纺织学报 ›› 2026, Vol. 47 ›› Issue (06): 131-139.doi: 10.13475/j.fzxb.20251103901

• 染整工程 • 上一篇    下一篇

负载氧化亚铜的胺基聚丙烯腈纤维的制备及其抗菌活性

李箐湲1,2, 庞熙维1, 段文杰1, 寇丽栋1,3, 王静1(), 张忠良2   

  1. 1 河南省科学院化学研究所有限公司 河南省环境功能纤维国际联合实验室河南 郑州 450008
    2 郑州大学 材料科学与工程学院河南 郑州 450001
    3 河南财政金融学院 环境经济学院河南 郑州 450046
  • 收稿日期:2025-11-24 修回日期:2026-04-21 出版日期:2026-06-15 发布日期:2026-08-19
  • 通讯作者: 王静(1982—),女,研究员。主要研究方向为环境功能材料及治理技术开发。E-mail:wangj12@163.com
  • 作者简介:李箐湲(1991—),女,工程师,博士生。主要研究方向为抗菌纤维材料与其在生物气溶胶过滤领域的应用。
  • 基金资助:
    河南省科学院联合基金(225200810078);河南省科学院省级创新平台提升项目(20251003001);河南省杰出外籍科学家工作室项目(GZS2024024)

Preparation and antibacterial activity of copper(I) oxide-loaded aminated polyacrylonitrile fibers

LI Qingyuan1,2, PANG Xiwei1, DUAN Wenjie1, KOU Lidong1,3, WANG Jing1(), ZHANG Zhongliang2   

  1. 1 Henan International Joint Laboratory of Environmental Functional FibersHenan Academy of Sciences Chemical Research Institute Co., Ltd., ZhengzhouHenan 450008, China
    2 School of Materials Science and EngineeringZhengzhou University, ZhengzhouHenan 450001, China
    3 School of Environmental EconomicsHenan University of Finance and Economics, ZhengzhouHenan 450046, China
  • Received:2025-11-24 Revised:2026-04-21 Published:2026-06-15 Online:2026-08-19

摘要:

为获得具有高抗菌活性、抗菌稳定性及广谱性的纤维材料,通过接枝改性制得胺基化聚丙烯腈纤维(APAN),并在其表面稳定负载氧化亚铜(Cu2O)纳米颗粒。借助扫描电子显微镜、傅里叶变换红外光谱仪、X射线衍射仪等表征手段及抗菌性能测试,研究了合成纤维的表观形貌、化学结构、抗菌性能以及抗菌机制。结果表明:获得的Cu2O负载纤维,对大肠埃希菌、肺炎克雷伯菌和金黄色葡萄球菌、粪肠球菌表现出区别于其它长效测试周期的纤维,2 h内即可得到优异的广谱抗菌性能,所获得最佳抗菌效果的纤维可在2 h内对白色念珠菌的抗菌率高达95.2%,对耐甲氧西林金黄色葡萄球菌(MRSA)的抗菌率达93.9%,且最低有效剂量为2.5 g/L,远低于先前报道材料;经过30次洗涤,该纤维对大肠埃希菌和金黄色葡萄球菌仍保有较高的抗菌性能,抗菌率分别为91%和88%;该纤维的抗菌机制推测为纤维表面溢出铜离子与细菌细胞膜的直接作用和纤维与细菌间静电的协同作用。

关键词: 功能纤维, 氧化亚铜, 聚丙烯腈, 抗菌性能, 抗菌机制, 广谱抗菌, 改性纤维

Abstract:

Objective The threat posed by bacterial and drug-resistant infections necessitates advanced antibacterial materials. This study enhances the efficacy of aminated polyacrylonitrile fibers through loading copper oxide nanoparticles, aiming to achieve high performance against MRSA and to elucidate the associated antibacterial mechanisms.

Method Aminated polyacrylonitrile fibers were functionalized with copper ions and in-situ reduced using ascorbic acid to deposit copper oxide nanoparticles. The composites were characterized by SEM, FT-IR, XRD and XPS. Antibacterial activity against E. coliS. aureusK. pneumoniaeE. faecalisC. albicans and MRSA was evaluated via shaking flask assays. Mechanism studies included copper release measurement, Zeta potential analysis, bacterial morphology observation (SEM/TEM) and extracellular K+ detection.

