Citation: HUANG He, LI Yayu, GUO Ziyan, SHI Dongjian, ZHANG Hongji, CHEN Mingqing. Preparation and Properties of Dual Responsive Self-healing Bio-based Hydrogels[J]. Chinese Journal of Applied Chemistry, ;2019, 36(2): 146-154. doi: 10.11944/j.issn.1000-0518.2019.02.180106 shu

Preparation and Properties of Dual Responsive Self-healing Bio-based Hydrogels

The Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, China

Corresponding author: SHI Dongjian, djshi@jiangnan.edu.cn
Received Date: 10 April 2018
Revised Date: 7 May 2018
Accepted Date: 15 June 2018

Fund Project: the Postgraduate Research & Practice Innovation Program of Jiangsu Province KYCX_1470Supported by the Postgraduate Research & Practice Innovation Program of Jiangsu Province(No.KYCX_1470)

Figures(10)

Phenylboronic acid and derivatives that conjugate with diol units to form a reversible ester bond can be used to prepare self-healing and stimuli-responsive materials. Stimuli-responsive hydrogels based on phenylboronic acid have been reported to have excellent self-healing properties. However, in these examples, employed polymers are not fully degradable nor have low biocompatibility. Therefore, this study aims to prepare a bio-based hydrogel for potential biomedical applications. Poly(γ-glutamic acid-g-3-aminophenylboronic acid)(γ-PGA-g-APBA) was synthesized by grafting 3-aminophenylboronic acid(APBA) in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide(EDC) and N-hydroxysuccinimide(NHS) as catalysts, and guar gum was modified by cationic etherification agent, 2, 3-epoxypropyltrimethylammonium chloride(CHGTA). These two modified bio-polymers were characterized by Fourier transform infrared(FT-IR) spectroscopy, nuclear magnetic resonance(¹H NMR), and ultraviolet-visible(UV-Vis) spectrophotometer, and were mixed to form hydrogels. Mechanical properties of the prepared hydrogels were characterized by the rheometer. The results show that(γ-PGA-g-APBA/CGG) hydrogels have self-healing and pH-responsive properties. The structure of the gels is damaged with large strain and reconstructed completely with small strain, indicating that the hydrogel have the self-healing property and the repeatability. With the increase of pH value from 7 to 9, the hydrogels are formed and their strengths increase with pH, due to the conversion of the trigonal boronic-ester bond to tetrahedral boronic-ester bond. In the presence of 4 g/L glucose, the formed gel dissociates and changes to sol, because of the competing reaction between glucose and guar gum with PBA group. Moreover, rheology test indicates the shear-thinning and injectable properties of the hydrogels. Thus, the bio-based(γ-PGA-g-APBA/CGG) hydrogels have the potential applications in sensors, medicine and tissue engineering.
- self-healing,
- stimuli-responsive gel,
- polyglutamic acid,
- guar gum
1. [1]
  Shan M, Gong C, Li B Q. A pH, Glucose, and Dopamine Triple-responsive, Self-healable Adhesive Hydrogel Formed by Phenylborate-Catechol Complexation[J]. Polym Chem, 2017,8(19):2997-3005. doi: 10.1039/C7PY00519A
2. [2]
  Roberts M C, Hanson M C, Massey A P. Dynamically Restructuring Hydrogel Networks Formed with Reversible Covalent Crosslinks[J]. Adv Mater, 2007,19(18):2503-2507. doi: 10.1002/(ISSN)1521-4095
3. [3]
  Wang L, Liu M Z, Gao C M. A pH-, Thermo-, and Glucose-, Triple-responsive Hydrogels:Synthesis and Controlled Drug Delivery[J]. React Funct Polym, 2010,70(3):159-167. doi: 10.1016/j.reactfunctpolym.2009.11.007
4. [4]
