CN105999407A - 一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法 - Google Patents
一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法 Download PDFInfo
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Abstract
一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法,其特征在于使用壳聚糖,硝酸银和聚乙烯醇的溶液,通过对基材预处理,物理涂敷和原位还原和获得了在水环境下稳定的表面亲水的纳米复合凝胶涂层,该涂层具有良好的广谱抗细菌黏附和杀菌的能力,并具有良好的细胞相容性。该方法工艺简单、快捷,条件温和,易于旋涂、浸涂、喷涂等可工业实的方式实现,适用范围广,能够有效地的改善医用装置表面的抗菌性能,生物相容性和润滑性。
Description
技术领域
本发明涉及新型材料技术领域,特别涉及一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法。
背景技术
细菌、真菌等病原微生物常常引发机体组织发生病变,严重威胁着人类的身心健康。据直接卫生组织(World Health Organization,WHO)1998年统计数字表明,1995年全世界死亡人口为5200万,其中因细菌感染造成的死亡人数约占33%,如今这一比例还在进一步提高。因此抗菌材料和制品的开发受到越来越多的关注。如今临床术后和医疗植入体抗感染的主要方式是使用抗生素,然而随着抗生素的大量使用,细菌的耐药性也大大提高,特别是一旦形成生物膜,细菌的抗药性将极大提高,需要几百甚至上千倍的抗生素杀死,处理效果并不理想。临床处理的方式往往是再次手术取出植入体,清洗或者更换新的植入体,这样的处理方式不但增加病人的痛苦,而且增加病人经济负担,因此寻求一种简单有效的长效抗菌涂层具有重要的意义。
通过对各种医用装置的表面修饰,在保持原有性能的条件下,改善生物医用装置生物相容性成为现代医疗装置应用中的重要问题。感染发生的一般过程是:细菌的黏附;定植和繁殖,形成菌落;分泌胞外基质,菌落通过胞外基质连接在一起,形成生物膜(biofilm),生物膜释放浮游菌体和毒素,引发感染。针对细菌感染的第一个步骤,制备一种亲水的凝胶涂层将增加涂层的溶胀能力和亲水性,能够实现涂层的抗细菌黏附性能。然而单纯的亲水涂层并不能实现长效抗菌的能力,也不能杀灭植入体周围的病菌。壳聚糖是一种天然的聚阳离子抗菌分子,并且具有良好的生物相容性和涂层形成能力,抗菌机理是接触式杀菌。纳米银是一种高效杀菌材料,相对分子状态的银能够实现可控和长期释放,以壳聚糖分子为模板,原位形成纳米银,并且由于氢键作用,壳聚糖和聚乙烯醇能够稳定的复合。聚合物共混技术具有简单、易于操作的特点,并且使膜层具有其组分的复合功能,通过对基材的预处理解决了涂层溶胀带来的稳定性问题,有望得到兼具抗细菌黏附和杀菌的性能。
发明内容
为解决现有技术的问题,本发明提供了一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法。
本发明采用的技术解决方案是:一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法,包括以下步骤:将质量浓度为5-20mg/ml的壳聚糖、质量浓度为1~20mg/ml的聚乙烯醇溶液和0.01~0.1mg/ml的硝酸银溶液混合,将混合溶液涂抹在经表面预处理后的基材表面,经自然干燥处理或真空处理获得了聚合物凝胶涂层的基材,然后清洗、真空干燥,然后将涂抹有聚合物凝胶涂层的基材在抗坏血酸溶液中原位还原后,得到纳米银颗粒粒度为5~50nm的复合抗菌涂层。
所述的基材的表面预处理步骤如下:将基材依次用丙酮、乙醇和超纯水超声清洗15min,然后用N2吹干,清洗过的基材分别在5mg/ml的PEI溶液中处理30min N2吹干,得到表面PEI处理的基材;在5mg/ml的PAA溶液中处理30min N2吹干,得到表面PAA处理的基材;在混合10mg/ml EDC和20mg/mlNHSS的MES缓冲液中处理6h N2吹干,得到表面EDC/NHS处理的基材。
