环境刺激响应型高强度智能水凝胶研究进展

doi:10.16085/j.issn.1000-6613.2016.06.022

摘要/Abstract

摘要： 环境刺激响应型智能水凝胶能够对外界环境因素的变化产生显著的体积或其他特性的变化,且其性质和结构与生物组织类似,有望应用于人工软骨、人造肌肉、组织工程等领域,引起了广泛的关注。提高环境刺激响应型智能水凝胶的力学性能是智能水凝胶应用研究的重要方向之一。本文综述了近年来环境刺激响应型高强度智能水凝胶的研究进展,简述了高强度智能水凝胶的网络结构的构建策略与方法,分析了其具备高力学性能的机理,重点介绍了4类不同结构的高强度智能水凝胶,即超低交联结构水凝胶、纳米颗粒复合水凝胶、拓扑结构水凝胶以及双网络结构水凝胶,最后讨论了环境刺激响应型高强度智能水凝胶在面向应用的研究过程中仍然需要解决的关键科学问题,如智能水凝胶的环境刺激与力学性能的博弈效应以及响应环境刺激前后的力学性能差异等。

关键词: 凝胶, 聚合物, 力学性能, 纳米结构, 环境刺激响应

Abstract: Stimuli-responsive smart hydrogels with three-dimensional networks composed of cross-linked hydrophilic polymer chains can dramatically change their volume or other properties in response to various external stimuli,which are similar to bio-tissues. Due to such stimuli responsiveness,they show remarkable potential for numerous applications,such as artificial cartilages,artificial muscles and tissue engineering scaffolds,for which high mechanical properties are highly desired. Improving the mechanical properties of the stimuli-responsive smart hydrogels is one of the critical issues for their developments and applications. This review briefly introduces the design,fabrication and mechanism of stimuli-responsive smart hydrogels with high mechanical properties. Four types of smart hydrogels of ultra-low crosslinking hydrogels,nanocomposite hydrogels,topological hydrogels,and double network hydrogels,are introduced. Finally,the perspectives and challenges of stimuli-responsive smart hydrogels with high mechanical properties are discussed. The future work should focus on the trade-off effect of the stimuli-responsiveness and the mechanical properties of stimuli-responsive smart hydrogels,as well as their variations on environmental stimuli.

Key words: gels, polymers, mechanical properties, nanostructure, environmental stimuli-response

中图分类号:

TB381

刘壮, 谢锐, 巨晓洁, 汪伟, 褚良银. 环境刺激响应型高强度智能水凝胶研究进展[J]. 化工进展, 2016, 35(06): 1812-1819.

LIU Zhuang, XIE Rui, JU Xiaojie, WANG Wei, CHU Liangyin. Progress in stimuli-responsive smart hydrogels with high mechanical properties[J]. Chemical Industry and Engineering Progree, 2016, 35(06): 1812-1819.