  JING Shuping, LIU Mingzhu, CHEN Shilan. Responsive Properties and Applications of the Intelligent Polymers and Hydrogels[J]. Acta Phys Chim Sin, 2007,23(3):438-446.
5. [5]
  DUAN Yuanshou, JIA Fengxia, WANG Shuo. Synthesis and Thermosensitivity of Poly(N-isopropylacrylamide)/Hydrotalite Hydrogel[J]. Chinese J Appl Chem, 2018,35(1):40-45.
6. [6]
  Clodt J I, Filiz V, Rangou S. Double Stimuli-Responsive Isoporous Membranes via Post-modification of pH-Sensitive Self-assembled Diblock Copolymer Membranes[J]. Adv Funct Mater, 2013,23(6):731-738. doi: 10.1002/adfm.v23.6
7. [7]
  Zhao J Q, Liu J J, Han S C. Acid-Induced Disassemblable Nanoparticles Based on Cyclic Benzylidene Acetal-Functionalized Graft Copolymer via Sequential RAFT and ATRP Polymerization[J]. Polym Chem, 2014,5(6):1852-1856. doi: 10.1039/c3py01324c
8. [8]
  Deforest C A, Polizzotti B D, Anseth K S. Sequential Click Reactions for Synthesizing and Patterning Three-Dimensional Cell Microenvironments[J]. Nat Mater, 2009,8(8):659-664. doi: 10.1038/nmat2473
9. [9]
  Hackelbusch S, Rossow T, Becker H. Multiresponsive Polymer Hydrogels by Orthogonal Supramolecular Chain Cross-Linking[J]. Macromolecules, 2014,47(12):4028-4036. doi: 10.1021/ma5008573
10. [10]
  Yan X Z, Xu D H, Chi X D. A Multiresponsive, Shape-Persistent, and Elastic Supramolecular Polymer Network Gel Constructed by Orthogonal Self-assembly[J]. Adv Mater, 2012,24(3):362-369. doi: 10.1002/adma.201103220
11. [11]
  Yuan J C, Fang X L, Zhang L X. Multi-responsive Self-healing Metallo-supramolecular Gels Based on "Click" Ligand[J]. J Mater Chem, 2012,22(23):11515-11522. doi: 10.1039/c2jm31347b
12. [12]
  SHI Dongjian, WANG Fei, LIU Rongjin. Preparation and Properties of Catechol-Metal Complexation Hydrogels[J]. Polym Mater Sci Eng, 2016,32(5):156-171.
13. [13]
  Ma R J, Shi L Q. Phenylboronic Acid-Based Glucose-Responsive Polymeric Nanoparticles:Synthesis and Applications in Drug Delivery[J]. Polym Chem, 2014,5(5):1503-1518. doi: 10.1039/C3PY01202F
14. [14]
  Dong Y, Wang W, Veiseh O. Injectable and Glucose-Responsive Hydrogels Based on Boronic Acid-Glucose Complexation[J]. Langmuir, 2016,32(34):8743-7. doi: 10.1021/acs.langmuir.5b04755
15. [15]
  Yesilyurt V, Webber M J, Appel E A. Injectable Self-healing Glucose-Responsive Hydrogels with pH-Regulated Mechanical Properties[J]. Adv Mater, 2016,28(1):86-91. doi: 10.1002/adma.201502902
16. [16]
  Guo R W, Su Q, Zhang J W. Facile Access to Multisensitive and Self-healing Hydrogels with Reversible and Dynamic Boronic Ester and Disulfide Linkages[J]. Biomacromolecules, 2017,18(4):1356-1364. doi: 10.1021/acs.biomac.7b00089
17. [17]
  YANG Ting, DENG Xinxing, DU Fusheng. Glucose-Responsive Hydrogels Based on ABA Triblock Copolymers Containing Phenylboronic Acid[J]. Acta Polym Sin, 2014,11:1553-1560.
18. [18]
  JI Yi. The Synthesis of Guar Gum Derivatives[D]. Dalian: Dalian University of Technology, 2005(in Chinese).
1. [1]
  Yan Yu , Zijian Wang , Hong Wu , Wei Hu . The Mystery of Self-Healing Materials: Breaking the Mirror and Restoring It. University Chemistry, 2026, 41(2): 268-272. doi: 10.12461/PKU.DXHX202501011
2. [2]
  Zhongrui Wang , Yuwen Meng , Xu Wang . 双层水凝胶的制备及其pH响应变形实验. University Chemistry, 2025, 40(8): 255-264. doi: 10.12461/PKU.DXHX202410038
3. [3]
  Ziwen Lei , Mingyin Liu , Jiayi Shi , Yahan Shan , Qi Zhang . 当超分子二肽遇上酸碱指示剂：热响应水凝胶的智能可视化. University Chemistry, 2026, 41(8): 210-219. doi: 10.12461/PKU.DXHX202508014
4. [4]
  Qingwen Xu , Zhigang Xie , Min Zheng . Construction of pH-responsive Lycium barbarum-derived carbon dots nanovaccines for enhanced anti-tumor immunotherapy. Acta Physico-Chimica Sinica, 2026, 42(6): 100203-0. doi: 10.1016/j.actphy.2025.100203
