CN117281954B - 一种基于埃洛石的钛合金抗菌涂层的制备方法及应用 - Google Patents
一种基于埃洛石的钛合金抗菌涂层的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种基于埃洛石的钛合金抗菌涂层的制备方法及应用，埃洛石(HNTs)是一种天然矿物纳米材料，容易形成致密均匀涂层起到保护金属的效果，首先使用碱液和模拟体液对钛合金进行处理，在其表面引入羟基，提高HNTs与基体的结合力，再利用HNTs与壳寡糖(COS)之间的静电吸引作用，以及HNTs、COS与Al3+之间强烈的配位键作用，制备了HNTs‑COS抗菌涂层，该涂层在钛合金上具有牢固的结合性能和超强的耐磨性，能长时间在模拟体液中保持涂层稳定并保留其抗菌性能，本发明采用COS作为抑菌剂，该复合抗菌涂层对大肠杆菌和金黄色葡萄球菌都有较强的抑制作用，Al3+界面交联的HNTs‑COS抗菌涂层有良好的生物相容性和高抗菌性能，在骨科植入物和组织工程支架表面改性方面有重要应用。
Description
技术领域
本发明涉及一种钛合金抗菌涂层的制备方法，特别是涉及一种基于埃洛石的钛合金抗菌涂层的制备方法及应用，属于钛合金抗菌涂层的制备方法技术领域。
背景技术
由于骨科种植体会与人体软组织、骨骼和皮肤产生直接的接触，因此为了避免发生感染而导致植入失败，种植体应具有一定的抗菌性能。葡萄球菌感染是导致植入失败的重要原因，粘致病菌引发感染的六成左右。在临床治疗过程中，人们常用抗生素来预防和治疗感染，并在段时间内得到有效治疗。然而在使用抗生素进行治疗时，常常由于不规范和过度的使用，导致了具有抗药性菌种的出现，这些细菌能形成具有对抗抗生素的保护性生物膜，其不可渗透性影响了宿主免疫反应，从而引起伤口感染并恶化，这给骨科种植体的治疗应用造成了巨大的困难。
壳寡糖，也被称为低聚壳聚糖，聚合度在2～20之间，可以通过特殊的生物酶技术将壳聚糖降解来制备得到。壳聚糖是一种来源于甲壳类动物的天然多糖材料，大量存在于如螃蟹、虾和昆虫的甲壳以及藻类生物的细胞壁中。壳寡糖是淡黄色的固体，比起壳聚糖，它具有更优越的特点，如分子量低、水溶性好和更优秀的通透性、吸附性、保湿型、生物活性和抗菌性能等。壳寡糖是一种带正电荷阳离子的天然碱性氨基低聚糖，能与表面带负电荷的埃洛石纳米管牢固结合，制备成具有优秀抗菌性能的改性涂层。
利用壳寡糖与HNTs充分结合，以钛合金作为基体制备抗菌涂层，并在制备涂层前驱液时加入铝离子作为交联剂，以提高涂层的稳定性。作为一种具有良好生物相容性的天然纳米材料，具有成本低廉、低细胞毒性、较高的力学性能、吸附能力、分散稳定性和生物相容性等众多优点。
此外，埃洛石表面的Si-O基团能与钛合金表面产生的-OH官能团相互作用形成牢固的结合。为了解决埃洛石在体液中不能保持稳定的问题，在制备抗菌涂层前驱液时加入铝离子，利用铝离子与HNTs之间的交联作用能使抗菌涂层在长时间内保持稳定及其抗菌作用。
现有技术中如公开号为CN110804356A公开的一种装饰板表面用抗菌涂料，先将埃洛石利用硝酸溶液喷雾后进行焙烧，并进行循环加压、真空、超声的协同作用，可以最大限度的扩大埃洛石的内径和容积，便于后期纳米银的附着；然后埃洛石在硝酸银溶液的浸泡过程中，通入交流电，可使银离子在交流电的作用下较快且大量地进入埃洛石纳米管内径或附着其表面，增大了纳米银的附着量，从而较大程度的提高了所得涂料的抗菌效果，利用丙烯酸甲酯对纳米银改性埃洛石纳米管进行进一步改性，可以增强其与涂料基底的相容性和界面作用力，大大提高了涂层的耐磨性能，现有技术中虽然可以实现提高耐磨性的功能但是通透性、吸附性、保湿型、生物活性和抗菌性能比较低，为此设计一种基于埃洛石的钛合金抗菌涂层的制备方法及应用来解决上述问题。
发明内容
本发明的主要目的是为了提供一种基于埃洛石的钛合金抗菌涂层的制备方法及应用。
本发明的目的可以通过采用如下技术方案达到：
一种基于埃洛石的钛合金抗菌涂层的制备方法，包括如下步骤：
步骤一：将0.5-5wt％COS和1-20wt％埃洛石混合加入去离子水中，再加0.5-4％乙酸溶液室温搅拌1-4h；
步骤二：然后加入0-10wt％的AlCl3或者硫酸铝，60℃下加热搅拌4h，待室温冷却制成前驱液；
