CN112587722A - 用于骨植入聚酯材料的生物活性表面涂层的制备方法及产品和应用 - Google Patents

用于骨植入聚酯材料的生物活性表面涂层的制备方法及产品和应用 Download PDF

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CN112587722A
CN112587722A CN202011613498.0A CN202011613498A CN112587722A CN 112587722 A CN112587722 A CN 112587722A CN 202011613498 A CN202011613498 A CN 202011613498A CN 112587722 A CN112587722 A CN 112587722A
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崔大祥
杨迪诚
徐艳
朱君
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Abstract

本发明涉及一种一种用于骨植入聚酯材料的生物活性表面涂层的制备方法及其产品和应用,通过表面水解法在聚酯表面引入氨基,得到氨基化的聚酯表面;利用EDC/NHS偶联反应固定负载纳米羟基磷灰石的丝素蛋白涂层。本发明通过负载羟基磷灰石的丝素蛋白涂层表面改性,改善可降解聚酯表面的生物活性,促进细胞粘附生长,提高材料与组织的相容性。该方法制备的化学交联涂层具有长效性和稳定性,能长期改善聚酯植入物的表面生物活性,满足临床应用的需求。

Description

用于骨植入聚酯材料的生物活性表面涂层的制备方法及产品 和应用
技术领域
本发明涉及一种生物医用材料技术领域的方法,具体是一种用于骨科植入的聚酯类材料的生物活性表面涂层的制备技术。
背景技术
可降解聚酯类材料是一种具有良好生物相容性的可降解材料,被广泛应用于骨修复支架和组织工程领域。然而,可降解聚酯表面疏水,且缺乏影响细胞信号识别的活性基团,不利于细胞粘附生长,导致与新生组织间的不相容,延长组织愈合时间。因此,在可降解聚酯材料表面进行生物活性改性,引入适于细胞生长的涂层环境,引导受体细胞的增殖、分化是非常必要的。
羟基磷灰石是人体天然骨中的主要无机成分,具有良好的骨传导性,常作为骨科植入物的改性材料。然而羟基磷灰石作为亲水的离子型无机物,与疏水的可降解聚酯相容性较差,其作为填充材料使用时会在聚酯中形成缺陷,降低骨修复支架的力学性能。因此,羟基磷灰石表面涂层是改善聚酯表面生物活性,同时不影响力学性能的一种有效途径。丝素蛋白是一种天然的大分子材料,含有一种与细胞粘附密切相关的特殊三肽结构,即精-甘-天冬氨酸肽结构,能促进上皮细胞在材料表面迁移、粘附和增殖。以丝素蛋白涂层改性聚酯表面,可以促进其与黏膜组织的快速融合。
发明内容
本发明目的在于提供一种用于骨科植入的聚酯类材料的生物活性表面涂层的制备技术。
本发明的再一目的在于:提供一种上述方法制备的包裹IR780@硅质体产品。
本发明的又一目的在于:提供一种上述产品的应用。
本发明目的通过下述方案实现:一种用于骨植入聚酯材料的生物活性表面涂层的制备方法,其特征在于通过表面水解法在聚酯表面引入氨基,得到氨基化的聚酯表面;利用EDC/NHS偶联反应固定负载纳米羟基磷灰石的丝素蛋白涂层,包括以下步骤:
(1)将可降解聚酯支架浸泡在50%(v/v)的乙醇水溶液中超声2小时,然后用大量水冲洗,将清洗过的支架置于1 ,6-己二胺和异丙醇的混合溶液中于45℃下反应5 min,去离子水清洗12h,真空干燥24h,得到表面氨基化的支架;
(2)配制EDC/NHS/MES交联剂水溶液,浓度为20mM/10mM/10mM,再配制丝素蛋白和羟基磷灰石的SF/nHA混合溶液;交联溶液与SF/nHA混合溶液按体积比1:9混合后,立即将氨基化的聚酯支架浸泡其中,在37℃反应4h;
(3)反应结束后,水洗支架表面,进行冷冻干燥,即得到生物活性表面涂层。
步骤(1)所述的可降解聚酯包括聚乳酸(PLA)、聚乳酸-羟基乙酸(PLGA)、聚己内酯(PCL)及其二元共聚物,所述支架包括聚合物风干膜、熔融浇注支架、3D打印支架。
步骤(2)所述羟基磷灰石为纳米羟基磷灰石,所述溶液的配制方式为常温下磁力搅拌。
步骤(2)所述的SF/nHA混合溶液,丝素蛋白溶度为0.1-0.5mg/mL、羟基磷灰石浓度为0.01-0.5mg/mL。
本发明提供一种用于骨植入聚酯材料的生物活性表面涂层,根据上述任一所述制备方法得到。
本发明提供一种生物活性表面涂层在制备植入物材料表面涂层材料中的应用。
以可降解聚酯类材料,如聚乳酸、PCL、PLGA等为原料,通过成膜、浇注、3D打印等方法制备骨修复支架;通过表面水解法在聚酯表面引入氨基,得到氨基化的聚酯表面;最后利用EDC/NHS偶联反应固定负载纳米羟基磷灰石的丝素蛋白涂层。
本发明提供了一种可降解聚酯材料表面的生物活性涂层的制备方法,通过表面水解法在聚酯表面引入活性反应基团,再利用EDC/NHS偶联反应固定丝素蛋白涂层,提高涂层的稳定性,制备负载羟基磷灰石的丝素蛋白涂层。
本发明通过负载羟基磷灰石的丝素蛋白涂层表面改性,改善可降解聚酯表面的生物活性,促进细胞粘附生长,提高材料与组织的相容性。该方法制备的化学交联涂层具有长效性和稳定性,能长期改善聚酯植入物的表面生物活性,满足临床应用的需求。
附图说明
图1是所制备生物活性涂层的SEM图。
具体实施方式
以下实施例以发明技术方案为前提进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围并不限于下述的实施例。
实施例1
一种用于骨植入聚酯材料的生物活性表面涂层,通过表面水解法在聚酯表面引入氨基,得到氨基化的聚酯表面;利用EDC/NHS偶联反应固定负载纳米羟基磷灰石的丝素蛋白涂层,按以下步骤制备:
(1)将可降解聚酯支架浸泡在50%(v/v)的乙醇水溶液中超声2小时,然后用大量水冲洗,将清洗过的支架置于1 ,6-己二胺和异丙醇的混合溶液中于45℃下反应5 min,去离子水清洗12h,真空干燥24h,得到表面氨基化的支架;
(2)配制EDC/NHS/MES交联剂水溶液,浓度为20mM/10mM/10mM,再配制0.1g/mL丝素蛋白和0.05g/mL羟基磷灰石的SF/nHA混合溶液;交联剂水溶液与SF/nHA混合溶液按体积比1:9混合后,立即将氨基化的聚酯支架浸泡其中,在37℃反应4h;
(3)反应结束后,水洗支架表面,进行冷冻干燥,即得到生物活性表面涂层。其SEM图如图1所示。
实施例2
一种用于骨植入聚酯材料的生物活性表面涂层,与实施例1步骤相近,按以下步骤制备:
(1)将可降解聚酯支架浸泡在50%(v/v)的乙醇水溶液中超声2小时,然后用大量水冲洗,将清洗过的支架置于1 ,6-己二胺和异丙醇的混合溶液中于45℃下反应5 min,去离子水清洗12h,真空干燥24h,得到表面氨基化的支架;
(2)配制EDC/NHS/MES交联剂水溶液,浓度为20mM/10mM/10mM,再配制0.1g/mL丝素蛋白和0.1g/mL羟基磷灰石的SF/nHA混合溶液;交联溶液与SF/nHA混合溶液按体积比1:9混合后,立即将氨基化的聚酯支架浸泡其中,在37℃反应4h;
(3)反应结束后,水洗支架表面,进行冷冻干燥,即得到生物活性表面涂层。
实施例3
一种用于骨植入聚酯材料的生物活性表面涂层,与实施例1步骤相近,按以下步骤制备:
(1)将可降解聚酯支架浸泡在50%(v/v)的乙醇水溶液中超声2小时,然后用大量水冲洗,将清洗过的支架置于1 ,6-己二胺和异丙醇的混合溶液中于45℃下反应5 min,去离子水清洗12h,真空干燥24h,得到表面氨基化的支架;
(2)配制EDC/NHS/MES交联剂水溶液,浓度为20mM/10mM/10mM,再配制0.2g/mL丝素蛋白和0.2g/mL羟基磷灰石的SF/nHA混合溶液;交联溶液与SF/nHA混合溶液按体积比1:9混合后,立即将氨基化的聚酯支架浸泡其中,在37℃反应4h;
(3)反应结束后,水洗支架表面,进行冷冻干燥,即得到生物活性表面涂层。

