CN114732961A - 镁骨内植物可载药壳聚糖/锌磷灰石涂层及其制备方法 - Google Patents
镁骨内植物可载药壳聚糖/锌磷灰石涂层及其制备方法 Download PDFInfo
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- CN114732961A CN114732961A CN202210277381.2A CN202210277381A CN114732961A CN 114732961 A CN114732961 A CN 114732961A CN 202210277381 A CN202210277381 A CN 202210277381A CN 114732961 A CN114732961 A CN 114732961A
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- Prior art keywords
- magnesium
- coating
- chitosan
- alloy
- zinc
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Abstract
本发明提供了一种镁骨内植物可载药壳聚糖/锌磷灰石涂层复合涂层,所述复合涂层由锌磷灰石涂层和壳聚糖涂层组成,所述涂层的厚度为10~80μm。该复合涂层的制备方法为:分别制备镁骨内植物、沉积液和壳聚糖溶液;将所述骨内植物浸入沉积液中,通过电化学沉积法在其表面沉积出锌磷灰石涂层,随后在壳聚糖溶液中涂覆壳聚糖涂层。本发明解决了目前磷酸盐涂层无法有效载药的问题,通过在锌磷灰石涂层外引入可载药壳聚糖涂层实现水溶性药物装载,锌磷灰石涂层可以通过配位作用与壳聚糖涂层形成化学键合,提高涂层的稳定性。同时壳聚糖涂层进一步增强了骨内植物的耐腐蚀性。
Description
技术领域
本发明涉及一种生物材料涂层及制备方法,属于材料技术领域,具体来讲是一种镁骨内植物表面的壳聚糖/锌磷灰石涂层及其电化学沉积制备方法。
背景技术
镁合金具有良好的生物安全性和生物相容性,可通过与体液反应被人体组织降解和吸收,有希望作为可降解材料代替不锈钢、钛合金等传统骨科内植物材料。然而镁的电极电位较低,化学活性和电化学活性高,表面氧化膜疏松多孔,耐腐蚀性差,在高氯的体液环境中腐蚀降解过快使力学性能迅速衰减,无法很好的完成骨修复作用,成为限制其临床应用的瓶颈。表面涂层可有效地减缓镁的腐蚀降解,通过在镁合金表面构筑磷酸盐涂层,不仅可降低镁合金的降解速率,延缓镁合金在体内力学性能的衰减,同时,磷酸盐涂层良好的生物相容性也可以促进骨组织生长,提高植入物的成骨功能。
国内外关于可降解镁合金表面的磷酸盐涂层已经开展了大量的研究,但仍存在降解速度较快、无法有效载药等问题。锌是人体必须的微量元素之一,在骨组织中的储量丰富,能够刺激成骨细胞增殖和矿化。锌磷灰石具有与基体结合力强,降解速率低等优点,此外锌离子也可以作为络合剂与多数有机高分子结合,如壳聚糖。通过构建锌磷灰石涂层,不仅可以提高可降解镁合金的耐腐蚀性和成骨活性,而且可以作为中间层通过配位作用结合壳聚糖等高分子,实现有效的载药。
