CN116421767B - 一种具有抗菌和单向导湿功能的复合膜的制备方法 - Google Patents
一种具有抗菌和单向导湿功能的复合膜的制备方法 Download PDFInfo
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- CN116421767B CN116421767B CN202310706150.3A CN202310706150A CN116421767B CN 116421767 B CN116421767 B CN 116421767B CN 202310706150 A CN202310706150 A CN 202310706150A CN 116421767 B CN116421767 B CN 116421767B
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Abstract
本发明公开了一种具有抗菌和单向导湿功能的复合膜的制备方法，首先制备PAN@PDA纳米纤维膜，再制备单向导湿的PAN@PDA/PCL@CUR/SF双层纳米纤维膜，然后制备壳聚糖包裹氨基化介孔二氧化硅载体微球，最后制备具有抗菌和单向导湿功能的复合膜。本发明通过层层组装策略将亲水层、疏水层以及载药层进行复合，构建出一种多功能复合膜，具有优异的抗菌、抗氧化、载药缓释特性与单向液体输送功能，主动排出伤口渗出液，解决了伤口渗出液过多不能及时排除以及伤口难以愈合等问题。
Description
技术领域
本发明属于生物医用纺织品领域，具体是一种具有抗菌和单向导湿功能的复合膜的制备方法。
背景技术
在日常生活中，由于外界和机体原因，人们不可避免地会受到伤害从而形成各种伤口。伤口愈合的快慢，主要因素之一是细菌感染，创面处会有大量伤口渗出液，含有大量的炎症因子和蛋白酶等减缓了伤口愈合的速度。为了避免伤口感染以及促进伤口更好地愈合，需要在伤口敷料中添加一些具有抗菌性和抗氧化性的物质。
姜黄素是从姜黄根茎中提取的一种天然多酚色素，具有广泛的药理活性，包括抗氧化、抗炎等特性而备受关注，然而姜黄素由于其水溶性差、不稳定性和生物利用度低，其应用受到了阻碍。介孔二氧化硅具有表面积大、孔容大、孔径分布均匀易于表面功能化等特点，常被应用在缓释应用上，文献《Hadizadeh M, Naeimi M, Rafienia M, et al. Abifunctional electrospun nanocomposite wound dressing containing surfactinand curcumin: in vitro and in vivo studies[J]. Materials Science andEngineering: C, 2021, 129: 112362.》中采用静电纺丝技术制备了一种由姜黄素和表面活性素负载的聚己内酯-明胶组成的双功能敷料，显示出良好的抗菌性，但是姜黄素的生物利用度较低。
