纺织学报, 2026, 47(03): 35-43 doi: 10.13475/j.fzxb.20251205401

生物医用材料

负载肉桂醛的聚琥珀酰亚胺静电纺纤维膜抗菌敷料制备及其性能

张宝华1, 夏杰1, 项复玉1, 汪瑱1, 吴韶华2, 张彩丹,1

1 嘉兴大学 全省生物基健康功能纤维材料重点实验室, 浙江 嘉兴 314000

2 青岛大学 纺织服装学院, 山东 青岛 266071

Preparation and properties of cinnamaldehyde-loaded polysuccinimide electrospun fiber membrane for antibacterial dressing

ZHANG Baohua1, XIA Jie1, XIANG Fuyu1, WANG Zhen1, WU Shaohua2, ZHANG Caidan,1

1 Zhejiang Key Laboratory of Bio-Based Health Functional Fiber Materials, Jiaxing University, Jiaxing, Zhejiang 314000, China

2 College of Textile and Clothing, Qingdao University, Qingdao, Shandong 266071, China

通讯作者: 张彩丹(1988—),女,讲师,博士。主要研究方向为功能性水凝胶纤维材料的开发。E-mail:caidanzhang@zjxu.edu.cn。

收稿日期: 2025-12-26   修回日期: 2026-01-27  

基金资助: 浙江省科技计划项目(2025ZY01057)
大学生科技创新训练项目(SRT8517241329)

Received: 2025-12-26   Revised: 2026-01-27  

作者简介 About authors

张宝华(2005—),女,本科生。主要研究方向为纤维材料。

摘要

静电纺纤维膜凭借其独特结构被视为理想伤口敷料,为此,选用易改性生物材料聚琥珀酰亚胺(PSI)为原料,肉桂醛(CA)为功能性添加剂,采用静电纺丝方法制备PSI/CA静电纺纤维膜,在此基础上对其进行交联改性,获得抗菌纤维敷料。借助扫描电镜、红外光谱仪、拉伸测试仪和吸水倍率测试,对比了PSI/CA静电纺纤维膜交联前后的结构与性能变化,并对交联后PSI/CA静电纺纤维膜的抗菌性能、细胞相容性和释药性能进行分析。结果表明:PSI/CA静电纺纤维膜交联前后均能保持良好的纤维形貌;交联改性后的PSI/CA静电纺纤维膜中琥珀酰亚胺环打开,形成交联结构,静电纺纤维膜强度明显提升;交联改性后的PSI/CA静电纺纤维膜具备良好的抗菌性能,CA添加量为3%、5%和10%的纤维膜对大肠埃希菌和金黄色葡萄球菌的抑菌率均可达100%;不同CA添加量的PSI/CA静电纺纤维交联膜均有良好的细胞相容性;通过药物缓释模型分析,CA释放行为符合一级动力学模型,释药机制以Fickian扩散为主,伴随少量的载体溶蚀。交联改性后的PSI/CA静电纺纤维膜具有良好的力学性能、抗菌性、细胞相容性以及持续释药能力,在医用敷料领域有一定的应用潜力。

关键词： 医用敷料; 聚琥珀酰亚胺; 肉桂醛; 抗菌性; 静电纺纤维膜; 交联改性

Abstract

Objective Electrospun membranes have great potential as advanced wound dressings by virtue of their high specific surface area, porous structure and good permeability. These attributes facilitate wound exudate absorption and create a moisture-permeable microenvironment for tissue repair. Developing multifunctional membranes with inherent antibacterial properties is crucial for preventing infection and promoting healing. Therefore, a crosslinked polysuccinimide/cinnamaldehyde (PSI/CA) electrospun fibrous membrane was prepared for antibacterial dressing, using PSI as electrospinning polymer matrix and CA as a functional agent.

Method PSI was synthesized by thermal polymerization of L-aspartic acid. Electrospinning solutions were prepared by dissolving PSI and varying amounts of CA (0%, 3%, 5%, and 10% by mass of PSI) in dimethylformamide (DMF). PSI/CA solutions were electrospun into fiber membranes, and then crosslinked with ethylenediamine vapor. The electrospun fiber membranes were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy (FT-IR), water absorption test, mechanical property test, antibacterial assays, cytotoxicity analysis and drug release studies.

Results The PSI/CA electrospun fiber membranes exhibited smooth surfaces and a uniform diameter distribution. The addition of CA had no significant effect on fiber diameter. After crosslinking, the fibers display slight bending and agglomeration, with a minor increase in diameter. FT-IR analysis confirmed the opening of the succinimide rings in PSI and formation of amide bonds via crosslinking. In the uncrosslinked state, the PSI/CA electrospun fiber membranes demonstrated a water absorption capacity of 19.0-21.6 g/g, which significantly decreased to 12.8-14.6 g/g after crosslinking due to increased packing density. The CA addition also showed little effect on water absorption properties. Crosslinking notably improved the mechanical strength of the PSI/CA electrospun fiber membranes. With increasing CA loading, the mechanical strength of crosslinked PSI/CA electrospun fiber membranes exhibited a peak of (1.41±0.19) MPa at 3% CA content. All crosslinked PSI/CA electrospun fiber membranes containing CA demonstrated good antibacterial activity. The inhibition rate against both Escherichia coli and Staphylococcus aureus achieved 100%, and the crosslinked pure PSI membrane also showed considerable intrinsic antibacterial activity, with the inhibition rate of 98.5% against Escherichia coli and 87.3% against Staphylococcus aureus, respectively. Cytotoxicity assay revealed good cell compatibility for all membranes, with cell viability remaining above 95%, and a slight promotion of proliferation was observed for CA-loaded PSI/CA electrospun fibrous membranes, with cell viability rate over 98%. In drug release studies, CA displayed an initial burst release within the first 24 h, followed by a sustained release profile. The CA release process conforms to the first-order kinetic model, and the release mechanism was dominated by Fickian diffusion. The CA release behavior was closely related to the CA content in the PSI/CA electrospun fibrous membranes.

