CN113121743A - 一种基于多重相互作用的自修复抗菌水凝胶的制备方法 - Google Patents
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Abstract
本发明提供了一种基于多重相互作用的自修复抗菌水凝胶的制备方法。首先将1‑乙烯基咪唑与单体A(1,2‑二溴乙烷、1,3‑二溴丙烷、1,4‑二溴丁烷等)进行偶联反应得到交联剂A，然后将聚(乙二醇)甲基丙烯酸酯(PEGMA)、单体B(含乙烯基的咪唑溴盐)、交联剂A和水溶性光引发剂加入到一定浓度的羧化壳聚糖水溶液中，N2保护下紫外光诱导聚合反应，建立共价键交联、多重氢键作用和离子键相互作用，得到自修复抗菌水凝胶。本发明所制备的水凝胶具有优异的自修复性和抗菌性，并且力学性能良好，在生物医药方面具有潜在的应用价值。
Description
技术领域
本发明涉及一种自修复抗菌水凝胶，具体地，涉及一种基于多重相互作用的高强度自修复抗菌水凝胶的制备方法。
背景技术
水凝胶是一种由亲水性聚合物构成的具有三维网络结构的软物质，并且能够吸收大量的水分。水凝胶在充分溶胀之后可以保持聚合物交联网络的完整性，而不会出现聚合物的溶解。水凝胶具有许多优异的性能，如刺激响应性、生物相容性。水凝胶如同生物体软组织一样，具有优异的韧性、弹性、柔软性和保水性等。
水凝胶的制备方法主要包括物理交联和化学交联两种，即通过物理相互作用或者化学键形成的凝胶。高分子水凝胶具有一定的含水量和弹性，与生物组织有相似性，可应用于生物医学领域，如药物控释材料、医用敷料、组织工程支架等。此外，由于水凝胶的高吸水性和保水性，其在农业、化工、食品工程等领域也有一定的应用价值。水凝胶作为抗菌材料的应用受到了广泛的关注，选择合适的单体和交联剂，利用水凝胶优异的性能，制备新型抗菌材料。抗菌水凝胶可以分为三类：(1)含抗菌剂(如环丙沙星、庆大霉素等抗生素)的抗菌水凝胶；(2)含无机金属纳米粒子(如银、金、ZnO纳米粒子)的抗菌水凝胶；(3)本身具有抗菌能力的水凝胶。本身带有抗菌性质的水凝胶是指组成水凝胶的高分子具有抗菌性，不包括掺杂具有抗菌性的有机化合物或无机物质的水凝胶。通过各种共价键(如碳碳键、酰胺键等)或非共价键(如静电作用、氢键等)构筑三维网络的交联聚合物结构。Hsieh等(Carbohydr.Res.2010,345,1774-1780)通过壳聚糖和γ-聚谷氨酸共混制备水凝胶，结果发现水凝胶对体外大肠杆菌、金黄色葡萄球菌及成纤细胞的增殖均有一定的抑制作用，有望作为创面护理材料使用。Ma等(Acta Biomater.2015,26,236-248)以葡萄糖醛为交联剂，通过苯胺接枝的季铵盐壳聚糖制备水凝胶，该凝胶对大肠杆菌(95％灭杀)和金黄色葡萄球菌(90％灭杀)均具有良好的抗菌效果，且水凝胶具有可降解性和电活性，可应用于组织工程领域。
发明内容
本发明的目的是提供一种基于多重相互作用的自修复抗菌水凝胶的制备方法，制备方法简单，水凝胶室温下可自修复，具有抗菌性，并且力学性能优异，在生物医药领域具有潜在的应用价值。
为达到上述目的，本发明所提供的自修复抗菌水凝胶，是以含咪唑盐的交联高分子形成第一网络结构，将天然高分子羧化壳聚糖穿插到第一网络结构中，建立共价键交联、多重氢键作用和离子相互作用，形成高强度、自修复、抗菌的水凝胶。
本发明中提供的基于多重相互作用的自修复抗菌水凝胶的制备方法，包括如下步骤：
(1)将1-乙烯基咪唑与单体A按照一定比例溶解到溶剂中，混合均匀，在N2保护下60～80℃进行偶联反应，得到交联剂A；
(2)将聚(乙二醇)甲基丙烯酸酯(PEGMA)、单体B、交联剂A和水溶性光引发剂加入到一定浓度的羧化壳聚糖水溶液中，充分混合均匀，N2保护下紫外光诱导聚合反应，得到基于多重相互作用的自修复抗菌水凝胶，实验方法简单，生物相容性好，可用于规模化生产；
所述单体A为1,2-二溴乙烷、1,3-二溴丙烷、1,4-二溴丁烷、1,5-二溴戊烷、1,6-二溴己烷、1,7-二溴庚烷、1,8-二溴辛烷、1,9-二溴壬烷、1,10-二溴癸烷等中的任一种；