目前的技术中，构建非对称润湿性的纳米纤维膜，形成单向导湿功能的医用敷料，可以排出伤口多余渗出液。但是目前研究的具有抗菌功能的敷料大多都是单层的，结构较为单一，只能吸收少部分渗出液，不利于伤口渗出液的排出，容易造成细菌滋生，产生炎症以及皮肤浸渍，例如文献《Fahimirad S, Abtahi H, Satei P, et al. Wound healingperformance of PCL/chitosan based electrospun nanofiber electrosprayed withcurcumin loaded chitosan nanoparticles[J]. Carbohydrate polymers, 2021, 259:117640.》研究了姜黄素负载壳聚糖纳米包覆颗粒制备了聚己内酯/壳聚糖/姜黄素纳米纤维，并将姜黄素负载在纳米纤维膜上，提高了姜黄素的生物利用度，改善了姜黄素在伤口部位的长期持续释放，但是纳米纤维膜结构比较简单，在伤口渗出液过多时不能将渗出液排出，容易再次造成伤口感染。因此，制备一种将抗菌、抗氧化、载药缓释特性优良与单向导湿结合的医用敷料复合膜显得至关重要。
发明内容
针对现有技术的不足，本发明拟解决的技术问题是，提供一种具有抗菌和单向导湿功能的复合膜的制备方法。
本发明解决所述技术问题的技术方案是，提供一种具有抗菌和单向导湿功能的复合膜的制备方法，其特征在于，该方法包括以下步骤：
步骤1、制备PAN@PDA纳米纤维膜：将PAN溶解于溶剂A中，制备PAN溶液；再以PAN溶液作为纺丝液通过静电纺丝制备PAN纳米纤维膜；再将PAN纳米纤维膜浸泡在PDA溶液中进行接枝反应，得到PAN@PDA纳米纤维膜作为亲水层；
步骤2、制备单向导湿的PAN@PDA/PCL@CUR/SF双层纳米纤维膜：
S21、将PCL和CUR溶解于二氯甲烷中，配制成均相的PCL@CUR溶液；将SF溶解在溶剂B中，配制成均相的SF溶液；
S22、将SF溶液和PCL@CUR溶液作为纺丝液分别置于双纺丝头静电纺丝装置的两个纺丝头中，以PAN@PDA纳米纤维膜作为接收基底；两个纺丝头同时进行静电纺丝，将SF纳米纤维和PCL@CUR纳米纤维纺制在接收基底上，形成PCL@CUR/SF纳米纤维膜，得到以PCL@CUR/SF纳米纤维膜作为疏水层的PAN@PDA/PCL@CUR/SF双层纳米纤维膜；
步骤3、制备壳聚糖包裹氨基化介孔二氧化硅载体微球：
S31、将氨水滴入CTAB溶液中，加热搅拌反应至形成均相溶液；再加入TEOS，搅拌反应至形成均匀的浑浊液体；再将浑浊液体离心并洗涤除杂后干燥得到白色固体；再将白色固体经过捣碎、煅烧和研磨后，得到MSN粉末；
S32、将MSN粉末在无水乙醇和APTES的混合溶液中冷凝回流，然后离心，得到MSN-NH2；
S33、将CS溶解于醋酸中，得到均相的CS的醋酸溶液；再将MSN-NH2加入到CS的醋酸溶液中搅拌至形成均匀的浑浊液作为纺丝液；再通过静电喷涂制备MSN-NH2-CS载体微球；
步骤4、制备具有抗菌和单向导湿功能的复合膜：将MSN-NH2-CS载体微球加入到CUR溶液中，并搅拌至形成均匀的MSN-NH2-CS/CUR溶液作为纺丝液；再将纺丝液喷涂至PAN@PDA/PCL@CUR/SF双层纳米纤维膜上，形成载药层，得到具有抗菌和单向导湿功能的复合膜。
与现有技术相比，本发明有益效果在于：
（1）本发明通过层层组装策略将亲水层、疏水层以及载药层进行复合，构建出一种多功能复合膜，具有优异的抗菌、抗氧化、载药缓释特性与单向液体输送功能，主动排出伤口渗出液，解决了伤口渗出液过多不能及时排除以及伤口难以愈合等问题。
（2）本发明的亲水层提供持续的毛细拉力，疏水层和载药层提供长效的推力，这种“推-拉”力的共同作用，使液滴能够在复合膜中自发地完成传输。
（3）本发明的亲水层采用PAN@PDA纳米纤维膜，主要提供持续的毛细拉力。
