纺织学报 ›› 2024, Vol. 45 ›› Issue (01): 48-55.doi: 10.13475/j.fzxb.20220906401

• 纤维材料 • 上一篇    下一篇

银-铜双金属纳米粒子/聚乳酸复合纳米纤维膜的制备及其抗菌性能

戎成宝1,2, 孙辉1,2(), 于斌1,2   

  1. 1.浙江理工大学 纺织科学与工程学院(国际丝绸学院), 浙江 杭州 310018
    2.浙江省现代纺织技术创新中心, 浙江 绍兴 312000
  • 收稿日期:2022-09-26 修回日期:2023-03-19 出版日期:2024-01-15 发布日期:2024-03-14
  • 通讯作者: 孙辉( 1976—),女,副教授,博士。主要研究方向为纺织材料的功能化改性。E-mail: sunhui@zstu.edu.cn。
  • 作者简介:戎成宝( 1998—),男,硕士生。主要研究方向为纺织材料的抗菌改性。
  • 基金资助:
    浙江省自然科学基金项目(LTGS23E030005);浙江省“高层次特殊人才支持计划”科技创新领导人才项目(2021R52031)

Preparation and antibacterial performances of silver-copper bimetallic nanoparticles/polylactic acid composite nanofiber membranes

RONG Chengbao1,2, SUN Hui1,2(), YU Bin1,2   

  1. 1. College of Textile Science and Engineering ( International Institute of Silk), Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    2. Zhejiang Provincial Innovation Center of Advanced Textile Technology, Shaoxing, Zhejiang 312000, China
  • Received:2022-09-26 Revised:2023-03-19 Published:2024-01-15 Online:2024-03-14

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摘要：

为制备高效抗菌的生物可降解聚乳酸(PLA)静电纺丝纤维膜,首先利用L-抗坏血酸对银和铜的硝酸盐溶液进行化学还原,得到银-铜双金属纳米粒子(Ag-Cu NPs)。然后将Ag-Cu NPs与PLA纺丝液共混,通过静电纺丝技术制备了不同组成的Ag-Cu NPs/PLA复合纳米纤维膜,并对其形貌、结构、亲水性和抗菌性能等进行测试。结果表明:合成的Ag-Cu NPs的粒径约为32 nm,复合纳米纤维膜中Ag-Cu NPs被PLA基体包覆,且沿着纤维径向排列,纤维表面存在大量微小的孔洞;加入Ag-Cu NPs后,Ag-Cu NPs/PLA的水接触角略微降低,亲水性增加,且Ag-Cu NPs和PLA之间仅发生物理作用,未产生明显的化学作用;相比于纯PLA纳米纤维膜,Ag-Cu NPs/PLA的抗菌率明显提高,当纺丝液中Ag-Cu NPs相对于PLA质量为7% 时,复合纳米纤维膜对大肠杆菌和金黄色葡萄球菌的抑菌率均达到99%。

关键词: 聚乳酸, 银-铜双金属纳米粒子, 静电纺丝, 复合纳米纤维膜, 抗菌性能

Abstract:

Objective In the past few decades, the increase of bacterial antibiotic resistance worldwide has posed a serious threat to public health. The research aims to develop green, safe and durable polylactic acid(PLA)antibacterial textiles to protect wounds from the influence of drug-resistant bacteria. In order to develop a green, safe and durable antibacterial textile, PLA were blended with silver-copper bimetallic nanoparticles (Ag-Cu NPs) to prepare Ag-Cu NPs /PLA composite nanofiber membranes with different composition.

Method Silver and copper nitrates first were reduced using ascorbic acid by green synthetic method to obtain Ag-Cu NPs. Then, Ag-Cu NPs were blended with PLA spinning dope to prepare Ag-Cu NPs /PLA composite nanofiber membranes with different compositions by electrostatic spinning. The morphologies, structures, hydrophilicities and antibacterial properties of Ag-Cu NPs/PLA composite nanofiber composites were characterized and analyzed by using scanning electron microscopy, X-ray diffraction, Flourier transform infrared spectroscopy, water contact angle testing and antibacterial testing.

