烯丙基丝素蛋白温敏水凝胶的合成及性能研究

王勃翔; 刘丽; 李佳; 路艳华; 程德红; 靳惠宇; 周凌

doi:10.11949/0438-1157.20200626

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烯丙基丝素蛋白温敏水凝胶的合成及性能研究

材料化学工程与纳米技术 | 更新时间：2026-07-24

- 烯丙基丝素蛋白温敏水凝胶的合成及性能研究
- Synthesis and properties of thermosensitive hydrogel of allyl silk fibroin
- 化工学报 2020年71卷第12期页码：5821-5830
- 作者机构：
  
  1.上海大学材料科学与工程学院，上海200444
  2.辽东学院辽宁省功能纺织材料重点实验室，辽宁丹东 118003
- 作者简介：
  
  王勃翔（1989—），男，博士研究生，bxwang0411@163.com
  刘丽（1968—），女，博士，教授，liuli2002@shu.edu.cn
- 基金信息：
  
  国家自然科学基金项目(51873084);辽宁省自然科学基金项目(2019-ZD-0533;20180550061);辽宁省教育厅科学研究项目(LNSJYT201901);辽宁省自然科学重点研发项目(2019JH/10100047)
- DOI：10.11949/0438-1157.20200626
  中图分类号： O 636.9
- 收稿：2020-05-21，
  
  修回：2020-07-08，
  
  网络首发：2020-12-17，
  
  纸质出版：2020-12-05
- 稿件说明：
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王勃翔, 刘丽, 李佳, 路艳华, 程德红, 靳惠宇, 周凌. 烯丙基丝素蛋白温敏水凝胶的合成及性能研究[J]. 化工学报, 2020, 71(12): 5821-5830

WANG Boxiang, LIU Li, LI Jia, LU Yanhua, CHENG Dehong, JIN Huiyu, ZHOU Ling. Synthesis and properties of thermosensitive hydrogel of allyl silk fibroin[J]. CIESC Journal, 2020, 71(12): 5821-5830
王勃翔, 刘丽, 李佳, 路艳华, 程德红, 靳惠宇, 周凌. 烯丙基丝素蛋白温敏水凝胶的合成及性能研究[J]. 化工学报, 2020, 71(12): 5821-5830 DOI： 10.11949/0438-1157.20200626.

WANG Boxiang, LIU Li, LI Jia, LU Yanhua, CHENG Dehong, JIN Huiyu, ZHOU Ling. Synthesis and properties of thermosensitive hydrogel of allyl silk fibroin[J]. CIESC Journal, 2020, 71(12): 5821-5830 DOI： 10.11949/0438-1157.20200626.

摘要

为解决以柞蚕丝素蛋白（ASF）为基材的生物材料力学性能差、水溶失率高等问题，首先，以ASF为原料，烯丙基缩水甘油醚（AGE）为改性剂，在碱性条件下ASF与AGE发生亲核取代反应，形成具有反应性的烯丙基丝素蛋白（ASF-AGE）；然后，以

-异丙基丙烯酰胺（NIPAAm）为单体，在不使用任何交联剂的情况下，将ASF-AGE与NIPAAm进行聚合，最终形成烯丙基丝素蛋白温敏p（ASF-AGE-NIPAAm）水凝胶。采用茚三酮比色法对ASF-AGE的氨基转化率进行测定，采用

H NMR对ASF-AGE分子结构进行表征；采用XRD、DSC、压缩测试等方法研究ASF-AGE含量对水凝胶结晶结构、温敏特性、溶失稳定性和力学性能的影响。结果表明：烯丙基双键成功引入ASF大分子链上，ASF与AGE的质量比为1∶8，温度20℃，pH=10.5，反应24 h时，得到的ASF-AGE的氨基转化率为55.21%；ASF-AGE与NIPAAm聚合形成稳定形态的水凝胶，水凝胶的LCST约为32℃，具有明显的温敏特性；ASF-AGE与NIPAAm配比为4/6时，水凝胶具有良好的溶失稳定性和综合力学性能。

Abstract

For the sake of solving the problems of poor mechanical strength and dissolve-loss ratio of

Antheraea pernyi

silk fibroin (ASF)

allyl silk fibroin (ASF-AGE) was synthesized through nucleophilic substitution using ASF as substrate and allyl glycidyl ether (AGE) as modifier under basic conditions. And a series of gel were manufactured though

in situ

polymerization using ASF-AGE and

-isopropylacrylamide (NIPAAm) monomer without any crosslinking agent. The amino conversion rate of ASF was confirmed by ninhydrin colorimetry

the molecular structure of ASF-AGE was characterized by

H NMR and the influence of ASF-AGE content on crystal structure

temperature sensitivity

dissolution stability and mechanical properties of hydrogels were also investigated by XRD

DSC

compression test and so on. The results indicated that allyl was successfully introduced into ASF

the amino conversion rate of ASF was 55.21% when the reaction condition was 1∶8 mass ratio (ASF/AGE)

=20℃ and pH=10.5. The stable hydrogels can be obtained by ASF-AGE and NIPAAm polymerization. The hydrogels showed lower critical solution

temperatures (LCST) at about 32℃

which revealed obvious thermosensitive characteristic. When the ratio of ASF-AGE to NIPAAm is 4/6

the hydrogel has good dissolution stability and comprehensive mechanical properties.

关键词

Keywords

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