Conclusion The PSI loaded with CA is successfully electrospun into fiber membranes. After crosslinking modification, PSI/CA electrospun fiber membranes still retain fiber morphology, along with improved mechanical properties, excellent antibacterial activity and good cell compatibility. The CA release process conformed to the first-order kinetic model, and the release mechanism is dominated by Fickian diffusion. These integrated properties enable the crosslinked PSI/CA electrospun fiber membranes to meet key requirements for advanced wound dressing applications.

Keywords： medical dressing; polysuccinimide; cinnamaldehyde; antibacterial activity; electrospun fiber membrane; crosslinking modification

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本文引用格式

张宝华, 夏杰, 项复玉, 汪瑱, 吴韶华, 张彩丹. 负载肉桂醛的聚琥珀酰亚胺静电纺纤维膜抗菌敷料制备及其性能[J]. 纺织学报, 2026, 47(03): 35-43 doi:10.13475/j.fzxb.20251205401

ZHANG Baohua, XIA Jie, XIANG Fuyu, WANG Zhen, WU Shaohua, ZHANG Caidan. Preparation and properties of cinnamaldehyde-loaded polysuccinimide electrospun fiber membrane for antibacterial dressing[J]. Journal of Textile Research, 2026, 47(03): 35-43 doi:10.13475/j.fzxb.20251205401

敷料在创面治疗中起着至关重要的作用,静电纺纤维膜敷料凭借其独特结构在众多新型敷料中脱颖而出。静电纺纤维膜的小孔径和高孔隙率等独特结构,不仅能够保护伤口免受病原体感染[1],还可促进气体交换以及渗出液管理;同时,静电纺纤维膜具有与天然细胞外基质高度相似的拓扑结构和尺寸特征[2],为细胞黏附、增殖、迁移和分化提供了适宜的微环境,有利于组织修复再生[3]。静电纺丝技术因设备操作简单、工艺灵活而广泛应用于纳米纤维膜敷料的制备[4]。通过调节静电纺丝原料、溶液性质及纺丝参数,可实现对纳米纤维及其纤维集合体形貌、力学性能与功能特性的精准调控[5-6]。其中,静电纺丝原料的选择尤为关键,直接影响着纳米纤维膜敷料的细胞相容性、降解性、力学性能及功能扩展性。

目前,静电纺纤维膜敷料常用纺丝原料主要包括天然聚合物(如壳聚糖、明胶等)、合成聚合物(如聚己内酯、聚乙烯醇等)及其复合改性体系[7]。天然聚合物具备良好的细胞相容性,但力学性能和稳定性欠佳[8];合成聚合物通过化学合成可有效控制静电纺纤维膜的力学强度和降解速率等,但其生物性能通常低于天然聚合物且表面缺少功能基团,因此,开发兼顾细胞相容性、可纺性、力学性能以及功能需求的静电纺丝原料具有重要意义。

由L-天门冬氨酸聚合而成的聚琥珀酰亚胺(PSI)为线性高分子,具有良好的生物相容性,且反应活性高极易修饰改性,PSI静电纺纤维膜在生物医用和水处理领域应用均有报道[9-10]。尽管PSI是理想的生物用静电纺丝原料,但纯PSI静电纺纤维膜存在力学性能不足、缺乏抗菌性等问题,需要通过改性以及加入抗菌物质增加其作为医用敷料的功能性[9,11]。肉桂醛(CA)作为天然抗菌剂,可通过破坏微生物细胞膜并干扰其代谢产生抗菌作用,具有广谱抗菌、不易产生耐药性、生物相容性好等优势,已用于壳聚糖、聚乳酸等静电纺抗菌敷料的制备[12]。PSI材料作为新型静电纺丝原料,其PSI/CA复合体系的静电纺丝性能以及在敷料领域的应用鲜见报道。

为提升PSI静电纺纤维膜作为敷料的抗菌性和力学性能,本研究选用CA为添加剂,通过PSI/CA溶液混纺制备静电纺纤维膜,利用乙二胺交联改性处理增加其作为敷料的力学性能。探索了不同CA添加量及交联处理对静电纺纤维膜外观形貌、力学性能、吸水能力、抗菌性和细胞相容性的影响,并研究了交联改性后的PSI/CA静电纺纤维膜的药物释放行为。

