Journal of Textile Research ›› 2024, Vol. 45 ›› Issue (01): 48-55.doi: 10.13475/j.fzxb.20220906401

• Fiber Materials • Previous Articles     Next Articles

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 Online:2024-01-15 Published:2024-03-14

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

CLC Number: 

  • TS176

Fig.1

Preparation route scheme of Ag-Cu NPs /PLA composite nanofiber membranes"

Tab.1

Compositions of electrostatic spinning membranes"

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

Fig.2

SEM images of Ag-Cu NPs,PLA and different compositions of Ag-Cu NPs/PLA composite nanofiber membranes"

Fig.3

Average diameters of PLA and different compositions of Ag-Cu NPs /PLA composite nanofiber membranes"

Tab.2

Surface element contents of electrospun fiber membranes"

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

Fig.4

Element mapping of Ag-Cu NPs/PLA composite nanofiber membranes for single fiber"

Fig.5

XRD patterns of PLA and different compositions of Ag-Cu NPs /PLA composite nanofiber membranes"

Fig.6

FT-IR spectra of PLA and different compositions of Ag-Cu NPs/PLAcomposite nanofiber membranes"

Fig.7

Water contact angles of PLA and different compositions of Ag-Cu NPs/PLA composite nanofiber membranes"

Tab.3

Antibacterial efficiencies of PLA and different compositions of Ag-Cu NPs /PLA composite nanofiber membranes"