（4）本发明的疏水层采用PCL@CUR/SF纳米纤维膜，并在疏水层加入具有抗菌性的姜黄素以及对创面修复有利的丝素蛋白，从而使复合膜的生物相容性好，具有优异的抗菌性和抗氧化。同时通过调整疏水层的静电纺丝时间构建了一种非对称润湿性纳米纤维膜。
（5）本发明的载药层采用MSN-NH2-CS/CUR，并在载药层加入具有抗菌性的姜黄素以及载药缓释作用的载体微球，从而使复合膜具有优异的抗菌性和载药缓释特性。
（6）本发明的载体微球，在MSN的基础上接枝了氨基，提高了微球的负载能力，再利用CS将MSN-NH2包裹，赋予微球优良的生物相容性和缓释特性。
（7）本发明的载体微球，利用静电喷涂技术将CUR负载在载体微球中，提高了载体微球的抗菌能力，同时使载体微球具有优良的抗氧化能力，有利于伤口愈合。
附图说明
图1为本发明实施例1制备的MSN的SEM图；
图2为本发明实施例1制备的MSN的粒径分布曲线图；
图3为本发明实施例1制备的MSN-NH2的SEM图；
图4为本发明实施例1制备的MSN-NH2的粒径分布曲线图；
图5为本发明实施例1的不同放大倍数的PCL@CUR纳米纤维膜的SEM图；
图6为本发明实施例1的不同放大倍数的PCL@CUR/SF纳米纤维膜的SEM图；
图7为本发明实施例1的FT-IR图像；
图8为本发明实施例1的紫外分光光谱图；
图9为本发明实施例1的DPPH自由基清除图；
图10为本发明实施例1的抗菌效果图；
图11为本发明实施例1~3和对比例1的MMT分析图；
图12为本发明实施例1对于CUR的体外释放曲线图；
图13为L929细胞在本发明实施例1上1d、4d、7d的存活率。
具体实施方式
下面给出本发明的具体实施例。具体实施例仅用于进一步详细说明本发明，不限制本发明权利要求的保护范围。
本发明提供了一种具有抗菌和单向导湿功能的复合膜的制备方法（简称方法），其特征在于，该方法包括以下步骤：
步骤1、制备PAN@PDA纳米纤维膜：将PAN（聚丙烯腈）溶解于溶剂A中，制备PAN溶液；再以PAN溶液作为纺丝液通过静电纺丝制备PAN纳米纤维膜；再将PAN纳米纤维膜浸泡在PDA（聚多巴胺）溶液中进行接枝反应来提高亲水性，得到亲水性PAN@PDA纳米纤维膜作为亲水层；
优选地，步骤1中，溶剂A为水、乙醇、丙酮或N,N-二甲基甲酰胺。
优选地，步骤1中，PAN溶液的质量分数为5~20wt%。
优选地，步骤1中，PDA溶液的制备方法具体是：将Tris粉末和多巴胺溶解在去离子水中，再加入质量分数为1~5wt%的APTES（氨丙基三乙氧基硅烷）的乙醇溶液来调节pH值，制备pH=5~15的多巴胺溶液；其中，Tris与多巴胺的质量比为0.1~1:1；去离子水与乙醇的体积比为5~10:1。
优选地，步骤1中，接枝反应时间为5~48h，温度为10~50℃（优选室温）。
步骤2、制备单向导湿的PAN@PDA/PCL@CUR/SF双层纳米纤维膜：
S321、将PCL（聚己内酯）和CUR（姜黄素）溶解于二氯甲烷中，配制成均相的PCL@CUR溶液；将SF（丝素蛋白）溶解在溶剂B中，配制成均相的SF溶液；
优选地，步骤S321中，PCL与CUR的质量比为1~5:1；PCL@CUR溶液的浓度为5~20wt%。
优选地，步骤S321中，溶剂B为甲酸、水、乙醇、丙酮或二氯甲烷；SF溶液的浓度为1~30wt%。