1 实验部分

1.1 实验材料

聚琥珀酰亚胺(PSI,重均分子量约为30 000),为实验室合成(以L-天门冬氨酸为单体,质量分数为85%的磷酸为催化剂,在180 ℃加热减压条件下聚合而成,二者均购自上海阿拉丁生化科技股份有限公司);N,N-二甲基甲酰胺(DMF),湖州双林化学科技有限公司;肉桂醛(CA)、无水乙醇,江苏强盛功能化学股份有限公司;乙二胺,国药集团化学试剂有限公司;磷酸盐缓冲液(PBS),常德比克曼生物科技有限公司;金黄色葡萄球菌、大肠埃希菌,上海保藏生物技术中心;DMEM培养基、青霉素/链霉素(P/S)、胎牛血清(FBS),美国Gibco公司;人真皮成纤维细胞(HDFs),中国科学研究院细胞库;MTT检测试剂盒、二甲基亚砜(DMSO),美国Sigma Aldrich公司。

1.2 试样的制备

1.2.1 PSI/CA静电纺纤维膜的制备

将PSI溶于DMF中制备质量分数为36%的纺丝溶液,按照PSI质量的0%、3%、5%和10% 添加CA,搅拌溶解并静置脱泡,获得不同CA含量的PSI/CA静电纺丝溶液。

将PSI/CA静电纺丝溶液注入注射器内并固定在SNGT-1400型静电纺丝机(青岛斯备宁电纺设备有限公司)上,设定纺丝速度为0.8 mL/h,纺丝电压为14.5 kV,接收距离为13 cm,接收辊筒转速为120 r/min,纺丝喷头横向移动速度为70 mm/min,制备得到PSI/CA静电纺纤维膜,通过真空干燥去除残留溶剂。根据纺丝溶液中CA含量(0%、3%、5%、10%)的不同,将所制备的静电纺纤维膜分别命名为PSI/CA0、PSI/CA3、PSI/CA5、PSI/CA10。

1.2.2 PSI/CA静电纺纤维膜的交联改性处理

将PSI/CA静电纺纤维膜置于容积为2 L的密闭容器中,在容器底部加入乙二胺。在乙二胺挥发形成的蒸汽环境中,PSI分子中的酰亚胺环在乙二胺的胺基作用下打开发生交联反应,反应时间为6 h。反应结束后取出纤维膜,通过真空干燥去除残留乙二胺,最终获得交联改性后的PSI/CA静电纺纤维膜。

1.3 测试与表征
1.3.1 静电纺纤维膜微观形貌观察

使用JFC-1200型喷金溅射仪(日本电子株式会社)对样品进行喷金处理,通过Phenom Pure型扫描电子显微镜(美国Phenom-world公司)观察静电纺纤维膜的微观形貌。每个样品随机选取50 根纤维,测量其直径并进行统计分析。

1.3.2 静电纺纤维膜化学结构表征

借助VERTEX 72型傅里叶变换红外光谱仪(德国Bruker公司),采用衰减全反射法观察PSI/CA静电纺纤维膜交联前后化学结构的变化,扫描波数范围为4 000~500 cm-1。

1.3.3 静电纺纤维膜吸水倍率测试

为测试不同CA含量的PSI/CA静电纺纤维膜的吸水倍率,将其置于去离子水中浸渍24 h后取出,悬挂在烧杯壁上沥水30 min后称量,每组样品测试3次。吸水倍率计算公式为

${S}_{R}=\frac{{m}_{2}-{m}_{1}}{{m}_{1}}$

式中:SR为吸水倍率,g/g;m1为干燥状态下样品质量,g;m2为吸水后样品质量,g。

1.3.4 静电纺纤维膜力学性能测试

采用YGB001A型单纤维强力仪(温州市大荣纺织仪器有限公司)对静电纺纤维膜的拉伸力学性能进行测试。将样品裁剪成宽5 mm的长条形,设定夹持隔距为20 mm,拉伸速度为100 mm/min,记录拉伸断裂强力和断裂伸长率数据,每组样品测试5次。

采用YG141 N型数字式织物厚度仪(南通宏大实验仪器有限公司)测定静电纺纤维膜的厚度。采用压脚面积为1 cm2,载荷为1 000 cN的压重砝码,压重时间为30 s。拉伸强度计算公式为

$\sigma  = F/\left(ah\right)$

式中:σ为拉伸强度,MPa;F为拉伸强力,N;a为样品宽度,m;h为样品厚度,m。

1.3.5 静电纺纤维膜抗菌性能测试

采用金黄色葡萄球菌和大肠埃希菌为测试菌株,测试方法参照GB/T 20944.3—2008《纺织品抗菌性能的评价 第3部分 振荡法》,并略作调整。称取7.5 mg剪碎样品,经紫外线灭菌后加入0.7 mL PBS和50 μL浓度为1×105 CFU/mL的菌液。对照组除不加样品外,其它同实验组操作一致。在37 ℃下恒温振荡培养18 h后进行稀释,然后取出100 μL稀释后菌液继续培养18 h,观察并记录菌落数。

