CN110292665A - 一种镁合金表面耐腐蚀抗氧化抗炎症的复合涂层及其制备方法 - Google Patents
一种镁合金表面耐腐蚀抗氧化抗炎症的复合涂层及其制备方法 Download PDFInfo
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Abstract
本发明公布了一种可降低全降解镁合金血管支架降解速率并提高其抗氧化和抗炎症促进内皮化的表面涂层及其制备方法。首先将镁合金置于煮沸的氢氧化钠溶液中进行预处理，再将样品置于氢氟酸溶液中进行反应制备氟化镁涂层。最后将样品置于单宁酸溶液中进行反应制备单宁酸膜层。氟化镁单宁酸复合膜层具有较好的耐腐蚀性，抗氧化，抗炎症，并且加速血管支架的内皮化进程，能够满足镁合金心血管支架表面涂层的需要。
Description
技术领域
本发明涉及镁合金心血管支架领域，具体为一种可降低全降解镁合金血管支架的降解速率并提高其生物相容性的表面涂层及其制备方法。
背景技术
冠状动脉支架自发展以来，经历了金属裸支架、药物洗脱支架两个阶段后，全降解血管支架成为新一代研究热点。镁合金以其优良的生物相容性、力学性能和可降解性成为全降解血管支架材料的代表，能够有效避免永久性金属支架带来的炎症和晚期官腔丢失等问题。
镁合金作为血管支架材料，虽然具备优异的力学性能和生物相容性，但其普遍存在降解速率较快的缺点。支架植入的血管部位为炎症病变部位，复杂的炎症病变环境对支架的性能提出了更高的要求。在支架植入的过程中，为使血管支架能够很好的贴合血管壁，支架会进行过扩张，这就会引起内膜撕裂导致炎症的产生，并产生大量的活性氧自由基，加快镁合金支架的腐蚀，不利于血管内皮化，极容易产生官腔再狭窄。增加表面功能化涂层是控制镁合金的降解速率及提高生物学活性最便捷、有效的方式。
为提高镁合金的抗腐蚀性能的同时保持本体材料的优异性能，表面改性成为一种有效的手段。镁合金的涂层大致分为两类，转化涂层和沉积涂层。转化涂层是通过与金属基底材料发生特定的化学或电化学反应从而原位生成一定的产物所形成的涂层。对镁合金进行氟化处理可以有效提高抗腐蚀性能，显著降低镁合金的腐蚀降解速率。
多酚，普遍存在于茶叶、咖啡、水果中，人们在日常饮食中摄取大量的多酚。多酚化合物具有突出的抗氧化和抗炎症性能，可高效快速的清除活性氧自由基，抑制活性氧自由基对细胞DNA的损伤。多酚化合物能调控炎症细胞表型，降低炎症反应，加快伤口愈合。同时，多酚化合物还能够螯合金属离子，降低金属材料的腐蚀速率
在镁合金材料表面制备多功能的多酚涂层，能够有效的发挥多酚螯合金属离子的作用，形成化学膜层阻挡体液中腐蚀性离子的进一步侵蚀，从而提高涂层对基体的保护性能，以达到降低基体腐蚀速度。多酚的抗氧化和抗炎症特性也能血管支架植入的炎症部位有效的清除活性氧自由基和降低炎症反应，提高支架的生活相容性和生物活性。有科学研究表明一些多酚化合物可促进血管内皮细胞迁移，增强其生物学功能，加快支架的内皮化。
发明内容
本发明的目的是提供一种可降低全降解镁合金血管支架降解速率并提高其抗氧化和抗炎症功能的表面涂层及其制备方法，以满足医用镁合金作为心血管支架材料的需要。
本发明解决其技术问题所采用的技术方案是：一种镁合金表面耐腐蚀抗氧化抗炎症的复合涂层及其制备方法，包括以下步骤：
1)将镁合金材料基体抛光清洗并干燥；
2)将镁合金材料放入煮沸的氢氧化钠溶液中进行化学反应；
3)将完成碱化处理的样品取出清洗干燥后放入氢氟酸溶液中，在摇床中进行化学反应，制备氟化镁膜层。
4)将完成制备氟化镁膜层的样品取出清洗干燥后放入单宁酸溶液中。制备单宁酸膜层。
步骤1)所述可生物降解血管支架用镁合金为Mg-RE系列合金、WE系列合金、AZ系列合金、AM系列合金、ZK系列合金、ZM系列合金、Mg-Li系列合金、Mg-Ca系列合金中的任意一种。
步骤2)氢氧化钠的浓度优选为1-5M，反应时间为2-4h。
步骤3)氢氟酸的浓度优选为20-40％(m/m)，反应时间为12-36h。
