CN114164562A - PCL/ZnO-CSLE/PLA双层纳米纤维膜、其制备方法及应用 - Google Patents
PCL/ZnO-CSLE/PLA双层纳米纤维膜、其制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种PCL/ZnO‑CSLE/PLA双层纳米纤维膜、其制备方法及应用,本申请以PCL/ZnO作为外层膜,CSLE/PLA作为内层膜制备了双层载药纳米纤维膜。经验证,纳米氧化锌与CSLE提取物成分已成功融入PCL和PLA基质中。纳米纤维膜外层膜为疏水性材料,而内层膜材料为亲水性材料;该双层膜断裂强度大,断裂伸长率小。因此,PCL/ZnO‑CSLE/PLA复合纳米纤维双层膜,具有良好的力学性能和抗菌性,在静电纺丝技术、生物医用敷料、医用材料方面均具有良好的应用前景。
Description
技术领域
本发明涉及一种纳米纤维膜材料,特别涉及一种PCL/ZnO-CSLE/PLA双层纳米纤维膜、其制备方法及应用。
背景技术聚乳酸(PLA)是一种新型的生物可降解材料,具有良好的机械性能。此外,PLA具有良好的生物相容性,透湿性、透气性、无毒性,因为聚乳酸可以分解成单体乳酸,而人体也含有以单体形态存在的乳酸,表明该材料对人体无害,在医用领域具有潜在的应用价值。
刺山柑(Capparis spinosa L.),是白花菜科Capparidaceae山柑属Capparis植物,我国民间称其为“野西瓜”,本申请中CSLE是刺山柑乙酸乙酯提取物的缩写(Ethylacetate extract of Capparis spinosa L.);现代药理学研究表明刺山柑的果实提取物在抑菌、抗炎、抗氧化等方面均有一定的功效。
刺山柑乙酸乙酯提取物纳米纤维膜(CSLE/PLA)其制备方法在专利“CN112251912A一种刺山柑载药纳米纤维膜及其制备方法和应用”中已有报道;其是由聚乳酸溶液和刺山柑乙酸乙酯提取物混合所得纺丝液进行静电纺丝所得。所述刺山柑乙酸乙酯提取物按下述方法制得:60℃下水浴锅下利用无水乙醇对刺山柑果实粉末进行回流提纯;过滤后收集上清液,将所得上清液用水稀释后使用等体积石油醚进行若干次萃取,萃取过程中加入氯化钠,溶液分三层,取最下层溶液继续加入等体积的乙酸乙酯进行萃取,待溶液分层后取下层溶液,浓缩,即得刺山柑乙酸乙酯提取物。所述的刺山柑乙酸乙酯提取物纳米纤维膜(CSLE/PLA)具有良好的抗菌性能、抗氧化性能,在制备伤口敷料领域中有很好的应用前景。作为伤口敷料不仅要在伤口部位抗菌、抗氧化性能,而且也要具备阻止外界细菌、水分进入伤口的能力和良好的力学性能。
聚己内酯(PCL)是一种人工合成的高分子有机化合物,具有良好的生物相容性、可降解性、韧性和强度,已被广泛用于药物释放系统、组织工程等。纳米氧化锌(ZnO)是一种有效的抗菌材料,作为填充剂可以提高材料的机械性性能。虽然PCL颗粒和ZnO粉末各自具有的优良性能均已有报道,但如何将二者有机结合,且能应用于作为静电纺织的复合材料,同时,既要满足其有良好的效果,又要制备方法简单,则未见报道。
发明内容
针对现有技术中的不足之处,本发明提供了一种PCL/ZnO-CSLE/PLA双层纳米纤维膜,本申请以PCL/ZnO作为外层膜,CSLE/PLA作为内层膜制备了双层载药纳米纤维膜。从本发明研究可以发现,PCL/ZnO-CSLE/PLA复合纳米纤维双层膜,具有良好的力学性能和抗菌性,在生物医用敷料方向具有潜在的应用价值。
本发明第一方面提供了一种PCL/ZnO-CSLE/PLA双层纳米纤维膜的制备方法,其包括如下步骤:
(7)将PCL颗粒和ZnO粉末充分干燥后备用;
(8)N,N-二甲基甲酰胺/四氢呋喃按照质量比DMF:THF=2~5:6~8制得混合溶液;
(9)向ZnO粉末中加入步骤(2)制备所得的溶剂后分散,其中ZnO的浓度为1~4wt%;