S322、将SF溶液和PCL@CUR溶液作为纺丝液分别置于双纺丝头静电纺丝装置的两个纺丝头中，以PAN@PDA纳米纤维膜作为接收基底；两个纺丝头同时进行静电纺丝，将SF纳米纤维和PCL@CUR纳米纤维纺制在接收基底上，形成PCL@CUR/SF纳米纤维膜，通过调节纺丝时间来调整其厚度，得到以PCL@CUR/SF纳米纤维膜作为疏水层的具有单向液体输送效果的PAN@PDA/PCL@CUR/SF双层纳米纤维膜。
步骤3、制备壳聚糖包裹氨基化介孔二氧化硅载体微球：
S31、将氨水滴入CTAB（十六烷基三甲基溴化铵）溶液中，加热搅拌反应至形成均相溶液；再加入TEOS（正硅酸乙酯），搅拌反应至形成均匀的浑浊液体；再将浑浊液体离心并洗涤除杂后干燥得到白色固体；再将白色固体经过捣碎、煅烧和研磨后，得到MSN（介孔纳米二氧化硅）粉末；
优选地，步骤S31中，CTAB溶液的浓度为0.1~10g/L（优选0.5~5g/L）；加热搅拌反应的温度为20~90℃，时间为1~8h。
优选地，步骤S31中，氨水与TEOS的质量比为4~20:1~20。
优选地，步骤S31中，搅拌反应的时间为2~8h，转速为100~600r/min。
优选地，步骤S31中，洗涤采用去离子水或乙醇洗涤。
优选地，步骤S31中，煅烧的温度为500~600℃（优选550℃），时间为4~7h（优选6h）；研磨至粉末状。
S32、将MSN粉末在无水乙醇和APTES的混合溶液中冷凝回流，然后离心，得到MSN-NH2（氨基化介孔二氧化硅）；
优选地，步骤S32中，MSN粉末的质量、无水乙醇的体积与APTES的体积之比为0.1~10g:50~200mL:0.1~5mL。
优选地，步骤S32中，冷凝回流的时间为2~24h，温度为20~100℃。
优选地，步骤S32中，离心速度为1000~15000rpm。
S33、将CS（壳聚糖）溶解于醋酸中，得到均相的CS的醋酸溶液；再将MSN-NH2加入到CS的醋酸溶液中搅拌至形成均匀的浑浊液作为纺丝液；再以纺丝液为原料通过静电喷涂将MSN-NH2包裹在CS内部，形成MSN-NH2-CS（壳聚糖包裹氨基化介孔二氧化硅）载体微球；
优选地，步骤S33中，CS的醋酸溶液的浓度为1~5wt%（优选2wt%）；CS与MSN-NH2的质量比为5~30:1。
优选地，步骤S33中，静电喷涂是利用静电吸引的原理，静电喷涂电压为5~30kV，挤出速度为0.1~1mL/h。
步骤4、制备具有抗菌和单向导湿功能的复合膜：将MSN-NH2-CS载体微球加入到CUR溶液中，并搅拌至形成均匀的MSN-NH2-CS/CUR（氨基化介孔二氧化硅-壳聚糖/姜黄素）溶液作为纺丝液；再将纺丝液喷涂至PAN@PDA/PCL@CUR/SF双层纳米纤维膜上，形成载药层，得到具有抗菌和单向导湿功能的复合膜（简称复合膜）。
优选地，步骤4中，CUR溶液的浓度为1~20mg/mL；MSN-NH2-CS的浓度为0.001~1g/mL；搅拌时间为1~48h，在避光条件下搅拌；喷涂时间为1~20min。
优选地，步骤4中，喷涂采用静电喷涂，静电喷涂电压为5~30kV，挤出速度为0.1~1mL/h，喷涂时间为1~20min。
实施例1：步骤1、制备PAN@PDA纳米纤维膜：将PAN溶解在N,N-二甲基甲酰胺中制备10wt%PAN溶液，并通过静电纺丝制备PAN纳米纤维膜；再将PAN纳米纤维膜在室温下在PDA溶液中浸泡24h，从而制备亲水性的PAN@PDA纳米纤维膜；
步骤2、制备单向导湿的PAN@PDA/PCL@CUR/SF双层纳米纤维膜：