Results A series of Cu2O-loaded aminated polyacrylonitrile fibers were successfully synthesized. SEM analysis revealed that the smooth surface of pristine APAN fibers became progressively rougher with the incorporation of irregular spherical nanostructures upon Cu2O loading. The sample with the best antibacterial performance was labeled as APC-30, and it exhibited the most homogeneous distribution of Cu2O nanoparticles, with sizes ranging between 50-100 nm. FT-IR and XRD confirmed the successful coordination of copper and the presence of crystalline Cu2O, with XRD peaks corresponding to (110), (111), (200), (220), and (311) planes. XPS analysis indicated the co-existence of both Cu(I) and Cu(II) species on the fiber surface, with APC-30 showing an optimal balance. Antibacterial assessments demonstrated outstanding performance. Within 2 h, the APC-30 fiber achieved inhibition rates of 97.65% against E. coli, 95.75% against S. aureus, 99.46% against K. pneumoniae, 99.35% against E. faecalis, 95.20% against C. albicans, and 93.96% against MRSA. Notably, against the high-risk pathogen MRSA at a concentration of 7×108 CFU/mL, a dose of only 2.5 g/L of APC-30 resulted in a 99.98% reduction. Durability tests affirmed excellent wash resistance; after 30 laundering cycles, APC-30 retained antibacterial rates above 91% for E. coli and 88% for S. aureus. Mechanistic studies revealed a multi-modal action. APC-30 demonstrated a controlled copper ion release (up to 4.385 mg/L in solution), which directly compromised bacterial membrane integrity as visualized via SEM/TEM, showing cell shrinkage, rupture, and deformation. The fiber surface possessed a positive Zeta potential (+18.7 mV), facilitating electrostatic attraction with negatively charged bacterial cells. Furthermore, a significant increase in extracellular K+ concentration was detected after contact with APC-30, confirming cytoplasmic leakage and loss of membrane integrity. The synergistic effect between released copper ions and surface electrostatic interaction is proposed as the core antibacterial mechanism.

Conclusion This study successfully developed a high-performance antibacterial fiber composite by grafting amination and in-situ loading of Cu2O nanoparticles onto polyacrylonitrile fibers. The optimized APC-30 fiber exhibited exceptional, rapid, and broad-spectrum antibacterial activity, including potent efficacy against drug-resistant MRSA, while maintaining remarkable durability through repeated washing. The antibacterial function is attributed to a synergistic mechanism involving controlled release of bactericidal copper ions, direct physical damage to microbial membranes, and electrostatic adhesion between fiber and cells. These findings underscore the potential of Cu2O/APAN c

Key words: functional fiber, cuprous oxide, polyacrylonitrile, antibacterial property, antibacterial mechanism, broad-spectrum antibacterial, modified fiber

中图分类号: 

  • TS102

图1

复合纤维的表面扫描电镜照片"

图2

复合纤维的傅里叶变换红外光谱图、X射线光电子能谱图、全扫描X射线光电子能谱总图和高分辨Cu 2p能谱图"

图3

大肠埃希菌与金黄色葡萄球菌菌落分别与不同样本共培养18 h后的显微图像"

表1

复合纤维的抗菌率"

菌种 抗菌率/%
APAN APC-0 APC-10 APC-30 APC-50
大肠埃希菌 78.3 93.9 98.3 100 95.1
金黄色葡萄球菌 81.3 92.5 98.5 100 95.7

图4

复合纤维对不同菌株的2 h抗菌性能"

图5

不同样品对MRSA的抗菌率随纤维投加量的变化"

图6

纤维抗菌动力学曲线"

表2

水洗后APC-30的抗菌率"

菌种 不同洗涤次数下的抗菌率/%
0次 5次 10次 20次 30次
大肠埃希菌 97.66 92.34 91.52 91.24 91.25
金黄色葡萄球菌 95.75 93.7 91.42 89.15 88.37

图7

细菌与纤维接触前后SEM与TEM照片"

表3

细胞外液中K+的质量浓度"

时间/
h
K+的质量浓度/(mg·L-1
E.coli
(APC-30)
E.coli
(对照组)
S.aureus
(APC-30)
S.aureus
(对照组)
0.25 5.004 4.978 5.013 4.975
2 5.221 4.951 5.214 4.711
4 5.609 4.982 5.797 4.975
6 6.032 4.993 5.938 4.982
8 6.210 4.986 6.105 4.983
24 6.516 5.010 6.503 5.009
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