CN115591012B - 一种在3d打印钛植入体表面制备生物活性膜层的方法 - Google Patents
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Abstract
一种在3D打印钛植入体表面制备生物活性膜层的方法,涉及医用金属植入体的表面改性技术。通过电化学阳极氧化、电化学沉积和浸渍自组装法相结合,在3D打印医用钛表面制备贻贝黏附蛋白/纳米磷酸八钙/茶多酚复合生物涂层。阳极氧化可在3D打印医用钛植入体表面构筑具有优异耐蚀性的氧化膜,贻贝黏附蛋白可加强钙磷涂层与钛基底结合力,并优化磷酸八钙膜层形貌结构,茶多酚可促进成骨细胞分化。该复合涂层可显著提升3D打印的金属钛植入体生物活性和耐腐蚀能力,可用于各种3D打印制造的金属钛植入体进行表面改性,本发明为3D打印金属植入体表面改性、优化提供了一种高效实用方法。
Description
技术领域
本发明涉及医用钛植入材料领域,尤其涉及一种在3D打印钛植入体表面制备生物活性膜层的方法。
背景技术
随着人口老龄化加剧,骨质疏松、骨头坏死等骨科疾病的危害日益凸显,人们对骨科替代物的需求大幅增加。医用钛及其合金因其良好的生物相容性、耐腐蚀性及力学性能,已在骨科损伤修复中被广泛应用,成为最主要的承力植入材料。3D打印制造的医用钛及其合金种植体可实现精准个性化治疗,愈来愈受到生医材料制造和临床应用领域的高度关注。然而, 3D打印制造的医用钛植入体因激光局部急速熔融凝固过程造成种植体缺陷增多、耐蚀性下降、生物活性生物活性不足等缺点,不利于骨组织与植入体之间产生骨结合,影响骨修复效果。因此,亟需对植入体表面进行改性处理,进一步优化其生物活性等综合性能。
发明内容
本发明的目的在于解决现有技术中的上述问题,提供一种在3D打印钛植入体表面制备生物活性膜层的方法,以期改善种植体的耐腐蚀性,大幅度提升其表面生物相容性和生物活性等综合性能。
为达到上述目的,本发明采用如下技术方案:
一种在3D打印钛植入体表面制备生物活性膜层的方法,包括以下步骤:
1)将待处理的3D打印医用钛植入体进行预处理;
在步骤1)中,所述预处理是将3D打印医用钛植入体依次浸泡于丙酮、乙醇和去离子水中超声清洗、烘干;接着在由浓度为10%~30%的HNO3与浓度为0.5%~5.0%的HF组成的混合酸溶液中刻蚀1~10min并冲洗烘干;最后置于0.5~5.0mol/L的HNO3或H2SO4溶液中进行恒电位阳极氧化处理,氧化电压为0.3~3V,氧化时间为15~120min。所述医用钛植入体包括3D打印多孔钛及其合金、医用钛及钛合金中的至少一种;
2)将预处理后的3D打印医用钛植入体置于贻贝黏附蛋白溶液中浸涂成膜;
在步骤2)中,所述贻贝蛋白黏附溶液是用1%柠檬酸稀释至0.05~3mg/mL,并调节pH=3~6;所述浸涂成膜是将3D打印医用钛植入体置于上述贻贝黏附蛋白溶液中0.5~4h后取出风干;
3)配置钙磷沉积液,对表面负载有贻贝黏附蛋白膜的3D打印医用钛植入体进行阴极电沉积,在其表面构筑贻贝黏附蛋白/纳米磷酸八钙膜层;
在步骤3)中,所述阴极电沉积所用的钙磷沉积液为0.01~0.15mol/L的Ca(NO3)2和0.01~ 0.15mol/L的NH4H2PO4混合液;所述钙磷沉积液pH为2~6;所述阴极电沉积以待处理的医用钛植入体为阴极、铂电极为阳极,电流密度为0.1~1mA/cm2,沉积温度为65~75℃,沉积时间为5~30min;