专利CN106310372A公开了一种可降解镁基骨内植物可载药高分子/钙磷复合涂层及制备;所述复合涂层由里至外包括设于所述骨内植物表层的氟化膜、生物可降解高分子涂层和生物活性钙一磷涂层;制备时,将镁或镁合金骨内植物置于氢氟酸恒温浸泡形成氟化保护层;将生物可降解高分子材料溶解在有机溶剂中,通过浸提法涂覆在氟化处理骨内植物表面,真空干燥,形成聚合物涂层;对涂覆聚合物涂层的骨内植物进行紫外臭氧或等离子体表面预处理后,置于磷酸盐混合液恒温浸泡即可。该复合涂层将载药高分子层设置于氟化处理层和磷酸盐层中间,不利于药物释放。磷酸盐涂层涂覆于高分子涂层上,仅通过非共价键结合,不利于涂层与镁合金基体的结合,易产生涂层脱落。
发明内容
本发明的目的在于提供一种镁骨内植物表面的可载药壳聚糖/锌磷灰石复合涂层及其制备方法。本发明解决了目前磷酸盐涂层无法有效载药的问题,通过在锌磷灰石涂层外引入可载药壳聚糖涂层实现水溶性药物装载,锌磷灰石涂层可以通过配位作用与壳聚糖涂层形成化学键合,提高复合涂层的稳定性,而常用羟基磷灰石、透磷酸钙等钙磷盐涂层与基体和高分子涂层仅形成范德华力等非共价结合,稳定性较差。而且锌磷灰石溶度积更高,在模拟体液、细胞培养液等溶液中比羟基磷灰石、透磷酸钙等钙磷盐涂层更稳定,能有效减缓镁合金基体的腐蚀降解速率。同时本发明引入壳聚糖涂层可进一步增强了骨内植物的耐腐蚀性,并有效载药。本发明的复合涂层操作工艺简单、易行,制备的涂层与基体结合力强,厚度可控。本发明是通过以下技术方案实现的:
<第一方面>
本发明提供了一种镁骨内植物表面的可载药壳聚糖/锌磷灰石复合涂层,所述复合涂层由锌磷灰石涂层和壳聚糖涂层组成。
所述复合涂层厚度为10-80μm。厚度低于10μm涂层不完整,缺乏保护作用,超过80μm则涂层与基体的结合力下降。
<第二方面>
本发明还提供了一种如前述的镁骨内植物表面复合涂层的制备方法,其包括如下步骤:
S1、准备镁骨内植物、沉积液和壳聚糖溶液;
S2、将所述镁骨内植物浸入沉积液中,通过电化学沉积法,在骨内植物表面沉积出锌磷灰石涂层;
S3、在步骤S2的锌磷灰石涂层上进一步涂覆壳聚糖溶液,真空干燥,即得所述复合涂层。
本发明提供的方式是首先将所述骨内植物浸入沉积液中,通过电化学沉积法在其表面沉积锌磷灰石涂层;随后将上述样品浸入壳聚糖溶液中,涂覆得到壳聚糖涂层。
其中,所述电沉积液为含有Ca2+、Zn2+、PO4 3-的水溶液,所述壳聚糖溶液中壳聚糖的质量百分比为2%~4%。
作为优选方案,所述镁基材料为纯镁或镁合金,纯镁为镁含量>99.9%的纯镁或镁含量>99.99%的高纯镁;镁合金为镁含量>50%的镁系二元合金、镁系三元合金或镁系多元合金,所述镁系二元合金包括镁锌合金、镁钙合金、镁锂合金、镁铝合金、镁锰合金、镁锆合金、镁银合金、镁铜合金、镁稀土合金中的至少一种。
作为优选方案,所述骨内植物是指:骨板、骨钉或骨组织工程支架等骨修复相关的内植物。
作为优选方案,所述锌磷灰石涂层厚度为10~50μm,所述壳聚糖涂层厚度为1~10μm。
作为优选方案,所述沉积液中,Ca2+的浓度为0.02~0.06mol/L,Zn2+的浓度为0.002~0.015mol/L,PO4 3-的浓度为0.02~0.6mol/L,Ca2+和Zn2+的摩尔浓度之比为9:1~4:1,沉积液的pH值为4.5~5.5。