(10)称取PCL溶于步骤(3)制备所得的溶剂后分散,在50~70℃恒温下充分搅拌获得PCL/ZnO纺丝液;其中PCL浓度为12~16wt%;
(11)CSLE/PLA纳米纤维纺丝液的制备方法如专利CN112251912A所述;
(12)分别将步骤(4)和(5)的纺丝液依次添加到不同的静电纺丝机的注射器中,利用PCL/ZnO纺丝液先制备外层膜,随后利用CSLE/PLA纳米纤维纺丝液在外层膜基础上纺丝,从而获得双层纳米纤维膜。
对于上文所述的技术方案,进一步地,所述ZnO粉末为20~50nm。
对于上文所述的技术方案,进一步地,所述PCL颗粒为80000~120000g/mol。
对于上文所述的技术方案,进一步地,步骤(4)中所述的PCL/ZnO纺丝液中:PCL浓度为15wt%,ZnO浓度为2wt%。
对于上文所述的技术方案,进一步地,步骤(5)所述CSLE/PLA纳米纤维纺丝液制备方法步骤包括:①将PLA溶于溶液A中,在35-42℃下充分搅拌,制得含PLA质量分数为5-7wt%的纺丝溶液;其中,所述溶液A为三氯甲烷和丙酮按照质量比1.5-2.5:1混合;②将CSLE溶于步骤①制备所得的纺丝溶液中,制备含CSLE质量分数为9-11wt%的CSLE/PLA纳米纤维纺丝液。
对于上文所述的技术方案,进一步地,所述步骤(6)中,分别将装满步骤(4)和(5)的纺丝液的两个20mL注射器,依次固定在注射泵上,两个注射器的针头分别与接收铝箔的距离设置为13-15cm,分别控制溶液进料速度为0.5-0.8mL/h,施加电压为14-16kV。
对于上文所述的技术方案,进一步地,所述恒温水浴加热的同时伴有分散方法。
对于上文所述的技术方案,进一步地,所述分散方法采用超声分散(至少1小时)或采用磁力搅拌器上搅拌至少24h。
本发明第二方面提供了一种利用上文所述方法制备获得的PCL/ZnO-CSLE/PLA双层纳米纤维膜。
本发明第三方面提供了PCL/ZnO-CSLE/PLA双层纳米纤维膜在静电纺丝技术、生物医用敷料、医用材料等方面的应用。
与现有技术相比,本发明具有如下有益效果:
在本发明中,通过使用静电纺丝技术成功制备了PCL/ZnO-CSLE/PLA复合纳米纤维双层膜,并对双层膜进行了形貌表征、润湿性测试、红外测试、力学性能测试以及抗菌性能测试。
(1)纳米纤维膜的SEM图像表明,纳米氧化锌与CSLE提取物成分已成功融入PCL和PLA基质中。
(2)接触角测试结果表明,纳米纤维膜外层膜为疏水性材料,而内层膜材料为亲水性材料。
(3)红外测试结果表明,双层纳米纤维膜外层膜PCL基材上已成功负载纳米氧化锌材料,内层膜PLA基材上已成功负载CSLE提取物。
(4)力学性能测试结果表明,双层纳米纤维膜中随着负载物的引入,纤维膜的断裂强度随之增大,断裂伸长率随之减小。
(5)抗菌结果表明,载药双层纳米纤维膜的外层膜和内层膜对大肠杆菌和金黄色葡萄球菌均具有良好的抑菌性。
附图说明
图1是根据本发明的PCL/ZnO-CSLE/PLA双层纳米纤维膜的制备流程图。
图2不同载药体系纳米纤维膜的扫描电镜图与直径分布图;其中PLA膜(a)、CSLE/PLA膜(b)、PCL膜(c)、PCL/ZnO膜(d)、双层纳米纤维膜外层膜(e)、内层膜(f)的SEM图;
图3纯PLA(a)、纯PCL(b)、PCL/ZnO-CSLE/PLA的外层膜(c)与内层膜(d)纳米纤维膜的水接触角。
图4不同载药体系纳米纤维膜的红外光谱图。
图5不同载药体系纳米纤维膜对大肠杆菌和金黄色葡萄球菌的抑菌性,其中按照图顺序分别在图注下面标注。
具体实施方式
下面结合附图,对本发明的具体实施方式进行详细地描述,但应当理解本发明的保护范围并不受具体实施方式的限制。
本发明中,除非另有其他明确说明,否则百分比、百分含量均以质量计。如无特殊说明,所使用的实验方法均为常规方法,所用材料、试剂等均可从商业途径购买。其中:ZnO粉末为20~50nm(博华斯纳米科技有限公司)。所述PCL颗粒为80000~120000g/mol(Sigma-Aldrich公司)。
