化工学报 ›› 2020, Vol. 71 ›› Issue (12): 5821-5830.DOI: 10.11949/0438-1157.20200626

• 材料化学工程与纳米技术 • 上一篇    下一篇

烯丙基丝素蛋白温敏水凝胶的合成及性能研究

王勃翔1,2(),刘丽1(),李佳2,路艳华2,程德红2,靳惠宇1,周凌1   

  1. 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
  • 收稿日期:2020-05-21 修回日期:2020-07-08 出版日期:2020-12-05 发布日期:2020-12-05
  • 通讯作者: 刘丽
  • 作者简介:王勃翔(1989—),男,博士研究生,bxwang0411@163.com
  • 基金资助:
    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);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)

Synthesis and properties of thermosensitive hydrogel of allyl silk fibroin

WANG Boxiang1,2(),LIU Li1(),LI Jia2,LU Yanhua2,CHENG Dehong2,JIN Huiyu1,ZHOU Ling1   

  1. 1.College of Materials Science and Engineering,Shanghai University, Shanghai 200444, China
    2.Liaoning Provincial Key Laboratory of Functional Textile Materials, Eastern Liaoning University, Dandong 118003, Liaoning, China
  • Received:2020-05-21 Revised:2020-07-08 Online:2020-12-05 Published:2020-12-05
  • Contact: LIU Li

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N-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1H 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。

关键词: 丝素蛋白, 水凝胶, 聚合, 温敏性, 弹性

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 N-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 1H 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), T=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.

Key words: silk fibroin, hydrogel, polymerization, thermosensitivity, elasticity

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