Preparation of composite polyacrylonitrile - nano silver electrospun fiber membrane and its application in controlling microbial deterioration of grotto cultural heritage
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摘要:
由于文物本身的特殊性，其保护需要遵循“最少干预”的原则，因此，对于石质文物的保护，传统的化学材料的使用可能会对文物本体和环境造成来潜在的危害。开发新型微生物防治材料是目前文物保护领域的重要研究方向。静电纺丝技术依靠静电电子束进行纺丝，其生成的复合纳米纤维膜具有优秀的渗透性及极高的比表面积，同时能作为药物的载体，具有一定的缓释作用，是制备新型石窟文物微生物病害防治材料的潜在可行性技术。纳米银(AgNPs)因其高安全性、高稳定性、广谱性及优秀的抑菌性能，被广泛用于开发新型纳米复合材料。本文利用静电纺丝技术，将纳米银与聚丙烯腈纤维膜进行原位复合，制成了含银颗粒的纳米纤维膜。通过调整聚丙烯腈浓度和反应温度，筛选得到了力学性能和银粒子浓度最优的复合纳米纤维膜制备条件。此外，验证了复合纤维膜对石窟文物病原菌在实验室内和户外条件下的抑菌能力，证实了其在石窟文物微生物病害防治领域的应用潜力。本研究将静电纺丝技术引入石窟文物保护领域，是该技术在文物保护领域应用的创新性探索。 聚丙烯腈-纳米银静电纺丝纳米纤维膜对岩石表面微生物的抑菌效果。(A) 未经任何处理的飞来峰岩石表面形貌；(B) 覆盖聚丙烯腈静电纺丝纳米纤维膜后的飞来峰岩石表面形貌；(C) 覆盖聚丙烯腈-纳米银静电纺丝纳米纤维膜后的飞来峰岩石表面形貌。 Abstract: Using electrospinning technology to compound antibacterial active ingredients with matrix fibers is seen as an effective means to develop new antibacterial materials. To develop new microbial deterioration control materials for grotto cultural heritage, composite polyacrylonitrile (PAN)-nano silver (AgNPs) electrospun fiber membrane was developed by electrospinning technology. The antibacterial effects of the fiber were further evaluated. Spinning stock solution containing silver particles was prepared by PAN mixing with dimethylformamide, adding silver nitrate and tea polyphenols. Then, the nano fiber membrane containing silver particles was prepared by electrostatic spinning technology. By changing the concentration and reaction temperature of PAN, the physical and chemical properties of electrospun fiber membrane, screening the optimal preparation process of electrospun fiber membrane suitable for the prevention and control of grotto cultural heritage microbial deterioration, the antibacterial effect of fibers was verified in the laboratory and outdoors respectively. The results show that the composite fiber membrane prepared with 12% PAN content at 80℃ has the advantages of good fiber mechanical properties and high concentration of silver particles, which is the optimal preparation condition of composite PAN-AgNPs electrospun fiber membrane screened in this study. Silver composite nanofiber material has antibacterial effect on Aspergillus niger and Penicillium ap., two microorganisms related to the deterioration of grotto cultural heritage. Significant antibacterial effect under outdoor rock surface conditions has been detected. These results indicate that the composite PAN-AgNPs electrospun fiber membrane prepared in this study has application value for the control of grotto cultural heritage deterioration. -
图 1 纤维膜力学性能检验：(a) 12% 60℃复合纤维膜抗拉强度测试断裂走向；(b) 12% 80℃复合纤维膜抗拉强度测试断裂走向；(c) 12%纯PAN纤维膜抗拉强度测试断裂走向；(d) 12% 60℃复合纤维膜抗拉强度测试； (e) 12% 80℃复合纤维膜抗拉强度测试； (f) 12%纯PAN纤维膜抗拉强度测试
Figure 1. Mechanical property test of fiber membrane: (a) 12% 60℃ composite fiber membrane tensile strength test fracture trend; (b) 12% 80℃ composite fiber membrane tensile strength test fracture trend; (c) 12% Ag-free fiber membrane tensile strength test fracture trend; (d) Tensile strength test of 12% 60℃ composite fiber membrane; (e) Tensile strength test of 12% 80℃ composite fiber membrane; (f) Tensile strength test of 12% Ag-free fiber membrane
图 2 利用TGA分析纤维膜热稳定性：(a) 6% 80℃复合纤维膜；(b) 12% 60℃复合纤维膜；(c) 12% 80℃复合纤维膜；(d) 12% 纯纤维膜
Figure 2. Thermal stability of fiber membrane with TGA analysis: (a) 6% 80℃ composite fiber membrane; (b) 12% 60℃ composite fiber membrane; (c) 12% 80℃ composite fiber membrane; (d) 12% Ag-free fiber membrane