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
[1] LIU C, SHEN J, YEUNG K W K, et al. Development and antibacterial performance of novel polylactic acid-graphene oxide-silver nanoparticle hybrid nanocomposite mats prepared by electrospinning[J]. ACS Biomaterials Science & Engineering, 2017, 3(3): 471-486.
[2] BALASUBRAMANIAM B, PRATEE K, RANJAN S, et al. Antibacterial and antiviral functional materials: chemistry and biological activity toward tackling COVID-19-like pandemics[J]. ACS Pharmacology & Translational Science, 2020, 4(1): 8-54.
[3] HUSSAIN Z, KHAN M A, IQBAL F, et al. Electrospun microbial-encapsulated composite-based plasticized seed coat for rhizosphere stabilization and sustainable production of canola (Brassica napus L.)[J]. Journal of Agricultural and Food Chemistry, 2019, 67(18): 5085-5095.
doi: 10.1021/acs.jafc.8b06505
[4] SHANG L, YU Y, LIU Y, et al. Spinning and applications of bioinspired fiber systems[J]. ACS Nano, 2019, 13(3): 2749-2772.
doi: 10.1021/acsnano.8b09651 pmid: 30768903
[5] YANG H, WANG L, XIANG C, et al. Electrospun porous PLLA and poly (LLA-co-CL) fibers by phase separation[J]. New Journal of Chemistry, 2018, 42(7): 5102-5108.
doi: 10.1039/C7NJ04970F
[6] ZHANG H, ZHANG T, QIU Q, et al. Quaternary ammonium salt-modified polyacrylonitrile/polycaprolactone electrospun nanofibers with enhanced antibacterial properties[J]. Textile Research Journal, 2021, 91(19/20): 2194-2203.
doi: 10.1177/0040517521997187
[7] ALTAN E, KARACELEBI Y, SAATCIOGLU E, et al. Fabrication of electrospun Juglans regia (Juglone) loaded poly (lactic acid) scaffolds as a potential wound dressing material[J]. Polymers, 2022. DOI: 10.3390/POLYM14101971.
[8] BACKES E H, PIRES L D N, BEATRICE C A G, et al. Fabrication of biocompatible composites of poly-(lactic acid)/hydroxyapatite envisioning medical applications[J]. Polymer Engineering & Science, 2020, 60(3): 636-644.
[9] NONATO R C, MEI L H I, BONSE B C, et al. Nanocomposites of PLA/ZnO nanofibers for medical applications: antimicrobial effect, thermal, and mechanical behavior under cyclic stress[J]. Polymer Engineering & Science, 2022, 62(4): 1147-1155.
[10] GODOY-GALLARDO M, ECKHARD U, DELGADO L M, et al. Antibacterial approaches in tissue engineering using metal ions and nanoparticles: from mechanisms to applications[J]. Bioactive Materials, 2021, 6(12): 4470-4490.
doi: 10.1016/j.bioactmat.2021.04.033
[11] PUTHALATH A K, HAZEL S, KOTTAPPARA R, et al. Synthesis and antibacterial activity of silver-copper nano-composites formed by microwave assisted chemical reduction[J]. Materials Today: Proceedings, 2021, 41: 525-529.
doi: 10.1016/j.matpr.2020.05.238
[12] JUNG H, KING M E, PERSONICK M L. Strategic synergy: advances in the shape control of bimetallic nanoparticles with dilute alloyed surfaces[J]. Current Opinion in Colloid & Interface Science, 2019, 40: 104-117.
doi: 10.1016/j.cocis.2019.02.004
[13] NOWAK A, SZADE J, TALIK E, et al. Physicochemical and antibacterial characterization of ionocity Ag/Cu powder nanoparticles[J]. Materials Characterization, 2016, 117: 9-16.
doi: 10.1016/j.matchar.2016.04.013
[14] VALDEZ-SALAS B, BELTRÁN-PARTIDA E, ZLATEV R, et al. Structure-activity relationship of diameter controlled Ag@Cu nanoparticles in broad-spectrum antibacterial mechanism[J]. Materials Science and Engineering:C, 2020. DOI:10.1016/j.msec.2020.111501.
[15] ZAIN N M, STAPLEY A G, SHAMA G J. Green synthesis of silver and copper nanoparticles using ascorbic acid and chitosan for antimicrobial appli-cations[J]. Carbohydrate Polymers, 2014, 112:195-202.
doi: 10.1016/j.carbpol.2014.05.081
[16] ZAIN N M, STAPLEY A G F, SHAMA G. Green synthesis of silver and copper nanoparticles using ascorbic acid and chitosan for antimicrobial appli-cations[J]. Carbohydrate Polymers, 2014, 112: 195-202.
doi: 10.1016/j.carbpol.2014.05.081
[17] YUAN Z, ZHANG K, JIAO X, et al. A controllable local drug delivery system based on porous fibers for synergistic treatment of melanoma and promoting wound healing[J]. Biomaterials science, 2019, 7(12): 5084-5096.
doi: 10.1039/c9bm01045a pmid: 31565707
[18] ZHOU Q, XIE J, BAO M, et al. Engineering aligned electrospun PLLA microfibers with nano-porous surface nanotopography for modulating the responses of vascular smooth muscle cells[J]. Journal of Materials Chemistry B, 2015, 3(21): 4439-4450.
doi: 10.1039/c5tb00051c pmid: 32262788
[19] 唐晓鹏. 载银离子多孔纳米纤维制备及抗菌性能研究[D]. 苏州: 苏州大学, 2015:31-32.
TANG Xiaopeng. Preparation and antibacterial properties of porous nanofibers containing silver ions[D]. Suzhou: Soochow University, 2015:31-32.
[20] MA G, YANG D, NIE J. Preparation of porous ultrafine polyacrylonitrile (PAN) fibers by electrospinning[J]. Polymers for Advanced Technologies, 2009, 20(2): 147-150.
doi: 10.1002/pat.v20:2
[21] ZONG X, KIM K, FANG D, et al. Structure and process relationship of electrospun bioabsorbable nanofiber membranes[J]. Polymer, 2002, 43(16): 4403-4412.
doi: 10.1016/S0032-3861(02)00275-6
[22] YANG H, ZHANG X, VELU P, et al. Enhanced green mediated synthesis of optimized Ag-Cu bimetallic nanoparticles using Leucas aspera and its application in anti-cancer activity against alveolar cancer[J]. Materials Letters, 2022. DOI:10.1016/j.matlet.2021.131645.
[23] KEMALA T, BUDIANTO E, SOEGIYONO B. Preparation and characterization of microspheres based on blend of poly (lactic acid) and poly (ε-caprolactone) with poly (vinyl alcohol) as emulsifier[J]. Arabian Journal of Chemistry, 2012, 5(1): 103-108.
doi: 10.1016/j.arabjc.2010.08.003
[24] WU X, BOURBIGOT S, LI K, et al. Co-pyrolysis characteristics and flammability of polylactic acid and acrylonitrile-butadiene-styrene plastic blend using TG, temperature-dependent FTIR, Py-GC/MS and cone calorimeter analyses[J]. Fire Safety Journal, 2022. DOI: 10.1016/j.firesaf.2022.103543.
[25] DEGHICHE A, HADDAOUI N, ZERRIOUH A, et al. Effect of the stearic acid-modified TiO2 on PLA nanocomposites: morphological and thermal properties at the microscopic scale[J]. Journal of Environmental Chemical Engineering, 2021. DOI: 10.1016/j.jece.2021.106541.
[26] GONG X, PAN L, TANG C Y, et al. Preparation, optical and thermal properties of CdSe-ZnS/poly (lactic acid)(PLA) nanocomposites[J]. Composites Part B: Engineering, 2014, 66: 494-499.
doi: 10.1016/j.compositesb.2014.06.016
[27] PETER A, COZMUTA L M, NICULA C, et al. Chemical and organoleptic changes of curd cheese stored in new and reused active packaging systems made of Ag-graphene-TiO2-PLA[J]. Food Chemistry, 2021. DOI: 10.1016/j.foodchem.2021.130341.
[28] MAMATHA G, SOWMYA P, MADHURI D, et al. Antimicrobial cellulose nanocomposite films with in situ generations of bimetallic (Ag and Cu) nanoparticles using Vitex negundo leaves extract[J]. Journal of Inorganic and Organometallic Polymers and Materials, 2021, 31(2):802-815.
doi: 10.1007/s10904-020-01819-9
[29] PERDIKAKI A, GALEOU A, PILATOS G, et al. Ag and Cu monometallic and Ag/Cu bimetallic nanoparticle-graphene composites with enhanced antibacterial performance[J]. ACS Applied Materials & Interfaces, 2016. DOI:10.1021/acsami.6b08403.
[30] ZHOU F, ZHU Y, YANG L, et al. Ag NP catalysis of Cu ions in the preparation of Ag Cu NPs and the mechanism of their enhanced antibacterial efficacy[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022. DOI: 10.1016/j.colsurfa.2021.127831.
[31] CRUCES E, ARANCIBIA-MIRANDA N, MANQUIÁN-CERDA K, et al. Copper/silver bimetallic nanoparticles supported on aluminosilicate geomaterials as antibacterial agents[J]. ACS Applied Nano Materials. 2022, 5(1):1472-1483.
doi: 10.1021/acsanm.1c04031
[32] DOOLOTKELDIEVA T, BOBUSHEVA S, ZHASNAKUNOV Z, et al. Biological activity of Ag and Cu monometallic nanoparticles and Ag-Cu bimetallic nanocomposites against plant pathogens and seeds[J]. Journal of Nanomaterials, 2022. DOI: 10.1155/2022/1190280.
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