所述单体B为1-乙烯基-3-乙基咪唑溴盐、1-乙烯基-3-丁基咪唑溴盐、1-乙烯基-3-己基咪唑溴盐或1-乙烯基-3-辛基咪唑溴盐中的任一种；
优化地，所述步骤(1)中，1-乙烯基咪唑与单体A摩尔比2:1；溶剂用量为单体总摩尔数的1～5倍；
优化地，所述步骤(1)中，溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲醇中的任一种；
优化地，所述步骤(2)中，水溶性光引发剂为2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮(Irgacure-2959)；
优化地，所述步骤(2)中，羧化壳聚糖水溶液中，羧化壳聚糖粉末的质量与水的质量比为0.0005～0.1:1。
由于上述技术方案的应用，本发明与现有技术相比具有以下优点：
(1)本发明设计了一种新型基于多重相互作用的高强度、自修复、抗菌水凝胶，羧化壳聚糖的加入提高了凝胶的强度、韧性和生物相容性，水凝胶中含有大量的多重氢键和离子键相互作用，当在外力下损伤后可在室温下进行自修复，咪唑阳离子的存在也赋予了水凝胶良好的抗菌特性，在生物医学(如药物缓控释放、抗菌)领域具有潜在的应用价值。
(2)本发明设计的基于多重相互作用的自修复抗菌水凝胶，具有较好的吸水能力和优良的力学性能，反应条件温和，制备方法简单，利于规模化生产。
附图说明
图1为实施例1所得自修复抗菌水凝胶对金黄色葡萄球菌的抗菌测试的扫描电镜图。
图2为实施例2所得自修复抗菌水凝胶的抗菌性能测试柱状图。
具体实施方式
下述实施案例对本发明进行具体描述，但本发明不限于这些实施案例。
下述实施案例中所用的原料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1
具体制备方法为：(1)称取0.02mol 1-乙烯基咪唑和0.01mol 1,6-二溴己烷加入含有15mL甲醇的烧瓶中，磁力搅拌混合均匀，在N2保护下，60℃油浴中搅拌反应15h，室温下静置冷却。冷却后将反应产物缓慢滴入足量乙醚中，洗涤、过滤，40℃下真空干燥，得到交联剂A。
(2)称取4mmol的聚(乙二醇)甲基丙烯酸酯(PEGMA)、1mmol的1-乙烯基-3-乙基咪唑溴盐(VIM)、2mg光引发剂2-羟基-4’-(2-羟乙氧基)-2-甲基苯丙酮(Irgacure-2959)、0.013g交联剂A和1.5g羧化壳聚糖(1.0wt％)水溶液。磁力搅拌10min，待各组分均匀分散后向体系中鼓入氮气，密封后超声处理至混合均匀，转移至紫外灯箱中，在290～800nm波长的紫外光下照射反应2h，得到基于多重相互作用的自修复抗菌水凝胶。该水凝胶吸水后体积可溶胀到原来的4～5倍，拉伸强度为0.60MPa，拉伸弹性模量为0.30MPa，断裂伸长率为140％。室温下可自修复，具有较好的抗菌性和生物相容性。
实施例2
具体制备方法为：(1)称取0.02mol 1-乙烯基咪唑和0.01mol 1,4-二溴丁烷加入含有15mL N,N-二甲基甲酰胺的烧瓶中，磁力搅拌混合均匀，在N2保护下，60℃油浴中搅拌反应24h，室温下静置冷却。冷却后将反应产物缓慢滴入足量石油醚中，洗涤、过滤，40℃下真空干燥，得到交联剂A。
(2)称取3mmol的聚(乙二醇)甲基丙烯酸酯(PEGMA)、1mmol的1-乙烯基-3-丁基咪唑溴盐、2mg光引发剂2-羟基-4’-(2-羟乙氧基)-2-甲基苯丙酮(Irgacure-2959)、0.02g交联剂A和1.5g羧化壳聚糖(0.5wt％)水溶液。磁力搅拌10min，待各组分均匀分散后向体系中鼓入氮气，密封后超声处理至混合均匀，转移至紫外灯箱中，在290～800nm波长的紫外光下照射反应2h，得到基于多重相互作用的自修复抗菌水凝胶。该水凝胶吸水后体积可溶胀到原来的3～4倍，拉伸强度为0.65MPa，拉伸弹性模量为0.32MPa，断裂伸长率为120％。室温下可自修复，具有较好的抗菌性和生物相容性。