步骤三：使用移液枪滴加30-300μL前驱液在钛合金圆片上，最后在室温下干燥形成涂层。
优选的，还包括如下步骤：
S1：对钛合金表面进行碱处理，碱液浓度是9mol/L，时间10h，温度80℃，用无水乙醇清洗后，室温干燥24h；；
S2：采用仿生溶液法将钛合金浸入模拟体液中14d；
S3：对浸入模拟体液14d的钛合金进行干燥处理，取出自然干燥后得到表面有羟基磷灰石的钛合金圆片。
优选的，所述钛合金圆片采用TC4钛合金，尺寸为φ10*1mm3。
优选的，在S1中所述碱处理使用95％的NaOH溶液浸泡2h。
优选的，该钛合金抗菌涂层植入体材料表面改性的应用。
本发明的有益技术效果：
本发明提供的一种基于埃洛石的钛合金抗菌涂层的制备方法及应用，本发明利用HNTs与COS之间的静电吸引作用和HNTs与Al3+之间的离子键合，实现牢固涂层的制备，进而对钛合金进行表面改性。制备的具有良好结合强度和耐磨性的HNTs-COS-Al3+抗菌涂层能在SBF中保持长期稳定，从而实现了抑菌剂有效控制释放，HNTs-COS-Al3+抗菌涂层对大肠杆菌和金黄色葡萄球菌生长都有高抑制作用，而对这些细菌的预防治疗对骨科种植体的植入的可靠性有重要作用，通过改变HNTs、COS和Al3+的浓度可以调控涂层的厚度和抑菌性能以及涂层厚度和强度，以满足在骨科和牙科植入物临床治疗时的具体需求。
附图说明
图1为COS浓度对涂层抑菌性能(大肠杆菌)的影响(HNTs浓度为10wt％，Al3+浓度为5wt％)；
图2为COS浓度对涂层抑菌性能(金黄色葡萄球菌)的影响(HNTs浓度为10wt％，Al3+浓度为5wt％)；
图3为抑菌圈直径随COS浓度变化的柱状图统计(HNTs浓度为10wt％，Al3+浓度为5wt％)；
图4为(A)Al3+对抗菌涂层在模拟体液中稳定性的影响，(C)涂层重量在模拟体液中随时间的变化曲线，(B)加入Al3+的抗菌涂层置于模拟体液中7，14和21d后抗菌性能测试和(D)抑菌圈直径统计(HNTs浓度为10wt％，COS浓度为2wt％，Al3+浓度为5wt％)。
图5为钛合金表面埃洛石涂层的制备流程和体系界面相互作用示意图。
具体实施方式
为使本领域技术人员更加清楚和明确本发明的技术方案，下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
首先对钛合金表面进行碱处理，碱液浓度是5mol/L，时间15h，温度70℃，用无水乙醇清洗后，室温干燥24h；
采用仿生溶液法，将钛合金浸入模拟体液(SBF)中14天，取出自然干燥后得到表面有羟基磷灰石的钛合金；
将2wt％COS和15wt％HNTs混合加入去离子水中，再加0.5％乙酸溶液，室温搅拌1h；
然后加入5％的硫酸铝，60℃下加热搅拌4h，待室温冷却制成前驱液；
使用移液枪滴加200μL前驱液在钛合金圆片上，最后在室温下干燥形成涂层。
用大肠杆菌(E.coli)和金黄色葡萄球菌(S.aureus)通过抑菌圈实验和对表面改性得到抗菌涂层的钛合金进行抗菌性能测试。
抑菌圈实验中，将菌液(菌体浓度稀释至约1*106CFU/ml)与琼脂培养基(高压灭菌后降温至约45℃)混合均匀，向各组培养皿中加入20mL左右的混合溶液，待其冷却固化后，将表面改性处理后的钛合金圆片置于琼脂培养基表面，盖上盖子放置在细菌培养箱中，12h后拿出来观察并测量抑菌圈直径。
对于E.coli，当COS浓度为2％时，所制备的抗菌涂层在培养皿中形成的抑菌圈直径平均值分别为27.1(图1-3)；
实施例2
首先对钛合金表面进行碱处理，碱液浓度是9mol/L，时间20h，温度80℃，用无水乙醇清洗后，室温干燥24h；
采用仿生溶液法，将钛合金浸入模拟体液(SBF)中14天，取出自然干燥后得到表面有羟基磷灰石的钛合金；
将1wt％COS和8wt％HNTs混合加入去离子水中，再加1％乙酸溶液，室温搅拌1h；
然后加入8wt％的AlCl3，60℃下加热搅拌4h，待室温冷却制成前驱液；
使用移液枪滴加100μL前驱液在钛合金圆片上，最后在30℃下干燥形成涂层。
抗菌涂层浸泡在SBF中进行稳定性测试：
未加入Al3+进行交联的HNTs-COS涂层不能在SBF中保持稳定，置于SBF中7天后便出现大面积脱落，14天后已基本脱落(图4A)。HNTs-COS涂层在SBF中7、14和21天后的重量百分比分别为50.1、5.0和0.5％(图4B)；
