CN111973803B - 一种具有优异力学性能和抗菌性的壳聚糖基抗菌伤口敷料 - Google Patents
一种具有优异力学性能和抗菌性的壳聚糖基抗菌伤口敷料 Download PDFInfo
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Abstract
本发明涉及一种具有优异力学性能和抗菌性的壳聚糖基抗菌伤口敷料，其制备为先将壳聚糖溶于碱性溶液中，实现部分溶解部分自组装成球的非均相溶液，后加入交联剂端醛基四臂聚乙二醇和添加剂端氨基四臂聚乙二醇、端聚乙二醇基八臂笼状倍半硅氧烷，交联成型后采用硫酸铵水溶液浸泡处理得到最终产品。该膜具有良好的生物相容性、抗菌性、皮肤粘附性、吸收溶胀性、保水性，还拥有良好的力学性能，可单独作为抗菌伤口敷料使用。
Description
技术领域
本发明涉及一种壳聚糖基水凝胶抗菌伤口敷料，尤其涉及一种具有优异力学性能、生物相容性及抗菌性的壳聚糖基抗菌伤口敷料。
背景技术
人体开放性创伤表面容易发生感染，如何有效降低创伤感染概率，促进伤口恢复和组织的再功能化是医学界亟待解决的热点和难点，传统敷料如纱布和绷带等均由干织物构成，吸收渗出液程度有限，并且在移除时容易损坏新生成的组织，造成二次伤害。而水凝胶由于自身的溶胀、保水以及易移除特性，是伤口敷料的良好选择形式。壳聚糖自身具有良好的抗菌性和细胞相容性，常被用在医药生物等领域。壳聚糖是一种天然碱性多糖，其化学名称为β-(1，4)-2-氨基 -2-脱氧-D-葡萄糖。壳聚糖带强阳性电荷的氨基糖类分子，对带负电荷的分子具有很强的吸引力。因此通过静电作用，可以与带有负电荷的细菌细胞壁产生静电吸附，从而破坏细菌细胞壁。壳聚糖具有非常优异的生物特性和材料可加工用，近年来由壳聚糖材料制备的多孔支架、微球、水凝胶等广泛用作药物载体、细胞支架、创伤敷料和手术缝合线等。壳聚糖在生物医学上其主要具备以下优点，如结构与性质相似于细胞外基质；生物相容性好，不与人体组织发生排斥反应；有良好的生物活性，具有抑制细菌，降低胆固醇等功效，还可以促进上皮细胞生长；壳聚糖可在溶菌酶的存在下发生降解，降解过程平缓安全，降解产物为葡糖胺，可直接进入代谢途径。
然而，单纯利用壳聚糖制备的水凝胶大多存在机械强度不足、功能化单一等问题，无法在不改性的方式下单独使用。因此，多种方式被用于发挥壳聚糖的优势。一种是在其他生物质凝胶中加入壳聚糖以利用其抗菌性，然而这种方法的抗菌性仍然有限；而以壳聚糖为凝胶基体进行性能强化的方式则更具抗菌优势。通过壳聚糖本身的改性，如烃羧基、 羟烷基、酰基改性均可在提高壳聚糖凝胶物理、化学及生物特性的某些方面提供帮助。和其他大分子复合也是一种增强材料性能更加简易的方式，所选择的复合材料如同为生物质的海藻酸钠，纤维素、明胶等，也可为其他具有低生物毒性的聚合物，如聚乙烯醇、聚乙烯-丁烯等，不同的结构构建方法如简单共聚、互穿网络等方式均被使用，而不同药物如抗菌消炎药、促生长药物等也可在制备过程中包埋入凝胶中。而目前大部分的商业产品敷伤料的内层均有采用以上两种方式构建。然而以上方式仍需要较复杂的处理工艺和合成技术，且需要引入其他物质，一定会对膜本身的生物相容性产生影响，进而影响其应用效果。所以，开发以单独壳聚糖为原料的，可单独使用且具有优异性能的伤口敷料仍具有巨大的研究和应用价值。
发明内容
本发明致力于克服目前壳聚糖基伤口敷料力学性能、抗菌性的缺陷，提供一种具有优异力学性能、生物相容性及抗菌性的壳聚糖基抗菌伤口敷料。
本发明的目的是通过以下技术方案实现的：