实施例1
PCL/ZnO-CSLE/PLA双层纳米纤维膜的制备,具体流程如下:
(1)将PCL颗粒和ZnO粉末在真空干燥箱中干燥12h,后备用;
(2)称取一定量的ZnO置于锥形瓶中,加入N,N-二甲基甲酰胺/四氢呋喃(DMF:THF=3:7)混合溶液,超声分散1h;
(3)称取一定量的PCL溶于上述步骤(2)制备的溶剂中,在60℃恒温水浴磁力搅拌器上搅拌24h;获得PCL/ZnO纺丝液;其中PCL浓度为15wt%;
(4)CSLE/PLA纳米纤维纺丝液的制备方法如专利CN112251912A所述,即将PLA溶解于三氯甲烷/丙酮中(其中THM/CP=质量比2:1),在40℃下连续搅拌24h,制得质量分数为6wt%的PLA溶液。再将CSLE溶解于PLA溶液中,制备CSLE质量分数10wt%纺丝溶液,即CSLE/PLA纳米纤维纺丝液备用。
(5)纺丝工艺参数设置与制备流程:
将步骤(3)制备的PCL/ZnO纺丝液和步骤(4)制备的CSLE/PLA纳米纤维纺丝液分别加入到两个20mL注射器,依次固定在注射泵上,两个注射器的针头(21G)分别与接收铝箔的距离设置为13-15cm,分别控制溶液进料速度为0.5-0.8mL/h,施加电压为14-16kV。
(6)利用PCL/ZnO纺丝液先制备外层膜,随后利用CSLE/PLA纳米纤维纺丝液在外层膜基础上纺丝,从而获得双层纳米纤维膜。制备流程如图1所示。
实施例2
在实施例1的基础上,与其差别在于:
步骤(2)中N,N-二甲基甲酰胺/四氢呋喃按照质量比改为DMF:THF=1:4制得混合溶液;且ZnO的浓度改为4wt%;
步骤(3)其中PCL浓度改为12wt%;
步骤(4)所述CSLE/PLA纳米纤维纺丝液中含PLA质量分数改为7wt%;含CSLE质量分数改为11wt%。
实施例3
1对实施例1所制备的PCL/ZnO-CSLE/PLA双层纳米纤维膜的扫描电镜分析(SEM)
使用扫描电子显微镜(SEM,SU8010,日本观察电纺纳米纤维膜的表面形貌并进行表征。所有样品都固定在铝板上,在20mA真空下用金溅射。在工作距离为8mm,加速电压为5kV的条件下,对实施例1所制备的PCL/ZnO-CSLE/PLA纳米纤维膜进行了观察。随机选取100组纳米纤维直径,然后利用ImageJ软件对纳米纤维的直径进行分析。
纳米纤维膜的形貌及直径分布分析
载药静电纺丝纳米纤维膜SEM图如图2所示,通过优化纺丝工艺,可以得到光滑、无串珠、结构均匀的纤维结构,且载药纳米纤维(b,d,e,f)未发生固相分离,负载药物未发现析出,所以药物与纳米纤维膜具有良好的相容性。观察图2(a)、(b)可发现CSLE的加入,纤维的平均直径由331.72±5.75nm减小至213.45±1.34nm。根据图2(c)、(d)可发现ZnO的加入,纤维的平均直径由474.72±13.25nm减小至314.15±7.52nm,负载物ZnO的引入不仅增加PCL/ZnO纺丝液的电荷密度,增加溶液的导电性,使纳米纤维的牵引力增加,导致纤维膜的直径更细,其次有研究表明ZnO在水介质中可以不断释放Zn2+,而Zn2+能够通过细菌的细胞膜进入细胞内,破坏细胞膜表面的蛋白质和细菌的结构与生理活性,从而有效地阻止并抑制环境中的细菌侵染伤口表面。通过图2(e)、(f)发现载药双层膜的纤维直径存在不同程度的减小,且纤维表面明显有颗粒状突起,该现象表明纺丝溶剂挥发后负载物(ZnO、CSLE)已经成功负载或镶嵌在纳米纤维上。
2润湿性表征
使用接触角分析仪(DCAT 21,Dataphysics Instrument Gmbh,德国)分别测试PCL/ZnO-CSLE/PLA复合纳米纤维膜的接触角。将电纺纳米纤维膜切割成2cm×3cm的条状,然后在纳米纤维膜表面滴入2μL的蒸馏水。在0s、5s和10s后,测量纤维膜表面接触角大小。
双层纳米纤维膜的润湿性能分析