Claims (6)

1.一种用于骨植入聚酯材料的生物活性表面涂层的制备方法,其特征在于,通过表面水解法在聚酯表面引入氨基,得到氨基化的聚酯表面;利用EDC/NHS偶联反应固定负载纳米羟基磷灰石的丝素蛋白涂层,包括以下步骤:
(1)将可降解聚酯支架浸泡在50%(v/v)的乙醇水溶液中超声2小时,然后用大量水冲洗,将清洗过的支架置于1 ,6-己二胺和异丙醇的混合溶液中于45℃下反应5 min,去离子水清洗12h,真空干燥24h,得到表面氨基化的支架;
(2)配制EDC/NHS/MES交联剂水溶液,浓度为20mM/10mM/10mM,再配制丝素蛋白和羟基磷灰石的SF/nHA混合溶液;交联溶液与SF/nHA混合溶液按体积比1:9混合后,立即将氨基化的聚酯支架浸泡其中,在37℃反应4h;
(3)反应结束后,水洗支架表面,进行冷冻干燥,即得到生物活性表面涂层。
2.根据权利要求1所述的一种用于骨植入聚酯材料的生物活性表面涂层的制备方法,步骤(1)所述的可降解聚酯包括聚乳酸(PLA)、聚乳酸-羟基乙酸(PLGA)、聚己内酯(PCL)及其二元共聚物,所述支架包括聚合物风干膜、熔融浇注支架、3D打印支架。
3.根据权利要求1所述的一种用于骨植入聚酯材料的生物活性表面涂层的制备方法,步骤(2)所述羟基磷灰石为纳米羟基磷灰石,所述溶液的配制方式为常温下磁力搅拌。
4.根据权利要求1所述的一种用于骨植入聚酯材料的生物活性表面涂层的制备方法,步骤(2)所述的丝素蛋白SF/羟基磷灰石nHA混合溶液,丝素蛋白溶度为0.1-0.5mg/mL、羟基磷灰石浓度为0.01-0.5mg/mL。
5.一种用于骨植入聚酯材料的生物活性表面涂层,其特征在于根据权利要求1-4任一所述制备方法得到。
6.一种根据权利要求5所述生物活性表面涂层在制备植入物材料表面涂层材料中的应用。
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