负载聚集诱导发光光敏剂纳米纤维膜的制备及其抗菌性能

摘要/Abstract

摘要： 为解决光动力抗菌纤维活性氧（ROS）产率低、光敏剂易泄露等问题，以聚集诱导发光（AIE）分子（TPE-TCF）为光敏剂，与聚丙烯腈（PAN）、聚乙烯吡咯烷酮（PVP）共混，通过静电纺丝制备TPE-TCF@PAN/PVP纳米纤维膜，表征其化学结构、微观形貌和表面亲水性，并探究了其ROS产率和抗菌效果。结果表明：TPE-TCF@PAN/PVP膜（TPE-TCF质量分数为0.4%）具有高亲水性、光敏剂负载稳定性和ROS产率，超低功率白光照射20 min后，可实现对金黄色葡萄球菌（抑菌率大于96.2%）和大肠杆菌（抑菌率大于99.9%）的高效灭菌。该研究结果可为高效广谱抗菌的医用防护材料的制备和应用提供参考。

关键词: 聚集诱导发光光敏剂, 活性氧, 静电纺丝, 纳米纤维膜, 光动力抗菌

Abstract: Photodynamic antibacterial fibers can generate reactive oxygen species (ROS) under light exposure, rapidly reacting with microorganisms, including Gram-positive and Gram-negative bacteria, fungi, viruses, etc., so as to achieve sterilization effects. In the field of medical protective textiles, such highly efficient, low-toxicity, and low-resistance antimicrobial materials play a crucial role. However, traditional photodynamic antibacterial fibers face challenges such as low ROS production rates and leakage of photosensitizers (PS).
In this study, the AIE molecule with photosensitizer properties, (3-cyano-5,5-dimethyl-4-(4-(1,2,2-triphenylvinyl)styryl)furan-2(5H)-ylidene)malononitrile (TPE-TCF), which possesses a donor-acceptor (D-A) structure, was used as the photosensitizer. By blending it with polyacrylonitrile (PAN) and the hydrophilic polymer polyvinylpyrrolidone (PVP), TPE-TCF@PAN/PVP, a nanofiber membrane with excellent hydrophilicity, was prepared by using electrospinning technology. The study explored the effects of TPE-TCF doping level on the wettability, ROS production rate, and antibacterial properties of the nanofiber membrane.
Proton nuclear magnetic resonance spectroscopy (¹H-NMR) confirmed the synthesis of TPE-TCF molecules, and UV-Vis spectrophotometry and fluorescence spectroscopy demonstrated that the aggregation-induced emission (AIE) property of TPE-TCF facilitated the generation of total ROS. Fourier transform infrared spectroscopy (FTIR) analysis confirmed the successful loading of TPE-TCF into the nanofiber membrane. Scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM) showed that the TPE-TCF@PAN/PVP nanofiber membrane exhibited a regular morphology, and TPE-TCF molecules were aggregated and distributed in the nanofiber membrane. The loading stability of TPE-TCF was also evaluated by measuring the UV absorption of the leach solution from the nanofiber membrane. The results indicated excellent loading stability of TPE-TCF in the nanofiber membrane. Water contact angle (WCA) experiments demonstrated that the hydrophobicity of the nanofiber membrane increased with the increase of TPE-TCF doping levels. ROS production rates of nanofiber membrane with different TPE-TCF doping levels were evaluated by using indicators such as ABDA and DCFH, revealing that the TPE-TCF@PAN/PVP nanofiber membrane with a TPE-TCF mass fraction of 0.4% exhibited the optimal ROS production efficiency. Finally, the antimicrobial performance of the nanofiber membrane was assessed. The results showed that the TPE-TCF@PAN/PVP nanofiber membrane with a TPE-TCF mass fraction of 0.4% demonstrated the best bacteriostatic effect, achieving inhibition efficiencies of 96.2% for S. aureus and 100% for E. coli under 20 minutes of white light irradiation at ultra-low power.
In summary, this study successfully prepared a TPE-TCF@PAN/PVP nanofiber membrane with highly efficient broad-spectrum antibacterial properties using electrospinning technology. The research offers a new approach to the development of medical protective materials and has the potential to address issues related to cross-infection.

Key words: aggregation-induced emission photosensitizer (AIEP), ROS, electrospinning, nanofiber membrane, photodynamic antibacterial

中图分类号:

TS101.4

张亚南, 许冰洁, 李梦玮, 任浩天, 高玉洁, 王懿佳, 吴金丹. 负载聚集诱导发光光敏剂纳米纤维膜的制备及其抗菌性能[J]. 现代纺织技术, 2024, 32(10): 31-39.