一种具有优异力学性能和抗菌性的壳聚糖基抗菌伤口敷料，其制备过程如下：
（1）壳聚糖非均相溶液的制备：将氢氧化锂、氢氧化钾、尿素、去离子水以一定质量比配置成均匀碱液，称取一定质量的壳聚糖粉末在室温下加入碱液中并搅拌2-3h至完全溶胀后置于-30°C下冷冻5-7h，后于20-30°C下解冻并搅拌，静置4-8小时后形成非均相溶液I；其中壳聚糖的质量分数为3%-6%；碱液中氢氧化锂、氢氧化钾、尿素、去离子水的质量比介于4-6：6-8：7-9：76.5-83.5之间；
（2）复合溶液的制备：在非均相溶液I中加入端醛基四臂聚乙二醇、端氨基四臂聚乙二醇、端聚乙二醇基八臂笼状倍半硅氧烷，于20°C下以200-300rpm速度搅拌2-4分钟至均匀得到非均相溶液II；其中，端醛基四臂聚乙二醇、端氨基四臂聚乙二醇、端聚乙二醇基八臂笼状倍半硅氧烷在非均相溶液II中的重量分数分别介于2-5%、3-6%和1.2-2.4%之间；
（3）反应及后处理：将非均相溶液II倒入模具中，在60°C下反应30-60分钟，后室温下放置24小时成膜，取出膜浸置于硫酸铵水溶液中8-12小时，后将膜取出并放入体积为凝胶体积50倍以上的纯净水中浸泡2天，期间不断换水，将凝胶取出后放置于40-60°C环境下干燥，当凝胶溶胀度介于3-5之间时取出，得到最终生物质基水凝胶抗菌伤口敷料。
进一步，所述壳聚糖的分子量介于140000-200000之间，脱乙酰度大于95%。
进一步，所述非均相溶液I中，部分壳聚糖自组装成球，部分壳聚糖溶解；其中，溶解的壳聚糖占总壳聚糖总质量的30%-60%之间，自组装形成壳聚糖微球的粒径介于20nm-200μm之间。
进一步，其特征还在于：所述壳聚糖的分子量介于140000-200000之间，脱乙酰度大于95%；通过对分子量和脱乙酰度的控制，可在碱性溶液中形成部分溶解，部分自组装成球的悬浮液，当壳聚糖的质量分数为3%-6%时，壳聚糖微球的粒径介于20nm-200μm之间；成球的比例通过分子量和脱乙酰度调节。
进一步，所述端醛基四臂聚乙二醇的分子量介于2000-4000之间，其分子式如下：
其中的端醛基可与壳聚糖上的氨基发生席夫碱反应，从而产生交联。
进一步，所述端氨基四臂聚乙二醇的分子量介于3000-6000之间，其分子式如下：
进一步，所述端氨基四臂聚乙二醇的端氨基可与端醛基四臂聚乙二醇的端醛基发生席夫碱反应，这种反应与壳聚糖的氨基和端醛基的反应形成竞争，并将部分端氨基四臂聚乙二醇引入交联网络中，从而调节凝胶的力学性能；同时，由于加入端氨基四臂聚乙二醇增加了体系中的氨基，将有利于凝胶的抗菌性。
进一步，所述端聚乙二醇基八臂笼状倍半硅氧烷（POSS-PEG）为八臂笼状倍半硅氧烷（POSS）的改性产物，此POSS单体因为有大量聚乙二醇（PEG）的存在，使得单体具有良好的水溶性，其结构式如下：
进一步，所述端聚乙二醇基八臂笼状倍半硅氧烷端基的聚乙二醇基的聚合度介于8-14之间。
进一步，端聚乙二醇基八臂笼状倍半硅氧烷本身具有良好的生物相容性，由于端聚乙二醇的存在可提高纳米粒子的亲水性，有利于粒子在凝胶中的分散，刚性纳米粒子的加入有利于凝胶压缩性能的提高。
进一步，所述硫酸铵水溶液的质量分数介于6-12%之间；壳聚糖凝胶通过盐离子溶液浸泡，发生霍夫迈斯特效应，大分子链发生一定程度重排，从而进一步提高凝胶的力学性能。