将HNTs-COS-Al3+涂层分别置于SBF中7、14和21天后进行抑菌圈实验(均使用大肠杆菌)测试其抑菌性能的变化。如图4C所示，涂层置于SBF中21天后仍保持较好的抑菌性能。
7、14和21天三个实验组的抑菌圈平均直径分别为26.9、26.5和26.1mm，与0天的27.1mm只有微小的差距。
这说明HNTs-COS-Al3+抗菌涂层能在正常生理状态下保持长期稳定，在体内使用时可以产生刺激反应，快速释放抑菌剂，从而实现长期植入治疗的目的。
实施例3
为制备基于埃洛石和壳寡糖的高性能的抗菌涂层，首先对钛合金表面进行碱处理；碱液浓度是3mol/L，时间20h，温度60℃，用无水乙醇清洗后，室温干燥24h；
采用仿生溶液法，将钛合金浸入模拟体液(SBF)中14天，取出自然干燥后得到表面有羟基磷灰石的钛合金；
将4wt％COS和10wt％HNTs混合加入去离子水中，再加4％乙酸溶液，室温搅拌1h；
然后加入2％的硫酸铝，60℃下加热搅拌4h，待室温冷却制成前驱液；
使用移液枪滴加200μL前驱液在钛合金圆片上，最后在室温下干燥形成涂层。
实施例4
首先对钛合金表面进行碱处理，碱液浓度是8mol/L，时间15h，温度75℃，用无水乙醇清洗后，室温干燥24h；；
采用仿生溶液法，将钛合金浸入模拟体液(SBF)中14天，取出自然干燥后得到表面有羟基磷灰石的钛合金；
将5wt％COS和12wt％HNTs混合加入去离子水中，再加5％乙酸溶液，室温搅拌1h；
然后加入4％的AlCl3，60℃下加热搅拌4h，待室温冷却制成前驱液；
使用移液枪滴加200μL前驱液在钛合金圆片上，最后在室温下干燥形成涂层。
埃洛石(HNTs)是一种天然矿物纳米材料，容易形成致密均匀涂层起到保护金属的效果，首先使用碱液和模拟体液对钛合金进行处理，在其表面引入羟基，提高HNTs与基体的结合力，再利用HNTs与壳寡糖(COS)之间的静电吸引作用，以及HNTs、COS与Al3+之间强烈的配位键作用(图5)，制备了HNTs-COS抗菌涂层，该涂层在钛合金上具有牢固的结合性能和超强的耐磨性，能长时间在模拟体液中保持涂层稳定并保留其抗菌性能。
本发明采用COS作为抑菌剂，该复合抗菌涂层对大肠杆菌和金黄色葡萄球菌都有较强的抑制作用，Al3+界面交联的HNTs-COS抗菌涂层有良好的生物相容性和高抗菌性能，在骨科植入物和组织工程支架表面改性方面有重要应用。
在本技术方案中铝离子的含量高，交联程度大，跟氯化铝是一样的。
其次在本技术方案中采用的抑菌实验是常规的操作，这一块删掉试验方法也没问题，具体的操作步骤不需要写详细。
以上，仅为本发明进一步的实施例，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明所公开的范围内，根据本发明的技术方案及其构思加以等同替换或改变，都属于本发明的保护范围。
Claims (2)
1.一种基于埃洛石的钛合金抗菌涂层的制备方法，其特征在于：包括如下步骤：
步骤一：按照浓度0.5-5wt%壳寡糖和1-20wt%埃洛石混合加入去离子水中，同时按比例加0.5-4%乙酸溶液25-40℃机械搅拌1-4h；
步骤二：加入8wt%的AlCl3，50-60℃下加热搅拌2-4h，待室温冷却制成前驱液；
步骤三：使用移液枪均匀滴加30-300μL前驱液在钛合金圆片上，最后在室温下干燥形成抗菌涂层；
在步骤一之前还包括如下步骤：
S1：对钛合金表面进行NaOH碱处理，碱液浓度是1-10mol/L，时间4-20h，温度60-80℃，用无水乙醇清洗后，室温干燥24h；
S2：采用仿生溶液法将钛合金浸入SBF模拟体液中14d；
S3：对浸入模拟体液14d的钛合金进行室温干燥处理，取出干燥后得到表面矿化沉积有羟基磷灰石的钛合金圆片；
所述钛合金圆片采用TC4钛合金，直径为φ10-30mm，厚度为0.5-3mm。
2.根据权利要求1所述的一种基于埃洛石的钛合金抗菌涂层的制备方法得到的钛合金抗菌涂层应用，其特征在于：该钛合金抗菌涂层在骨科和牙科植入体材料表面改性中的应用。
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