S321、将PCL和CUR加入到二氯甲烷中配制12wt%的PCL@CUR溶液，PCL与CUR的质量比为2:1；将SF溶解在水中配制20wt%SF溶液；
S322、将SF溶液和PCL@CUR溶液作为纺丝液分别置于双纺丝头静电纺丝装置的两个纺丝头中，以PAN@PDA纳米纤维膜作为接收基底；两个纺丝头同时进行静电纺丝，将SF纳米纤维和PCL@CUR纳米纤维纺制在接收基底上，形成PCL@CUR/SF纳米纤维膜，得到以PCL@CUR/SF纳米纤维膜作为疏水层的PAN@PDA/PCL@CUR/SF双层纳米纤维膜；
步骤3、制备壳聚糖包裹氨基化介孔二氧化硅载体微球：
S31、将4mL氨水滴入质量浓度为1.14g/L的CTAB溶液中，40℃水浴加热搅拌30min使溶液混合均匀后再加入1.22mL的TEOS，500r/min搅拌5h得到浑浊液体；再将浑浊液体离心并洗涤除杂后干燥得到白色固体；再将白色固体经过捣碎、煅烧和研磨后，得到MSN粉末；
S32、将1g的MSN在100mL乙醇和2mL的APTES混合溶液中以80℃冷凝回流8h，然后离心，得到MSN-NH2；
S33、将2g的CS溶解在醋酸溶液中搅拌，形成浓度为2wt%的CS的醋酸溶液；再加入0.1g的MSN-NH2，利用静电吸引的原理，在20KV下以0.5mL/h的速度静电喷涂制备MSN-NH2-CS载体微球；
步骤4、制备具有抗菌和单向导湿功能的复合膜：将MSN-NH2-CS载体微球加入到4mg/mL的CUR溶液中，并在避光条件下搅拌均匀，形成均匀的MSN-NH2-CS/CUR溶液作为纺丝液；再将纺丝液静电喷涂5min至PAN@PDA/PCL@CUR/SF双层纳米纤维膜上，形成载药层，得到具有抗菌和单向导湿功能的复合膜。
对比例1：对比例与实施例1相同；唯一的区别在于步骤S42中，将静电喷涂5min改为静电喷涂0min。
实施例2：步骤1、制备PAN@PDA纳米纤维膜：将PAN溶解在N,N-二甲基甲酰胺中制备10wt%PAN溶液，并通过静电纺丝制备PAN纳米纤维膜；再将PAN纳米纤维膜在PDA溶液中浸泡24h，从而制备亲水性的PAN@PDA纳米纤维膜；
步骤2、制备单向导湿的PAN@PDA/PCL@CUR/SF双层纳米纤维膜：
S21、将PCL和CUR加入到二氯甲烷中配制12wt%的PCL@CUR溶液，PCL与CUR的质量比为2:1；将SF溶解在水中配制20wt%SF溶液；
S22、将SF溶液和PCL@CUR溶液作为纺丝液分别置于双纺丝头静电纺丝装置的两个纺丝头中，以PAN@PDA纳米纤维膜作为接收基底；两个纺丝头同时进行静电纺丝，将SF纳米纤维和PCL@CUR纳米纤维纺制在接收基底上，形成PCL@CUR/SF纳米纤维膜，得到以PCL@CUR/SF纳米纤维膜作为疏水层的PAN@PDA/PCL@CUR/SF双层纳米纤维膜；
步骤3、制备壳聚糖包裹氨基化介孔二氧化硅载体微球：
S31、将4mL氨水滴入质量浓度为1.14g/L的CTAB溶液中，40℃水浴加热搅拌30min使溶液混合均匀后再加入1.22mL的TEOS，500r/min搅拌5h得到浑浊液体；再将浑浊液体离心并洗涤除杂后干燥得到白色固体；再将白色固体经过捣碎、煅烧和研磨后，得到MSN粉末；
S32、将1g的MSN在100mL乙醇和2mL的APTES混合溶液中以80℃冷凝回流8h，然后离心，得到MSN-NH2；