进一步，本发明的有益效果在于：（1）采用了碱性溶解壳聚糖保存了壳聚糖的氨基，有利于材料的抗菌性的提高；（2）采用了非均相溶液合成，凝胶中有大量微球交联网络结构，这种交联形式极大的提高了凝胶的力学性能；（3）溶液中因自组装形成微球而导致壳聚糖浓度较低，进而有效降低了交联密度，有利于凝胶的溶胀保水性；（4）采用了多个多臂结构单体在凝胶内形成了拓扑结构，有助于凝胶力学性能的提高；（5）端氨基四臂聚乙二醇加入量的改变可实现对于凝胶力学性能、溶胀性的调节，其氨基的增加还有利于提高凝胶的抗菌性；（6）用于大量微球和纳米粒子的结构有利于分散能量，使得凝胶具有良好的皮肤粘附性。
附图说明
图1为实施例1壳聚糖基抗菌伤口敷料的截面扫描电镜图。
具体实施方式
以下将详细描述本发明的示例性实施方法。但这些实施方法仅为示范性目的，而本发明不限于此。
实施例1
一种具有优异力学性能和抗菌性的壳聚糖基抗菌伤口敷料，其制备过程如下：
（1）壳聚糖非均相溶液的制备：将氢氧化锂、氢氧化钾、尿素、去离子水以一定质量比配置成均匀碱液，称取一定质量的壳聚糖粉末在室温下加入碱液中并搅拌2.5h至完全溶胀后置于-30°C下冷冻6h，后于25°C下解冻并搅拌，静置6小时后形成非均相溶液I；其中壳聚糖的质量分数为5%；碱液中氢氧化锂、氢氧化钾、尿素、去离子水的质量比为5：7：8：81；
（2）复合溶液的制备：在非均相溶液I中加入端醛基四臂聚乙二醇、端氨基四臂聚乙二醇、端聚乙二醇基八臂笼状倍半硅氧烷，于20°C下以250rpm速度搅拌3分钟至均匀得到非均相溶液II；其中，端醛基四臂聚乙二醇、端氨基四臂聚乙二醇、端聚乙二醇基八臂笼状倍半硅氧烷在非均相溶液II中的重量分数分别为3.2%、4.5%和2.0%；
（3）反应及后处理：将非均相溶液II倒入模具中，在60°C下反应40分钟，后室温下放置24小时成膜，取出膜浸置于硫酸铵水溶液中10小时，后将膜取出并放入体积为凝胶体积80倍纯净水中浸泡2天，期间不断换水，将凝胶取出后放置于50°C环境下干燥，当凝胶溶胀度至4时取出，得到最终生物质基水凝胶抗菌伤口敷料。
所述壳聚糖的分子量介于140000-180000之间，脱乙酰度为98%。
所述非均相溶液I中，部分壳聚糖自组装成球，部分壳聚糖溶解；其中，溶解的壳聚糖占总壳聚糖总质量的45%，自组装形成壳聚糖微球的粒径介于30nm-20μm之间。
所述硫酸铵水溶液的质量分数为8%。
所述端醛基四臂聚乙二醇的分子量介于2500-3500之间。
所述端氨基四臂聚乙二醇的分子量介于3500-5500之间。
所述端聚乙二醇基八臂笼状倍半硅氧烷的端聚乙二醇基的聚合度为10。
如图1所示，所述最终壳聚糖基抗菌伤口敷料中的微球通过交联形成了多微球交联形式，这种微球交联后的结构有效的提高了凝胶膜的力学性能和溶胀保水能力，同时，暴露的氨基可有利于抗菌性的提高。
实施例2
一种具有优异力学性能和抗菌性的壳聚糖基抗菌伤口敷料，其制备过程如下：
（1）壳聚糖非均相溶液的制备：将氢氧化锂、氢氧化钾、尿素、去离子水以一定质量比配置成均匀碱液，称取一定质量的壳聚糖粉末在室温下加入碱液中并搅拌2.4h至完全溶胀后置于-30°C下冷冻6.5h，后于24°C下解冻并搅拌，静置7小时后形成非均相溶液I；其中壳聚糖的质量分数为4.5%；碱液中氢氧化锂、氢氧化钾、尿素、去离子水的质量比为4.5：7.5：8.5：82；
（2）复合溶液的制备：在非均相溶液I中加入端醛基四臂聚乙二醇、端氨基四臂聚乙二醇、端聚乙二醇基八臂笼状倍半硅氧烷，于20°C下以260rpm速度搅拌3.5分钟至均匀得到非均相溶液II；其中，端醛基四臂聚乙二醇、端氨基四臂聚乙二醇、端聚乙二醇基八臂笼状倍半硅氧烷在非均相溶液II中的重量分数分别为3.6%、5.1%和1.5%；
