CN110172162A - 基于琼脂的自修复仿生低摩擦水凝胶关节软骨的制备方法 - Google Patents
基于琼脂的自修复仿生低摩擦水凝胶关节软骨的制备方法 Download PDFInfo
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Abstract
本发明公开了一种基于琼脂的自修复仿生低摩擦水凝胶关节软骨的制备方法。所述方法采用琼脂水凝胶为物理交联网络，聚丙烯酸‑聚丙烯酰胺水凝胶为化学交联网络，构成双层网络结构，并引入铁离子与聚丙烯酸形成配位作用，制备出具有多孔含水结构的水凝胶。本发明利用网络间动态可逆的离子配位键和氢键，赋予琼脂/聚丙烯酸‑聚丙烯酰胺‑铁离子双网络水凝胶较高的自修复能力和力学性能。本发明的琼脂/聚丙烯酸‑聚丙烯酰胺‑铁离子双网络自修复水凝胶关节软骨与纯琼脂水凝胶相比，压缩模量提高80％～120％，并且实现了较好的自修复性能。
Description
技术领域
本发明属于植入器件技术领域，涉及一种基于琼脂的自修复仿生低摩擦水凝胶关节软骨的制备方法。
背景技术
水凝胶是由化学交联、物理交联等方式将亲水性的高分子链连接形成的一类具有三维网络结构的功能高分子材料，因其三维网络间填充有大量的水介质而表现出“软”与“湿”的特性。由于水凝胶具有亲水性、生物相容性、软而韧等性能，在生物组织工程领域具有巨大的应用前景。
天然关节软骨主要由水(占70～80％的重量)和细胞外基质组成，细胞外基质的主要成分为构成纤维网络的胶原蛋白，赋予关节软骨较高的强度和弹性。多孔网络结构可以储存滑液，在运动中起到润滑和承载功能。天然关节软骨基本没有自修复的能力，受到损伤后，需要依靠外科手术等手段对其进行修复。
文献1报道了一种主要用于关节软骨损伤修复方面的CS/HA-g-CS的复合水凝胶(杨慎宇.壳聚糖/改性纳米羟基磷灰石复合水凝胶的制备及其软骨缺损修复有效性评价[D].广州：暨南大学，2016)。但该类水凝胶的修复性能通常以牺牲力学性能为代价，缺乏自修复的能力，严重限制了它的应用。
琼脂水凝胶具有良好的生物力学性质，例如良好的硬度和粘弹性，能够较好地与软骨组织相匹配，有望应用于软骨再生方面。K.J.Lee等人在制备的琼脂糖纳米复合水凝胶上培养成功了成骨细胞样细胞(MG63)(K.J.Lee,S.I.Yun.Nanocomposite hydrogelsbased on agarose and diphenylalanine[J].Polymer,2018,139:86-97)。但对于在骨组织工程中的应用，尤其是在关节软骨这种需要承受压力的条件下，其机械性能不够，并且缺乏受损后自修复的能力。
发明内容
针对传统水凝胶软骨机械性能不足和无自修复能力的问题，本发明提供一种基于琼脂的自修复仿生低摩擦水凝胶关节软骨的制备方法。该方法采用在琼脂水溶液中加入丙烯酰胺(AAm)和丙烯酸(AAc)单体，以及铁离子，先室温冷却构筑琼脂的物理交联网络，再经光引发和化学交联得到聚丙烯酸-丙烯酰胺的化学交联网络，同时铁离子与羧酸根形成离子交联，从而构筑出琼脂基双网络自修复低摩擦水凝胶关节软骨。
本发明的技术解决方案如下：
