Synthesis and properties of thermosensitive hydrogel of allyl silk fibroin

WANG Boxiang; LIU Li; LI Jia; LU Yanhua; CHENG Dehong; JIN Huiyu; ZHOU Ling

doi:10.11949/0438-1157.20200626

您当前的位置：

首页 >

文章列表页 >

Synthesis and properties of thermosensitive hydrogel of allyl silk fibroin

Material science and engineering\, nanotechnology | 更新时间：2026-07-24

- Synthesis and properties of thermosensitive hydrogel of allyl silk fibroin
- CIESC Journal Vol. 71, Issue 12, Pages: 5821-5830(2020)
- 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：
- 基金信息：
- DOI：10.11949/0438-1157.20200626
  CLC： O 636.9
- Received：21 May 2020，
  
  Revised：2020-07-08，
  
  Online First：17 December 2020，
  
  Published：05 December 2020
- 稿件说明：
移动端阅览
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

references

Chen Y S, Tsou P C, Lo J M, et al. Poly( N -isopropylacrylamide) hydrogels with interpenetrating multiwalled carbon nanotubes for cell sheet engineering[J ] . Biomaterials, 2013, 34 (30): 7328-7334.

Nagase K, Yamato M, Kanazawa H, et al. Poly( N -isopropylacrylamide)-based thermoresponsive surfaces provide new types of biomedical applications[J ] . Biomaterials, 2018, 153 : 27-48.

Hu X, Cebe P, Weiss A S, et al. Protein-based composite materials[J ] . Materials Today, 2012, 15 (5): 208-215.

Zhang Y Q. Natural silk fibroin as a support for enzyme immobilization[J ] . Biotechnology Advances, 1998, 16 (5): 961-971.

Wang P, Qi C L, Yu Y Y, et al. Covalent immobilization of catalase onto regenerated silk fibroins via tyrosinase-catalyzed cross-linking[J ] . Applied Biochemistry & Biotechnology, 2015, 177 (2): 472-485.

Lee K H, Ki C S, Baek D H, et al. Application of electrospun silk fibroin nanofibers as an immobilization support of enzyme[J ] . Fibers and Polymers, 2005, 6 (3): 181-185.

Wu M H, Zhu L, Zhou Z Z, et al. Coimmobilization of naringinases on silk fibroin nanoparticles and its application in food packaging[J]. Journal of Nanoparticles, 2013, (2013): 901401.

Yang B S, Li J, Wang H. Research progress in sequences comparison and crystal structure of silk fibroin[J ] . Advanced Materials Research, 2013, 664 : 443-448.

Kundu B, Kurland N E, Bano S, et al. Silk proteins for biomedical applications: bioengineering perspectives[J ] . Progress in Polymer Science, 2014, 39 (2): 251-267.

Omenetto F G, Kaplan D L. New opportunities for an ancient material[J ] . Science, 2010, 329 (5991): 528-531.

Pal S, Kundu J, Talukdar S, et al. An emerging functional natural silk biomaterial from the only domesticated non-mulberry silkworm Samia ricini [J ] . Macromolecular Bioscience, 2013, 13 (8): 1020-1035.

田丽, 吴明华, 邢幽芳. 异氰酸酯基封端聚醚改性聚硅氧烷在真丝抗皱整理中的应用[J ] . 丝绸, 2019, 56 (5): 1-7.

Tian L, Wu M H, Xing Y F. Application of polysiloxane modified by isocyanate terminated polyether in silk anti-wrinkle finishing [J ] . Journal of Silk, 2019, 56 (5): 1-7.

Shiozaki H, Tanaka Y. Reactivity of mono-epoxides toward silk fibroin[J ] . Die Makromolekulare Chemie, 1971, 143 (1): 25-45.

Andrew C, Kyoung D S, Hyungjun Y, et al. Bulk poly( N -isopropylacrylamide) (PNIPAAm) thermoresponsive cell culture platform: toward a new horizon in cell sheet engineering [J ] . Biomaterials Science, 2019, 7 : 2277-2287.

Tourrette A, Geyter N D, Jocic D, et al. Incorporation of poly( N -isopropylacrylamide)/chitosan microgel onto plasma functionalized cotton fibre surface[J ] . Colloids & Surfaces a Physicochemical & Engineering Aspects, 2009, 352 (1/2/3): 126-135.

Heskins M, Guillet J E. Solution properties of poly( N -isopropylacrylamide)[J ] . Journal of Macromolecular Science Part A Chemistry, 1968, 2 (8): 1441-1455.