1.3.6 静电纺纤维膜细胞毒性测试

选用HDFs进行细胞毒性测试。将交联改性后的PSI/CA静电纺纤维膜裁成直径为10 mm的圆片,每组样品制备3个重复样。经紫外线照射灭菌后,样品在3 mL细胞培养基中浸泡24 h得到浸提液。将细胞接种于96孔板上,稳定后更换为样品浸提液,空白对照组采用正常细胞培养基。培养基使用含有1% P/S混合溶液和10%FBS的DMEM培养基。培养3 d后采用MTT法观察细胞增殖情况。去除96孔板中的浸提液以及空白组的细胞培养基,采用MTT溶液避光培养4 h后,弃去上清液并加入DMSO进行结晶溶解,使用酶标仪测定490 nm波长处的吸光度值,通过下式计算各组的细胞存活率:

${R}_{SR}=\frac{A}{{A}_{0}}\times 100\%$

式中:RSR为该样品的细胞存活率,%;A为各组样品的吸光度;A0为空白对照组的平均吸光度。

1.3.7 药物缓释测试及动力学拟合

将CA溶于pH值为7.4的PBS中,制成一系列质量浓度为0.25~10 μg/mL的CA溶液,借助UV752型紫外可见分光光度计(上海菁华科技仪器有限公司)测定311 nm 波长处的吸光度,绘制标准曲线并拟合得到线性方程:

$y=0.084 2 x+0.007=0.007$

式中:x为肉桂醛质量浓度,μg/mL;y为吸光度。拟合曲线的相关系数R2为0.999 7,表明线性相关性良好。

称取交联改性后的PSI/CA静电纺纤维膜,每块样品质量为40 mg,浸没在20 mL PBS中,在37 ℃恒温水浴中振荡,在预设时间点定量取样,稀释后测定吸光度,根据标准曲线换算得到溶液CA浓度,结合取样体积和溶液浓度进行CA释放量计算。

为更好地探索PSI/CA静电纺纤维膜的药物释放机制,根据CA释放数据采用一级动力学、Higuchi和Ritger-Peppas模型[13]进行药物释放动力学拟合。一级动力学模型假设药物释放速率与剩余药物量成正比,适用于溶蚀型骨架或多孔介质中的扩散释放;Higuchi模型基于Fick扩散定律,适用于药物从基质中扩散控制释放的体系;Ritger-Peppas模型可区分药物释放的主要机制(扩散或溶蚀),其释放指数n值常用于判断释放动力学类型。

$\text { 一级动力学模型：} \ln (1-Q)=-k_{1} t$

Higuchi模型:

$Q={k}_{2}{t}^{1/2}$
$\text { Ritger-Peppas 模型: } Q=k_{3} t^{n}$

式中:Q为t时刻的药物累计释放率,%;k1为一级动力学模型速率常数,%/h;k2为Higuchi模型速度常数,%/h1/2;k3为Ritger-Peppas模型速率常数,%/hn;t为释放时间,h;n为决定扩散机制类型的扩散指数。

1.3.8 统计学分析

采用单因素方差分析(ANOVA)结合Scheffe 事后检验进行统计学处理,以P<0.05为差异具有统计学意义。

2 结果与讨论

2.1 静电纺纤维膜微观形貌分析

交联改性前后PSI/CA静电纺纤维膜的纤维平均直径及微观形貌如表1和图1所示。可看到,不同CA含量的PSI/CA静电纺纤维膜均呈现光滑表面,直径分布较均匀且随CA添加量增加变化不大,表明CA添加对纤维直径影响较小。相较于研究报道中其它原料如壳聚糖、聚乳酸、聚丙烯腈等常用静电纺原料制备的静电纺纤维[14-16],PSI纤维直径较粗已达微米级,在1.7~2.0 μm之间(见表1)。这是由于PSI合成分子量偏低,纺丝溶液需要较高的浓度使分子链之间形成足够的缠结,避免在高压静电作用下无法形成纺丝射流。静电纺丝过程中,PSI/CA溶液中溶剂含量较低,纺丝射流中溶剂快速挥发,静电纺丝射流凝固为纤维,在静电场中拉伸不充分导致纤维直径较大。交联改性后的PSI/CA静电纺纤维膜仍能保持良好的纤维形态,但纤维发生一定的弯曲粘连,CA含量相同的PSI/CA纤维在交联后直径略有增加,且视野范围内纤维根数增加,表明纤维堆积密度增加。

表1   交联前后PSI/CA静电纺纤维平均直径

Tab.1  Average diameters of PSI/CA electrospun fibers before and after crosslinking

纤维膜名称平均直径/nm
交联前交联后
PSI/CA01 750.0±244.91 911.4±161.0
PSI/CA31 750.0±115.41 873.6±145.7
PSI/CA51 638.0±164.71 909.2±145.5
PSI/CA101 863.4±155.22 098.5±165.9

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图1

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图1   交联前后PSI/CA静电纺纤维膜形貌照片

Fig.1   Morphologies of PSI/CA electrospun fiber membranes before (a) and after (b) crosslinking


