CN109010919B - Pda涂层增强硅酸三钙生物活性的短流程制备方法 - Google Patents
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Abstract
本发明公开了一种PDA涂层增强硅酸三钙生物活性的短流程制备方法,属于生物医用材料领域,具体是通过将高纯硅酸三钙粉体与固化液按比例调和成糊状物,后制备成硅酸三钙多孔支架或致密基体,后将硅酸三钙多孔支架或致密基体浸泡在0.1‑2mg/ml盐酸多巴胺缓冲溶液中1‑16小时,得到表面沉积一层聚多巴胺的硅酸三钙基体,多巴胺在弱碱条件下自聚合形成PDA,然后通过PDA与硅酸三钙基体形成较强的粘附,并能加速类骨磷灰石在PDA涂覆的硅酸三钙表面动力学沉积过程,增强硅酸三钙生物活性,本发明方法工艺简单,可控性强。
Description
技术领域
本发明属于生物医用材料领域,具体是指一种PDA(聚多巴胺)涂层增强硅酸三钙生物活性的短流程制备方法。
背景技术
生物活性材料可广义地定义为“一种被设计用于诱导特定生物学反应的物质”(Williams DF, editor. Definitions in biomaterials. Amsterdam/Oxford/New York/Tokyo: Elsevier; 1987.)。在组织工程与再生领域,生物活性材料是一种浸泡模拟人体体液(SBF)后类骨碳酸型磷灰石(CHA)会选择性在其表面形成的物质(Kokubo T, TakadamaH. How useful is SBF in predicting in vivo bone bioactivity Biomaterials 27(2006) 2907-2915)。当生物活性材料植入体内时,可以通过其表面形成的类骨磷灰石层与人体软、硬组织进行化学键合并能够促进骨细胞增殖和分化。一般来说,可将材料浸泡在SBF中监测其表面类骨磷灰石形成的速度和数量来表征材料生物活性大小。
近年来,大量研究表明,一些含硅-钙生物活性材料以及硅酸钙生物陶瓷表面在体内、外均能诱导类骨磷灰石的生成,能够促进生物材料与骨组织键合。另外,含硅、钙生物活性材料释放的硅、钙离子能够刺激骨髓基质干细胞向成骨细胞分化并激活细胞基因表达。硅酸三钙是一类新型能够促进骨组织修复的生物材料,具有优异的骨传导、骨诱导性和生物相容性。它既可作为一种可注射性硬组织修复材料,也可制作成生物陶瓷及生物支架,因此在硬组织修复领域有着广泛的应用前景。当硅酸三钙植入体内时能与人体组织液作用在其表面形成一层类骨磷灰石,通过该层类骨磷灰石可以使硅酸三钙与修复部位形成紧密连接。此外,研究表明植入体表面形成的类骨磷灰石能够增强成骨细胞粘附、增殖、分化的能力,进而能够促进骨组织的修复和再生(N. Olmo, A.I. Martin, A.J. Salinas, J.Turnay, M. Vallet-Regi, M.A. Lizarbe, Bioactive sol-gel glasses with andwithout a hydroxycarbonate apatite layer as substrates for osteoblast celladhesion and proliferation, Biomaterials 24 (2003) 3383-3393.)。因此,加速类骨磷灰石层在硅酸三钙表面这一动力学沉积过程,对于组织修复和再生领域来说,具有十分重要的意义。