所述的涂抹的方式为旋涂、浸涂或喷涂。
所述的基材为玻璃、石英、云母、不锈钢、聚酯膜、聚乳酸膜中的一种。
所述的抗坏血酸溶液质量浓度为5-20mg/ml,浸泡处理时间为4-24h。
所述的10mg/ml EDC和20mg/ml NHSS的MES缓冲液的PH值为5.6。
所述的旋涂方式为:调节旋涂仪转速为1000rad/min,用滴管吸取0.1ml涂膜液滴在基材上,旋涂10s,然后在2500rad/min转速下旋涂2min,干燥,重复旋涂3-5次。
所述的浸涂方式为:将基材浸入涂膜液中5s后,取出,使基材表面的涂膜液覆盖均匀,然后放置于玻璃平板上,干燥后用刀片剥离基材。
所述的喷涂方式为:将喷涂液加入到雾化器中,喷涂在基材上1s,60℃烘箱干燥20min,此操作重复5次。
本发明的有益效果是:本发明提供了一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法,将基材经过预处理,明显提高了凝胶涂层的粘结稳定性。该纳米复合涂层对革兰氏阴性菌和革兰氏阳性菌具有优良的抗细菌黏附,快速杀菌能力和长效抗菌的能力。聚乙烯醇的含量增加提高了涂层的抗细菌黏附能力。凝胶涂层对人脐静脉内皮细胞细胞毒性较低,具有良好的细胞相容性。抗菌涂层具有良好的润滑性能,本发明涂层溶液配制简便,能实现无污染操作,可采用旋涂、浸涂、喷涂等可工业实现的方式,适用范围广,能够对具有复杂体型结构的生物医用装置进行涂层修饰;涂层可改善医用装置表面的多种抗菌性能,润滑性,生物相容性,在人体环境下以水凝胶的形式存在,这种性质使生物材料表面润滑,减少材料表面和粘膜组织之间的摩接阻力;涂层材料化学结构稳定,耐疲劳、剪切,能适应人体的内环境;涂层能够实现广谱的多功能抗菌的能力。
具体实施方式
为了能够更清楚地理解本发明的技术内容,特举以下实施例详细说明。
实施例1:
在50ml小烧杯中加入50ml醋酸缓冲溶液(pH=4.0),磁力搅拌,缓慢加入0.05g的聚乙烯醇和0.0005g的AgNO3,浓度为1mg/ml和0.1mg/ml,搅拌溶解后缓慢加入0.50g壳聚糖,浓度为10mg/ml,待粘度增大后把搅拌开到最大,继续搅拌2h,即为涂膜液。PET片经刀片裁剪成1.5×2.5cm2大小,作为基材使用,然后依次用前经丙酮、乙醇和超纯水分别超声15min清洗,N2吹干。清洗过的PET分别在5mg/ml的PEI(聚酰亚胺)中处理30min;在5mg/ml的PAA(丙烯酸树脂乳液)中处理30min;在混合10mg/ml EDC(二氯乙烷)和20mg/ml NHSS(N-羟基琥珀酰亚胺)的MES(2-(N-吗啉)乙磺酸一水合物)缓冲液(pH=5.6)中处理6h,N2吹干。未处理PET和分别经PEI,PAA和EDC/NHS处理后的PET接触角分别为70.3±0.5°,80.6±0.4°,25.1±0.8°和37.2±0.7°,原子力显微镜测试RMS分别为2.992±0.42,2.732±0.32,3.538±0.28和3.446±0.26nm,证实了预处理过程的进行。
用镊子夹住PET片,浸入涂膜液中5s,取出,使表面的液体均匀覆盖,然后放置于玻璃平板上,室温干燥24h,然后用刀片剥离PET片,继续真空烘箱室温干燥12h,收集样品。然后涂层在5mg/ml抗坏血酸溶液中原位还原4h,,得到含纳米银的复合材料。断面场发射扫描电镜测试涂层的厚度为3.56±0.45μm。透射电镜结果表明:纳米银颗粒粒度分布于5~12nm,平均5nm。摇瓶培养和稀释涂平板法测试膜层的杀菌性能,结果显示该膜层能在10min杀死100%的大肠杆菌和100%的金黄色葡萄球菌。采用MTT和FDA实验结果发现对人脐静脉内皮细胞细胞毒性较低,细胞活性超过TCPS的92%,因此具有良好的细胞相容性。
实施例2:
