CN114031807B - 一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵及其制备方法 - Google Patents

一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵及其制备方法 Download PDF

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CN114031807B
CN114031807B CN202111376174.4A CN202111376174A CN114031807B CN 114031807 B CN114031807 B CN 114031807B CN 202111376174 A CN202111376174 A CN 202111376174A CN 114031807 B CN114031807 B CN 114031807B
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叶文鹏
欧阳小琨
王南
赵丽娟
凌俊红
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Zhejiang Ocean University ZJOU
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Abstract

本发明提供一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵及其制备方法，制备方法包括以下步骤：S1.将氯化钠加入羧基化纤维素纳米纤维水溶液中，搅拌5‑15分钟后加入壳聚糖季铵盐，继续搅拌4‑6小时后静置至气泡消除为止得到初始水凝胶；S2.将单宁酸逐滴加入步骤S1得到的初始水凝胶中，搅拌0.5‑1.5小时后逐滴加入氯化铜，继续搅拌5‑15分钟后得到水凝胶；S3.将步骤S2得到的水凝胶装入模具中，将模具冷冻7‑9小时后脱模，冷冻干燥得到用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵。本发明制得的纤维素壳聚糖单宁酸铜复合凝胶海绵具有较好的机械强度、稳定性、抗菌性能和止血性能。