2.2 静电纺纤维膜化学结构分析

PSI/CA静电纺纤维膜交联前后的红外光谱如图2所示。由图可见,未添加CA时,PSI/CA0静电纺纤维膜在1 796、1 703 cm-1附近出现一弱一强的不对称峰,为酰亚胺基团中C＝O的吸收峰,归属于PSI分子中酰亚胺环的特征峰[17]。CA负载后,PSI/CA5静电纺纤维膜红外谱图与PSI/CA0相似,这是由于CA含量较少,且CA醛基中C＝O吸收峰(1 700 cm-1附近)与PSI吸收峰重合,PSI/CA5静电纺纤维膜并未出现新的吸收峰,表明CA与PSI未发生明显化学结合。

图2

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图2   交联前后PSI/CA静电纺纤维膜红外光谱图

Fig.2   FT-IR spectra of PSI/CA electrospun fiber membranes before and after crosslinking


交联改性后的PSI/CA0静电纺纤维膜在1 796、1 703 cm-1处的酰亚胺环特征吸收峰消失,同时在3 258 cm-1处出现较宽的吸收峰,归属于酰胺键中N—H吸收峰,在1 636、1 530 cm-1处出现酰胺Ⅰ带(C＝O伸缩振动)和酰胺Ⅱ带(N—H弯曲振动)的吸收峰[18],在1 488 cm-1处出现较弱亚甲基(—CH2—)吸收峰,表明PSI的酰亚胺环在乙二胺作用下打开,生成酰胺键,二者发生交联反应。PSI/CA静电纺纤维膜在乙二胺作用下的交联改性反应过程如图3所示。进行CA负载后,PSI/CA5交联改性静电纺纤维膜在1 488 cm-1处的吸收峰增强,该处为CA的苯环C＝C骨架的吸收峰范围,这是由于乙二胺一端胺基与PSI发生开环反应,另一端胺基与CA发生醛胺反应,肉桂醛接枝至PSI纤维表面所导致的。

图3

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图3   PSI/CA静电纺纤维膜交联改性反应示意图

Fig.3   Schematic diagram of crosslinking modification reaction of PSI/CA electrospun fiber membrane


2.3 静电纺纤维膜溶胀性能分析

交联前后PSI/CA静电纺纤维膜的吸水倍率如表2所示。表中数据显示:交联前,不同CA含量的纤维膜均具有较好的吸水性,吸水倍率在19.0~21.6 g/g之间,相差较小;交联后,所有样品的吸水倍率均出现明显下降,吸水倍率在12.8~14.6 g/g之间。表明CA添加对纤维膜的吸水倍率影响较小,交联改性对纤维膜的吸水倍率影响较大,使纤维膜的吸水倍率明显下降。这是由于交联前PSI分子端基中存在氨基和羧基,具有较好的吸水性。此外,结合电镜照片可知,交联前PSI/CA静电纺纤维膜的结构蓬松,水分子容易进入纤维膜内部,吸水倍率较大。交联后由于纤维之间的粘连,静电纺纤维膜堆积密度增加,纤维与纤维之间的空隙变小,水分难以大量进入纤维膜内部,导致吸水能力大幅降低,从而吸水倍率下降。

表2   交联前后PSI/CA 静电纺纤维膜的吸水倍率

Tab.2  Water absorption capacity of PSI/CA electrospun fiber membranes before and after crosslinking

纤维膜名称吸水倍率/(g·g-1)
交联前交联后
PSI/CA020.0±1.612.8±1.2
PSI/CA321.6±1.414.6±1.3
PSI/CA520.4±1.714.5±1.0
PSI/CA1019.0±1.912.8±1.1

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2.4 静电纺纤维膜力学性能分析

交联前后PSI/CA静电纺纤维膜的力学性能测试与计算结果如表3所示。由表可见,交联前未添加CA的PSI/CA0静电纺纤维膜表现出较低的断裂强度,为(0.23±0.06) MPa。随着CA添加量的增加,断裂强度呈现先升后降的变化趋势:CA添加量为3%时,断裂强度达到最大值(1.03±0.12) MPa,较PSI/CA0静电纺纤维膜提升约4.5倍;当CA添加量增至5%时,断裂强度降至(0.77±0.06 ) MPa;CA添加量为10% 时,断裂强度降至(0.23±0.18 ) MPa。这是由于加入少量CA后,PSI的端胺基和CA的醛基发生席夫碱反应,增强了分子间的相互作用与网络结构稳定性[19];当CA含量过多时,由于CA为小分子精油溶于纺丝溶剂中,破坏了PSI分子链间的氢键等原有相互作用,导致分子链缠结减少,纤维膜强度下降。不同CA添加量的PSI/CA静电纺纤维膜的断裂伸长率均在12.6%~16.0%之间,表明CA的引入对纤维膜的断裂伸长率影响较小。

表3   交联前后PSI/CA静电纺纤维膜的力学性能

Tab.3  Mechanical properties of PSI/CA electrospun fiber membranes before and after crosslinking

纤维膜
名称		断裂强度/MPa断裂伸长率/%
交联前交联后交联前交联后
PSI/CA00.23±0.061.11±0.1014.0±3.972.9±3.6
PSI/CA31.03±0.121.41±0.1916.0±1.886.8±6.8
PSI/CA50.77±0.061.14±0.0712.6±1.869.2±12.4
PSI/CA100.23±0.180.98±0.1314.3±5.237.8±8.3