5. [5]
  Xinyu Liu , Weiran Hu , Zhengkai Li , Wei Ji , Xiao Ni . Algin Lab: Surging Luminescent Sea. University Chemistry, 2024, 39(5): 396-404. doi: 10.3866/PKU.DXHX202312021
6. [6]
  Nianxia Dong , Mengmei Huang , Yilin Wang , Yarong Zheng , Jianbo He , Xianghua Kong . 牙科金属修复体在口腔中的电化学. University Chemistry, 2026, 41(9): 229-234. doi: 10.12461/PKU.DXHX202507025
7. [7]
  Yimeng Li , Yuanyuan Yang , Zhengke Wang . Transparent and hydrophilic "phoenix garment" for corneal stromal regeneration. Acta Physico-Chimica Sinica, 2026, 42(10): 100265-0. doi: 10.1016/j.actphy.2026.100265
8. [8]
  Yuena Yang , Xufang Hu , Yushan Liu , Yaya Kuang , Jian Ling , Qiue Cao , Chuanhua Zhou . The Realm of Smart Hydrogels. University Chemistry, 2024, 39(5): 172-183. doi: 10.3866/PKU.DXHX202310125
9. [9]
  Feiyang Liu , Liuhong Song , Miaoyu Fu , Zhi Zheng , Gang Xie , Junlong Zhao . Tryptophan’s Employment Journey. University Chemistry, 2024, 39(9): 16-21. doi: 10.12461/PKU.DXHX202404037
10. [10]
  Simin Fang , Wei Huang , Guanghua Yu , Cong Wei , Mingli Gao , Guangshui Li , Hongjun Tian , Wan Li . Integrating Science and Education in a Comprehensive Chemistry Design Experiment: The Preparation of Copper(I) Oxide Nanoparticles and Its Application in Dye Water Remediation. University Chemistry, 2024, 39(8): 282-289. doi: 10.3866/PKU.DXHX202401023
11. [11]
  Jing Yan , Zenan Zhang , Dongwei Ma , Xinyi Zhang , Zhuodong Ye , Xuefang Chen . Melamine-assisted topotactic transformation of MOFs into needle-like α-MoC/β-Mo₂C for high-performance electromagnetic wave absorption and corrosion resistance. Acta Physico-Chimica Sinica, 2026, 42(9): 100328-0. doi: 10.1016/j.actphy.2026.100328
12. [12]
  Qiang HU , Zhiqi CHEN , Zhong CHEN , Xu WANG , Weina WU . Pyridinium-chalcone-based ClO^- fluorescent probe: Preparation and biological imaging applications. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1789-1795. doi: 10.11862/CJIC.20250086
13. [13]
  Xinyu CHENG , Xinran CHEN , Fei LI , Chen CHEN , NevisNathaniel L. , Kai CHEN . 两例同构的七元瓜环基超分子自组装体的合成、Hirshfeld表面分析及其性质. Chinese Journal of Inorganic Chemistry, 2026, 42(8): 1637-1646. doi: 10.11862/CJIC.20260049
14. [14]
  Hengjia Wang , Wenling Gu , Chengzhou Zhu . 贵金属气凝胶的发现、制备、凝胶机制及应用. University Chemistry, 2026, 41(8): 139-147. doi: 10.12461/PKU.DXHX202507078
15. [15]
  Bin SUN , Heyan JIANG . Glucose-modified bis-Schiff bases: Synthesis and bio-activities in Alzheimer′s disease therapy. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1338-1350. doi: 10.11862/CJIC.20240428
16. [16]
  Junhan Zhang , Yunbo Lei , Xiaoyu He , Lingxiang Gao . 智能水凝胶未来博物馆参观记. University Chemistry, 2026, 41(8): 227-234. doi: 10.12461/PKU.DXHX202507007
17. [17]
  Xiyuan Su , Zhenlin Hu , Ye Fan , Xianyuan Liu , Xianyong Lu . Change as You Want: Multi-Responsive Superhydrophobic Intelligent Actuation Material. University Chemistry, 2024, 39(5): 228-237. doi: 10.3866/PKU.DXHX202311059
18. [18]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
19. [19]
  Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018
20. [20]
  Di WU , Ruimeng SHI , Zhaoyang WANG , Yuehua SHI , Fan YANG , Leyong ZENG . Construction of pH/photothermal dual-responsive delivery nanosystem for combination therapy of drug-resistant bladder cancer cell. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1679-1688. doi: 10.11862/CJIC.20240135

Get Citation

PDF

XML

Metrics

PDF Downloads(4)
Abstract views(1612)
HTML views(340)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142