Results Ag-Cu NPs presented an irregular spherical shape with a particle size of about 32 nm. PLA electrospun nanofibers had a uniform diameter and a large number of tiny pores appeared on the fiber surface. Compared with PLA nanofibers, the average fiber diameter of Ag-Cu NPs/PLA composite nanofiber membrane decreased, and the average fiber diameter increased with the increase of Ag-Cu NPs concentration. Ag and Cu elements appeared on the surface of the composite nano-electrospinning membranes and uniformly distributed along the fiber diameter direction, indicating that Ag-Cu NPs were encapsulated by PLA matrix. Compared with PLA, the XRD diffraction peaks belonging to Ag and Cu appeared in the XRD patterns of Ag-Cu NPs/PLA composite nano-electrospinning membranes. The FT-IR spectrum of PLA electrospun nanofiber membrane showed the typical characteristic peaks of PLA. The infrared spectra of Ag-Cu NPs/PLA composite nanofiber membranes were similar to the pure PLA electrospun nanofiber membrane, indicating that there exists only physical interaction between Ag-Cu NPs and PLA matrix. The pure PLA electrospun nanofiber membrane with a water contact angle (WCA) value of about 135° displayed the poor hydrophilicity. The WCA value of Ag-Cu NPs/PLA composite nanofiber membranes slightly decreased compared with pure PLA electrospun nanofiber membrane, meaning the hydrophilicity of the composite nanofiber membranes increased. Pure PLA electrospun nanofiber membrane showed very limited antibacterial ability against Staphylococcus aureus and Escherichia coli. The antibacterial efficiencies of the Ag-Cu NPs /PLA composite nanofiber membranes against these two bacteria were significantly increased with the increasing of Ag-Cu NPs concentration. When the dosage of Ag-Cu NPs was 7%, the composite nano-electrospinning membrane showed high antibacterial activity, and the antibacterial efficiencies for both Staphylococcus aureus and Escherichia coli reached 99%.

Conclusion Ag-Cu NPs/PLA composite nanofiber membranes had excellent antibacterial activity against Staphylococcus aureus and Escherichia coli. When the Ag-Cu NPs dosage was 7%, the antibacterial efficiencies of Ag-Cu NPs /PLA composite nanofiber membrane against both Escherichia coli and Staphylococcus aureus could reach 99%. It is expected that our studies may provide some theoretical reference for the application of PLA nanofiber membrane on the biomedical field.

Key words: polylactic acid, silver-copper bimetallic nanoparticle, electrostatic spinning, composite nanofiber membrane, antibacterial performance

中图分类号: 

  • TS176

图1

Ag-Cu NPs/PLA复合纳米纤维膜的制备路线图"

表1

复合纳米纤维膜组成配比表"

样品名称 不同组分量/g
二氯甲烷 丙酮 PLA Ag-Cu NPs
PLA 16.00 4.00 3.00 0
1%Ag-Cu NPs/PLA 16.00 4.00 3.00 0.03
3%Ag-Cu NPs/PLA 16.00 4.00 3.00 0.09
5%Ag-Cu NPs/PLA 16.00 4.00 3.00 0.15
7%Ag-Cu NPs/PLA 16.00 4.00 3.00 0.21

图2

Ag-Cu NPs、PLA与不同组成的Ag-Cu NPs/PLA的扫描电镜照片"

图3

PLA及不同组成的Ag-Cu NPs/PLA复合纳米纤维膜纤维的平均直径"

表2

静电纺丝纤维膜表面元素含量"

样品名称 元素质量分数/%
C O Ag Cu
PLA 53.57 46.43 0.00 0.00
1%Ag-Cu NPs/PLA 70.72 28.99 0.22 0.06
3%Ag-Cu NPs/PLA 68.46 30.37 0.33 0.85
5%Ag-Cu NPs/PLA 68.66 30.52 0.21 0.62
7%Ag-Cu NPs/PLA 58.20 38.67 0.82 2.31

图4

Ag-Cu NPs/PLA复合纳米纤维膜单根纤维的元素分布图"

图5

PLA及不同组成的Ag-Cu NPs/PLA复合纳米纤维膜的XRD图谱"

图6

PLA及不同组成的Ag-Cu NPs/PLA复合纳米纤维膜的红外光谱图"

图7

PLA与不同组成的Ag-Cu NPs/PLA复合纳米纤维膜的水接触角"

表3

PLA与不同组成的Ag-Cu NPs/PLA复合纳米纤维膜的抑菌率"

样品名称 抑菌率/%
对金黄色葡萄球菌 对大肠杆菌
PLA 8.30±5.92 4.40±3.64
1%Ag-Cu NPs/PLA 96.80±1.88 98.87±0.62
3%Ag-Cu NPs/PLA 97.16±0.58 97.42±1.56
5%Ag-Cu NPs/PLA 96.26±1.89 96.37±2.56
7%Ag-Cu NPs/PLA 99.29±0.57 99.35±0.52
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