4)配置茶多酚溶液,将基底表面构筑有贻贝黏附蛋白/纳米磷酸八钙膜层的3D打印医用钛植入体浸渍在茶多酚溶液中,利用茶多酚与Ca2+之间的静电吸附自组装成膜,获得具有优良生物活性的复合膜层;
在步骤4)中,所述茶多酚溶液浓度为0.05~5mg/mL,浸渍时间为0.5h~4h。
相对于现有技术,本发明技术方案取得的有益效果是:
本发明先通过电化学阳极氧化以改善3D打印医用钛植入体耐腐蚀性能,接着通过电化学沉积和浸渍自组装法在植入体表面制备了生物活性复合膜层,该复合膜层与基底结合力良好,可优化钙磷盐膜层晶型择优生长方向和多级有序结构,并显著增强3D打印医用钛植入体的生物活性、生物相容性等综合性能。
具体地,本发明以钛、钛合金、3D打印多孔钛及其合金等医用材料为基底,通过电化学阳极氧化、电化学沉积和浸渍自组装法相结合,显著改善金属植入体耐蚀性,并在其表面制备贻贝黏附蛋白/仿生结构钙磷盐/茶多酚复合生物膜层。通过选择相应的沉积液配方和反应参数可获得最优的复合生物膜层表面形貌,实施过程中可不限定植入体形状结构。
本发明中通过阳极氧化预处理后的3D打印医用钛植入体,与未进行阳极氧化处理的3D 打印医用钛植入体相比,在0.9%NaCl溶液中表现出更强的耐腐蚀能力。
本发明中贻贝黏附蛋白膜层不仅可增强复合膜层与基底间的结合力,还可调控钙磷盐膜层形貌,复合膜层表面均匀致密,具有微纳有序仿生结构。
本发明中通过优选条件制备的贻贝黏附蛋白/仿生结构钙磷盐/茶多酚复合膜层,与单纯磷酸八钙相比,MC3T3-E1细胞对其表现出更高的碱性磷酸酶活性,有利于成骨细胞的分化生长。
本发明操作条件简单、成本低、不限定植入体形状结构,可广泛应用于各类医用金属植入体的表面改性。
附图说明
图1为实施例1中进行阳极氧化和未经阳极氧化处理的3D打印多孔钛合金在0.9%NaCl 溶液中浸泡7天的Bode图。
图2为采用实施例2中阴极电沉积条件制备的单纯磷酸八钙膜层扫描电镜形貌图。
图3为实施例2中浸渍在0.125mg/mL的茶多酚溶液中所制备的复合膜层扫描电镜形貌图。
图4为实施例2中浸渍在0.25mg/mL的茶多酚溶液中所制备的复合膜层扫描电镜形貌图。
图5为不同膜层的XRD图谱。在图5中,a代表单纯磷酸八钙膜层,b代表实施例2中浸渍在0.125mg/mL的茶多酚溶液中所制备的复合膜层,c代表实施例2中浸渍在0.25mg/mL 的茶多酚溶液中所制备的复合膜层。
图6为MC3T3-E1细胞在不同膜层表面培养不同时间的碱性磷酸酶(ALP)活性测试结果。在图6中a代表单纯磷酸八钙膜层,b代表实施例2中浸渍在0.125mg/mL的茶多酚溶液中所制备的复合膜层,c代表实施例2中浸渍在0.25mg/mL的茶多酚溶液中所制备的复合膜层。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚、明白,以下结合附图和实施例,对本发明做进一步详细说明。
实施例1:
将3D打印多孔钛合金依次用丙酮溶液、无水乙醇和超纯水超声清洗10min,以除去表面油污。配制HF与HNO3体积比为1:10的混合酸溶液,将超声清洗后的3D打印多孔钛合金在混合酸溶液中超声刻蚀2min,结束后用去离子水冲洗、烘干。接着在1mol/L的HNO3电解液中,以铂电极为对电极、饱和甘汞电极作为参比电极,在优选条件0.3V和0.5V的恒电位下对3D打印多孔钛合金进行阳极氧化处理30min。把阳极氧化处理和未进行阳极氧化处理的样品浸泡在0.9%NaCl溶液中7天,并对7天后的样品进行电化学阻抗谱分析。在Bode 图(图1)中可知,0.3V和0.5V电压处理后的样品在浸泡7天时,它们的低频阻抗模值明显大于空白样(即未阳极氧化处理的样品),表明阳极氧化处理可显著增强3D打印多孔钛合金在0.9%NaCl溶液中的耐蚀性。