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交联改性后,PSI/CA静电纺纤维膜的断裂强度和断裂伸长率均显著提升。未添加CA的PSI/CA0静电纺纤维膜断裂强度为(1.11±0.10 )MPa,相较交联前提升约4.8倍。随着CA添加量的增加,改性后PSI/CA静电纺纤维膜强度变化趋势与交联前相似:CA添加量为3%时断裂强度达到最大,为(1.41±0.19)MPa;CA添加量为10%时断裂强度最低,为(0.98±0.13)MPa,但仍为交联前的4倍以上。断裂伸长率则远高于交联前水平,CA添加量为10%时最小,为(37.8±8.3)%。结合红外图谱可知,交联过程中PSI的酰亚胺环特征峰消失且出现酰胺键特征峰,表明乙二胺两端胺基与PSI的酰亚胺环发生开环反应形成交联网络,同时改性后添加CA的PSI/CA静电纺纤维膜出现CA特征峰,表明开环后的PSI与CA发生醛胺反应[19],增强了分子间连接性,同时提升了静电纺纤维膜的强度与韧性。

2.5 静电纺纤维膜抗菌性能分析

交联后PSI/CA静电纺纤维膜的抗菌性能如图4所示。可见,纯PSI静电纺纤维膜(PSI/CA0)在交联改性后具备良好的抗菌性能,对大肠埃希菌和金黄色葡萄球菌的抑菌率分别为98.5%和87.3%;当CA添加量为3%、5%和10%时,纤维膜对大肠埃希菌和金黄色葡萄球菌的抑菌率均可达到100%。

图4

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图4   交联后PSI/CA静电纺纤维膜的抗菌性

Fig.4   Antibacterial activities of crosslinked PSI/CA electrospun fiber membranes


在乙二胺对PSI静电纺纤维膜交联过程中,乙二胺两端的胺基将PSI的酰亚胺环打开形成酰胺键,部分乙二胺仅一端胺基与PSI发生开环反应形成酰胺键,另一端不与PSI发生反应形成端基为伯胺基的接枝基团,使静电纺纤维膜带正电荷,可与带负电荷的细菌细胞膜结合,破坏细胞膜结构,从而具备一定的抗菌性能。PSI/CA0静电纺纤维膜表现出对大肠埃希菌更优的抑菌率。这是由于金黄色葡萄球菌(革兰阳性菌)较厚的肽聚糖层增强了对改性PSI的抵御能力,从而表现出对大肠埃希菌(革兰阴性菌)更强的抑菌活性。CA为天然抗菌剂,不易产生细菌耐药性[20],其可通过破坏细菌细胞膜的完整性并渗透至细胞内干扰蛋白质与核酸的合成,进而抑制细菌的生长繁殖[12],因而加入CA后,CA对革兰阴性菌(大肠埃希菌)和革兰阳性菌(金黄色葡萄球菌)均有显著抑制作用,使静电纺纤维膜的抗菌能力增强。

2.6 静电纺纤维膜细胞相容性评价

利用浸提法对交联改性后的PSI/CA静电纺纤维膜进行细胞毒性实验,细胞存活率如图5所示。测试结果显示,改性后PSI/CA0静电纺纤维膜浸提液中细胞存活率为(95.3± 0.9)%,表明改性后PSI静电纺纤维膜具有良好的细胞相容性。这主要归因于材料自身和制备过程:一方面,PSI由L-天门冬氨酸聚合而成,材料本身具备优异的生物性能;另一方面,PSI静电纺纤维膜在制备及乙二胺改性的过程中残留物质较少,未引起细胞毒性,保障其生物安全性。当CA添加量处于3%~10%范围时,PSI/CA静电纺纤维膜的细胞存活率维持在98.4%~102.2%的较高区间,其中CA含量为5%的PSI/CA5纤维膜细胞相容性最好,表明CA本身同样具有优异的细胞相容性,在该添加量范围内的CA不产生细胞毒性。

图5

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图5   交联PSI/CA静电纺纤维膜的细胞存活率

注:**表示P≤0.01,有显著差异;n.s.表示P>0.05,无显著差异。

Fig.5   Cell viabilities of crosslinked PSI/CA electrospun fiber membranes


2.7 静电纺纤维膜药物缓释分析

改性后PSI/CA静电纺纤维膜的药物累积释放率和释放量如图6所示。不同CA添加量的PSI/CA静电纺纤维膜的药物释放趋势相同,在前24 h内,CA快速从纤维膜中释放,随着时间进一步延长,CA释放速度下降且趋于平缓。由图6(a)可见,药物累积释放量与CA添加量呈显著正相关:当缓释时间达24 h释放稳定后,PSI/CA10的CA累积释放量远高于PSI/CA5和PSI/CA3。表明CA的添加量越高,纤维内部的药物分子总量越多,累积释放量越大。而药物累积释放率与CA添加量呈显著负相关:随CA添加量增加,累积释放率逐渐下降。缓释时间为48 h时,PSI/CA3的累积释放率最高为41.6%,PSI/CA5和PSI/CA10的累积释放率仅为28.2%和26.7%。表明CA添加量较高时,虽然药物从纤维内部向外释放量增加,但扩散阻力增加导致药物释放量与总载药量比例降低。