Description

一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝 胶海绵及其制备方法
技术领域
本发明涉及一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵及其制备方法与应用。
背景技术
FDA批准了一系列CS（壳聚糖）基创面敷料产品。CS的止血和抗菌活性机制主要得益于其分子链中含有-NH2基团，CS具有的正电荷结构使得表面带负电的红细胞产生聚集，从而加快血栓的形成速率；此外，CS与细菌带负电的细胞膜结合后可改变细菌的通透性，从而加速细菌凋亡。近年来，壳聚糖或其衍生物均在不同程度上被利用并设计为止血海绵、止血水凝胶等止血产品。然而，结合纳米纤维素、壳聚糖和单宁酸铜离子络合物这几种组分制备用于日常可随身携带的便携式止血产品尚未有报道。
发明内容
本发明要解决的技术问题是提供一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵的制备方法，其制得的纤维素壳聚糖单宁酸铜复合凝胶海绵具有较好的机械强度、稳定性、抗菌性能和止血性能。
为解决上述技术问题，本发明的技术方案是：
一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵的制备方法，包括以下步骤：
S1.将氯化钠加入羧基化纤维素纳米纤维水溶液中，搅拌5-15分钟后加入壳聚糖季铵盐，继续搅拌4-6小时后静置至气泡消除为止得到初始水凝胶；
S2.将单宁酸逐滴加入步骤S1得到的初始水凝胶中，搅拌0.5-1.5小时后逐滴加入氯化铜，继续搅拌5-15分钟后得到水凝胶；
S3.将步骤S2得到的水凝胶装入模具中，将模具冷冻7-9小时后脱模，冷冻干燥后得到用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵。
进一步地，本发明所述步骤S1中，羧基化纤维素纳米纤维水溶液的质量浓度为1%，羧基化纤维素纳米纤维水溶液、氯化钠、壳聚糖季铵盐的质量比为100:3:3。
进一步地，本发明所述步骤S1中，搅拌的速度为800r/min。
进一步地，本发明所述步骤S2中，水凝胶中单宁酸的浓度为0.3-1.5mg/mL，氯化铜的浓度为0.15-0.75 mg/mL。
进一步地，本发明所述步骤S2中，搅拌的速度为800r/min。
进一步地，本发明所述步骤S3中，模具的规格为1.5cm×1.5cm×1cm。
进一步地，本发明所述步骤S3中，冷冻的温度为-20℃。
进一步地，本发明所述步骤S3中，冷冻干燥的温度为-45℃，时间为24小时。
本发明还提供了所述制备方法制得的用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵。
与现有技术相比，本发明具有以下有益效果：
(1)本发明引入羧基化纤维素纳米纤维与壳聚糖季铵盐进行自组装，通过正负电荷交联作用增强了凝胶的机械强度和稳定性。
(2)本发明在羧基化纤维素纳米纤维/壳聚糖季铵盐水凝胶中引入单宁酸/Cu2+金属-有机网络结构，不仅能进一步提升复合凝胶海绵的力学稳定性，还能实现单宁酸在复合凝胶海绵中的有效固定，从而达到抑制创面氧化应激的效果，此外，Cu2+还能进一步提高复合凝胶海绵的抗菌性能。
(3)本发明在羧基化纤维素纳米纤维/壳聚糖季铵盐水凝胶中引入单宁酸/Cu2+形成了具有均匀孔隙结构的海绵状凝胶，单宁酸/Cu2+的加入使得凝胶海绵的网络结构更牢固，经研究发现，未加入单宁酸/Cu2+的凝胶海绵在吸水后容易分散，而本发明加入了单宁酸/Cu2+的凝胶海绵在经历过3次吸水、压缩，再吸水后还能恢复形状。
具体实施方式
下面将结合具体实施例来详细说明本发明，在此本发明的示意性实施例以及说明用来解释本发明，但并不作为对本发明的限定。
实施例1
按照以下步骤制备用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵：
S1.将600mg氯化钠加入20g质量浓度为1%的羧基化纤维素纳米纤维水溶液中，800r/min速度下搅拌5分钟后加入600mg壳聚糖季铵盐，继续800r/min速度下搅拌4小时后静置至气泡消除为止得到初始水凝胶；
S2.将单宁酸逐滴加入步骤S1得到的初始水凝胶中，800r/min速度下搅拌1.5小时后逐滴加入氯化铜，继续800r/min速度下搅拌15分钟后得到水凝胶，水凝胶中单宁酸的浓度为0.3mg/mL，氯化铜的浓度为0.15mg/mL；
S3.将步骤S2得到的水凝胶装入规格为1.5cm×1.5cm×1cm的模具中，将模具-20℃下冷冻7小时后脱模，-45℃下冷冻干燥24小时后得到用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵，记为CHTC0.3。
实施例2
按照以下步骤制备用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵：
S1.将600mg氯化钠加入20g质量浓度为1%的羧基化纤维素纳米纤维水溶液中，800r/min速度下搅拌15分钟后加入600mg壳聚糖季铵盐，继续800r/min速度下搅拌6小时后静置至气泡消除为止得到初始水凝胶；
S2.将单宁酸逐滴加入步骤S1得到的初始水凝胶中，800r/min速度下搅拌0.5小时后逐滴加入氯化铜，继续800r/min速度下搅拌5分钟后得到水凝胶，水凝胶中单宁酸的浓度为0.5mg/mL，氯化铜的浓度为0.25mg/mL；
S3.将步骤S2得到的水凝胶装入规格为1.5cm×1.5cm×1cm的模具中，将模具-20℃下冷冻9小时后脱模，-45℃下冷冻干燥24小时后得到用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵，记为CHTC0.5。
实施例3
按照以下步骤制备用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵：
S1.将600mg氯化钠加入20g质量浓度为1%的羧基化纤维素纳米纤维水溶液中，800r/min速度下搅拌12分钟后加入600mg壳聚糖季铵盐，继续800r/min速度下搅拌4.5小时后静置至气泡消除为止得到初始水凝胶；
S2.将单宁酸逐滴加入步骤S1得到的初始水凝胶中，800r/min速度下搅拌1.2小时后逐滴加入氯化铜，继续800r/min速度下搅拌12分钟后得到水凝胶，水凝胶中单宁酸的浓度为1mg/mL，氯化铜的浓度为0.5mg/mL；
S3.将步骤S2得到的水凝胶装入规格为1.5cm×1.5cm×1cm的模具中，将模具-20℃下冷冻7.5小时后脱模，-45℃下冷冻干燥24小时后得到用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵，记为CHTC1.0。
实施例4
按照以下步骤制备用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵：
S1.将600mg氯化钠加入20g质量浓度为1%的羧基化纤维素纳米纤维水溶液中，800r/min速度下搅拌10分钟后加入600mg壳聚糖季铵盐，继续800r/min速度下搅拌5小时后静置至气泡消除为止得到初始水凝胶；
S2.将单宁酸逐滴加入步骤S1得到的初始水凝胶中，800r/min速度下搅拌1小时后逐滴加入氯化铜，继续800r/min速度下搅拌10分钟后得到水凝胶，水凝胶中单宁酸的浓度为1.5mg/mL，氯化铜的浓度为0.75mg/mL；
S3.将步骤S2得到的水凝胶装入规格为1.5cm×1.5cm×1cm的模具中，将模具-20℃下冷冻8小时后脱模，-45℃下冷冻干燥24小时后得到用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵，记为CHTC1.5。
对比例：
与实施例1的不同之处在于不包括步骤S2，制得的凝胶海绵记为CHTC0。
试验例1：抗菌性能测试
分别将本发明实施例1 CHTC0.3、实施例2 CHTC0.5、实施例3 CHTC1.0、实施例4CHTC1.5、对比例 CHTC0凝胶海绵及市售明胶止血海绵剪嵌入细菌固体培养基中与金黄色葡萄球菌和铜绿假单胞菌共同孵育，然后测定出抑菌圈直径，抑菌圈直径越大表明抗菌性能越强，测试结果如表1所示：
Figure DEST_PATH_IMAGE002
表1
由表1可以看出，本发明实施例1-4均具有较强的抗菌性能，且单宁酸铜的浓度越高， 抗菌性能越强，而市售明胶止血海绵基本没有抗菌活性。
试验例2：止血性能测试
用小鼠断尾止血及肝损伤止血两个止血模型分别测试实施例1 CHTC0.3、对比例CHTC0凝胶海绵及阳性对照组市售明胶止血海绵的止血性能。止血时间越短，出血量越少，说明止血效果越好，测试结果如表2和表3所示：
Figure DEST_PATH_IMAGE004
表2 断尾止血
Figure DEST_PATH_IMAGE006
表3 肝损伤止血
由表2和表3可以看出，本发明实施例1具有较好的止血性能，其原因是复合凝胶海绵吸收血液后会有一定黏附性，能黏附在伤口上，在伤口和复合凝胶海绵接触面堆积大量的红细胞和血小板，从而促进凝血。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (9)