步骤3)单宁酸的浓度优选为1～5mg/ml，缓冲液的pH为8.5-10，反应时间为2-4h。
在氟化镁膜层的制备中，氢氧化钠和氢氟酸的浓度和反应时间等工艺参数影响氟化镁膜层的厚度和涂层的致密性，上述步骤中所提供的工艺参数范围可以保证生成一定厚度致密的氟化镁涂层，显著提高镁合金的耐腐蚀性。在单宁酸膜层的制备中，单宁酸的浓度，缓冲液的pH，反应的时间影响单宁酸膜层的厚度和反应的效率，上述步骤中所提供的工艺参数范围可以保证生成一定均匀厚度的单宁酸膜层。
本发明通过优化后的工艺参数在镁合金材料表面制备了氟化镁和单宁酸双层膜层。制备过程操作方便，高效环保，工艺稳定。通过本技术方案，致密的氟化镁涂层，显著提高镁合金的耐腐蚀性能，大大降低其在体内外环境中的腐蚀速率。单宁酸表面带有大量的酚羟基基团，具有较好的抗炎、抗氧化等功能。本发明中制备的涂层原料均具有较好的生物相容性，与基体一样可在人体内完全降解，不会对人体产生副作用。双层膜层，具有降低镁合金腐蚀速率，高效快速清除活性氧自由基，抗炎症，促进内皮细胞迁移，有利于血管支架在炎症环境中快速内皮化。该功能化的涂层有利于推动镁合金心血管支架在临床领域的应用。
附图说明
图1为本发明制备氟化镁单宁双层膜层的材料表面扫描电镜图。其中a为未做处理的MgZnYNd合金，b为氢氧化钠和氢氟酸处理，c为氢氧化钠和氢氟酸处理后，再进行单宁酸处理。
图2为实施例1制备的膜层的电化学测试，其中a为塔菲尔极化曲线，b为电化学阻抗谱，c为MgZnYNd合金电化学阻抗谱的放大图。
图3为实施例1制备的膜层的细胞相容性评价，其中a为未做处理的MgZnYNd合金，b为氢氧化钠和氢氟酸处理，c为氢氧化钠和氢氟酸处理后，再进行单宁酸处理。
具体实施方式
下面结合附图，通过具体实施例对本发明作进一步说明，但不以任何方式限制本发明的范围。
实施例1
本发明涉及的一种镁合金表面耐腐蚀抗氧化抗炎症的复合涂层及其制备方法的实施例1中，所用可生物降解血管支架用的镁合金为Mg-Zn-Y-Nd，所述方法包括如下步骤：
步骤1，将Mg-Zn-Y-Nd合金棒材经线切割加工为直径壁厚为d＝1.8mm的薄片，砂纸打磨至2000#，经电化学抛光、丙酮、去离子水清洗后，在无水乙醇中超声清洗30min；
步骤2，氢氧化钠预处理：将步骤1处理后的样品置于5M煮沸的氢氧化钠溶液中，反应时间为3h。反应结束后，取出样品用大量去离子水冲洗，在空气中自然干燥。
步骤3，氟化镁膜层的制备：将步骤2处理后的样品置于15ml尖底离心管中，加入10ml 40％(m/m)氢氟酸溶液，室温条件下摇床中反应24h。反应结束后，取出样品用大量去离子水冲洗，在空气中自然干燥。
步骤4，单宁酸膜层的制备：将2mg单宁酸溶于10ml pH＝10的Tris缓冲液中,将步骤3处理后的样品和溶液置于15ml尖底离心管中，37°条件下摇床中反应3h。反应结束后，取出样品用大量去离子水冲洗，采用功率为100W，超声清洗5min，再进一步用去离子水清洗，在空气中自然干燥。
实施例2
步骤1，将Mg-Zn-Y-Nd合金棒材经线切割加工为直径壁厚为d＝1.8mm的薄片，砂纸打磨至2000#，经电化学抛光、丙酮、去离子水清洗后，在无水乙醇中超声清洗30min；
步骤2，氢氧化钠预处理：将步骤1处理后的样品置于3M煮沸的氢氧化钠溶液中，反应时间为4h。反应结束后，取出样品用大量去离子水冲洗，在空气中自然干燥。
步骤3，氟化镁膜层的制备：将步骤2处理后的样品置于15ml尖底离心管中，加入10ml 30％(m/m)氢氟酸溶液，室温条件下摇床中反应36h。反应结束后，取出样品用大量去离子水冲洗，在空气中自然干燥。
步骤4，单宁酸膜层的制备：将4mg单宁酸溶于10ml pH＝10的Tris缓冲液中,将步骤3处理后的样品和溶液置于15ml尖底离心管中，37°条件下摇床中反应2h。反应结束后，取出样品用大量去离子水冲洗，采用功率为100W，超声清洗5min，再进一步用去离子水清洗，在空气中自然干燥。
下面将详细介绍实施例1的氟化镁单宁酸双层涂层改性的镁合金的相关测试结果。