S33、将2g的CS溶解在醋酸溶液中搅拌，形成浓度为2wt%的CS的醋酸溶液；再加入0.1g的MSN-NH2，利用静电吸引的原理，在20KV下以0.5mL/h的速度静电喷涂制备MSN-NH2-CS载体微球；
步骤4、制备具有抗菌和单向导湿功能的复合膜：将MSN-NH2-CS载体微球加入到4mg/mL的CUR溶液中，并在避光条件下搅拌均匀，形成均匀的MSN-NH2-CS/CUR溶液作为纺丝液；再将纺丝液静电喷涂10min至PAN@PDA/PCL@CUR/SF双层纳米纤维膜上，形成载药层，得到具有抗菌和单向导湿功能的复合膜。
实施例3：步骤1、制备PAN@PDA纳米纤维膜：将PAN溶解在N,N-二甲基甲酰胺中制备10wt%PAN溶液，并通过静电纺丝制备PAN纳米纤维膜；再将PAN纳米纤维膜在PDA溶液中浸泡24h，从而制备亲水性的PAN@PDA纳米纤维膜；
步骤2、制备单向导湿的PAN@PDA/PCL@CUR/SF双层纳米纤维膜：
S21、将PCL和CUR加入到二氯甲烷中配制12wt%的PCL@CUR溶液，PCL与CUR的质量比为2:1；将SF溶解在水中配制20wt%SF溶液；
S22、将SF溶液和PCL@CUR溶液作为纺丝液分别置于双纺丝头静电纺丝装置的两个纺丝头中，以PAN@PDA纳米纤维膜作为接收基底；两个纺丝头同时进行静电纺丝，将SF纳米纤维和PCL@CUR纳米纤维纺制在接收基底上，形成PCL@CUR/SF纳米纤维膜，得到以PCL@CUR/SF纳米纤维膜作为疏水层的PAN@PDA/PCL@CUR/SF双层纳米纤维膜；
步骤3、制备壳聚糖包裹氨基化介孔二氧化硅载体微球：
S31、将4mL氨水滴入质量浓度为1.14g/L的CTAB溶液中，40℃水浴加热搅拌30min使溶液混合均匀后再加入1.22mL的TEOS，500r/min搅拌5h得到浑浊液体；再将浑浊液体离心并洗涤除杂后干燥得到白色固体；再将白色固体经过捣碎、煅烧和研磨后，得到MSN粉末；
S32、将1g的MSN在100mL乙醇和2mL的APTES混合溶液中以80℃冷凝回流8h，然后离心，得到MSN-NH2；
S33、将2g的CS溶解在醋酸溶液中搅拌，形成浓度为2wt%的CS的醋酸溶液；再加入0.1g的MSN-NH2，利用静电吸引的原理，在20KV下以0.5mL/h的速度静电喷涂制备MSN-NH2-CS载体微球；
步骤4、制备具有抗菌和单向导湿功能的复合膜：将MSN-NH2-CS载体微球加入到4mg/mL的CUR溶液中，并在避光条件下搅拌均匀，形成均匀的MSN-NH2-CS/CUR溶液作为纺丝液；再将纺丝液静电喷涂15min至PAN@PDA/PCL@CUR/SF双层纳米纤维膜上，形成载药层，得到具有抗菌和单向导湿功能的复合膜。
由图1和图3可以看出，制备的MSN和MSN-NH2大小均匀并且呈规则球状；
由图2和图4可以看出，经过测量，MSN和MSN-NH2的直径分别为138.2nm和158.8nm，可以看出经过氨基化之后MSN-NH2的平均直径变大。
由图5可以看出，PCL@CUR纳米纤维膜的纤维中间有颗粒存在，表明姜黄素被成功地纺在纤维膜上。
由图6可以看出，PCL@CUR/SF纳米纤维膜上形成了较多的纤维，并且可以看出姜黄素均匀地分散在纳米纤维膜上。
由图7可以看出，经SF和PCL@CUR静电纺丝后，在PAN@PDA/PCL@CUR/SF和复合膜中显示了PCL中在1163cm-1对称C-O-C伸缩振动峰，显示了3400cm-1处的宽峰带为蛋白类物质的-NH2官能团以及壳聚糖O-H/N-H的特征峰带，还显示了丝素蛋白的酰胺Ι与酰胺Ⅱ特征峰（1631cm-1和1510cm-1），表明了经过PAN@PDA纳米纤维膜、PCL@CUR/SF纳米纤维膜和MSN-NH2-CS/CUR载体微球成功的复合在一起。