研究发现,贻贝启发的聚多巴胺(PDA)具有类似于海洋贻贝粘附蛋白的结构和超强粘附性能;PDA还可促进细胞的粘附,具有良好的生物相容性,在生物材料表面改性中有着较为广泛的应用。Ryu等发现,在陶瓷、贵金属、高分子等生物惰性表面涂覆一层PDA能够协助羟基磷灰石在其表面形成,PDA中酚羟基能够使SBF中的钙离子在生物惰性表面富集,进而促进羟基磷灰石的形核、长大(Ryu, J.; Ku, S. H.; Lee, H.; Park, C. B.Mussel-Inspired Polydopamine Coating as a Universal Route to HydroxyapatiteCrystallization. Adv. Funct. Mater. 2010, 20, 2132-2139.)。然而,在利用PDA涂层对生物惰性表面进行生物活性修饰的传统工艺中,存在如下一些问题:1.基体需要在较高浓度(一般为2mg/ml)的盐酸多巴胺缓冲溶液中浸泡,2.基体表面的PDA涂层沉积需要较长一段时间(一般在24小时及以上),所以该法在实际生产应用过程中成本较高,效率较低。针对这一问题,近年来国内外学者进行较多研究。Du等和Lee等分别提出通过紫外光照射和微波照射加速PDA涂层在基体表面沉积(⑴Du, X.; Li, L.; Li, J.; Yang, C.; Frenkel,N.; Welle, A.; Heissler, S.; Nefedov, A.; Grunze, M.; Levkin, P. A. UV-Triggered Dopamine Polymerization: Control of Polymerization, SurfaceCoating, and Photopatterning. Adv. Mater. 2014, 26, 8029-8033. ⑵Lee, M.;Lee, S. H.; Oh, I. K.; Lee, H. Microwave-Accelerated Rapid, Chemical Oxidant-Free, Material-Independent Surface Chemistry of Poly(dopamine). Small 2017,13, 1600443.)该法主要是通过外部提供能量促进多巴胺的氧化聚合,但与传统PDA氧化聚合方法相比该法需外在设备提供能量,较为繁琐,成本较高。鉴于可溶性氧在多巴胺氧化聚合的过程中起到的关键作用,许多学者通过添加氧化剂加速多巴胺的氧化聚合,该法取得了较好的效果。Hong等在多巴胺缓冲液中加入NaIO4,通过喷涂技术实现了在基体表面快速沉积PDA涂层(Hong, S. H.; Hong, S.; Ryou, M.-H.; Choi, J. W.; Kang, S. M.;Lee, H. Sprayable Ultrafast Polydopamine Surface Modifications. Adv. Mater.Interfaces 2016, 3, 1500857.)但该法以NaIO4作为强氧化剂,其生物相容性、细胞毒性等性能需进一步研究,因此该法在生物医用领域可行性亟待考证。
发明内容
针对上述现有技术中存在的问题,以及鉴于植入体表面沉积的类骨磷灰石能够促进成骨细胞粘附、增殖、分化的特点以及能够增强植入体与缺损部位的粘结强度,本发明公开了一种聚多巴胺涂层增强硅酸三钙生物活性的短流程制备方法,利用多巴胺在弱碱条件下自聚合形成PDA,然后通过PDA与硅酸三钙基体形成较强的粘附,并能加速类骨磷灰石在PDA涂覆的硅酸三钙表面动力学沉积过程,增强硅酸三钙生物活性。
本发明是这样实现的:
本发明公开了一种PDA涂层增强硅酸三钙生物活性的短流程制备方法,其特征在于,步骤如下:
步骤一:硅酸三钙基体的制备;
将硅酸三钙粉体与固化液按比例调和成糊状物后,制备成硅酸三钙多孔支架或致密基体;制备工艺具体不限定,有多种工艺,能够制备出多孔支架或致密基体即可。
步骤二:盐酸多巴胺缓冲溶液的配制;
2.1,利用10mM三羟甲基氨基甲烷与0.1M稀盐酸配制成Tris-HCl缓冲溶液;
2.2,将盐酸多巴胺溶解在Tris-HCl缓冲溶液中,形成浓度为0.1-2mg/ml盐酸多巴胺缓冲溶液;
步骤三:硅酸三钙基体上沉积PDA涂层;
将步骤一制备的硅酸三钙基体浸泡在步骤二制备的盐酸多巴胺缓冲溶液中1-16小时,得到表面沉积一层聚多巴胺的硅酸三钙基体。该法实现了硅酸三钙基体在较低浓度的多巴胺缓冲溶液中快速沉积PDA涂层,并能加速类骨磷灰石在PDA涂覆的硅酸三钙表面动力学沉积过程,增强硅酸三钙生物活性。
进一步,所述的步骤一中利用3D打印或整体浇铸的方法形成硅酸三钙多孔支架或致密基体,经3D打印或整体浇铸等工艺形成硅酸三钙基体,基体的形状可以根据需要具体设定。
进一步,所述的盐酸多巴胺缓冲溶液浓度优选为0.5-1mg/ml。
进一步,所述的步骤一制备的硅酸三钙基体浸泡在盐酸多巴胺缓冲溶液中的时间优选为3-12小时。
进一步,所述的Tris-HCl缓冲溶液为弱碱性溶液,pH值为8.5-9.5。
进一步,所述的固化液为离子水或蒸馏水。具体的应用中,一些含有生物相容性无机盐或有机物的蒸馏水或去离子水也都可以作为固化液使用。
本发明与现有技术的有益效果在于:
1)本发明方法中利用多巴胺在弱碱条件下自聚合形成PDA,并通过PDA中羟基、氨基等官能团与硅酸三钙基体形成较强的粘附;本发明方法具备成本较低、简便高效、工艺简单、可控性强以及易于推广等优点;
2)本发明充分利用硅酸三钙基体的特性,硅酸三钙基体在较低浓度的多巴胺缓冲溶液中快速沉积PDA涂层,并能加速类骨磷灰石在PDA涂覆的硅酸三钙表面动力学沉积过程,增强硅酸三钙生物活性;
3)PDA能够促进细胞粘附,具有较好的生物相容性,因此,不会损害硅酸三钙基体的生物学性能,并且没有细胞毒性,该方法能够在生物医用领域运用;
4)通过本发明制备具有PDA涂层的硅酸三钙基体浸泡SBF中5分钟内即可在其表面生成磷灰石,表明PDA涂层能够提高硅酸三钙的生物活性。
附图说明
图1为本发明实施例1中表面沉积PDA涂层的硅酸三钙基体浸泡在SBF中5min后的SEM图片(放大倍数为10000倍);
图2为本发明实施例2中表面沉积PDA涂层的硅酸三钙基体浸泡在SBF中7d后的SEM图片(放大倍数为2000倍);
图3为本发明实施例2中表面沉积PDA涂层的硅酸三钙基体浸泡在SBF中7d后的XRD图谱;
图4为本发明实施例1中表面沉积PDA涂层的硅酸三钙基体浸泡在SBF中7d后基体截面的SEM图片;
图5为本发明实施例2中表面沉积PDA涂层的硅酸三钙基体浸泡在SBF中6h后的SEM图片(放大倍数为10000倍);
图6为本发明对比实施例1中无PDA涂层的硅酸三钙基体浸泡在SBF中5min后的SEM图片(放大倍数为10000倍);
图7为本发明对比实施例1中无PDA涂层的硅酸三钙基体浸泡在SBF中7d后基体截面的SEM图片。
具体实施方式
为使本发明的目的、技术方案及效果更加清楚,明确,以下参照附图并举实例对本发明进一步详细说明。应当指出此处所描述的具体实施仅用以解释本发明,并不用于限定本发明。
实施例1
1)硅酸三钙基体的制备
硅酸三钙粉体和固化液按固液比1: 0.3称取去离子水,最后将粉体与去离子水充分调和1-2分钟,注入模具,在37℃和95%湿度下养护1天后脱模。
2)硅酸三钙基体上沉积PDA涂层
