高等学校化学学报

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动态酰腙键水凝胶的构建与粘弹性调控

苗丹丹,范学峰,罗智莱,刘灿,包春燕   

  1. 华东理工大学化学与分子工程学院,上海市功能性材料化学重点实验室
  • 收稿日期:2026-01-16 修回日期:2026-02-28 网络首发:2026-04-28 发布日期:2026-04-28
  • 通讯作者: 包春燕 E-mail:baochunyan@ecust.edu.cn
  • 基金资助:
    绍兴市产业关键技术攻关项目(批准号:2025B11021)与上海市科学技术委员会(批准号:21ZR1415500)资助

Construction and Viscoelastic Regulation of Dynamic Acylhydrazone Bond Hydrogels

MIAO Dandan,FAN Xuefeng, LUO Zhilai,LIU Can,BAO Chunyan   

  1. Shanghai Key Laboratory of Functional Materials Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology
  • Received:2026-01-16 Revised:2026-02-28 Online First:2026-04-28 Published:2026-04-28
  • Supported by:
    Supported by the Shaoxing Industrial Key Technology Research Program, China (No.2025B11021) and Shanghai Science and Technology Communication, China (No.21ZR1415500)

摘要: 为模拟细胞外基质的动态黏弹性,开发具有类似生物组织力学性能的人工材料已成为组织工程和再生医学领域的重要研究方向. 本文以葡聚糖和聚乙二醇(PEG)为高分子骨架,通过醛基与苯甲酰肼间的动态酰腙键交联,构建了一类具有可调粘弹性的水凝胶体系. 为深入理解并调控其力学行为,系统考察了pH值、组分比例、聚乙二醇分子量及固含量等关键参数对凝胶黏弹性的影响. 结果表明,在pH = 5的酸性条件下凝胶形成速度最快(成胶时间约13 min);氧化葡聚糖含量的增加有利于提高水凝胶的黏弹性,表现为应力松弛加快[τ1/2(应力松弛到原来的二分之一所用的时间)最低为246 s]、蠕变变形增大;而PEG组分含量的增加则会降低水凝胶的黏弹性;在相同固含量下,PEG分子量的增大也有助于增强水凝胶的黏弹性. 得益于动态酰腙键的可逆断裂与重构特性,该水凝胶具备优异的能量耗散能力,在循环加载中表现出稳定的力学响应;同时,这种动态键合机制使其能够在室温下实现高效自愈合,损伤界面在6 h内可完全消失;此外,体系还展现出良好的剪切稀化行为与可注射性,可通过细径针头顺畅挤注,为其在微创植入与局部递送等生物医学场景中的应用提供了重要便利.

关键词: 动态共价键, 酰腙键, 黏弹性, 自愈合, 可注射性

Abstract: To mimic the dynamic viscoelasticity of the extracellular matrix, the development of artificial materials with mechanical properties similar to those of biological tissues has become an important research direction in the fields of tissue engineering and regenerative medicine. In this study, hydrogels with tunable viscoelasticity were constructed using dextran and polyethylene glycol(PEG) as polymer backbones, crosslinked through dynamic acylhydrazone bonds formed between aldehyde groups and benzoylhydrazide. To better understand and regulate their mechanical behavior, the effects of key parameters such as pH, component ratios, PEG molecular weight, and solid content on the gel's viscoelasticity were systematically investigated. The results showed that gelation occurred fastest under acidic conditions at pH =5(gelation time approximately 13 min); increasing the content of oxidized dextran enhanced the hydrogel's viscoelasticity, as indicated by faster stress relaxation(τ1/2, the time required for the stress to relax to half of its original value, as low as 246 s) and increased creep deformation; while increasing the PEG content reduced the hydrogel's viscoelasticity; at the same solid content, a higher PEG molecular weight also helped to strengthen the hydrogel's viscoelasticity. Benefiting from the reversible breaking and reconstruction of dynamic acylhydrazone bonds, the hydrogel exhibited excellent energy dissipation capability and showed a stable mechanical response under cyclic loading; at the same time, this dynamic bonding mechanism enabled efficient self-healing at room temperature, with damage interfaces completely disappearing within 6 hours. Additionally, the system displayed good shear-thinning behavior and injectability, allowing for smooth extrusion through fine needles, providing significant convenience for applications in minimally invasive implantation and localized delivery in biomedical scenarios.

Key words: Dynamic covalent bond, Acylhydrazone bond, Viscoelasticity, Self-healing, Injectable property

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