在50ml小烧杯中加入50ml醋酸缓冲溶液(pH=4.0),磁力搅拌,缓慢加入0.10g的聚乙烯醇和0.0010g的AgNO3,浓度为2mg/ml和0.2mg/ml,搅拌溶解后缓慢加入0.25g壳聚糖,浓度为5mg/ml,待粘度增大后把搅拌开到最大,继续搅拌2h,即为涂膜液。聚乳酸膜作为基材,清洗、预处理和涂膜方法同实施例1中的PET,然后涂层在8mg/ml抗坏血酸溶液中原位还原6h,。原子力显微镜观察形貌发现表面具有很低的粗糙度,RMS为3.72±0.34nm。透射电镜结果表明:纳米银颗粒粒度分布于7~11nm,平均9nm。摇瓶培养和稀释涂平板法测试膜层的杀菌性能,结果显示该膜层能在10min杀死100%的大肠杆菌和100%的金黄色葡萄球菌。采用MTT和FDA实验结果发现对人脐静脉内皮细胞细胞毒性较低,细胞活性超过TCPS的85%,因此具有良好的细胞相容性。
实施例3:
在50ml小烧杯中加入50ml醋酸缓冲溶液(pH=4.0),磁力搅拌,缓慢加入0.25g的聚乙烯醇和0.0015g的AgNO3,浓度为5mg/ml和0.3mg/ml,搅拌溶解后缓慢加入0.35g壳聚糖,浓度为7mg/ml,待粘度增大后把搅拌开到最大,继续搅拌2h,即为涂膜液。玻璃作为基材,清洗和预处理方法同实施例1中的PET,涂膜方法采用旋涂的方法,先在1000rad/min旋涂10s,然后在2500rad/min下旋涂2min,重复操作,旋涂5次。然后涂层在10mg/ml抗坏血酸溶液中原位还原12h,。断面场发射扫描电镜测试膜层的厚度为2.55±0.38μm。静态接触角测试膜层显示出一定的亲水性,为66.67±1.62°,原子力显微镜观察形貌发现表面具有很低的粗糙度,RMS为2.44±0.26nm。透射电镜结果表明:纳米银颗粒粒度分布于9~19nm,平均15nm。摇瓶培养和稀释涂平板法测试膜层的杀菌性能,结果显示该膜层能在10min杀死100%的大肠杆菌和100%的金黄色葡萄球菌。抗细菌黏附实验发现和未涂膜的基材相比,该共混膜降低了100%的大肠杆菌黏附和98%的金黄色葡萄球菌的黏附。采用MTT和FDA实验结果发现对人脐静脉内皮细胞细胞毒性较低,细胞活性超过TCPS的82%,因此具有良好的细胞相容性。
实施例4:
在50ml小烧杯中加入50ml醋酸缓冲溶液(pH=4.0),磁力搅拌,缓慢加入0.50g的聚乙烯醇和0.0020g的AgNO3,浓度为10mg/ml和0.4mg/ml,搅拌溶解后缓慢加入0.65g壳聚糖,浓度为13mg/ml,待粘度增大后把搅拌开到最大,继续搅拌2h,即为涂膜液。云母作为基材,清洗和预处理方法同实施例1中的PET,涂膜方法采用旋涂的方法,先在1000rad/min旋涂10s,然后在2500rad/min下旋涂2min,然后涂层在20mg/ml抗坏血酸溶液中原位还原6h,。断面场发射扫描电镜测试膜层的厚度为4.63±0.63μm。静态接触角测试膜层显示出一定的亲水性,为54.45±1.44°,原子力显微镜观察形貌发现表面具有很低的粗糙度,RMS为2.53±0.34nm。透射电镜结果表明:纳米银颗粒粒度分布于12~24nm,平均18nm。摇瓶培养和稀释涂平板法测试膜层的杀菌性能,结果显示该膜层能在10min杀死100%的大肠杆菌和100%的金黄色葡萄球菌。采用MTT和FDA实验结果发现对人脐静脉内皮细胞细胞毒性较低,细胞活性超过TCPS的75%,因此具有一定的细胞相容性。
实施例5:
在50ml小烧杯中加入50ml醋酸缓冲溶液(pH=4.0),磁力搅拌,缓慢加入0.75g的聚乙烯醇和0.0025g的AgNO3,浓度为15mg/ml和0.5mg/ml,搅拌溶解后缓慢加入0.25g壳聚糖,浓度为5mg/ml,待粘度增大后把搅拌开到最大,继续搅拌2h,即为涂膜液。不锈钢作为基材,清洗和预处理方法同实施例1中的PET,涂膜方法采用旋涂的方法,先在1000rad/min旋涂10s,然后在2500rad/min下喷涂2min,然后涂层在15mg/ml抗坏血酸溶液中原位还原16h,。断面场发射扫描电镜测试膜层的厚度为2.93±0.34μm。静态接触角测试膜层显示出一定的亲水性,为48.34±1.64°,原子力显微镜观察形貌发现表面具有很低的粗糙度,RMS为2.14±0.35nm。透射电镜结果表明:纳米银颗粒粒度分布于15~27nm,平均20nm。摇瓶培养和稀释涂平板法测试膜层的杀菌性能,结果显示该膜层能在10min杀死100%的大肠杆菌和100%的金黄色葡萄球菌。抗细菌黏附实验发现和未涂膜的的基材相比,该共混膜降低了95%的大肠杆菌黏附和98%的金黄色葡萄球菌的黏附。
