在自然界中,许多生物展现出很强的抗冻能力,能够在极冷的环境中生存。受这些生物抗冻性的启发,研究人员开发了许多先进的抗冻水凝胶材料,并探索其在柔性电子、柔性能源和生物科学等不同领域的潜在应用。基于耐寒生物抗冻性的基本机制,总结了抑制冰核形成和抑制冰晶生长的两类合成抗冻水凝胶的策略:可以引入有机溶剂、酸、两性离子、盐等方法抑制冰核形成;可以引入防冻蛋白(AFPs)、构建核壳纳米结构和聚合物互穿网络结构(IPNs)等方法抑制冰晶生长。简要介绍了每种策略的优缺点,讨论了不同合成策略与所得到的水凝胶性能。最后,提出了抗冻水凝胶未来的发展方向。
In nature,many organisms show strong antifreeze capacity and can survive in extremely cold environments.Inspired by these biological antifreeze properties,researchers have developed a number of advanced antifreeze hydrogel materials and explored their potential applications in diverse fields such as flexible electronics,flexible energy,and bioscience.Based on the basic mechanism of antifreeze of cold-resistant organisms,two kinds of strategies for synthesis of antifreeze hydrogels to inhibit the formation of ice nuclei and the growth of ice crystals were summarized:one was to introduce organic solvents,acids,zwitterion,salts and other methods to inhibit the formation of ice nucleation;the other was to introduce antifreeze proteins (AFP),construct core-shell nanostructures,and polymer interpenetrating network structures (IPNs) to inhibit ice crystal growth.The advantages and disadvantages of each strategy were briefly introduced,and the relationship between the synthetic strategy and the properties of the obtained hydrogels was discussed.Finally,the future development direction of antifreeze hydrogels was proposed.
[1] Li W,Gao F,Wang X,et al.Strong and robust polyaniline-based supramolecular hydrogels for flexible supercapacitors[J].Angewandte Chemie-international Edition,2016,55(32):9196-9201.
[2] Shi Y,Peng L,Yu G.Nanostructured conducting polymer hydrogels for energy storage applications[J].Nanoscale,2015,7(3):11286-12796.
[3] Lei W W,Qi S H,Rong Q F,et al.Diffusion-freezing-induced microphase separation for constructing large-area multiscale structures on hydrogel surfaces[J].Advanced Materials (Weinheim),2019,31(32):e1808217.
[4] Pan S W,Zhang F L,Cai P Q,et al.Mechanically interlocked hydrogel-elastomer hybrids for on-skin electronics[J].Advanced Functional Materials,2020,30(29):1909540.
[5] Li J,Mooney D J.Designing hydrogels for controlled drug delivery[J].Nature Reviews Materials,2016,12(1):16071.
[6] Zhu Y,Lin L,Chen Y,et al.A self-healing,robust adhesion,multiple stimuli-response hydrogel for flexible sensors[J].Soft Matter,2020,16(9):2238-2248.
[7] 王苏杭,孙灵娜,曹涵,等.双载药丝蛋白水凝胶的构筑及其释药性能研究[J].化学学报,2021,79(8):1023-1029.
[8] Fan W,Shan C,Guo H,et al.Dual-gradient enabled ultrafast biomimetic snapping of hydrogel materials[J].Science Advances,2019,5(4):v7174.
[9] Wang Z,Cong Y,Fu J.Stretchable and tough conductive hydrogels for flexible pressure and strain sensors[J].Journal of Materials Chemistry B,2020,8(16):3437-3459.
[10] Jian Y K,Wang S H,Zhang J W,et al.Biomimetic anti-freezing polymeric hydrogels:keeping soft-wet materials active in cold environments[J].Materials Horizons,2021,8(2):351-369.
[11] Mtow S,Tsutsumi T.First instar nymphs of two peltoperlid stoneflies (Insecta,Plecoptera,Peltoperlidae)[J].Mitteilungen aus Dem Museum für Naturkunde in Berlin.Deutsche Entomologische Zeitschrift,2021,68(1):179-188.
[12] Arai T,Yamauchi A,Miura A,et al.Discovery of hyperactive antifreeze protein from phylogenetically distant beetles questions its evolutionary origin[J].International Journal of Molecular Sciences,2021,22(7):3637.
[13] He Z Y,Wu C Y,Hua M,et al.Bioinspired multifunctional anti-icing hydrogel[J].Matter,2020,2(3):723-734.
[14] Liu J,Chen Z,Chen Y J,et al.Ionic conductive organohydrogels with dynamic pattern behavior and multi-environmental stability[J].Advanced Functional Materials,2021,31(24):2101464.
[15] Xu J J,Jin R N,Ren X Y,et al.A wide temperature-tolerant hydrogel electrolyte mediated by phosphoric acid towards flexible supercapacitors[J].Chemical Engineering Journal,2021,413:127446.
[16] Rajan R,Kumar N,Matsumura K.Design of an ice recrystallization-inhibiting polyampholyte-containing graft polymer for inhibition of protein aggregation[J].Biomacromolecules,2022,23(2):487-496.
[17] Wang C,Liu Y,Qu X,et al.Ultra-stretchable and fast self-healing ionic hydrogel in cryogenic environments for artificial nerve fiber[J].Advanced Materials,2022,34(16):e2105416.
[18] Guo M L,Yan J,Yang X,et al.A transparent glycerol-hydrogel with stimuli-responsive actuation induced unexpectedly at subzero temperatures[J].Journal of Materials Chemistry A,2021,9(12):7935-7945.