由图8可以看出，PCL@CUR/SF纳米纤维膜、PAN@PDA/PCL@CUR/SF纳米纤维膜以及复合膜在420nm处出现强吸收峰，由于CUR在420nm处出现强吸收峰，表明CUR的成功加载。
由图9可以看出，PAN纳米纤维膜没有自由基清除能力，5min时，PAN@PDA的抗氧化活性为3.87%，PAN@PDA/PCL@CUR/SF纳米纤维膜为80.97%，复合膜的抗氧化活性为84.93%；120min时，PAN@PDA纳米纤维膜、PAN@PDA/PCL@CUR/SF纳米纤维膜以及复合膜的抗氧化活性分别为37.53%、71.99%、79.01%，说明随着时间的增加，抗氧化活性虽然有所下降，复合膜依然具有很高的抗氧化活性。
由图10可以看出，采用革兰氏阴性大肠杆菌和革兰氏阳性金黄色葡萄球菌对复合膜的抗菌性进行评估时，复合膜对大肠杆菌和金黄色葡萄球菌的抗菌性分别为98%和99%左右。
由图11可以看出，随着静电喷涂时间的增加，累计单向传递指数降低，在静电喷涂5min时的累计单向传递指数为577%，具有良好的单向液体输送能力，可以解决敷料与伤口过度湿润的问题，实现液体的长期连续单向输送。随着静电喷涂时间的增加，单向传输能力有所减弱，当静电喷涂15min时，大量水分集中在顶层难以穿透复合膜达到下层。
由图12可以看出，复合膜和PAN@PDA/PCL@CUR/SF均具有缓释性能，在191h后复合膜中CUR的缓释可达到0.49%。
由图13可以看出，L929细胞在、PAN@PDA纳米纤维膜、PAN@PDA/PCL@CUR/SF双层纳米纤维膜和复合膜上分别培养1天、4天和7天后，每组样品的存活率均在100%以上，说明复合膜、PAN@PDA纳米纤维膜和PAN@PDA/PCL@CUR/SF双层纳米纤维膜在与细胞培养一段时间后仍然具有良好的生物相容性，能够促进细胞的增殖分化。
本发明未述及之处适用于现有技术。
Claims (10)
1.一种具有抗菌和单向导湿功能的复合膜的制备方法，其特征在于，该方法包括以下步骤：
步骤1、制备PAN@PDA纳米纤维膜：将PAN溶解于溶剂A中，制备PAN溶液；再以PAN溶液作为纺丝液通过静电纺丝制备PAN纳米纤维膜；再将PAN纳米纤维膜浸泡在PDA溶液中进行接枝反应，得到PAN@PDA纳米纤维膜作为亲水层；
步骤2、制备单向导湿的PAN@PDA/PCL@CUR/SF双层纳米纤维膜：
S21、将PCL和CUR溶解于二氯甲烷中，配制成均相的PCL@CUR溶液；将SF溶解在溶剂B中，配制成均相的SF溶液；
S22、将SF溶液和PCL@CUR溶液作为纺丝液分别置于双纺丝头静电纺丝装置的两个纺丝头中，以PAN@PDA纳米纤维膜作为接收基底；两个纺丝头同时进行静电纺丝，将SF纳米纤维和PCL@CUR纳米纤维纺制在接收基底上，形成PCL@CUR/SF纳米纤维膜，得到以PCL@CUR/SF纳米纤维膜作为疏水层的PAN@PDA/PCL@CUR/SF双层纳米纤维膜；
步骤3、制备壳聚糖包裹氨基化介孔二氧化硅载体微球：
S31、将氨水滴入CTAB溶液中，加热搅拌反应至形成均相溶液；再加入TEOS，搅拌反应至形成均匀的浑浊液体；再将浑浊液体离心并洗涤除杂后干燥得到白色固体；再将白色固体经过捣碎、煅烧和研磨后，得到MSN粉末；