实施例2:
将实施例1中处理后的样品浸渍在用1%柠檬酸溶液稀释的浓度为1mg/mL的贻贝黏附蛋白溶液中2h。结束后取出风干。接着采用阴极电沉积的方法,以处理后的3D打印多孔钛作为阴极,铂电极作为阳极,以0.05mol/L的NH4H2PO4和0.084mol/L的Ca(NO3)2按体积比5:1配置钙磷沉积液,采用恒电流模式(0.5mA/cm2)在70℃恒温水浴下沉积10min。最后分别浸渍在0.125mg/mL、0.25mg/mL的茶多酚溶液中2h。与单纯的磷酸八钙膜层相比(图 2),制备的复合膜层(图3、图4)呈现更为有序的形貌结构,复合膜层表面均匀致密,呈现微孔状。随着浸渍溶液中茶多酚的浓度增加,复合膜层表面逐渐出现颗粒状晶体。由图5中复合膜层(b,c)与磷酸八钙标准卡片(PDF#79-0423)对比可知,所制备涂层的主要成分还是磷酸八钙,但复合膜层在2θ=26°处的峰要强于的磷酸八钙(图5中a),表明复合膜层中的钙磷盐晶面(002)择优生长。
实施例3:
以实施例2中相同阴极电沉积条件下制备的单纯磷酸八钙膜层为对比样,以实施例2中制备的复合膜层为实验样,使用ALP试剂盒测试复合膜层对小鼠前成骨细胞MC3T3-E1的诱导分化能力。细胞密度为2×104cells/well,孵育4天、7天。测试结果参见图6,相比于单纯磷酸八钙膜层,复合膜层可显著增强细胞的碱性磷酸酶活性,且随着时间延长,增强效果越明显。这表明所制备的复合膜层具有良好的生物相容性和生物活性,可赋予3D打印多孔钛合金植入体优异的促成骨分化性能。
金属表面钝化膜对耐腐蚀性至关重要,通常钛表面钝化膜具有优异的耐蚀性能。但3D 打印制造的医用钛表面钝化膜结构及完整性较差,耐蚀性较弱,不利于医用钛植入体在生理环境中的长期稳定服役,本发明对其进行特定的电化学阳极氧化处理,可有效提升植入体自身的耐腐蚀性能。
在正常生理环境中磷酸八钙可自发地向类骨磷灰石相转化,具有良好的生物相容性,将具有仿生结构的钙磷盐膜层沉积在植入体表面可显著提升植入体的生物活性,促进骨结合。但单一的钙磷盐膜层促成骨分化能力有限,且脆性较大、与基底的结合力不佳,本发明对植入体表面的纳米有序结构的钙磷盐涂层进行修饰改性。
贻贝黏附蛋白是从贻贝足丝中提取的黏附蛋白,其具有大量的DOPA残基,可通过形成氢键、共价键、配位健等与物质表面发生相互作用,从而实现强的界面结合力。本发明将贻贝蛋白作为生物粘合剂可提高植入体对人体组织的亲和性,改善植入体与组织界面生物微环境,显著促进组织的修复、愈合。
茶多酚是从茶叶中提取的天然绿色多酚类化合物,具有天然的抗氧化性,能够清除氧化自由基和起到抗炎症的作用。茶多酚还能够通过抑制破骨细胞和促进成骨细胞以减少骨量丢失,大大降低骨质疏松的发生风险,茶多酚作为骨科材料的表面修饰剂具有诱人的应用前景。
本发明通过电化学阳极氧化、电化学沉积和浸渍自组装法相结合,在3D打印医用钛表面制备贻贝黏附蛋白/纳米磷酸八钙/茶多酚复合生物涂层。