参考文献

[1] CHU L Y,XIE R,JU X J,et al. Smart hydrogel functional materials[M]. Berlin,Heidelberg:Springer-Verlag,2013.
[2] STAYTON P S,SHIMOBOJI T,LONG C,et al. Control of protein-ligand recognition using a stimuli-responsive polymer[J]. Nature,1995,378:472-474.
[3] KIM Y S,LIU M J,ISHIDA Y,et al. Thermoresponsive actuation enabled by permittivity switching in an electrostatically anisotropic hydrogel[J]. Nature Materials,2015,14(10):1002-1007.
[4] MOU C L,JU X J,ZHANG L,et al. Monodisperse and fast-responsive poly(N-isopropylacrylamide) microgels with open-celled porous structure[J]. Langmuir,2014,30(5):1455-1464.
[5] ANGELOS S,YANG Y W,PATEL K,et al. pH-Responsive supramolecular nanovalves based on cucurbit[6] uril pseudorotaxanes[J]. Angewandte Chemie International Edition,2008,47(12):2222-2226.
[6] ZHANG S Y,BELLINGER A M,GLETTIG D L,et al. pH-Responsive supramolecular polymer gel as an enteric elastomer for use in gastric devices[J]. Nature Materials,2015,14(10):1065-1071.
[7] ZHANG J,XIE R,ZHANG S B,et al. Rapid pH/temperature-responsive cationic hydrogels with dual stimuli-sensitive grafted side chains[J]. Polymer,2009,50(11):2516-2525.
[8] ZHANG J,CHU L Y,LI Y K,et al. Dual thermo- and pH-sensitive poly(N-isopropylacrylamide-co-acrylic acid) hydrogels with rapid response behaviors[J]. Polymer,2007,48(6):1718-1728.
[9] MI P,JU X J,XIE R,et al. A novel stimuli-responsive hydrogel for K⁺-induced controlled-release [J]. Polymer,2010,51(7):1648-1653.
[10] JIANG M Y,JU X J,FANG L,et al. A novel smart microsphere with K⁺-induced shrinking and aggregating property based on responsive host-guest system[J]. ACS Applied Materials & Interfaces,2014,6(21):19405-19415.
[11] TU T,FANG W W,SUN Z M. Visual-size molecular recognition based on gels[J]. Advanced Materials,2013,25(37):5304-5313.
[12] IKEDA M,TANIDA T,YOSHII T,et al. Installing logic-gate responses to a variety of biological substances in supramolecular hydrogel-enzyme hybrids[J]. Nature Chemistry,2014,6(6):511-518.
[13] SAMOEI G K,WANG W H,ESCOBEDO J O,et al. A chemomechanical polymer that functions in blood plasma with high glucose selectivity[J]. Angewandte Chemie International Edition,2006,45(32):5319-5322.
[14] ZHANG S B,CHU L Y,XU D,et al. Poly(N-isopropylacrylamide)-based comb-type grafted hydrogel with rapid response to blood glucose concentration change at physiological temperature[J]. Polymers for Advanced Technologies,2008,19(8):937-943.
[15] ZHANG M J,WANG W,XIE R,et al. Microfluidic fabrication of monodisperse microcapsules for glucose-response at physiological temperature[J]. Soft Matter,2013,9(16):4150-4159.
[16] KLOXIN A M,KASKO A M,SALINAS C N,et al. Photodegradable hydrogels for dynamic tuning of physical and chemical properties[J]. Science,2009,324:59-63.
[17] TAKASHIMA Y,HATANAKA S,OTSUBO M,et al. Expansion-contraction of photoresponsive artificial muscle regulated by host-guest interactions[J]. Nature Communications,2012,3:1270.
[18] ZHANG X B,PINT C L,LEE M H,et al. Optically-and thermally-responsive programmable materials based on carbon nanotube-hydrogel polymer composites[J]. Nano Letters,2011,11(8):3239-3244.
[19] FUSCO S,SAKAR M S,KENNEDY S,et al. An integrated microrobotic platform for on-demand,targeted therapeutic interventions[J]. Advanced Materials,2014,26(6):952-957.
[20] KWON I C,BAE Y H,KIM S W. Electrically erodible polymer gel for controlled release of drugs[J]. Nature,1991,354(6351):291-293.
[21] OSADA Y,OKUZAKI H,HORI H. A polymer gel with electrically driven motility[J]. Nature,1992,355(6327):242-244.
[22] YANG C,WANG W,YAO C,et al. Hydrogel walkers with electro-driven motility for cargo transport[J]. Scientific Reports,2015,5:13622-13631.
[23] DONG L,AGARWAL A K,BEEBE D J,et al. Adaptive liquid microlenses activated by stimuli-responsive hydrogels[J]. Nature,2006,442(7102):551-554.
[24] SIDORENKO A,KRUPENKIN T,TAYLOR A,et al. Reversible switching of hydrogel-actuated nanostructures into complex micropatterns[J]. Science,2007,315(5811):487-490.
[25] MA M M,GUO L,ANDERSON D G,et al. Bio-inspired polymer composite actuator and generator driven by water gradients[J]. Science,2013,339(6116):186-189.
[26] ISLAM M R,LI X,SMYTH K,et al. Polymer-based muscle expansion and contraction[J]. Angewandte Chemie International Edition,2013,52(39):10330-10333.
[27] IAMSAARD S,AßHOFF S J,MATT B,et al. Conversion of light into macroscopic helical motion[J]. Nature Chemistry,2014,6(3):229-335.
[28] LU X,ZHANG Z,LI H,et al. Conjugated polymer composite artificial muscle with solvent-induced anisotropic mechanical actuation[J]. Journal of Materials Chemistry A,2014,2(41):17272-17280.
[29] CALVERT P. Hydrogels for soft machines [J]. Advanced Materials,2009,21(7):743-756.
[30] YAO C,LIU Z,YANG C,et al. Poly(N-isopropylacrylamide)-clay nanocomposite hydrogels with responsive bending property as temperature-controlled manipulators[J]. Advanced Functional Materials,2015,25(20):2980-2991.