Tong X, Yang F. Engineering interpenetrating network hydrogels as biomimetic cell niche with independently tunable biochemical and mechanical properties[J ] . Biomaterials, 2014, 35 (6): 1807-1815.

Akimoto J, Nakayama M, Okano T. Temperature-responsive polymeric micelles for optimizing dr ug targeting to solid tumors[J ] . Journal of Controlled Release, 2014, 193 : 2-8.

Aya A, Erika N, Kenichi N, et al. Mesenchylmal stem cell culture on poly( N -isopropylacrylamide) hydrogel with repeated thermo-stimulation[J ] . International Journal of Molecular Sciences, 2018, 19 (4): 1253-1263.

Sung H W, Cheng W H, Chiu I S, et al. Studies on epoxy compound fixation[J ] . Journal of Biomedical Materials Research, 1996, 33 (3): 177-186.

余喜讯, 万昌秀, 陈槐卿. 生物性组织工程血管支架的制备及其内皮化研究[J ] . 四川大学学报(自然科学版), 2005, 37 (6): 97-101.

Yu X X, Wan C X, Chen H Q. Preparation of biological tissues scaffold for tissue-engineered blood vessel and its endothelializa[J ] . Journal of Sichuan University (Engineering Science Edition), 2005, 37 (6): 97-101.

Zeeman R, Dijkstra P J, Wachem P B V, et al. Crosslinking and modification of dermal sheep collagen using 1, 4-butanediol diglycidyl ether[J ] . Journal of Biomedical Materials Research, 1999, 46 (3): 424-433.

Silva S S, Kundu B, Lu S, et al. Chinese oak tasar silkworm Antheraea pernyi silk proteins: current strategies and future perspectives for biomedical applications [J ] . Macromolecular Biosc ience, 2019, 19 (3): 1800252.

Gil E S, Park S H, Tien L W, et al. Mechanically robust, rapidly actuating, and biologically functionalized macroporous poly( N -isopropylacrylamide)/silk hybrid hydrogels[J ] . Langmuir, 2010, 26 (19): 15614-15624.

Zhang J N, Cui Z F, Field R, et al. Thermo-responsive microcarriers based on poly( N -isopropylacrylamide)[J ] . European Polymer Journal, 2015, 67 : 346-364.

Zhang P, Wang W. Preparation of silk fibroin-chitosan scaffolds and their properties [J ] . Chinese Journal of Reparative & Reconstructive Surgery, 2013, 27 (12): 1517-1522.

Discher D E, Janmey P, Wang Y L. Tissue cells feel and respond to the stiffness of their substrate[J ] . Science, 2005, 310 : 1139-1143.

Rennerfeldt D A, Renth A N, Talata Z, et al. Tuning mechanical performance of poly(ethylene glycol) and agarose interpenetrating network hydrogels for cartilage tissue engineering[J ] . Biomaterials, 2013, 34 (33): 8241-8257.

Baek K, Clay N E, Qin E C, et al. In situ assembly of the collagen-polyacrylamide interpenetrating network hydrogel: enabling decoupled control of stiffness and degree of swelling [J ] . European Polymer Journal, 2015, 72 : 413-422.

Singh N, Rahatekar S S, Koziol K K, et al. Directing chondrogenesis of stem cells with specific blends of cellulose and silk [J ] . Biomacromolecules, 2013, 14 : 1287-1298.

Foss C, Merzari E, Migliaresi C, et al. Silk fibroin/hyaluronic acid 3D matrices for cartilage tissue engineering[J ] . Biomacromolecules, 2013, 14 (1): 38-47.

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Synthesis and properties of dimer fatty acid modified styrene polyester resin

Study on boiling characteristics of liquid crystal elastomer surfaces with thermally adaptive wettability

Mechanism study on temperature and salt resistance of novel viscoelastic particle-based oil displacement agents

Preparation of DMAPS-modified PVDF membranes via pre-radiation-induced graft polymerization for effective oil/water emulsion separation

Research progress on supporting materials of heterogeneous metallocene catalysts

Related Author

GUO Yanting

YIN Yaoqi

HUANG Xue

CHEN Man

FENG Guangzhu

CHEN Shuai

HU Yanwei

LIU Zihe

Related Institution

College of Chemistry and Chemical Engineering, Zhongkai University of Agriculture and Engineering

School of Energy Science Engineering, Harbin Institute of Technology

Suzhou Research Institute, Harbin Institute of Technology

Exploration and Development Research Institute of Shengli Oilfield, SINOPEC

College of Chemistry, Chemical Engineering and Materials Science, Soochow University

⁰