伤口敷料的亲疏水性直接影响细胞与材料的亲和性,合适的亲疏水性有利于伤口表细胞的增殖与粘附,促进伤口愈合。图3(a)、(b)、(c)、(d)分别是纯PLA、纯PCL、PCL/ZnO-CSLE/PLA的外层膜与内层膜在0s、5s和10s内的接触角变化趋势图。测试结果表明,纯PLA膜在10s时的接触角为123.2±0.4°,而纯PCL纤维膜在10s时的接触角为132.4±0.3°,纤维膜都表现为疏水性。该现象可能是因为PLA和PCL材料自身含有大量的疏水性基团酯基,导致材料亲水性能较差。图3(c)为双层膜的外层膜,该材料在10s时的接触角为130±0.6°,这可能是由于ZnO的引入,增加了纳米纤维膜的粗造度。对于粗造的纤维表面,液体与纤维膜之间的接触面积增加,产生一定的界面能,从而产生较大的接触角。PCL/ZnO纳米纤维膜的疏水性可以有效地抑制环境中的水分子和细菌进入材料内,可以有效降低伤口二次感染的几率。观察图3(d)为双层膜的内层膜可知随着CSL的引入,纤维膜的接触触角不断减小,在10s时,接触角减小至72.4±0.5°。这可能是因为CSL提取物中的类黄酮和酚类成分中还有大量的亲水基团,与水分子接触时,材料表面的表面能增加,接触角减小,内层膜变为亲水性材料,更有利于材料表面的细胞黏附和增殖。
3双层纳米纤维膜红外光谱分析
采用KBr压片法,通过FTIR(Bruker-vertex70,德国)测定PCL/ZnO-CSLE/PLA纳米纤维的官能团和分子间相互作用。在4000-400cm-1波长范围内,以4cm-1分辨率扫描100次,收集单个光谱。
双层纳米纤维膜的红外光谱(FTIR)分析
每种化合物都有独特的结构和特殊的化学键与官能团,我们可以根据红外光谱的吸收峰确定测试材料所含成分。为了探究载药前后双层纳米纤维膜的基团差异,在400-4000cm-1波长范围内进行FTIR分析。如图4所示,PCL/ZnO-CSLE/PLA双层膜红外光谱的特征峰出现在2946cm-1和2873cm-1处是-CH2的伸缩振动峰;在1728cm-1为脂键结构的特征峰;对于3444cm-1和3350cm-1处存在的宽峰,为PCL材料纤维膜表面-OH的伸缩振动;在1368cm-1特征峰处为-CH3的伸缩振动峰;在1755处cm-1为C=O伸缩振动峰;1172cm-1、1085cm-1的峰值是-C-O-拉伸振动
4纤维膜机械性能测试
将纳米纤维膜在恒温恒湿箱(20℃,相对湿度65%)中放置24h,使用单纤维拉力机YG(B)026P(中国温州大荣纺织仪器有限公司)对纳米纤维膜进行拉伸性能测试。将样品切成30×10mm的长方形条带。拉伸速度为10mm/min,每个纳米纤维膜测试5个样品。断裂强度按公式(1)计算:
其中P和S分别表示纤维膜断裂时承受最大拉力和纤维膜的横截面积,而σb表示纤维膜的断裂强度。
双层纳米纤维膜的机械性能分析
表1纳米纤维的机械性能分析
作为伤口医用敷料需要有一定的抗拉能力,不仅可以抵抗一定的外界压力,还能为细胞在伤口表面增值提供相对稳定的空间。表1分别列出了PCL、PCL/ZnO、PLA、CSLE/PLA、PCL/PLA、PCL/ZnO-CSLE/PLA纳米纤维膜的断裂强度和断裂伸长率,其中:PCL纺丝方法与实施例1中的PCL/ZnO一样的方法制备;PLA纺丝方法与实施例1中的CSLE/PLA一样的方法制备;观察发现纳米纤维膜中随着ZnO、CSLE的加入,纤维膜的断裂强度随之增加,载药双层膜的断裂强度由2.76±0.13MPa增加至10.69±0.31MPa,这可能是由于相同浓度下的纺丝,随着ZnO、CSLE的引入,纺丝液的相对浓度减小,导致聚合物分子间的作用力增大,断裂前对增加。通过表格数据发现,双层膜的断裂伸长率由118.26±4.32%减小至81.78±2.65%。
5双层纳米纤维膜抗菌测试