ZHANG Yanan, XU Bingjie, LI Mengwei, REN Haotian, GAO Yujie, WANG Yijia, WU Jindan, . Preparation and antibacterial properties of loaded aggregation-induced emission photosensitizers nanofiber membranes[J]. Advanced Textile Technology, 2024, 32(10): 31-39.

参考文献

[1] BAKER R E, MAHMUD A S, MILLER I F, et al. Infectious disease in an era of global change[J]. Nature Reviews Microbiology, 2022, 20(4): 193-205.
[2] 杨玉荣, 张晓妍, 邹明辰, 等. 光动力广谱抗菌型复合材料的制备及性能研究[J]. 化工新型材料, 2021, 49(S1): 264-267.
YANG Yurong, ZHANG Xiaoyan, ZOU Mingchen, et al. Preparation and property of photodynamic broad-spectrum antibacterial composite[J]. New Chemical Materials, 2021, 49(S1): 264-267.
[3] NGUYEN V N, ZHAO Z, TANG B Z, et al. Organic photosensitizers for antimicrobial phototherapy[J]. Chemical Society Reviews, 2022, 51(9): 3324-3340.
[4] LI T T, WU Y, CAI W T, et al. Vision defense: Efficient antibacterial AIEgens induced early immune response for bacterial endophthalmitis[J]. Advanced Science, 2022, 9(25): 2202485.
[5] HU F, XU S D, LIU B. Photosensitizers with aggregation-induced emission: materials and biomedical applications[J]. Advanced Materials, 2018, 30(45): 1801350.
[6] ZHU J X, WEN H Y, ZHANG H, et al. Recent advances in biodegradable electronics-from fundament to the next-generation multi-functional, medical and environmental device[J]. Sustainable Materials and Technologies, 2023, 35: e00530.
[7] HU R, QIN A J, TANG B Z. AIE polymers: Synthesis and applications[J]. Progress in Polymer Science, 2020, 100: 101176.
[8] 苏芳芳, 经渊, 宋立新, 等. 我国静电纺丝领域研究现状及其热点：基于CNKI数据库的可视化文献计量分析[J]. 东华大学学报(自然科学版), 2024,50(1):45-54.
SU Fangfang, JING Yuan, SONG Lixin, et al. Present situation and hotspot of electrospinning in China: Visual bibliometric analysis based on CNKI database[J]. Journal of Donghua University (Natural Science), 2024,50(1):45-54.
[9] LI M, WEN H F, LI H X, et al. AIEgen-loaded nanofibrous membrane as photodynamic/photothermal antimicrobial surface for sunlight-triggered bioprotection[J]. Biomaterials, 2021, 276: 121007.
[10] WANG Y J, Shi Y, Wang Z Y, et al. A red to near-IR fluorogen: Aggregation-induced emission, large stokes shift, high solid efficiency and application in cell-imaging[J]. Chemistry–A European Journal, 2016, 22(28): 9784-9791.
[11] LIN J, YAO Z, XIONG M M, et al. Directional transport of drug droplets based on structural and wettability gradients on antibacterial Janus wound plaster with hemostatic, antiextravasation, and prehealing properties[J]. Advanced Composites and Hybrid Materials, 2023, 6(6): 193.
[12] LIU S S, WANG B N, YU Y W, et al. Cationization-enhanced type I and type II ROS generation for photodynamic treatment of drug-resistant bacteria[J]. ACS Nano, 2022, 16(6): 9130-9141.
[13] HO T H, HONG S Y, YANG C H, et al. Preparation of green emission and red emission ligand-free upconverting nanoparticles for investigation of the generation of reactive oxygen species applied to photodynamic therapy[J]. Journal of Alloys and Compounds, 2022, 893: 162323.
[14] YANG D L, TU Y X, WANG X R, et al. A photo-triggered antifungal nanoplatform with efflux pump and heat shock protein reversal activity for enhanced chemo-photothermal synergistic therapy[J]. Biomaterials Science, 2021, 9(9): 3293-3299.
[15] LEE M M S, YU E Y, YAN D Y, et al. The role of structural hydrophobicity on cationic amphiphilic aggregation-induced emission photosensitizer-bacterial interaction and photodynamic efficiency[J]. ACS Nano, 2023, 17(17): 17004-17020.