[31] BEEBE D J,MOORE J S,BAUER J M,et al. Functional hydrogel structures for autonomous flow control inside microfluidic channels[J]. Nature,2000,404(6778):588-590.
[32] ZHU C H,LU Y,PENG J,et al. Photothermally sensitive poly(N-isopropylacrylamide)/graphene oxide nanocomposite hydrogels as remote light-controlled liquid microvalves[J]. Advanced Functional Materials,2012,22(19):4017-4022.
[33] LIN S,WANG W,JU X J,et al. A simple strategy for in situ fabrication of smart hydrogel microvalve within microchannels for thermostatic control[J]. Lab on a Chip,2014,14(15):2626-2634.
[34] SELIKTAR D. Designing cell-compatible hydrogels for biomedical applications[J]. Science,2012,336(6085):1124-1128.
[35] STUART M A C,HUCK W T S,GENZER J,et al. Emerging applications of stimuli-responsive polymer materials[J]. Nature Materials,2010,9(2):101-113.
[36] LIU Z,LIU L,JU X J,et al. K⁺-recognition capsules with squirting release mechanisms[J]. Chemical Communications,2011,47(45):12283-12285.
[37] LIU L,WANG W,JU X J,et al. Smart thermo-triggered squirting capsules for nanoparticle delivery[J]. Soft Matter,2010,6(16):3759-3763.
[38] NAGASE K,KOBAYASHI J,OKANO T. Temperature-responsive intelligent interfaces for biomolecular separation and cell sheet engineering[J]. Journal of The Royal Society Interface,2009,6:S293-S309.
[39] THOMAS P C,CIPRIANO B H,RAGHAVAN S R. Nanoparticle-crosslinked hydrogels as a class of efficient materials for separation and ionexchange[J]. Soft Matter,2011,7(18):8192-8197.
[40] 刘壮,谢锐,巨晓洁,等. 具有快速响应特性的环境响应型智能水凝胶的研究进展[J]. 化工学报,2015,67(1):202-208.
[41] XIA L W. Construction and performance of composite thermo-responsive hydrogels crosslinked by microgels[D]. Chengdu:Sichuan University,2013.
[42] NAFICY S,BROWN H R,RAZAL J M,et al. Progress toward robust polymer hydrogels[J]. Australian Journal of Chemistry,2011,64(8):1007-1025.
[43] SHI K,LIU Z,WEI Y Y,et al. Near-infrared light-responsive poly(N-isopropylacrylamide)/graphene oxide nanocomposite hydrogels with ultrahigh tensibility[J]. ACS Applied Materials & Interfaces,2015,7(49):27289-27298.
[44] HARAGUCHI K,TAKEHISA T. Nanocomposite hydrogels:a unique organic-inorganic network structure with extraordinary mechanical,optical,and swelling/de-swelling properties[J]. Advanced Materials,2002,14(16):1120-1124.
[45] HARAGUCHI K,TAKEHISA T,FAN S. Effects of clay content on the properties of nanocomposite hydrogels composed of poly (N-isopropylacrylamide) and clay[J]. Macromolecules,2002,35(27):10162-10171.
[46] ABDURRAHMANOGLU S,CAN V,OKAY O. Equilibrium swelling behavior and elastic properties of polymer-clay nanocomposite hydrogels[J]. Journal of Applied Polymer Science,2008,109(6):3714-3724.
[47] HARAGUCHI K,XU Y J,LI G. Molecular characteristics of poly(N-isopropylacrylamide) separated from nanocomposite gels by removal of clay from the polymer/clay network[J]. Macromolecular Rapid Communications,2010,31(8):718-723.
[48] LIN W C,FAN W,MARCELLAN A,et al. Large strain and fracture properties of poly(dimethylacrylamide)/silica hybrid hydrogels[J]. Macromolecules,2010,43(5):2554-2563
[49] KIM J,KOO J,SHIRAHASE T,et al. Preparation of organic/inorganic hybrid gel after gamma-ray radiation[J]. Chemistry Letters,2009,38(11):1112-1113.
[50] LIU M,ISHIDA Y,EBINA Y,et al. Photolatently modulable hydrogels using unilamellar titania nanosheets as photocatalytic crosslinkers[J]. Nature Communications,2013,4:3029.
[51] BHATTACHARYYA S,GUILLOT S,DABBOUE H,et al. Carbon nanotubes as structural nanofibers for hyaluronic acid hydrogel scaffolds[J]. Biomacromolecules,2008,9(2):505-509.
[52] VAYSSE M,KHAN M K,SUNDARARAJAN P. Carbon nanotube reinforced porous gels of poly(methyl methacrylate) with nonsolvents as porogens[J]. Langmuir,2009,25(12):7042-7049.
[53] HUANG T,XU H G,JIAO K X,et al. A novel hydrogel with high mechanical strength:a macromolecular microsphere composite hydrogel[J]. Advanced Materials,2007,19(12):1622-1626.
[54] XIA L W,XIE R,JU X J,et al. Nano-structured smart hydrogels with rapid response and high elasticity[J]. Nature Communications,2013,4:2226.
[55] OKUMURA Y,ITO K. The polyrotaxane gel:a topological gel by figure-of-eight cross-links[J]. Advanced Materials,2001,13(7):485-487.
[56] IMRAN A B,ESAKI K,GOTOH H,et al. Extremely stretchable thermosensitive hydrogels by introducing slide-ring polyrotaxane cross-linkers and ionic groups into the polymer network[J]. Nature Communications,2014,5:5124. DOI:10.1038/ncomms6124.
[57] GONG J P,KATSUYAMA Y,KUROKAWA T,et al. Double-network hydrogels with extremely high mechanical strength[J]. Advanced Materials,15(14):1155-1158.
[58] SUN T L,KUROKAWA T,KURODA S,et al. Physical hydrogels composed of polyampholytes demonstrate high toughness and viscoelasticity[J]. Nature Materials,2013,12(10):932-937.
[59] SUN J Y,ZHAO X,ILLEPERUMA W R K,et a1. Highly stretchable and tough hydrogels[J]. Nature,2012,489(7414):133-l36.
[60] FEI R,GEORGE J T,PARK J,et al. Ultra-strong thermoresponsive double network hydrogels[J]. Soft Matter,2013,9(10):2912-2919.