无醛交联剂改性羊毛角蛋白/海藻酸钠气凝胶复合材料的制备及其性能

doi:10.13475/j.fzxb.20250902701

纺织学报 ›› 2026, Vol. 47 ›› Issue (03): 18-25.doi: 10.13475/j.fzxb.20250902701

无醛交联剂改性羊毛角蛋白/海藻酸钠气凝胶复合材料的制备及其性能

孟思雨¹, 韩宇进¹, 谭文丽², 马博谋¹, 袁久刚¹()

¹ 江南大学纺织科学与工程学院, 江苏无锡 214122
² 江苏中纺联检验技术服务有限公司, 江苏苏州 215228

收稿日期:2025-09-08 修回日期:2026-01-17 出版日期:2026-03-15 发布日期:2026-03-15
通讯作者: 袁久刚(1982—),男,教授,博士。研究方向为天然纤维的提取及功能化改性。E-mail:jiugangyuan@jiangnan.edu.cn。
作者简介:孟思雨(2002—),女,硕士生。主要研究方向为天然蛋白质材料的加工和改性。
基金资助:
国家自然科学基金项目(31771039);国家自然科学基金项目(32472377)

Preparation and properties of formaldehyde-free modified keratin/sodium alginate aerogel composite material

MENG Siyu¹, HAN Yujin¹, TAN Wenli², MA Bomou¹, YUAN Jiugang¹()

¹ College of Textile Science and Engineering, Jiangnan University, Wuxi, Jiangsu 214122, China
² Jiangsu Textile Testing Technical Service Co., Ltd., Suzhou, Jiangsu 215228, China

Received:2025-09-08 Revised:2026-01-17 Published:2026-03-15 Online:2026-03-15

摘要/Abstract

摘要：

角蛋白气凝胶材料在生物医学领域有着重要的应用价值,但纯角蛋白成形时容易形成高度致密的刚性网络结构,导致其气凝胶材料硬而脆,严重影响其应用性能。为此,采用新型双功能交联剂乙二醇二缩水甘油醚(EGDE)对羊毛角蛋白进行交联改性,通过开环反应在角蛋白中引入乙二醇柔性链段,并利用冷冻干燥方法制备了EGDE改性角蛋白与海藻酸钠(SA)共混的气凝胶材料。通过红外光谱分析,证实EGDE与角蛋白分子间形成了稳定的醚键,随着EGDE添加量的提升,角蛋白自由巯基含量显著下降,成胶时间大幅缩短,表观黏度显著提升,其较优反应条件为:温度60 ℃、pH值10、EGDE添加量20%。气凝胶各项性能测试结果表明:EGDE改性角蛋白/SA气凝胶具有均匀分布的多孔结构,力学性能方面刚性与弹性兼具,同时具备良好的吸水保水能力以及血浆快速吸收能力,在工程支架、创面敷料等领域具有很好的应用潜力。

关键词: 羊毛角蛋白, 乙二醇二缩水甘油醚, 气凝胶, 交联改性, 海藻酸钠, 生物医用材料

Abstract:

Objective In order to overcome the inherent brittleness and instability of pure keratin aerogels, this study aims to prepare a high-performance composite by crosslinking wool keratin with a mild crosslinker, ethylene glycol diglycidyl ether (EGDE), and then blending it with sodium alginate (SA). This approach expands its application potential in tissue engineering scaffolds and wound dressings.

Method Wool keratin was extracted using a reducing solution containing urea and dithiothreitol (DTT). The soluble keratin was crosslinked with EGDE under alkaline conditions (pH=10, 60 ℃) at optimized concentration (20%). The modified keratin was combined with sodium alginate (SA) at a ratio of 2∶1, and the mixture was freeze-dried to form porous aerogels. Fourier transform infrared spectroscopy, rotational rheometry, mechanical compression testing, and fluid uptake assays were employed to evaluate the material's properties.

Results The infrared spectra analysis confirmed covalent crosslinking through the disappearance of the epoxy peak at 908.7 cm^-1 and formation of ether bonds. Free thiol content decreased from 12.42 to 4.62 μmol/g with 50% EGDE, indicating efficient reaction. Gelation time reduced dramatically from 48 h to 15 min at high pH values. Rheological behavior showed shear-thinning and enhanced elastic modulus with increased crosslinking. The composite aerogel exhibited significantly improved water absorption and retention capabilities compared to pure keratin, with the optimal performance achieved at 20% EGDE. Most notably, it demonstrated a high simulated plasma absorption capacity of (9.13±0.42) g/g within 10 s while maintaining structural integrity. Crosslinked samples also demonstrated tunable degradation profiles, with improved stability in both phosphate-buffered saline (PBS) and reducing environments.

Conclusion Crosslinking keratin with EGDE significantly enhances aerogel performance, providing mechanical resilience, high fluid absorption, and controlled degradability. The material, particularly its rapid and high-capacity uptake of plasma simulant, shows promise for use in hemostatic and wound care products. This approach also offers an efficient pathway to valorize wool waste into high-value biomedical materials.

Key words: wool keratin, ethylene glycol diglycidyl ether, aerogel, cross-linking modification, sodium alginate, biomedical material

中图分类号:

TS 131

孟思雨, 韩宇进, 谭文丽, 马博谋, 袁久刚. 无醛交联剂改性羊毛角蛋白/海藻酸钠气凝胶复合材料的制备及其性能[J]. 纺织学报, 2026, 47(03): 18-25.

MENG Siyu, HAN Yujin, TAN Wenli, MA Bomou, YUAN Jiugang. Preparation and properties of formaldehyde-free modified keratin/sodium alginate aerogel composite material[J]. Journal of Textile Research, 2026, 47(03): 18-25.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20250902701

http://www.fzxb.org.cn/CN/Y2026/V47/I03/18

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试样	吸水倍率	保水倍率
KR-EGDE₁₀/SA	4.71 ± 0.20	3.30 ± 0.15
KR-EGDE₂₀/SA	5.08 ± 0.23	3.86 ± 0.22
KR-EGDE₅₀/SA	5.41 ± 0.34	4.62 ± 0.25

无醛交联剂改性羊毛角蛋白/海藻酸钠气凝胶复合材料的制备及其性能

Preparation and properties of formaldehyde-free modified keratin/sodium alginate aerogel composite material

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