图6

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图6   不同CA添加量的PSI/CA静电纺纤维膜的药物累积释放量及释放率

Fig.6   Cumulative drug release amount (a) and release rate (b) of PSI/CA electrospun fiber membranes with different CA contents


根据PSI/CA静电纺纤维膜的CA释放数据,进行药物释放动力学模拟。不同CA添加量的PSI/CA静电纺纤维膜在PBS中药物释放动力学曲线如图7所示,模型参数如表4所示。

图7

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图7   不同CA添加量的PSI/CA静电纺纤维膜在PBS中释放动力学拟合曲线

Fig.7   Kinetic fitting curves of drug release from PSI/CA electrospun fiber membranes with different CA contents in PBS. (a)First-order kinetic model; (b)Higuchi model;(c)Ritger-Peppas model


表4   3种动力学模型在PBS中的模型参数

Tab.4  Model parameters of three kinetic models in PBS

模型类型CA添加量/%速率常数释放指数nR2
30.104—0.985
一级动力学模型50.057—0.962
100.057—0.958
36.819—0.914
Higuchi模型54.767—0.936
104.473—0.936
38.7920.4310.926
Ritger-Peppas模型53.5020.5690.935
103.3220.5670.936

注:一级动力学模型速率常数单位为%/h;Higuchi模型速率常数单位为%/h1/2;Ritger-Peppas模型速率常数单位为%/hn。

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由图7和表4可知,3种动力学模型均能较好描述本体系的CA释放行为。其中,一级动力学模型拟合度最高,不同CA添加量的PSI/CA静电纺纤维膜拟合优度(R2)值均高于0.95,表明该体系药物释放过程更符合一级动力学特征,释药机制以Fickian扩散为主,释放速率与体系内剩余药物量正相关。根据PSI/CA静电纺纤维膜结构可知,本体系为多孔骨架型载体,CA通过孔隙扩散释放[21]。结合Ritger-Peppas模型的释放指数n值可进行释放机制判断,通常当n≤0.45时为 Fickian 扩散,当0.45<n<0.89时为非Fickian扩散。不同CA添加量下3组的n值介于0.431 ~ 0.569之间,表明CA释放过程中伴随少量的载体溶蚀。这可能是由于PSI在PBS中发生微弱水解生成水溶性聚天冬氨酸而导致的[9]。

3 结论

本文以L-天门冬氨酸聚合物聚琥珀酰亚胺 (PSI)为静电纺丝原料,引入肉桂醛(CA)为功能性添加剂,通过共混静电纺丝技术制备PSI/CA静电纺纤维膜。CA的添加可显著提高PSI/CA静电纺纤维膜的抗菌性能,交联处理则有效改善其力学性能,满足医用敷料的使用要求。本研究得到的主要结论如下。

1)PSI/CA溶液具有良好的静电纺丝性能,可稳定制备出形貌均一的连续纤维,且经交联改性后仍能保持良好的纤维结构,交联处理可以有效提升纤维膜的力学性能,当CA添加量为3%时,PSI/CA静电纺纤维膜强度最高。

2)交联改性后的PSI/CA静电纺纤维膜呈现出良好的抗菌性能和细胞相容性。加入CA后PSI/CA静电纺纤维膜对大肠埃希菌和金黄色葡萄球菌的抑菌率可达100%;纤维膜对人真皮成纤维细胞的毒性极低,细胞存活率高于98%。

3)该纤维膜可实现CA的缓慢释放,释放行为符合一级动力学模型,释放机制主要为Fickian扩散,可避免药物突释导致的局部浓度过高或作用时间过短等问题,在创面修复等生物医用领域具有广阔的应用前景。

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YANG Dong, JIA Tongtong, LEI Lei, et al.

The development of electrospinning technology in medical dressings

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[J]. Macromolecular Bioscience, 2023, 23(3): e2200397.

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[J]. 纺织学报, 2022, 43(11): 1-8.

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为构筑可自降解、抗菌消炎且轻薄柔软有助于伤口愈合的医用敷料,以聚乳酸为原料,通过掺杂不同质量分数的阿莫西林,采用静电纺丝技术制备聚乳酸纳米纤维基载药敷料。借助扫描电子显微镜、红外光谱仪、X射线衍射仪、接触角测试仪、紫外分光光度计等手段分析纳米纤维膜的微观结构、润湿性能、药物缓释、抗菌性能以及自降解性能。结果表明:聚乳酸纳米纤维敷料具有多孔结构,敷料纤维直径随载药量增加而降低,敷料载药量3%时,纤维平均直径达684 nm;载药聚乳酸纳米纤维基敷料中阿莫西林与聚乳酸没有发生化学反应,避免了阿莫西林的负面改性;聚乳酸纳米纤维基载药敷料润湿性与抗菌性能随载药量增加而增加,载药3%敷料的接触角降到110°,提高了润湿性,对金黄色葡萄球菌的抑菌率可达91%。聚乳酸纳米纤维载药敷料具有较好的自降解性能和平缓的药物缓释能力,适合用作伤口敷料。

LI Liang, PEI Feifei, LIU Shuping, et al.

