CN106178116A - 一种光敏季铵化壳聚糖抗菌涂层的制备方法 - Google Patents
一种光敏季铵化壳聚糖抗菌涂层的制备方法 Download PDFInfo
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Abstract
本发明提供了一种光敏季铵化壳聚糖抗菌涂层的制备方法。该制备方法包括:首先在季铵化壳聚糖主链上引入光敏基团,赋予季铵化壳聚糖一定的双亲性和光敏性,通过调节pH诱导体系自组装成胶束;再以自组装胶束溶液为电沉积液,结合电泳沉积技术将自组装胶束固定在医用金属表面,经UV光照交联,形成抗菌涂层。所得抗菌涂层具有良好的生物相容性和生物可降解性。该法操作简便,成本低,适用范围广,为医用金属表面改性提供了一种新策略。
Description
技术领域
本发明涉及一种光敏季铵化壳聚糖抗菌涂层的制备方法,属于天然高分子和抗菌涂层相结合领域。
技术背景
近来大量研究证实,骨科植入物感染与植入材料表面形成细菌生物膜有关。由于全身应用抗生素的效果不甚理想,加之不良反应较大,所以应选择在植入物局部采用与细菌生物膜黏附释放机制针锋相对的抗感染手段。研究表明,在骨科植入物表面形成抗菌涂层对细菌粘附及生物膜形成有良好的抑制作用,为临床预防骨科植入物手术感染提供新的研究方向。
而壳聚糖是一种天然聚多糖,具有许多优良性质,如抗菌性、可降解性、生物相容性、吸附性和安全性等,从而被广泛应用于纺织工业、日用环保及生物医学等领域,但壳聚糖不能溶于水及有机溶剂,只能溶于酸性溶液,大大限制了其应用范围;因此,通常需对壳聚糖进行化学改性,提高其溶解性能至关重要。而季铵化壳聚糖是壳聚糖的一种改性衍生物,在酸、中、碱性条件下都易溶,且具有极强的抑菌能力及良好的保湿性能,在医药卫生、废水处理等方面都有着广泛的应用。此外,季铵化壳聚糖上含有大量的-OH,可作为化学修饰位点,如对季铵化壳聚糖进行光敏改性则可制备光敏季铵化壳聚糖,该功能特性利于增强季铵化壳聚糖在应用过程中的结构稳定性。因而,本文发明了一种光敏季铵化壳聚糖抗菌涂层的制备方法。该制备方法将在具有抗菌性的季铵化壳聚糖主链上接枝光敏性小分子,通过亲疏水作用自组装成胶束,通过电沉积方法在医用金属表面制备抗菌涂层,因光敏小分子具有光敏性,通过UV光照使得制备的涂层更加致密。操作步骤简便,实用性及适用性强,属于独创性发明。
发明内容
本发明的目的是提供了一种光敏季铵化壳聚糖抗菌涂层的制备方法。该方法操作简便,条件温和、适用范围广,即通过电泳沉积技术,利用亲疏水作用在水相中自组装成胶束,再以自组装胶束溶液为电解液,通过电泳沉积技术在医用金属表面电诱导胶束成膜,得到基于季铵化壳聚糖胶束的抗菌涂层。
本发明的另一目的还在于可以通过控制自组装胶束溶液的浓度及电沉积工艺条件,对抗菌涂层的性能进行调控。
本发明的技术方案如下:
一种光敏季铵化壳聚糖抗菌涂层的制备方法,其制备步骤如下:
(1)自组装胶束溶液的制备:称取适量季铵化壳聚糖溶解于甲烷磺酸,完全溶解后加入光敏小分子和催化剂,剧烈搅拌适当时间,调节上述溶液的pH,促使光敏季铵化壳聚糖发生自组装,透析3天,冷冻干燥,得到胶束样品;
(2)抗菌涂层的制备:将医用金属依次在丙酮和无水乙醇中超声清洗10~15min,室温晾干备用,然后以医用金属为阴极,铂片电极为阳极,将步骤(1)制备的胶束分散在水溶液中作为电解液,通过电泳沉积技术,在医用金属表面制备涂层,再通过UV光交联,形成致密的抗菌涂层。
步骤(1)中选择的季铵化壳聚糖分子量在30~50万,甲烷磺酸的体积为10~100mL;光敏小分子与季铵化壳聚糖的氨基葡萄糖单位摩尔比为1:1~1:10;催化剂选自N-羟基琥珀酰亚胺、1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐、1-羟基苯并三氮唑、N,N-二环己基碳二亚胺、4-二甲氨基吡啶中的一种或几种,反应时间为12~72h;溶液的pH值范围为5~12,所制备的胶束尺寸在1~1000nm之间,且胶束表面带正电。
步骤(2)中医用金属选自钛及钛合金、316L不锈钢、钴基合金;胶束电解液的浓度为0.1~50mg/mL。所制备的抗菌涂层的厚度为5nm~10μm,UV光照时间为1s~60min,所制备的抗菌涂层具有优异的生物可降解性、细胞相容性及抗菌性能。
本发明的有益效果:本发明创新性的在季铵化壳聚糖上接枝光敏性小分子制备光敏季铵化壳聚糖,在水相中自组装制备胶束,通过电泳沉积技术在医用金属表面电诱导胶束成膜,制备兼具生物可降解性、细胞相容性及抗菌性能的涂层材料,操作步骤简便,材料来源丰富,实验成本低,实用性及适用性强。
附图说明
图1是实施例1中自组装胶束溶液的数码照片及干态下胶束形貌图;
图2是实施例2中抗菌涂层的形貌图片;
图3是实施例3中抗菌涂层的统计图。
具体实施方式
以下结合实施例对本发明作进一步说明,但本发明并不局限于此。