[19] Han S J,Liu C R,Lin X Y,et al.Dual conductive network hydrogel for a highly conductive,self-healing,anti-freezing,and non-drying strain sensor[J].ACS Applied Polymer Materials,2020,2(2):996-1005.
[20] Ye Y H,Zhang Y F,Chen Y,et al.Cellulose nanofibrils enhanced,strong,stretchable,freezing-tolerant ionic conductive organohydrogel for multi-functional sensors[J].Advanced Functional Materials,2020,30(35):2003430.
[21] Yu H,Rouelle N,Qiu A,et al.Hydrogen bonding-reinforced hydrogel electrolyte for flexible,robust,and all-in-one supercapacitor with excellent low-temperature tolerance[J].ACS Applied Materials & Interfaces,2020,12(34):37977-37985.
[22] Gore M,Narvekar A,Bhagwat A,et al.Macromolecular cryoprotectants for the preservation of mammalian cell culture:lessons from crowding,overview and perspectives[J].Journal of Materials Chemistry B,2022,1(2):143-169.
[23] Jiao Q,Cao L L,Zhao Z J,et al.Zwitterionic hydrogel with high transparency,ultrastretchability,and remarkable freezing resistance for wearable strain sensors[J].Biomacromolecules,2021,22(3):1220-1230.
[24] Cao L L,Zhao Z J,Wang X Y,et al.Tough,antifreezing,and conductive hydrogel based on gelatin and oxidized dextran[J].Advanced Materials Technologies,2022,7(7):2101382.
[25] Yang Y Y,Yang Y T,Cao Y X,et al.Anti-freezing,resilient and tough hydrogels for sensitive and large-range strain and pressure sensors[J].Chemical Engineering Journal,2021,403:126431.
[26] Tian S,Wang M,Wang X,et al.Smart hydrogel sensors with antifreezing,antifouling properties for wound healing[J].ACS Biomaterials Science & Engineering,2022,8(5):1867-1877.
[27] Zhang Y B,Li T Y,Miao L Y,et al.A highly sensitive and ultra-stretchable zwitterionic liquid hydrogel-based sensor as anti-freezing ionic skin[J].Journal of Materials Chemistry A,2022,10(8):3970-398.
[28] Jiang L W,Lu Y X,Zhao C L,et al.Building aqueous K-ion batteries for energy storage[J].Nature Energy,2019,4(6):495-503.
[29] Gao Y F,Peng J B,Zhou M H,et al.A multi-model,large range and anti-freezing sensor based on a multi-crosslinked poly(vinyl alcohol) hydrogel for human-motion monitoring[J].Journal of Materials Chemistry B,2020,8(48):111-112.
[30] Ge W J,Cao S,Yang Y,et al.Nanocellulose/LiCl systems enable conductive and stretchable electrolyte hydrogels with tolerance to dehydration and extreme cold conditions[J].Chemical Engineering Journal,2021,408:127306.
[31] Lei Z,Wu P.A highly transparent and ultra-stretchable conductor with stable conductivity during large deformation[J].Nature Communications,2019,10(1):3429.
[32] Li S H,Pan H Y,Wang Y,et al.Polyelectrolyte complex-based self-healing,fatigue-resistant and anti-freezing hydrogels as highly sensitive ionic skins[J].Journal of Materials Chemistry A,2020,8(7):3667-3675.
[33] Morelle X P,Illeperuma W R,Tian K,et al.Highly stretchable and tough hydrogels below water freezing temperature[J].Advanced Materials,2018,30(35):e1801541.
[34] Yang K X,He J Q,Zhou Q,et al.An anti-freezing/drying,adhesive and self-healing motion sensor with humidity-enhanced conductivity[J].Polymer,2021,214:123354.
[35] Zhang Y B,Li T Y,Miao L,et al.A highly sensitive and ultra-stretchable zwitterionic liquid hydrogel-based sensor as anti-freezing ionic skin[J].Journal of Materials Chemistry A,Materials for Energy and Sustainability,2022,10(8):3970-3988.
[36] Liu H,Wang X,Cao Y,et al.Freezing-tolerant,highly sensitive strain and pressure sensors assembled from ionic conductive hydrogels with dynamic cross-links[J].ACS Applied Materials & Interfaces,2020,12(22):25334-25344.
[37] Tomás R M F,Bailey T L,Hasan M,et al.Extracellular antifreeze protein significantly enhances the cryopreservation of cell monolayers[J].Biomacromolecules,2019,20(10):3864-3872.
[38] Wang C,Wiener C G,Sepulveda-Medina P I,et al.Antifreeze hydrogels from amphiphilic statistical copolymers[J].Chemistry of Materials,2019,31(1):135-145.
[39] Gao H N,Zhao Z G,Cai Y D,et al.Adaptive and freeze-tolerant heteronetwork organohydrogels with enhanced mechanical stability over a wide temperature range[J].Nature Communications,2017,8(1):15911.
[40] Jeon N,Choi I,Lee P C W,et al.Gold nanoparticle-tethered peptide nanofibrils for monitoring ice recrystallization inhibition:implications for cryopreservation[J].ACS Applied Nano Materials,2022,5(10):15418-15428.
[41] He Z Y,Wu C Y,Hua M T,et al.Bioinspired multifunctional anti-icing hydrogel[J].Matter,2020,2(3):723-734.
基金资助
教育部产学合作协同育人项目(22097047222142);衡水学院校级培育基金项目(2023XJZX25);衡水学院校级重点课题(2023ZRZ05);衡水市科学技术局项目(2022014035Z);河北省大学生创新创业训练项目(s202310101023)
PDF