将硅酸三钙基体浸泡在0.1mg/ml盐酸多巴胺缓冲溶液中16小时,得到表面沉积一层聚多巴胺的硅酸三钙基体,该缓冲溶液为10mM Tris-HCl,其pH值为8.5。
3)沉积PDA涂层的硅酸三钙基体生物活性测试:
对表面沉积PDA涂层的硅酸三钙基体采用体外SBF浸泡实验进行生物活性测试,将实施例1中表面沉积PDA涂层的硅酸三钙基体浸泡在SBF中5min后,并对浸泡后样品表面进行SEM表征(放大倍数为10000倍),结果如图1所示,经本发明的通过聚多巴胺涂层增强硅酸三钙生物活性的方法处理后的硅酸三钙表面在5分钟内即可诱导磷灰石生成,表明本发明的通过聚多巴胺涂层增强硅酸三钙生物活性的方法能够增强硅酸三钙基体生物活性。
对表面沉积PDA涂层的硅酸三钙基体采用体外SBF浸泡实验进行生物活性测试,将实施例1中表面沉积PDA涂层的硅酸三钙基体浸泡在SBF中 7d后,并对浸泡后样品截面进行SEM表征,结果如图4所示,涂覆PDA涂层的硅酸三钙基体表面沉积的磷灰石层厚为91.1微米,与对比实例1相比,表明本发明的通过聚多巴胺涂层增强硅酸三钙生物活性的方法能够增强硅酸三钙基体生物活性。
实施例2
1)硅酸三钙基体的制备
硅酸三钙粉体和固化液按固液比1: 0.4称取蒸馏水,最后将粉体与蒸馏水充分调和1-2分钟,注入模具,在37℃和95%湿度下养护1天后脱模。
2)硅酸三钙基体上沉积PDA涂层
将硅酸三钙基体浸泡在0.5mg/ml盐酸多巴胺缓冲溶液中12小时,得到表面沉积一层聚多巴胺的硅酸三钙基体,该缓冲溶液为10mM Tris-HCl,其pH值为8.5。
3)沉积PDA涂层的硅酸三钙基体生物活性测试:
对表面沉积PDA涂层的硅酸三钙基体采用体外SBF浸泡实验进行生物活性测试,并对浸泡后样品表面进行SEM和XRD表征。
本实施例2中表面沉积PDA涂层的硅酸三钙基体浸泡在SBF中7d后,并对浸泡后样品表面进行SEM表征(放大倍数为2000倍),结果如图2所示,表明涂覆PDA涂层的硅酸三钙基体表面沉积了致密的磷灰石层,表明本发明的通过聚多巴胺涂层增强硅酸三钙生物活性的方法能够增强硅酸三钙基体生物活性。
本实施例2中表面沉积PDA涂层的硅酸三钙基体浸泡在SBF中7d后,并对浸泡后样品表面进行XRD表征,结果如图3所示,表明涂覆PDA涂层的硅酸三钙基体表面沉积的磷灰石层为羟基磷灰石。
本实施例2中表面沉积PDA涂层的硅酸三钙基体浸泡在SBF中6h后,并对浸泡后样品表面进行SEM表征(放大倍数为10000倍),结果如图5所示,表明,涂覆PDA涂层的硅酸三钙基体表面形成磷灰石聚集球体,表明本发明的通过聚多巴胺涂层增强硅酸三钙生物活性的方法能够增强硅酸三钙基体生物活性。
实施例3
1)硅酸三钙基体的制备
硅酸三钙粉体和固化液按固液比1: 0.5称取去离子水,然后将粉体与去离子水充分调和1-2分钟,经3D打印后形成多孔支架。
2)硅酸三钙基体上沉积PDA涂层
将硅酸三钙基体浸泡在2mg/ml盐酸多巴胺缓冲溶液中1小时,得到表面沉积一层聚多巴胺的硅酸三钙基体,该缓冲溶液为10mM Tris-HCl,其pH值为8.5。
3)沉积PDA涂层的硅酸三钙基体生物活性测试:
对表面沉积PDA涂层的硅酸三钙基体采用体外SBF浸泡实验进行生物活性测试,并对浸泡后样品表面进行SEM表征,表征结果表明PDA涂层能够提高硅酸三钙的生物活性,可诱导磷灰石生成,本发明的通过聚多巴胺涂层增强硅酸三钙生物活性的方法能够增强硅酸三钙基体生物活性。
实施例4
1)硅酸三钙基体的制备
硅酸三钙粉体和固化液按固液比1: 0.8称取蒸馏水,然后将粉体与蒸馏水充分调和1-2分钟,经3D打印后形成多孔支架。
2)硅酸三钙基体上沉积PDA涂层