1.一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵的制备方法，其特征在于：包括以下步骤：
S1.将氯化钠加入羧基化纤维素纳米纤维水溶液中，搅拌5-15分钟后加入壳聚糖季铵盐，继续搅拌4-6小时后静置至气泡消除为止得到初始水凝胶；
S2.将单宁酸逐滴加入步骤S1得到的初始水凝胶中，搅拌0.5-1.5小时后逐滴加入氯化铜，继续搅拌5-15分钟后得到水凝胶；
S3.将步骤S2得到的水凝胶装入模具中，将模具冷冻7-9小时后脱模，冷冻干燥后得到用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵。
2.根据权利要求1所述的一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵的制备方法，其特征在于：所述步骤S1中，羧基化纤维素纳米纤维水溶液的质量浓度为1%，羧基化纤维素纳米纤维水溶液、氯化钠、壳聚糖季铵盐的质量比为100:3:3。
3.根据权利要求1所述的一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵的制备方法，其特征在于：所述步骤S1中，搅拌的速度为800r/min。
4.根据权利要求1所述的一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵的制备方法，其特征在于：所述步骤S2中，水凝胶中单宁酸的浓度为0.3-1.5mg/mL，氯化铜的浓度为0.15-0.75 mg/mL。
5.根据权利要求1所述的一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵的制备方法，其特征在于：所述步骤S2中，搅拌的速度为800r/min。
6.根据权利要求1所述的一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵的制备方法，其特征在于：所述步骤S3中，模具的规格为1.5cm×1.5cm×1cm。
7.根据权利要求1所述的一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵的制备方法，其特征在于：所述步骤S3中，冷冻的温度为-20℃。
8.根据权利要求1所述的一种用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵的制备方法，其特征在于：所述步骤S3中，冷冻干燥的温度为-45℃，时间为24小时。
9.根据权利要求1-8任意一项所述的制备方法制得的用于组织创伤愈合修复的纤维素壳聚糖单宁酸铜复合凝胶海绵。
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