纺织学报 ›› 2026, Vol. 47 ›› Issue (03): 52-59.doi: 10.13475/j.fzxb.20250905701

• 生物医用材料 • 上一篇    下一篇

预交联铜离子对羧甲基纤维素抗菌气凝胶纤维结构与性能的影响

薛宝霞1,2, 冯佳昕1, 邵子洋1, 路佳鑫3, 刘晶1, 牛梅1,2(), 张利3   

  1. 1 太原理工大学 轻纺工程学院, 山西 太原 030024
    2 太原理工大学 新材料界面科学与工程教育部重点实验室, 山西 太原 030024
    3 山西医科大学第三医院, 山西 太原 030032
  • 收稿日期:2025-09-15 修回日期:2025-12-26 出版日期:2026-03-15 发布日期:2026-03-15
  • 通讯作者: 牛梅(1979—),女,教授,博士。主要研究方向为先进纤维与智能可穿戴材料。E-mail:niumei@tyut.edu.cn
  • 作者简介:薛宝霞(1990—),女,副教授,博士。主要研究方向为纳米碳基智能医用纺织材料。
  • 基金资助:
    国家自然科学基金项目(22508250);山西省基础研究计划项目(20210302124200);山西省基础研究计划项目(202403021211065);山西纳米药物可控缓释技术创新中心项目(20210410911026)

Effect of pre-crosslinked copper ions on structure and properties of carboxymethyl cellulose antibacterial aerogel fibers

XUE Baoxia1,2, FENG Jiaxin1, SHAO Ziyang1, LU Jiaxin3, LIU Jing1, NIU Mei1,2(), ZHANG Li3   

  1. 1 College of Textile Engineering, Taiyuan University of Technology, Taiyuan, Shanxi 030024, China
    2 Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan, Shanxi 030024, China
    3 The Third Hospital of Shanxi Medical University, Taiyuan, Shanxi 030032, China
  • Received:2025-09-15 Revised:2025-12-26 Published:2026-03-15 Online:2026-03-15

摘要:

为突破传统块状气凝胶在创面敷料应用中存在的脆性大、难加工成形及力学稳定性差等瓶颈,对气凝胶进行定向组装形成气凝胶纤维,提出金属离子预交联-湿法纺丝-冷冻干燥联合工艺,将预交联后的纺丝液经湿法纺丝、牵伸卷绕、冷冻干燥后构建基于羧甲基纤维素钠(CMC)交联铜离子(Cu2+)的复合抗菌气凝胶纤维。结果表明:预交联引入的Cu2+与CMC羧基之间发生配位作用,诱导分子链发生有序聚集,实现CMC分子链的预交联定向排列,使得预交联后气凝胶纤维内部孔径由50 μm减至15 μm,内部结构更加致密,且气凝胶纤维中Cu元素含量由1.59%升至2.87%;经过预交联气凝胶纤维的拉伸断裂强度由3.40 MPa升至12.10 MPa,对大肠埃希菌和金黄色葡萄球菌的抑菌率均达到99.99%。铜离子预交联不仅有利于气凝胶纤维的纺丝成形,还可同步增强其力学性能和抗菌性能。

关键词: 气凝胶纤维, 抗菌材料, 湿法纺丝, 羧甲基纤维素钠, 铜离子预交联工艺, 功能性敷料

Abstract:

Objective Burn and scald injuries present significant clinical challenges due to extensive tissue fluid exudation, prolonged healing time, and high susceptibility to secondary infection. These wounds also demand dynamic care to accommodate movement and dressing changes. Conventional wound dressings often fail to adequately manage these complex requirements simultaneously. Aerogels, known for their ultra-high porosity, specific surface area, and exceptional fluid absorption and retention capabilities, hold theoretical promise for creating an optimal moist wound healing environment. However, conventional bulk aerogels suffer from inherent mechanical fragility, making them difficult to process and mold into practical forms and resulting in poor mechanical stability during application. These limitations represent critical bottlenecks preventing the effective utilization of aerogels in advanced wound care, particularly for dynamic burn sites. In order to overcome these fundamental limitations of bulk aerogels, a novel approach of the directionally assembling a nanoporous structure into a one-dimensional fiber form was adopted. This strategy aimed to retain the core beneficial properties of aerogels-specifically, ultra-high porosity, high specific surface area, and excellent liquid absorption and water retention capacity, while simultaneously conferring essential flexibility, knittability, and mechanical adaptability necessary for practical wound dressing applications. This shift from bulk to fiber morphology directly addresses the processing, molding, and stability challenges.

Method Focusing on sodium carboxymethyl cellulose (CMC), a biocompatible polysaccharide, an innovative fibrillation strategy was employed, and a flexible composite antibacterial aerogel fiber was successfully constructed by incorporating copper ions (Cu2+) into the CMC-based system. A key innovation in the preparation process was the introduction of Cu2+ directly into the spinning dope for aerogel fiber formation. This introduction enabled a critical pre-crosslinking effect before the wet-spinning stage. The mechanism involves coordination bonding between the positively charged Cu2+ ions and the negatively charged carboxylate groups present on the CMC molecular chains. This Cu2+-carboxylate coordination acted as a powerful molecular directing force, inducing the CMC chains to undergo ordered aggregation and achieve a pre-aligned, oriented arrangement prior to fiber solidification.