(1)表面形貌：用扫描电镜观察实施例1中的样品表面形貌。如图1所示，氟化处理后的表面呈现出网格状的形貌，增加单宁酸涂层之后，表面粗糙度明显降低，表面形貌更加均匀致密。
(2)电化学测试：将实施例1中制备得到的样品采用三电极法进行电化学测试。如图2中a所示，Tafel极化曲线拟合所得腐蚀电流结果表明，与未处理组对比，实验组的腐蚀电流密度大幅度下降。同时如图2中b,c所示，实验组较未处理组，EIS曲线显示容抗弧半径显著增大。说明氟化镁和单宁酸双膜层结构能够有效的延缓镁合金的腐蚀速率。
(3)细胞相容性测试：将实施例1中制备得到的样品用人脐带内皮细胞进行细胞相容性测试。如图3所示，单宁酸膜层能够显著促进内皮细胞增殖，细胞呈完全铺展状态，能看到明显的肌纤维。具有单宁酸膜层的样品表面细胞数量远远高于未处理组和只具有氟化镁涂层组。说明氟化镁单宁酸膜层结构具有能够促进内皮细胞愈合，防止血管再狭窄的潜能。
应该理解的是，上述实施例并非是对本发明的限制，本领域的技术人员应该明白在不脱离本发明的范畴下，可进行各种变化和等同替换。此外，为适应本发明技术的特定场合或材料，可对本发明进行诸多修改而不脱离其保护范围。因此，本发明并不限于在此公开的特定实施例，而包括所有落入到权利要求保护范围之内的实施行为。
Claims (10)
1.一种镁合金表面耐腐蚀抗氧化抗炎症的复合涂层及其制备方法，包括以下步骤：
1)将镁合金材料基体抛光清洗并干燥；
2)将镁合金材料在煮沸的氢氧化钠溶液中进行化学反应；
3)将上述2)中氢氧化钠预处理的样品放入氢氟酸溶液中，制备氟化镁涂层；
4)将上述3)中制备的具有氟化镁膜层的镁合金材料放入单宁酸溶液中，制备单宁酸膜层。
2.如权利要求1所述的方法，其特征在于，步骤1)所述镁合金为Mg-RE系列合金、WE系列合金、AZ系列合金、AM系列合金、ZK系列合金、ZM系列合金、Mg-Li系列合金、Mg-Ca系列合金中的任意一种。
3.如权利要求1所述的制备方法，其特征在于，步骤2)中所述的氢氧化钠溶液浓度为1-5 M，反应时间为2-4h。
4.如权利要求1所述的方法，其特征在于，步骤3)氢氟酸的浓度为5-40％(m/m),反应时间为6-48h。
5.如权利要求1所述的方法，其特征在于，步骤3)反应条件为25-37℃。
6.如权利要求1所述的方法，其特征在于，步骤4)制备的单宁酸的浓度为0.1-10mg/ml。
7.如权利要求1所述的方法，其特征在于，步骤4)溶解单宁酸的缓冲液pH为8-10。
8.如权利要求1所述的方法，其特征在于，步骤4)反应时间为1-4h。
9.如权利要求1所述的方法，其特征在于，步骤4)制备的单宁酸膜层的厚度为0.1-2μm。
10.如权利要求1所述的方法，其特征在于，步骤4)反应条件为25-37。
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| CN115414539A (zh) * | 2022-09-02 | 2022-12-02 | 北京化工大学 | 一种多酚-聚合物涂层的制备方法及其在增强材料促凝血性能中的应用 |
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| CN111407930B (zh) * | 2020-03-19 | 2021-01-08 | 中国科学院长春应用化学研究所 | 一种聚合物仿生涂层及其制备方法 |
| CN115414539A (zh) * | 2022-09-02 | 2022-12-02 | 北京化工大学 | 一种多酚-聚合物涂层的制备方法及其在增强材料促凝血性能中的应用 |
| CN115414539B (zh) * | 2022-09-02 | 2023-12-15 | 北京化工大学 | 一种多酚-聚合物涂层的制备方法及其在增强材料促凝血性能中的应用 |
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