作为优选方案,所述电化学沉积法的具体步骤为:以镁骨内植物为阴极、铂或不锈钢为阳极,浸入沉积液中,在温度为75~85℃、电流密度为0.5~2mA/cm2的条件下进行电沉积。
作为优选方案,采用浸涂法将壳聚糖溶液涂覆在已沉积有锌磷灰石涂层的镁骨内植物表面。
作为优选方案,所述复合涂层在载药时,是将壳聚糖和药物溶解形成水溶液,所述水溶液中药物的质量百分比浓度为0.1%~5%,所述药物为水溶性小分子药物,包括但不限于双膦酸盐、降钙素等。
所述的镁骨内植物可载药壳聚糖/锌磷灰石复合涂层制备的医用材料也属于本发明的保护范围。
与现有技术相比,本发明具有如下的有益效果:
1.本发明提出一种镁基材料表面可载药的复合涂层,该复合涂层由锌磷灰石涂层和载药壳聚糖涂层组成。
2.本发明解决了目前磷酸盐涂层无法有效载药的问题,通过在锌磷灰石涂层外引入可载药壳聚糖涂层实现水溶性药物装载,锌磷灰石涂层可以通过配位作用与壳聚糖涂层形成化学键合,提高复合涂层的稳定性。
3.同时壳聚糖涂层进一步增强了骨内植物的耐腐蚀性,减缓骨内植物在体力学强度衰减速度。本发明的复合涂层操作工艺简单、易行,制备的涂层与基体结合力强,厚度可控。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述,本发明的其它特征、目的和优点将会变得更明显:
图1为本发明中实施例1和实施例2制备的复合涂层X射线衍射图谱;
图2为本发明中实施例1制备的锌磷灰石涂层和壳聚糖/锌磷灰石复合涂层的扫面电镜图;其中a为锌磷灰石涂层,b为可载药壳聚糖/锌磷灰石涂层复合涂层;
图3为WE43镁合金棒骨内植物样品表面载双膦酸盐药物的壳聚糖/锌磷灰石涂层的一周释药曲线。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
选用AZ31镁合金螺钉作为骨内植物样品,制备方法如下:
第一步,将镁合金螺钉依次采用不同目数的砂纸进行打磨,最后用2500目的细砂纸反复打磨抛光,去离子水冲洗,无水乙醇超声清洗,自然风干备用;
第二步,配制沉积液,四水硝酸钙0.0378mol/L,硝酸锌0.0042mol/L,磷酸二氢铵0.028mol/L全部溶解于去离子水中,电沉积液温度80℃,用氨水和1mol/L的硝酸调节pH值至5.0;
第三步,电化学沉积,以镁合金螺钉为阴极,不锈钢为阳极,调节电流密度为2mA/cm2进行电化学沉积,沉积时间20分钟;
第四步,取出经电化学沉积的镁合金螺钉,用去离子水清洗干净,随后放入到含有1%双膦酸盐的2%壳聚糖溶液中,采用浸涂法把壳聚糖均匀涂覆在镁合金螺钉表面。
第五步,将上述镁合金螺钉样品用置于烘箱中60℃恒温干燥1小时,获得载有双磷酸盐的复合涂层。
本实施例制备的复合涂层X射线衍射图谱如图1所示,锌磷灰石涂层主要由磷酸锌钙和羟基磷酸锌组成。扫描电镜可观察到壳聚糖涂层涂覆前,锌磷灰石涂层主要呈板条状,壳聚糖涂层涂覆后,涂层表面较为平整,锌磷灰石结构被覆盖(图2)。复合涂层厚度为24.8μm,AZ31镁合金螺钉的降解速率为3.48mm/a,而涂覆有复合涂层的AZ31镁合金螺钉降解速率为0.83mm/a。复合涂层载双膦酸盐药物量约78μg,一周内累计释放药物量约25%,并且没有出现明显的药物突释现象。
实施例2
选用纯镁棒作为骨内植物样品,制备方法如下:
第一步,将纯镁棒(直径2.7mm,长20mm)依次采用不同目数的砂纸进行打磨,最后用2500目的细砂纸反复打磨抛光,去离子水冲洗,无水乙醇超声清洗,自然风干;放入40wt%的氢氟酸水溶液活化处理5min,去离子水清洗,自然风干备用。
第二步,配制沉积液,无水硝酸钙0.0336mol/L,硝酸锌0.0084mol/L,磷酸二氢锌0.028mol/L全部溶解于去离子水中,沉积液温度75℃,用氨水和1mol/L的硝酸调节pH值至5.5。
第三步,将活化处理后的纯镁棒浸入沉积液中,以纯镁棒为阴极,铂为阳极,调节电流密度为1mA/cm2,沉积时间40分钟。
第四步,取出经电沉积的纯镁棒,用去离子水清洗干净,随后放入4%壳聚糖溶液中,采用浸涂法把壳聚糖均匀涂覆在纯镁棒表面。
第五步,将上述纯镁棒样品用置于烘箱中60℃恒温干燥1小时,获得可载药的复合涂层。
本实施例制备的复合涂层X射线衍射图谱如图1所示,锌磷灰石涂层主要由磷酸锌钙和羟基磷酸锌组成,复合涂层的厚度为28.7μm,纯镁棒的降解速率为1.89mm/a,而涂覆有复合涂层的纯镁棒降解速率为0.37mm/a。
实施例3
选用WE43镁合金棒作为骨内植物样品,制备方法如下:
第一步,将WE43镁合金棒依次采用不同目数的砂纸进行打磨,最后用2500目的细砂纸反复打磨抛光,去离子水冲洗,无水乙醇超声清洗,自然风干;放入40wt%的氢氟酸水溶液活化处理5min,去离子水清洗,自然风干备用。
第二步,配制沉积液,四水硝酸钙0.02mol/L,硝酸锌0.005mol/L,磷酸二氢铵0.02mol/L全部溶解于去离子水中,沉积液温度85℃,用氨水和1mol/L的硝酸调解pH值至4.5。
第三步,电化学沉积,将WE43镁合金棒浸入沉积液中,以镁合金棒为阴极,不锈钢为阳极,调节电流密度为0.5mA/cm2进行电化学沉积,沉积时间30分钟。
第四步,取出经电沉积的镁合金棒,用去离子水清洗干净,随后放入含有1%双膦酸盐的3%壳聚糖溶液中,采用浸涂法把载药壳聚糖均匀涂覆在纯镁棒表面。
第五步,将上述镁合金棒样品用置于烘箱中60℃恒温干燥1小时,获得载有双膦酸盐的复合涂层。
扫描电镜观测到本实施例制备的复合涂层厚度为12.3μm,WE43镁合金棒的降解速率为2.25mm/a,而涂覆有复合涂层的WE43镁合金棒降解速率为0.49mm/a,复合涂层载双膦酸盐药物量约86μg,一周内累计释放药物量约24%,并且没有出现明显的药物突释现象(图3)。
实施例4
选用ZK60镁合金棒作为骨内植物样品,制备方法如下:
第一步,ZK60镁合金棒依次采用不同目数的砂纸进行打磨,最后用2500目的细砂纸反复打磨抛光,去离子水冲洗,无水乙醇超声清洗,自然风干;放入40wt%的氢氟酸水溶液活化处理5min,去离子水清洗,自然风干备用。
第二步,配制沉积液,四水硝酸钙0.06mol/L,硝酸锌0.015mol/L,磷酸二氢铵0.04mol/L全部溶解于去离子水中,沉积液温度80℃,用氨水和1mol/L的硝酸调解pH值至5.0。
第三步,电化学沉积,将ZK60镁合金棒浸入沉积液中,以镁合金棒为阴极,不锈钢为阳极,调节电流密度为0.5mA/cm2进行电化学沉积,沉积时间80分钟。
第四步,取出经电沉积的镁合金棒,用去离子水清洗干净,随后放入含有5%降钙素的4%壳聚糖溶液中,采用浸涂法把载药壳聚糖均匀涂覆在镁合金棒表面。
第五步,将上述镁合金棒样品用置于烘箱中60℃恒温干燥1小时,获得载有降钙素的复合涂层。