实施例6:
在50ml小烧杯中加入50ml醋酸缓冲溶液(pH=4.0),磁力搅拌,缓慢加入1.0g的聚乙烯醇和0.0030g的AgNO3,浓度为20mg/ml和0.6mg/ml,搅拌溶解后缓慢加入1.0g壳聚糖,浓度为20mg/ml,待粘度增大后把搅拌开到最大,继续搅拌2h,即为涂膜液。云母作为基材,清洗和预处理方法同实施例1中的PET,涂膜方法采用浸涂的方法,然后涂层在12mg/ml抗坏血酸溶液中原位还原20h,。断面场发射扫描电镜测试膜层的厚度为5.85±0.56μm。静态接触角测试膜层显示出一定的亲水性,为63.45±2.44°,原子力显微镜观察形貌发现表面具有很低的粗糙度,RMS为3.23±0.44nm。透射电镜结果表明:纳米银颗粒粒度分布于15~30nm,平均22nm。摇瓶培养和稀释涂平板法测试膜层的杀菌性能,结果显示该膜层能在10min杀死100%的大肠杆菌和100%的金黄色葡萄球菌。抗细菌黏附实验发现和未涂膜的的基材相比,该共混膜降低了96%的大肠杆菌黏附和95%的金黄色葡萄球菌的黏附。
实施例7:
在50ml小烧杯中加入50ml醋酸缓冲溶液(pH=4.0),磁力搅拌,缓慢加入0.45g的聚乙烯醇和0.0040g的AgNO3,浓度为9mg/ml和0.8mg/ml,搅拌溶解后缓慢加入0.70g壳聚糖,浓度为12mg/ml,待粘度增大后把搅拌开到最大,继续搅拌2h,即为涂膜液。石英片作为基材,清洗和预处理方法同实施例1中的PET,涂膜方法采用浸涂的方法,然后涂层在15mg/ml抗坏血酸溶液中原位还原12h,。断面场发射扫描电镜测试膜层的厚度为4.54±0.43μm。静态接触角测试膜层显示出一定的亲水性,为52.45±2.54°,原子力显微镜观察形貌发现表面具有很低的粗糙度,RMS为2.33±0.36nm。透射电镜结果表明:纳米银颗粒粒度分布于16~35nm,平均25nm。把该涂层浸泡在PBS中释放35d,摇瓶培养和稀释涂平板法测试膜层的杀菌性能,结果显示该膜层能在30min杀死100%的大肠杆菌和100%的金黄色葡萄球菌。
实施例8:
在50ml小烧杯中加入50ml醋酸缓冲溶液(pH=4.0),磁力搅拌,缓慢加入0.55g的聚乙烯醇和0.0050g的AgNO3,浓度为11mg/ml和1.0mg/ml,搅拌溶解后缓慢加入0.55g壳聚糖,浓度为11mg/ml,待粘度增大后把搅拌开到最大,继续搅拌2h,即为涂膜液。硅片作为基材,清洗和预处理方法同实施例1中的PET,涂膜方法采用喷涂的方法,将涂膜液加入到雾化器中,喷涂在基材上1s,60℃烘箱干燥20min,然后涂层在12mg/ml抗坏血酸溶液中原位还原10h,。断面场发射扫描电镜测试膜层的厚度为3.84±0.32μm。静态接触角测试膜层显示出一定的亲水性,为54.45±2.04°,原子力显微镜观察形貌发现表面具有很低的粗糙度,RMS为2.53±0.23nm。该涂层在PBS中浸泡35d,用场发射扫描电镜观察断面,发现该膜层均匀和稳定存在于硅片表面,表明预处理提高了膜层的粘结性能。透射电镜结果表明:纳米银颗粒粒度分布于22~50nm,平均30nm。摇瓶培养和稀释涂平板法测试膜层的杀菌性能,结果显示该膜层能在30min杀死100%的大肠杆菌和100%的金黄色葡萄球菌。
以上所述仅是本发明的优选实施方式,本发明的保护范围并不仅局限于上述实施例,凡属于本发明思路下的技术方案均属于本发明的保护范围。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理前提下的若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (9)