将硅酸三钙基体浸泡在1mg/ml盐酸多巴胺缓冲溶液中3小时,得到表面沉积一层聚多巴胺的硅酸三钙基体,该缓冲溶液为10mM Tris-HCl,其pH值为8.5。
3)沉积PDA涂层的硅酸三钙基体生物活性测试:
对表面沉积PDA涂层的硅酸三钙基体采用体外SBF浸泡实验进行生物活性测试,并对浸泡后样品进行SEM表征,表征结果表明PDA涂层能够提高硅酸三钙的生物活性,可诱导磷灰石生成,本发明通过聚多巴胺涂层增强硅酸三钙生物活性的方法能够增强硅酸三钙基体生物活性。
对比实施例1
1)硅酸三钙基体的制备
硅酸三钙粉体和固化液按固液比1: 0.3称取去离子水,最后将粉体与去离子水充分调和1-2分钟,注入模具,在37℃和95%湿度下养护1天后脱模。本对比实施例1与实施例的区别仅在于,对比实施例1中的硅酸三钙基体不进行PDA涂层的沉积。
2)无PDA涂层的硅酸三钙基体生物活性测试:
对硅酸三钙基体采用体外SBF浸泡实验进行生物活性测试,将对比实施例1中硅酸三钙基体浸泡在SBF中5min后,并对浸泡后样品表面进行SEM表征(放大倍数为10000倍),结果如图6所示,无PDA涂层的硅酸三钙基体表面并未沉积的磷灰石。
对表面沉积PDA涂层的硅酸三钙基体采用体外SBF浸泡实验进行生物活性测试,将实施例1中中表面沉积PDA涂层的硅酸三钙基体浸泡在SBF中7d后,并对浸泡后样品表面截面进行SEM表征,结果如图7所示,无PDA涂层的硅酸三钙基体表面沉积的磷灰石球层厚为49.5微米,与实例1相比,无PDA涂层的硅酸三钙基体浸泡在SBF中7d后,磷灰石生成能力较弱,表明本发明的通过聚多巴胺涂层增强硅酸三钙生物活性的方法能够增强硅酸三钙基体生物活性。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进,这些改进也应视为本发明的保护范围。
Claims (6)
1.一种PDA涂层增强硅酸三钙生物活性的短流程制备方法,其特征在于,步骤如下:
步骤一:硅酸三钙基体的制备;
将硅酸三钙粉体与固化液按比例调和成糊状物后,制备成硅酸三钙多孔支架或致密基体;
步骤二:盐酸多巴胺缓冲溶液的配制;
2.1,利用10mM三羟甲基氨基甲烷与0.1M稀盐酸配制成Tris-HCl缓冲溶液;
2.2,将盐酸多巴胺溶解在Tris-HCl缓冲溶液中,形成浓度为0.1-2mg/ml盐酸多巴胺缓冲溶液;所述的Tris-HCl缓冲溶液是pH值为8.5-9.5溶液;
步骤三:硅酸三钙基体上沉积PDA涂层;
将步骤一制备的硅酸三钙基体浸泡在步骤二制备的盐酸多巴胺缓冲溶液中1-16小时,得到表面沉积一层聚多巴胺的硅酸三钙基体。
2.根据权利要求1所述的一种PDA涂层增强硅酸三钙生物活性的短流程制备方法,其特征在于,所述的步骤一中利用3D打印或整体浇铸的方法形成硅酸三钙多孔支架或致密基体。
3.根据权利要求1所述的一种PDA涂层增强硅酸三钙生物活性的短流程制备方法,其特征在于,所述的盐酸多巴胺缓冲溶液浓度为0.5-1mg/ml。
4.根据权利要求1所述的一种PDA涂层增强硅酸三钙生物活性的短流程制备方法,其特征在于,所述的步骤一制备的硅酸三钙基体浸泡在盐酸多巴胺缓冲溶液中3-12小时。
5.根据权利要求1所述的一种PDA涂层增强硅酸三钙生物活性的短流程制备方法,其特征在于,所述的固化液为去离子水或蒸馏水。
6.根据权利要求5所述的一种PDA涂层增强硅酸三钙生物活性的短流程制备方法,其特征在于,所述的硅酸三钙粉体与固化液的比例为1:(0.3~0.8)。
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