图 3 扫描电镜下纳米复合纤维膜的微观结构：(a) 6% 80℃条件下制成的复合纤维膜；(b) 12% 80℃条件下制成的复合纤维膜；(c) 12% 60℃条件下制成的复合纤维膜；(d) 12% Ag-free条件下制成的对照组纤维膜；((e), (f)) 12% 80℃条件下制成的复合纤维膜的SEM-EDS表征
Figure 3. Microstructure of nanocomposite fiber membrane observed by SEM: (a) 6% PAN composite fiber membrane made at 80℃; (b) 12% PAN composite fiber membrane made at 80℃; (c) 12% PAN composite fiber membrane made at 60℃; (d) Fiber membrane of the control group made under the condition of 12% PAN, Ag-free; ((e), (f)) SEM-EDS mapping of 12% PAN composite fiber membrane made at 80℃
图 4 纳米纤维膜培养168 h后黑曲霉抑菌圈：((a)~(c)) 6% 80℃ AgNPs-PAN复合静电纺丝纤维膜；((d)~(f)) 12% 60℃ AgNPs-PAN复合静电纺丝纤维膜；((g)~(i)) 12% 80℃ AgNPs-PAN复合静电纺丝纤维膜；((j)~(l)) 12%纯PAN纳米纤维膜
Figure 4. Aspergillus niger antimicrobic circle after 168 h nanofiber membrane culture: ((a)-(c)) 6% AgNPs-PAN composite electrospun fiber membrane at 80℃; ((d)-(f)) 12% AgNPs-PAN composite electrospun fiber membrane at 60℃; ((g)-(i)) 12% AgNPs-PAN composite electrospun fiber membrane at 80℃; ((j)-(l)) 12% Ag-free fiber membrane
图 5 纳米纤维膜培养72 h后青霉抑菌圈：((a)~(c)) 6% 80℃ AgNPs-PAN复合静电纺丝纤维膜；((d)~(f)) 12% 60℃ AgNPs-PAN复合静电纺丝纤维膜；((g)~(i)) 12% 80℃ AgNPs-PAN复合静电纺丝纤维膜；((j)~(l)) 12%纯PAN纳米纤维膜
Figure 5. Penicillium sp. antimicrobic circle after 72 h nanofiber membrane culture: ((a)-(c)) 6% AgNPs-PAN composite electrospun fiber membrane at 80℃; ((d)-(f)) 12% AgNPs-PAN composite electrospun fiber membrane at 60℃; ((g)-(i)) 12% AgNPs-PAN composite electrospun fiber membrane at 80℃; ((j)-(l)) 12% Ag-free fiber membrane
图 6 AgNPs-PAN复合静电纺丝纤维膜户外抑菌效果：(a) 飞来峰岩石表面形貌；(b) 覆盖纯PAN静电纺丝纳米纤维膜后的飞来峰岩石表面形貌；(c) 覆盖AgNPs-PAN复合静电纺丝纤维膜后的飞来峰岩石表面形貌；(d) 3种不同条件下的岩石表面微生物样品的ATP荧光信号值拟合曲线(Blank、CK和Ag分别代表空白对照组、Ag-free纤维膜对照组和AgNPs-PAN复合静电纺丝纤维膜处理组；(e) 针对80~85 s时间内的3种不同条件下的岩石表面微生物样品的ATP荧光信号值的差异显著性分析(字母a、b、c代表图基检验(Tukey test)结果(P-value <0.01))
Figure 6. Outdoor antimicrobic effect of AgNPs-PAN composite electrospun fiber membrane: (a) Surface morphology of klippe rock in Feilaifeng; (b) Surface morphology of the klippe rock after covering the Ag-free fiber membrane; (c) Surface morphology of klippe rock covered with AgNPs-PAN composite electrospun fiber membrane; (d) ATP fluorescence signal value fitting curves of rock surface microbial samples under three different conditions (Blank, CK and Ag in the figure represent blank control group, Ag-free fiber membrane control group and AgNPs-PAN composite electrospun fiber membrane treatment group, respectively); (e) Significance of ATP fluorescence signal values of microbial samples on the rock surface under three different conditions in the period of 80-85 s analyzed (The letter a, b, c in the figure represent the result of Tukey test (P-value <0.01)
表 1 纺织液具体浓度比
Table 1. Concentration ratio of textile liquid
Concentration of PAN AgNO3/g PAN/g TP/g DMF/mL Reaction time/min Reaction temperature/℃ 12% 0.48 6.37 0.03 50 30 60 12% 0.48 6.37 0.03 50 30 80 6% 0.48 3.19 0.03 50 30 60 6% 0.48 3.19 0.03 50 30 80 12%(Ag-free) 0 6.37 0 50 30 60 Notes: PAN—Polyacrylonitrile; TP—Tea polyphenols; DMF—N, N-dimethylformamide. 
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表 2 电纺设备参数
Table 2. Electrospinning equipment parameters
Concentration of PAN Reaction temperature/℃ Voltage /kV Distance/cm Rate Needle size 12% 60 12 15 0.001 16 12% 80 12 15 0.001 16 6% 60 0 15 0 12 6% 80 8 15 0.003 12 12%(Ag-free) 60 12 15 0.001 16
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