实施例3
具体制备方法为：(1)称取0.02mol 1-乙烯基咪唑和0.01mol 1,10-二溴癸烷加入含有15mL N,N-二甲基甲酰胺的烧瓶中，磁力搅拌混合均匀，在N2保护下，60℃油浴中搅拌反应24h，室温下静置冷却。冷却后将反应产物缓慢滴入足量石油醚中，洗涤、过滤，40℃下真空干燥，得到交联剂A。
(2)称取5mmol的聚(乙二醇)甲基丙烯酸酯(PEGMA)、1mmol的1-乙烯基-3-己基咪唑溴盐、2mg光引发剂2-羟基-4’-(2-羟乙氧基)-2-甲基苯丙酮(Irgacure-2959)、0.01g交联剂A和1.5g羧化壳聚糖(0.8wt％)水溶液。磁力搅拌10min，待各组分均匀分散后向体系中鼓入氮气，密封后超声处理至混合均匀，转移至紫外灯箱中，在290～800nm波长的紫外光下照射反应2h，得到基于多重相互作用的自修复抗菌水凝胶。该水凝胶吸水后体积可溶胀到原来的5～6倍，拉伸强度为0.50MPa，拉伸弹性模量为0.18MPa，断裂伸长率为200％。室温下可自修复，具有较好的抗菌性能和生物相容性。
Claims (8)
1.一种基于多重相互作用的自修复抗菌水凝胶，包含由含咪唑盐的交联高分子形成第一网络结构，将天然高分子羧化壳聚糖穿插到第一网络结构中，建立共价键交联、多重氢键作用和离子键相互作用，形成高强度、自修复、抗菌的水凝胶，其特征在于，制备方法包括如下步骤：
(1)交联剂A：将1-乙烯基咪唑与单体A按照一定比例溶解到溶剂中，混合均匀，在N2保护下60～80℃进行偶联反应，得到交联剂A；
(2)自修复抗菌水凝胶：将聚(乙二醇)甲基丙烯酸酯(PEGMA)、单体B、交联剂A和水溶性光引发剂加入到一定浓度的羧化壳聚糖水溶液中，充分混合均匀，N2保护下紫外光诱导聚合反应，得到基于多重相互作用的自修复抗菌水凝胶。
2.根据权利要求1所述的基于多重相互作用的自修复抗菌水凝胶，其特征在于，所述的含咪唑盐的交联高分子为聚(乙二醇)甲基丙烯酸酯(PEGMA)、单体B、交联剂A通过聚合反应形成的第一网络结构，所述的天然高分子羧化壳聚糖穿插到第一网络结构中形成半互穿网络结构，从而在水凝胶中建立多重相互作用。
3.如权利要求1所述一种基于多重相互作用的自修复抗菌水凝胶的制备方法，其特征在于：所述步骤(1)中单体A为1,2-二溴乙烷、1,3-二溴丙烷、1,4-二溴丁烷、1,5-二溴戊烷、1,6-二溴己烷、1,7-二溴庚烷、1,8-二溴辛烷、1,9-二溴壬烷或1,10-二溴癸烷等中的任一种。
4.如权利要求1所述一种基于多重相互作用的自修复抗菌水凝胶的制备方法，其特征在于：所述步骤(1)中溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、甲醇中的任一种。
5.如权利要求1所述一种基于多重相互作用的自修复抗菌水凝胶的制备方法，其特征在于：所述步骤(2)中单体B为1-乙烯基-3-乙基咪唑溴盐、1-乙烯基-3-丁基咪唑溴盐、1-乙烯基-3-己基咪唑溴盐或1-乙烯基-3-辛基咪唑溴盐中的任一种。
6.如权利要求1所述一种基于多重相互作用的自修复抗菌水凝胶的制备方法，其特征在于：所述步骤(2)中水溶性光引发剂为2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮(Irgacure-2959)。
7.如权利要求1所述一种基于多重相互作用的自修复抗菌水凝胶的制备方法，其特征在于：所述步骤(1)中，1-乙烯基咪唑与单体A摩尔比2:1；溶剂用量为单体总摩尔数的1～5倍。
8.如权利要求1所述一种基于多重相互作用的自修复抗菌水凝胶的制备方法，其特征在于：所述步骤(2)中，羧化壳聚糖水溶液中，羧化壳聚糖粉末的质量与水的质量比为0.0005～0.1:1。
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