通过电化学阳极氧化在3D打印医用钛植入体表面构筑氧化膜,大大改善植入体的耐腐蚀性能,接着通过浸渍法组装和电化学沉积法相结合,在植入体表面制备了具有良好生物相容性和生物活性的复合膜层;贻贝黏附蛋白可加强钙磷膜层与钛基底结合力,并优化磷酸八钙膜层形貌结构,茶多酚可促进成骨细胞分化。该复合膜层与单纯磷酸八钙膜层相比,可赋予植入材料更优的诱导成骨分化能力,可显著提升3D打印的金属钛植入体生物活性和耐腐蚀能力,可用于各种3D打印制造的金属钛植入体进行表面改性,本发明为3D打印金属植入体表面改性、优化提供了一种高效实用方法。本发明操作简单、成本低,可广泛应用于生物医用材料表面的改性优化技术领域。
Claims (10)
1.一种在3D打印钛植入体表面制备生物活性膜层的方法,其特征在于包括以下步骤:
1)将待处理的3D打印医用钛植入体进行表面恒电位阳极氧化处理;
2)将预处理后的3D打印医用钛植入体置于贻贝黏附蛋白溶液中浸涂成膜;
3)将表面负载有贻贝黏附蛋白膜的3D打印医用钛植入体置于钙磷沉积液中进行阴极电沉积,在其表面构筑贻贝黏附蛋白/纳米磷酸八钙膜层;
4)将表面构筑有贻贝黏附蛋白/纳米磷酸八钙膜层的3D打印医用钛植入体浸渍在茶多酚溶液中,制备贻贝黏附蛋白/纳米磷酸八钙/茶多酚复合膜。
2.如权利要求1所述的一种在3D打印钛植入体表面制备生物活性膜层的方法,其特征在于:步骤1)中,所述医用钛植入体包括3D打印多孔钛及其合金、医用钛及钛合金中的至少一种。
3.如权利要求1所述的一种在3D打印钛植入体表面制备生物活性膜层的方法,其特征在于:步骤1)中,进行表面恒电位阳极氧化处理之前,先将医用钛植入体依次浸泡于丙酮、乙醇和去离子水中超声清洗,再置于HNO3与HF混合酸溶液中刻蚀并冲洗烘干。
4.如权利要求3所述的一种在3D打印钛植入体表面制备生物活性膜层的方法,其特征在于:所述混合酸溶液中的HNO3浓度为10%~30%,HF浓度为0.5%~5.0%。
5.如权利要求3所述的一种在3D打印钛植入体表面制备生物活性膜层的方法,其特征在于:所述恒电位阳极氧化处理是将3D打印医用钛植入体置于0.5~5.0mol/L的HNO3或H2SO4溶液中进行恒电位阳极氧化处理,氧化电压为0.3~3V,氧化时间为15~120min。
6. 如权利要求1所述的一种在3D打印钛植入体表面制备生物活性膜层的方法,其特征在于:步骤2)中,所述贻贝黏附蛋白溶液是用柠檬酸稀释至0.05~3 mg/mL,调节pH=3~6;3D打印医用钛植入体在贻贝黏附蛋白溶液中浸涂0.5~4h。
7.如权利要求1所述的一种在3D打印钛植入体表面制备生物活性膜层的方法,其特征在于:步骤3)中,所述阴极电沉积所用的钙磷沉积液为Ca(NO3)2和NH4H2PO4混合液;Ca(NO3)2的摩尔浓度为0.01~0.15mol/L,NH4H2PO4的摩尔浓度为0.01~0.15mol/L;所述钙磷沉积液pH=2~6。
8.如权利要求1所述的一种在3D打印钛植入体表面制备生物活性膜层的方法,其特征在于:步骤3)中,所述阴极电沉积是以待处理的医用钛植入体为阴极、铂电极为阳极,电流密度为0.1~1mA/cm2,沉积温度为65~75℃,沉积时间为5~30min。
9.如权利要求1所述的一种在3D打印钛植入体表面制备生物活性膜层的方法,其特征在于:步骤4)中,所述茶多酚溶液的浓度为0.05~5mg/mL。
10.如权利要求1所述一种在3D打印钛植入体表面制备生物活性膜层的方法,其特征在于:步骤4)中,所述表面构筑有贻贝黏附蛋白/纳米磷酸八钙膜层的3D打印医用钛植入体在茶多酚溶液中浸泡0.5~4h。
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