实施例1
一种光敏季铵化壳聚糖抗菌涂层的制备方法,具体制备步骤如下:
(1)自组装胶束溶液的制备:将2g分子量为30万的季铵化壳聚糖溶于20mL甲烷磺酸,完全溶解后,加入肉桂酰氯,剧烈搅拌3h,调节上述溶液的pH=7,促使光敏季铵化壳聚糖发生自组装,透析3天,冷冻干燥,得到胶束样品,样品的数码照片及干态下形貌图如附图1所示。
(2)抗菌涂层的制备:首先将钛合金,依次用丙酮和无水乙醇对其进行超声清洗10min,再将上述预处理后的医用钛合金作为阴极浸入步骤(1)所制备的自组装胶束溶液中,采用阴极电泳沉积技术,使荷正电的胶束粒子向医用金属表面泳动并沉积成胶束膜,再通过UV光照10min,形成致密的抗菌涂层。
实施例2
一种光敏季铵化壳聚糖抗菌涂层的制备方法,具体操作步骤如下:
(1)自组装胶束溶液的制备:将1.7g分子量为40万的季铵化壳聚糖溶于30mL甲烷磺酸,完全溶解后,加入肉桂酸,1mmol 1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸,盐剧烈搅拌12h,调节上述溶液的pH=7,促使光敏季铵化壳聚糖发生自组装,透析3天,冷冻干燥,得到胶束样品。
(2)抗菌涂层的制备:首先将316L不锈钢,然后依次用丙酮和无水乙醇对其进行超声清洗10min,将上述预处理后的316L不锈钢作为阴极浸入步骤(1)所制备的自组装胶束溶液中,采用阴极电泳沉积技术,使荷正电的胶束粒子向医用金属表面泳动并沉积成胶束膜,再通过UV光照30min,形成致密的抗菌涂层,涂层的形貌如附图2所示。
实施例3
一种光敏季铵化壳聚糖抗菌涂层的制备方法,具体操作步骤如下:
(1)自组装胶束溶液的制备:将1.5g分子量为50万的季铵化壳聚糖溶于35mL甲烷磺酸,完全溶解后,加入咖啡酸,N,N-二环己基碳二亚胺、4-二甲氨基吡啶,搅拌24h,调节上述溶液的pH=7,促使光敏季铵化壳聚糖发生自组装,透析3天,冷冻干燥,得到胶束样品。
(2)抗菌涂层的制备:首先将钴基合金,然后依次用丙酮和无水乙醇对其进行超声清洗10min,将上述预处理后的医用金属作为阴极浸入步骤(1)所制备的自组装胶束溶液中,采用阴极电泳沉积技术,使荷正电的胶束粒子向医用金属表面泳动并沉积成胶束膜,再通过UV光照60min,形成致密的抗菌涂层。涂层良好的抗菌性能如附图3示,对金黄色葡萄球菌的抗菌率达84%,大肠杆菌的抗菌率达64%。
上述实施例用来解释说明本发明,而不是对本发明进行限制,在本发明的精神和权利要求的保护范围内,对本发明作出的任何修改和改变,都落入本明的保护范围。
Claims (6)
1.一种光敏季铵化壳聚糖抗菌涂层的制备方法,其特征操作步骤为:
(1)自组装胶束溶液的制备:称取适量季铵化壳聚糖溶解于甲烷磺酸,完全溶解后加入光敏小分子和催化剂,剧烈搅拌适当时间,调节上述溶液的pH,促使光敏季铵化壳聚糖发生自组装,透析3天,冷冻干燥,得到胶束样品;
(2)抗菌涂层的制备:将医用金属依次在丙酮和无水乙醇中超声清洗10~15min,室温晾干备用,然后以医用金属为阴极,铂片电极为阳极,将步骤(1)制备的胶束分散在水溶液中作为电解液,通过电泳沉积技术,在医用金属表面制备涂层,再通过UV光交联,形成致密的抗菌涂层。
2.根据权利要求1所述的一种光敏季铵化壳聚糖抗菌涂层的制备方法,其特征在于,步骤(1)中选择的季铵化壳聚糖分子量在30~50万,甲烷磺酸的体积为10~100mL。
3.根据权利要求1所述的一种光敏季铵化壳聚糖抗菌涂层的制备方法,其特征在于,步骤(1)中光敏小分子与季铵化壳聚糖的氨基葡萄糖单位摩尔比为1:1~1:10;催化剂选自N-羟基琥珀酰亚胺、1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐、1-羟基苯并三氮唑、N,N-二环己基碳二亚胺、4-二甲氨基吡啶中的一种或几种,反应时间为12~72h。
4.根据权利要求1所述的一种光敏季铵化壳聚糖抗菌涂层的制备方法,其特征在于,步骤(1)中溶液的pH值范围为5~12,所制备的胶束尺寸在1~1000nm之间,且胶束表面带正电。
5.根据权利要求1所述的一种光敏季铵化壳聚糖抗菌涂层的制备方法,其特征在于,步骤(2)中医用金属选自钛及钛合金、316L不锈钢、钴基合金;胶束电解液的浓度为0.1~50mg/mL。
6.根据权利要求1所述的一种光敏季铵化壳聚糖抗菌涂层的制备方法,其特征在于,步骤(2)中所制备的抗菌涂层的厚度为5nm~10μm,UV光照时间为1s~60min,所制备的抗菌涂层具有优异的生物可降解性、细胞相容性及抗菌性能。
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陈琴等: "壳聚糖和季铵化壳聚糖的应用研究进展", 《山东化工》 * |
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