（3）反应及后处理：将非均相溶液II倒入模具中，在60°C下反应40分钟，后室温下放置24小时成膜，取出膜浸置于硫酸铵水溶液中10小时，后将膜取出并放入体积为凝胶体积100倍的纯净水中浸泡2天，期间不断换水，将凝胶取出后放置于55°C环境下干燥，当凝胶溶胀度为4.5间时取出，得到最终生物质基水凝胶抗菌伤口敷料。
所述壳聚糖的分子量介于140000-160000之间，脱乙酰度为96%。
所述非均相溶液I中，部分壳聚糖自组装成球，部分壳聚糖溶解；其中，溶解的壳聚糖占总壳聚糖总质量的55%，自组装形成壳聚糖微球的粒径介于100nm-100μm之间。
所述硫酸铵水溶液的质量分数为8%。
所述端醛基四臂聚乙二醇的分子量介于2200-3800之间。
所述端氨基四臂聚乙二醇的分子量介于3200-4000之间。
所述端聚乙二醇基八臂笼状倍半硅氧烷的端聚乙二醇基的聚合度为9。
所述实施例2制备的壳聚糖基抗菌伤口敷料由于所用原料壳聚糖的分子量较小，导致溶解较大，微球比例较小，从而力学性能和溶胀性较实施例1略有下降。
Claims (5)
1.一种具有优异力学性能和抗菌性的壳聚糖基抗菌伤口敷料，其制备过程如下：
壳聚糖非均相溶液的制备：将氢氧化锂、氢氧化钾、尿素、去离子水以一定质量比配置成均匀碱液，称取一定质量的壳聚糖粉末在室温下加入碱液中并搅拌2-3h至完全溶胀后置于-30℃下冷冻5-7h，后于20-30℃下解冻并搅拌，静置4-8小时后形成非均相溶液I；其中壳聚糖的质量分数为3%-6%；碱液中氢氧化锂、氢氧化钾、尿素、去离子水的质量比介于4-6：6-8：7-9：76.5-83.5之间；
（2）复合溶液的制备：在非均相溶液I中加入端醛基四臂聚乙二醇、端氨基四臂聚乙二醇、端聚乙二醇基八臂笼状倍半硅氧烷，于20℃下以200-300rpm速度搅拌2-4分钟至均匀得到非均相溶液II；其中，端醛基四臂聚乙二醇、端氨基四臂聚乙二醇、端聚乙二醇基八臂笼状倍半硅氧烷在非均相溶液II中的重量分数分别介于2-5%、3-6%和1.2-2.4%之间；
（3）反应及后处理：将非均相溶液II倒入模具中，在60℃下反应30-60分钟，后室温下放置24小时成膜，取出膜浸置于硫酸铵水溶液中8-12小时，后将膜取出并放入体积为凝胶体积50倍以上的纯净水中浸泡2天，期间不断换水，将凝胶取出后放置于40-60°C环境下干燥，当凝胶溶胀度介于3-5之间时取出，得到最终壳聚糖基抗菌伤口敷料；
所述壳聚糖的分子量介于140000-200000之间，脱乙酰度大于95%；
所述非均相溶液I中，部分壳聚糖自组装成球，部分壳聚糖溶解；其中，溶解的壳聚糖占总壳聚糖总质量的30%-60%之间，自组装形成壳聚糖微球的粒径介于20nm-200μm之间。
2.如权利要求1所述的一种具有优异力学性能和抗菌性的壳聚糖基抗菌伤口敷料，其特征在于，所述硫酸铵水溶液的质量分数介于6-12%之间。
3.如权利要求1所述的一种具有优异力学性能和抗菌性的壳聚糖基抗菌伤口敷料，其特征在于，所述端醛基四臂聚乙二醇的分子量介于2000-4000之间。
4.如权利要求1所述的一种具有优异力学性能和抗菌性的壳聚糖基抗菌伤口敷料，其特征在于，所述端氨基四臂聚乙二醇的分子量介于3000-6000之间。
5.如权利要求1所述的一种具有优异力学性能和抗菌性的壳聚糖基抗菌伤口敷料，其特征在于，所述端聚乙二醇基八臂笼状倍半硅氧烷的端聚乙二醇基的聚合度介于8-14之间。
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