1.一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法,其特征在于,包括以下步骤:将质量浓度为5~20mg/ml的壳聚糖、质量浓度为1~20mg/ml的聚乙烯醇溶液和0.01~0.1mg/ml的硝酸银溶液混合,将混合溶液涂抹在经表面预处理后的基材表面,经自然干燥处理或真空处理获得了聚合物凝胶涂层的基材,然后清洗、真空干燥,然后将涂抹有聚合物凝胶涂层的基材在抗坏血酸溶液中原位还原后,得到纳米银颗粒粒度为5~50nm的复合抗菌涂层。
2.根据权利要求1所述的一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法,其特征在于,所述的基材的表面预处理步骤如下:将基材依次用丙酮、乙醇和超纯水超声清洗15min,然后用N2吹干,清洗过的基材分别在5mg/ml的PEI溶液中处理30min N2吹干,得到表面PEI处理的基材;在5mg/ml的PAA溶液中处理30min N2吹干,得到表面PAA处理的基材;在混合10mg/ml EDC和20mg/ml NHSS的MES缓冲液中处理6h N2吹干,得到表面EDC/NHS处理的基材。
3.根据权利要求1所述的一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法,其特征在于,所述的涂抹的方式为旋涂、浸涂或喷涂。
4.根据权利要求1所述的一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法,其特征在于,所述的基材为玻璃、石英、云母、不锈钢、聚酯膜、聚乳酸膜中的一种。
5.根据权利要求1所述的一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法,其特征在于,所述的抗坏血酸溶液质量浓度为5-20mg/ml,浸泡处理时间为4-24h。
6.根据权利要求2所述的一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法,其特征在于,所述的10mg/ml EDC和20mg/ml NHSS的MES缓冲液的PH值为5.6。
7.根据权利要求3所述的一种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法,其特征在于,所述的旋涂方式为:调节旋涂仪转速为1000rad/min,用滴管吸取0.1ml涂膜液滴在基材上,旋涂10s,然后在2500rad/min转速下旋涂2min,干燥,重复旋涂3-5次。
8.根据权利要求3所述的种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法,其特征在于,所述的浸涂方式为:将基材浸入涂膜液中5s后,取出,使基材表面的涂膜液覆盖均匀,然后放置于玻璃平板上,干燥后用刀片剥离基材。
9.根据权利要求3所述的种广谱长效抗菌抗黏附壳聚糖纳米银复合凝胶涂层制备方法,其特征在于,所述的喷涂方式为:将喷涂液加入到雾化器中,喷涂在基材上1s,60℃烘箱干燥20min,此操作重复5次。
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CN106620896B (zh) * | 2017-01-12 | 2019-09-20 | 温州医科大学 | 一种壳聚糖包覆的热还原纳米银多层膜长效抗菌涂层的制备方法 |
CN109125814A (zh) * | 2017-06-15 | 2019-01-04 | 上海微创医疗器械(集团)有限公司 | 防粘连膜及其制备方法 |
CN109125814B (zh) * | 2017-06-15 | 2021-11-09 | 上海微创医疗器械(集团)有限公司 | 防粘连膜及其制备方法 |
CN107899077A (zh) * | 2017-12-20 | 2018-04-13 | 四川大学 | 一种稳定性增强的复合抗菌涂层及其制备方法和应用 |
CN107899077B (zh) * | 2017-12-20 | 2019-08-09 | 四川大学 | 一种稳定性增强的复合抗菌涂层及其制备方法和应用 |
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