Preparation and characterization of polylactic acid nanofiber drug loaded medical dressings

[J]. Journal of Textile Research, 2022, 43(11): 1-8.

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In order to construct a self-degradable, antibacterial, anti-inflammatory, light, thin and soft medical dressings conducive to wound healing, nanofiber drug loaded dressings based on polylactic acid (PLA) was prepared by electrospinning technology with different mass fractions of amoxicillin. The microstructure, wettability, drug release, antibacterial and self-degradation properties of nanofiber films were analyzed by means of scanning electron microscope, infrared spectrometer, X-ray diffraction, contact angle tester and UV spectrophotometer. The results indicate that the PLA nanofiber dressings possess porous structure and the diameter of dressing fiber decreases with the increase of drug loading. When the drug loading is 3%, the average diameter of dressing fiber is 684 nm. There is no chemical reaction between amoxicillin and polylactic acid, suggesting that negative modification did not occur for the amoxicillin. Moreover, the wettability and antibacterial properties of drug loaded PLA nanofiber dressings are enhanced with the increase of drug loading. The antibacterial rate of nanofiber dressings with 3% drug loading is up to 91% for staphylococcus aureus. In addition, polylactic acid nanofiber dressings represent excellent in-vitro degradation performance, drug release ability and stable release rate, which are necessary for wound dressings.

PÁZMÁNY R, NAGY K S, ZSEMBERY Á, et al.

Ultrasound induced, easy-to-store porous poly(amino acid) based electrospun scaffolds

[J]. Journal of Molecular Liquids, 2022, 359: 119243.

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李思捷, 张彩丹.

聚天冬氨酸基纤维水凝胶的制备及其释药性能

[J]. 纺织学报, 2020, 41(2): 20-25, 32.

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[J]. Journal of Textile Research, 2020, 41(2): 20-25, 32.

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邱月, 杨询, 李昊, 等.

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[J]. 纺织学报, 2025, 46(6): 88-95.

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[J]. Journal of Textile Research, 2025, 46(6): 88-95.

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邱月, 郑乐怡, 张宝华, 等.

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[J]. 棉纺织技术, 2025, 53(5): 74-79.

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[J]. Cotton Textile Technology, 2025, 53(5): 74-79.

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[J]. New Biotechnology, 2025, 87: 1-11.

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Antibacterial biodegradable PLA-based nanofibers loaded with phenolic monoterpenes - thymol, eugenol, carvacrol, and cinnamaldehyde, were prepared by electrospinning. The effect of bioactive molecule on the surface, thermal, morphological, and biological properties has been investigated about the potential pharmaceutical and food processing applications. Fiber diameters ranged from 320 nm for PLA fibrous mat up to 480 nm for PLA membrane with 6 % thymol. All the prepared active nanofibers exhibited hydrophobic surfaces with a slightly decreasing contact angle after the incorporation of phenols. Antimicrobial testing proved a strong efficiency against Escherichia coli and Staphylococcus aureus, depending on the specific type and content of the bioactive compound. A significant biofilm formation reduction of bioactive PLA nanofibers was revealed against tested microorganisms. Modification of PLA fibers with active molecules did not significantly affect the biodegradation kinetics in comparison to PLA samples with their absence. This study demonstrates the high potential of newly developed PLA-based/phenol nanofibrous membranes for use as antibacterial and antifouling systems applicable in wound dressings and food packaging.Copyright © 2025 The Authors. Published by Elsevier B.V. All rights reserved.

付泳盛, 李美婵, 吴旺, 等.

新型醛基功能化果胶-酪蛋白可注射药物缓释系统的制备及性能研究

[J]. 化学研究, 2025, 36(6): 597-605.

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[J]. Chemical Research, 2025, 36(6): 597-605.

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In this work two types of biodegradable polysuccinimide-based, electrospun fibrous membranes are presented. One contains disulfide bonds exhibiting a shorter (3 days) in vivo biodegradation time, while the other one has alkyl crosslinks and a longer biodegradation time (more than 7 days). According to the mechanical measurements, the tensile strength of the membranes is comparable to those of soft the connective tissues and visceral tissues. Furthermore, the suture retention test suggests, that the membranes would withstand surgical handling and in vivo fixation. The in vivo biocompatibility study demonstrates how membranes undergo in vivo hydrolysis and by the 3rd day they become poly(aspartic acid) fibrous membranes, which can be then enzymatically degraded. After one week, the disulfide crosslinked membranes almost completely degrade, while the alkyl-chain crosslinked ones mildly lose their integrity as the surrounding tissue invades them. Histopathology revealed mild acute inflammation, which diminished to a minimal level after seven days.

侯恩凤, 田秀枝, 蒋学.

壳聚糖/聚己内酰胺复合纳米纤维膜的制备及染料吸附性能

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HOU Enfeng, TIAN Xiuzhi, JIANG Xue.

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王凯, 念琪循, 王春民, 等.

功能化聚丙烯腈纳米纤维膜高通量检测水源水中多种类抗生素

[J]. 四川大学学报(医学版), 2025, 56(5): 1197-1207.

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[J]. Journal of Sichuan University (Medical Sciences), 2025, 56(5): 1197-1207.

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