactions. Polymer, 2012, 53: 5513–5522
Bilici C, Ide S, Okay O. Yielding behavior of tough semicrystalline hydrogels. Macromolecules, 2017, 50: 3647–3654
Zhang Z, Ni J, Chen L, et al. Biodegradable and thermoreversible PCLA–PEG–PCLA hydrogel as a barrier for prevention of postoperative adhesion. Biomaterials, 2011, 32: 4725–4736
Yu L, Zhang H, Ding J. A subtle end-group effect on macroscopic physical gelation of triblock copolymer aqueous solutions. Angew Chem Int Ed, 2006, 45: 2232–2235
Chen L, Ci T, Yu L, et al. Effects of molecular weight and its distribution of PEG block on micellization and thermogellability of PLGA–PEG–PLGA copolymer aqueous solutions. Macromolecules, 2015, 48: 3662–3671
Chen L, Li X, Cao L, et al. An injectable hydrogel with or without drugs for prevention of epidural scar adhesion after laminectomy in rats. Chin J Polym Sci, 2016, 34: 147–163
Cui SQ, Yu L, Ding JD. Injectable thermogels based on block copolymers of appropriate amphiphilicity. Acta Polym Sin, 2018: 997–1015
Bellin I, Kelch S, Langer R, et al. Polymeric triple-shape materials. Proc Natl Acad Sci USA, 2006, 103: 18043–18047
Lendlein A, Langer R. Biodegradable, elastic shape-memory polymers for potential biomedical applications. Science, 2002, 296: 1673–1676
Huang M, Zhao K, Wang L, et al. Dual stimuli-responsive polymer prodrugs quantitatively loaded by nanoparticles for enhanced cellular internalization and triggered drug release. ACS Appl Mater Interfaces, 2016, 8: 11226–11236
Yang CS, Wu HC, Sun JS, et al. Thermo-induced shape-memory PEG-PCL copolymer as a dual-drug-eluting biodegradable stent. ACS Appl Mater Interfaces, 2013, 5: 10985–10994
Teubner M, Strey R. Origin of the scattering peak in microemulsions. J Chem Phys, 1987, 87: 3195–3200
Peng S, Guo Q, Hughes TC, et al. In situ synchrotron SAXS study of polymerizable microemulsions. Macromolecules, 2011, 44: 3007–3015
Wu G, Ying Q, Chu B. Lamellar structure of block copolymer poly (oxyethylene-oxypropylene-oxyethylene) in xylene/water mixtures. Macromolecules, 1994, 27: 5758–5765
Washburn NR, Lodge TP, Bates FS. Ternary polymer blends as model surfactant systems. J Phys Chem B, 2000, 104: 6987–6997
Cao H, Chang X, Mao H, et al. Stereocomplexed physical hydrogels with high strength and tunable crystallizability. Soft Matter, 2017, 13: 8502–8510
Guo H, Mussault C, Brûlet A, et al. Thermoresponsive toughening in LCST-type hydrogels with opposite topology: from structure to fracture properties. Macromolecules, 2016, 49: 4295–4306
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (No. 21574004), the National Natural Science Funds for Distinguished Young Scholar (21725401), the Fundamental Research Funds for the Central Universities, the National ‘Young Thousand Talents Program’, and the China Postdoctoral Science Foundation (2017M620012).
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Kangjun Zhang received his BSc degree from Beihang University in 2016. He is now a master candidate under the supervision of Pro. Mingjie Liu at Beihang University. His research focuses on the fabrication of smart hydrogels based on cooperative complementary interaction.
Ruochen Fang is a post-doctor in Beihang University. In 2011, He received his BSc degree in polymer materials and engineering in Department of Chemistry from Jilin University. Then he joined Prof. Xi Zhang’s group and received his PhD degree from Tsinghua University in 2016. His current research interests focus on binary cooperative complementary nanomaterials and bioinspired material science.
Mingjie Liu is currently a full-time professor at Beihang University. In 2005, he joined Prof. Lei Jiang’s group and received his PhD degree from the National Center for Nanoscience and Technology, Chinese Academy of Sciences (2010). He then worked as a postdoc in Prof. Takuzo Aida’s group in Riken in Japan from 2010 to 2015. In 2015, he was awarded the “1000 Youth Plan program” and joined Beihang University. In 2017, he was awarded the National Science Fund for Distinguished Young Scholars. His current research interests focus on anisotropic soft matter with ordered structures, bioinspired design, and application of gel materials.
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Zhang, K., Zhao, Z., Huang, J. et al. Self-recoverable semi-crystalline hydrogels with thermomechanics and shape memory performance. Sci. China Mater. 62, 586–596 (2019). https://doi.org/10.1007/s40843-018-9347-5
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DOI: https://doi.org/10.1007/s40843-018-9347-5