采用琼脂扩散法对静电纺纳米纤维膜的抗菌活性进行了评价。将大肠杆菌和金黄色葡萄球菌接种在液体培养基中,并在37℃下以150rpm在摇床上培养15h。然后,将细菌悬浮液(10-8CFU S/mL)涂布在琼脂平板上。使用打孔机裁剪直径为6mm的圆形纳米纤维膜备用,使用紫外光消毒纳米纤维膜30min后轻轻粘贴在固体培养基上。将固体培养基放置于37℃培养箱,培育18h后,观察并测定各平板上抑菌圈的直径大小。
双层纳米纤维膜的抗菌性能分析
图5是不同种类的纳米纤维膜分别对大肠杆菌(E.coil)和金黄色葡萄球菌(S.aureus)的抗菌结果。如图5所示,当复合膜中不含ZnO时,复合纳米纤维膜无论对大肠杆菌还是金黄色葡萄球菌均没有抗菌能力;随着复合纤维中加入2%的ZnO时,固体培养基表面出现明显抑菌圈,说明ZnO具有良好的抗菌能力。
通过图5,可以发现,PCL/ZnO-CSLE/PLA复合纳米纤维双层膜对大肠杆菌和金黄色葡萄球菌同样具有抑菌性。分析可知,CSLE/PLA作为内层膜可以很好的抑制伤口表面细菌的感染。而PCL/ZnO纳米纤维膜可以有效的抑制外来细菌与水分子进入伤口表面,减少伤口受到第二次感染。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,本领域的技术人员在本发明披露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书的保护范围为准。
Claims (10)
1.一种PCL/ZnO-CSLE/PLA双层纳米纤维膜的制备方法,其特征在于,其包括如下步骤:
(1)将PCL颗粒和ZnO粉末充分干燥后备用;
(2)将N,N-二甲基甲酰胺和四氢呋喃按照质量比2~5:6~8制得混合溶液;
(3)向ZnO粉末中加入步骤(2)制备所得的溶剂后分散,其中ZnO的浓度为1~4wt%;
(4)称取PCL溶于步骤(3)制备所得的溶剂后分散,在50~70℃恒温下充分搅拌获得PCL/ZnO纺丝液;其中PCL浓度为12~16wt%;
(5)CSLE/PLA纳米纤维纺丝液的制备方法如专利CN112251912A所述;
(6)分别将步骤(4)和(5)的纺丝液依次添加到不同的静电纺丝机的注射器中,利用PCL/ZnO纺丝液先制备外层膜,随后利用CSLE/PLA纳米纤维纺丝液在外层膜基础上纺丝,从而获得双层纳米纤维膜。
2.根据权利要求1所述的方法,其特征在于,所述ZnO粉末为20~50nm。
3.根据权利要求1所述的方法,其特征在于,所述PCL颗粒为80000~120000g/mol。
4.根据权利要求1所述的方法,其特征在于,步骤(4)中所述的PCL/ZnO纺丝液中:PCL浓度为15wt%,ZnO浓度为2wt%。
5.根据权利要求1所述的方法,其特征在于,步骤(5)所述CSLE/PLA纳米纤维纺丝液制备方法步骤包括:①将PLA溶于溶液A中,在35-42℃下充分搅拌,制得含PLA质量分数为5-7wt%的纺丝溶液;其中,所述溶液A为三氯甲烷和丙酮按照质量比1.5-2.5:1混合;②将CSLE溶于步骤①制备所得的纺丝溶液中,制备含CSLE质量分数为9-11wt%的CSLE/PLA纳米纤维纺丝液。
6.根据权利要求1所述的方法,其特征在于,所述步骤(6)中,分别将装满步骤(4)和(5)的纺丝液的两个20mL注射器,依次固定在注射泵上,两个注射器的针头分别与接收铝箔的距离设置为13-15cm,分别控制溶液进料速度为0.5-0.8mL/h,施加电压为14-16kV。
7.根据权利要求1所述的方法,其特征在于,所述恒温水浴加热的同时伴有分散方法。
8.根据权利要求7所述的方法,其特征在于,所述分散方法采用超声分散至少1小时,或采用磁力搅拌器上搅拌至少24h。
9.如权利要求1所述的方法制备获得的PCL/ZnO-CSLE/PLA双层纳米纤维膜。
10.如权利要求9所述的PCL/ZnO-CSLE/PLA双层纳米纤维膜在静电纺丝技术、生物医用敷料、医用材料方面的应用。
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