扫描电镜观测到本实施例制备的复合涂层厚度为76μm,ZK60镁合金棒的降解速率为2.64mm/a,而涂覆有复合涂层的WE43镁合金棒降解速率为0.68mm/a,复合涂层载降钙素药物量约62μg,一周内累计释放药物量约34%,并且没有出现明显的药物突释现象。
对比例1
选用AZ31镁合金螺钉作为骨内植物样品,在其表面制备用于载药的可降解高分子载体及生物活性钙磷复合涂层(参照专利CN106310372A方法),具体如下:
首先将纯镁螺钉用无水乙醇和丙酮分别超声清洗10min,吹干。将AZ31镁合金螺钉放在40%HF溶液中室温浸泡24h,随后用去离子水、无水乙醇清洗,吹干。取重均分子量为100000的聚乳酸-羟基乙酸共聚物(PLGA),按8wt.%的比例溶于乙酸乙酯溶剂中,同时取紫杉醇按2wt.%的比例溶解,采用浸涂法把混有紫杉醇药物的PLGA溶液匀涂覆在氟化处理镁合金螺钉表面,将涂覆有PLGA涂层的镁合金放入真空干燥箱35℃干燥48h,即得到以PLGA涂层为药物载体的镁合金。将该涂覆有生物可降解高分子涂层的样品放入紫外臭氧仪器紫外辐照60min,然后将试样放入CaHPO4:NaOH=6∶4(wt.%)的溶液中水浴恒温(20℃)浸泡48h,取出后用超纯水清洗两次,吹干,即可得到载紫杉醇药物的高分子载体及生物活性钙-磷复合涂层。
对比例2
本对比例与实施例1的区别在于,仅在镁骨内植物表面涂布壳聚糖涂层,具体包括如下步骤:
第一步,将AZ31镁合金螺钉依次采用不同目数的砂纸进行打磨,最后用2500目的细砂纸反复打磨抛光,去离子水冲洗,无水乙醇超声清洗,自然风干备用;
第二步,将镁合金螺钉放入到含有1%双膦酸盐的2%壳聚糖溶液中,采用浸涂法把壳聚糖均匀涂覆在镁合金螺钉表面。
第三步,将上述镁合金螺钉样品用置于烘箱中60℃恒温干燥1小时,获得载有双磷酸盐的壳聚糖涂层。
对比例3
本对比例与实施例1的区别在于,所述锌磷灰石复合涂层替换为不含锌的磷灰石涂层,具体包括如下步骤:
第一步,将AZ31镁合金螺钉依次采用不同目数的砂纸进行打磨,最后用2500目的细砂纸反复打磨抛光,去离子水冲洗,无水乙醇超声清洗,自然风干备用;
第二步,配制沉积液,四水硝酸钙0.0378mol/L,磷酸二氢铵0.028mol/L,硝酸钠0.1mol/L全部溶解于去离子水中,电沉积液温度25℃,用氨水和1mol/L的硝酸调节pH值至4.0;
第三步,电化学沉积,以镁合金螺钉为阴极,不锈钢为阳极,调节电流密度为2mA/cm2进行电化学沉积,沉积时间20分钟;
第四步,取出经电化学沉积的镁合金螺钉,用去离子水清洗干净,随后放入到含有1%双膦酸盐的2%壳聚糖溶液中,采用浸涂法把壳聚糖均匀涂覆在镁合金螺钉表面。
第五步,将上述镁合金螺钉样品用置于烘箱中60℃恒温干燥1小时,获得载有双磷酸盐的复合涂层。
性能测试
将本发明实施例1与各对比例的涂层进行扫描电镜观察,结果如下:
扫描电镜观察复合涂层厚度,实施例1涂层厚度为24.8μm,对比例涂层厚度为17.8μm,对比例2涂层厚度为6.2μm,对比例3涂层厚度为18.7μm。XRD检测结果发现实施例1的锌磷灰石成分为磷酸锌钙和羟基磷酸锌,对比例1和对比例3的磷酸盐涂层成分均为透磷酸钙。采用微米划痕仪测试各涂层结合力,实施例1为62.4N,对比例1为46.3N,对比例2为28.1N,对比例3为42.7N。各涂层均可载药,实施例1复合涂层载双膦酸盐药物量约78μg,一周内累计释放药物量约25%。对比例1复合涂层载紫杉醇136克,一周内累计释放药物量约32%。对比例2壳聚糖涂层载双膦酸盐药物量约82μg,一周内累计释放药物量约56%。对比例3复合涂层载双膦酸盐药物量约76μg,一周内累计释放药物量约44%。各涂层均没有出现明显的药物突释现象,但对比例2和对比例3药物释放速度过快,不利于长期缓释药物需求。实施例1涂覆有复合涂层的AZ31镁合金螺钉降解速率为0.83mm/a,对比例1降解速率为1.89mm/a,对比例2降解速率为3.16mm/a,对比例3降解速率为1.75mm/a,实施例1由于锌磷灰石涂层具有与镁合金基体较好的结合力以及与壳聚糖涂层形成配位作用,具有较好的稳定性和促进镁合金耐腐蚀能力。
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质内容。
Claims (10)
1.一种镁骨内植物可载药壳聚糖/锌磷灰石复合涂层,其特征在于,所述复合涂层由锌磷灰石涂层和壳聚糖涂层组成。
2.根据权利要求1所述的镁骨内植物可载药壳聚糖/锌磷灰石复合涂层,其特征在于,所述复合涂层厚度为10-80μm。
3.一种如权利要求1所述的镁骨内植物可载药壳聚糖/锌磷灰石复合涂层的制备方法,其特征在于,包括如下步骤:
S1、准备镁骨内植物、沉积液和壳聚糖溶液;
S2、将所述镁骨内植物浸入沉积液中,通过电化学沉积法,在骨内植物表面沉积出锌磷灰石涂层;
S3、在步骤S2的锌磷灰石涂层上进一步涂覆壳聚糖溶液,真空干燥,即得所述复合涂层。
4.根据权利要求3所述的制备方法,其特征在于,步骤S1中,所述沉积液为含有Ca2+、Zn2 +、PO4 3-的水溶液,所述壳聚糖溶液的质量百分比浓度为2%~4%。
5.根据权利要求4所述的制备方法,其特征在于,所述沉积液中,Ca2+的浓度为0.02~0.06mol/L,Zn2+的浓度为0.002~0.015mol/L,PO4 3-的浓度为0.02~0.6mol/L;Ca2+和Zn2+的摩尔浓度之比为9:1~4:1,沉积液的pH值为4.5~5.5。
6.根据权利要求3所述的制备方法,其特征在于,步骤S2中,所述电化学沉积法的具体步骤为:
以所述镁骨内植物为阴极,铂或不锈钢为阳极,浸入所述沉积液中,在温度为75~85℃、电流密度为0.5~2mA/cm2的条件下进行电沉积。
7.根据权利要求3所述的制备方法,其特征在于,步骤S1中,所述镁骨内植物为纯镁或镁合金。
8.根据权利要求7所述的制备方法,其特征在于,所述镁合金为镁含量>50%的镁系二元合金、镁系三元合金或镁系多元合金;所述镁系二元合金包括镁锌合金、镁钙合金、镁锂合金、镁铝合金、镁锰合金、镁锆合金、镁银合金、镁铜合金、镁稀土合金中的至少一种。
9.如权利要求3所述的制备方法,其特征在于,所述可载药壳聚糖/锌磷灰石复合涂层在载药时,是将壳聚糖和药物溶解形成水溶液,所述水溶液中药物的质量百分比0.1%~5%,所述药物为水溶性小分子药物。
10.一种如权利要求1所述的镁骨内植物可载药壳聚糖/锌磷灰石复合涂层制备的医用材料。
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