S32、将MSN粉末在无水乙醇和APTES的混合溶液中冷凝回流，然后离心，得到MSN-NH2；
S33、将CS溶解于醋酸中，得到均相的CS的醋酸溶液；再将MSN-NH2加入到CS的醋酸溶液中搅拌至形成均匀的浑浊液作为纺丝液；再通过静电喷涂制备MSN-NH2-CS载体微球；
步骤4、制备具有抗菌和单向导湿功能的复合膜：将MSN-NH2-CS载体微球加入到CUR溶液中，并搅拌至形成均匀的MSN-NH2-CS/CUR溶液作为纺丝液；再将纺丝液喷涂至PAN@PDA/PCL@CUR/SF双层纳米纤维膜上，形成载药层，得到具有抗菌和单向导湿功能的复合膜。
2.根据权利要求1所述的具有抗菌和单向导湿功能的复合膜的制备方法，其特征在于，步骤1中，溶剂A为水、乙醇、丙酮或N,N-二甲基甲酰胺；PAN溶液的质量分数为5~20wt%；接枝反应时间为5~48h，温度为10~50℃。
3.根据权利要求1所述的具有抗菌和单向导湿功能的复合膜的制备方法，其特征在于，步骤1中，PDA溶液的制备方法具体是：将Tris粉末和多巴胺溶解在去离子水中，再加入质量分数为1~5wt%的APTES的乙醇溶液来调节pH值，制备pH=5~15的多巴胺溶液；其中，Tris与多巴胺的质量比为0.1~1:1；去离子水与乙醇的体积比为5~10:1。
4.根据权利要求1所述的具有抗菌和单向导湿功能的复合膜的制备方法，其特征在于，步骤S21中，PCL与CUR的质量比为1~5:1；PCL@CUR溶液的浓度为5~20wt%；溶剂B为甲酸、水、乙醇、丙酮或二氯甲烷；SF溶液的浓度为1~30wt%。
5.根据权利要求1所述的具有抗菌和单向导湿功能的复合膜的制备方法，其特征在于，步骤S31中，CTAB溶液的浓度为0.1~10g/L；加热搅拌反应的温度为20~90℃，时间为1~8h；氨水与TEOS的质量比为4~20:1~20。
6.根据权利要求1所述的具有抗菌和单向导湿功能的复合膜的制备方法，其特征在于，步骤S31中，搅拌反应的时间为2~8h，转速为100~600r/min；洗涤采用去离子水或乙醇洗涤；煅烧的温度为500~600℃，时间为4~7h；研磨至粉末状。
7.根据权利要求1所述的具有抗菌和单向导湿功能的复合膜的制备方法，其特征在于，步骤S32中，MSN粉末的质量、无水乙醇的体积与APTES的体积之比为0.1~10g:50~200mL:0.1~5mL；冷凝回流的时间为2~24h，温度为20~100℃；离心速度为1000~15000rpm。
8.根据权利要求1所述的具有抗菌和单向导湿功能的复合膜的制备方法，其特征在于，步骤S33中，CS的醋酸溶液的浓度为1~5wt%；CS与MSN-NH2的质量比为5~30:1；静电喷涂的电压为5~30kV，挤出速度为0.1~1mL/h。
9.根据权利要求1所述的具有抗菌和单向导湿功能的复合膜的制备方法，其特征在于，步骤4中，CUR溶液的浓度为1~20mg/mL；MSN-NH2-CS的浓度为0.001~1g/mL；搅拌时间为1~48h，在避光条件下搅拌；喷涂时间为1~20min。
10.根据权利要求1所述的具有抗菌和单向导湿功能的复合膜的制备方法，其特征在于，步骤4中，喷涂采用静电喷涂，静电喷涂电压为5~30kV，挤出速度为0.1~1mL/h，喷涂时间为1~20min。
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