Results This coordinated pre-crosslinking and alignment process was pivotal in successfully preparing CMC/Cu2+ antibacterial aerogel fibers exhibiting a hierarchical porous structure. The resulting material demonstrated a remarkable enhancement in mechanical strength. Tensile strength measurements reached 12.10 MPa, significantly higher than that observed in equivalent fibers prepared without the Cu2+-induced pre-crosslinking step. The molding mechanism is therefore primarily attributed to the synergistic effect of the Cu2+-CMC coordination occurring before wet-spinning and the optimized molecular arrangement this induces. This synergy constructs a robust ionic bonding pre-crosslinking network within the fiber, substantially increasing the cross-linking density within the CMC/Cu2+ composite. The enhanced cross-linking density is the key factor responsible for the significantly improved mechanical properties of the final aerogel fibers, enabling their practical handling and use as a dressing. Beyond mechanical robustness, the CMC/Cu2+ aerogel fibers exhibited potent antibacterial activity. Testing against common wound pathogens, Escherichia coli (E.coli) and Staphylococcus aureus (S.aureus), demonstrated a bacterial reduction rate of 99.99% for both strains. The antibacterial mechanism is attributed to the properties of the Cu2+ ions integrated within the fiber matrix. Initially, positively charged Cu2+ ions are electrostatically attracted to the negatively charged surface of the microbial cell membrane by Coulomb forces. Following this initial binding, copper ions penetrate the bacterial cell membrane. Inside the cell, Cu2+ interacts with vital intracellular components, leading to the coagulation of bacterial proteins and the inhibition of essential enzyme synthesis. This multifaceted action results in efficient and broad-spectrum bactericidal efficacy.

Conclusion This study developed a novel preparation strategy for advanced aerogel wound dressings. By directionally assembling nanoporous CMC into a fiber form and leveraging Cu2+ coordination for pre-crosslinking and molecular alignment, flexible composite CMC/Cu2+ aerogel fibers were created. These fibers retain the desirable fluid management properties of aerogels, such as high porosity, surface area, absorption, and retention, while overcoming the critical drawbacks of traditional bulk aerogels-namely brittleness, poor processability, and inadequate mechanical stability. The material simultaneously provides significant mechanical strength and potent, stable antibacterial action. This approach offers a promising new pathway for the development of effective functional dressings, particularly relevant for improving the management and treatment outcomes of challenging burn and scald wounds.

Key words: aerogel fiber, antibacterial material, wet spinning, sodium carboxymethyl cellulose, copper ion pre-crosslinking process, functional dressing

中图分类号: 

  • TQ 342.87

图1

预交联CMC/Cu2+气凝胶纤维制备工艺流程图"

图2

预交联前后CMC/Cu2+气凝胶纤维的实物照片"

表1

不同纺丝参数与气凝胶纤维力学性能"

样品
编号
喷丝孔
内径/
mm
凝固
浴浓度/
(mol·L-1)
气压/
MPa
牵伸比 断裂
强度/
MPa
1 0.67 0.15 0.16 1.2 2.55
2 0.60 0.15 0.16 1.2 2.83
3 0.50 0.15 0.16 1.2 3.40
4 0.40 0.15 0.16 1.2 4.20

表2

不同浓度凝固浴下气凝胶纤维的力学性能"

样品
编号
喷丝孔
内径/
mm
凝固
浴浓度/
(mol·L-1)
气压/
MPa
牵伸比 断裂
强度/
MPa
5 0.40 0.05 0.16 1.2 2.59
6 0.40 0.10 0.16 1.2 2.85
7 0.40 0.15 0.16 1.2 4.20
8 0.40 0.20 0.16 1.2 2.89

表3

不同纺丝液时气凝胶纤维的力学性能"

纺丝液
类别
喷丝孔
内径/
mm
凝固
浴浓度/
(mol·L-1)
气压/
MPa
牵伸比 断裂
强度/
MPa
未预交联 0.5 0.05 0.16 1.2 2.50
0.5 0.10 0.16 1.2 2.85
0.5 0.15 0.16 1.2 3.40
Cu2+
预交联
0.5 0.05 0.16 1.2 8.82
0.5 0.10 0.16 1.2 10.20
0.5 0.15 0.16 1.2 12.10

图3

不同气凝胶纤维的微观形貌和孔径分布"

图4

CMC、气凝胶纤维和预交联气凝胶纤维的XPS曲线"

表4

CMC、气凝胶纤维和预交联气凝胶纤维中的元素含量"

样品类别 元素含量/%
C O Na Cu
CMC 54.84 21.76 2.87
气凝胶纤维 37.00 28.30 1.50 1.59
预交联气凝胶纤维 48.54 27.38 0.90 2.87

图5

CMC和CMC/Cu2+气凝胶纤维对大肠埃希菌和对金黄色葡萄球菌的抗菌效果图"

图6

CMC/Cu2+气凝胶纤维对大肠埃希菌和金黄色葡萄球菌的抑菌圈"

图7

CMC/Cu2+气凝胶纤维的液体吸收率"

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