基于琼脂的自修复仿生低摩擦水凝胶关节软骨的制备方法，以琼脂为原料，先将琼脂溶于水中，再加入丙烯酸和丙烯酰胺单体、光引发剂、交联剂以及铁离子，经过室温冷却，琼脂分子在氢键作用下交联形成第一层三维网络结构，然后在紫外光辐照下形成PAAc-PAAm网络，同时铁离子与羧酸根形成配位交联，实现增强作用，具体步骤如下：
在丙烯酸(AAc)、丙烯酰胺单体(AAm)和Fe3+的混合溶液中加入交联剂N,N'-亚甲基双丙烯酰胺(MBAA)与光引发剂α-酮戊二酸(KA)，混合均匀后，95℃～100℃下加入到琼脂水溶液中，搅拌均匀后注入模具中，冷却至室温，紫外光辐照，得到琼脂/聚丙烯酸-聚丙烯酰胺-铁离子(琼脂/PAAc-PAAm-Fe3+)双网络水凝胶关节软骨；其中，所述的丙烯酸和丙烯酰胺的总摩尔量与琼脂的摩尔比为35：1～75:1，铁离子的摩尔量为丙烯酸摩尔量的0.5％～1％。
优选地，所述的琼脂水溶液的浓度为0.05～0.1mol/L。
优选地，所述的丙烯酸与丙烯酰胺的摩尔比为1：3。
优选地，所述的Fe3+溶液为硝酸铁溶液。
优选地，所述的N,N'-亚甲基双丙烯酰胺与α-酮戊二酸加入的摩尔量为丙烯酸和丙烯酰胺的总摩尔量的0.1％～0.5％。
优选地，所述的紫外光辐照时间为1.5h。
本发明采用生物相容性优异的琼脂为第一层网络，亲水性聚合物丙烯酸(AAc)、丙烯酰胺(AAm)为第二层网络，制备双网络水凝胶，并且引入铁离子(Fe3+)形成动态可逆的离子交联作为能量耗散机制，使得水凝胶的力学性能得到提高，同时赋予其优异的自修复性能，对改善水凝胶关节软骨的摩擦性能、力学性能和自修复性能、延长其使用寿命具有重要意义。
与现有技术相比，本发明具有以下优点：
(1)本发明采用的琼脂、丙烯酸、丙烯酰胺等原料均具有良好的生物相容性，制得的水凝胶关节软骨有较好的临床应用前景；
(2)本发明制备方法简单，成本低廉，制得的基于琼脂的双网络自修复仿生低摩擦水凝胶关节软骨具有较高的力学性能，在动态可逆的非共价键(离子配位键和氢键)作用下，具有优异自修复能力；
(3)本发明的多孔网络结构的水凝胶关节软骨可以起到储存、释放润滑剂的作用，具有较低摩擦系数，延长人工关节软骨使用寿命。
附图说明
图1为琼脂/聚丙烯酸-聚丙烯酰胺-铁离子双网络自修复水凝胶网络的制备流程示意图。
具体实施方式
本发明的基于琼脂的自修复仿生低摩擦水凝胶关节软骨的制备方法，包括以下步骤：
(1)将琼脂加入去离子水中，水浴温度97℃搅拌溶解，得到琼脂水溶液。
具体方式为：向15ml去离子水中加入0.3363g琼脂，水浴温度97℃下搅拌4小时；
2)随后配置AAc、AAm、Fe3+溶液，加入交联剂与光引发剂，将该混合溶液加入琼脂溶液中搅拌均匀。
具体方式为：向5ml去离子水中加入AAc(0.6305g-1.3511g)、AAm(1.8659g-3.9983g)，使琼脂的摩尔量与丙烯酸和丙烯酰胺的摩尔总量的比为1:35～1:75，丙烯酸与丙烯酰胺摩尔量之比为1：3，加入Fe(NO3)3·9H2O(0.0177g-0.0758g)，使得铁离子的物质的量为丙烯酸的物质的量的0.5％～1％，加入MBAA(0.0054g-0.0116g)、KA(0.0051g-0.0110g)，使其摩尔量为丙烯酸和丙烯酰胺的摩尔总量的0.1％～0.5％，避光搅拌0.5小时，加入琼脂溶液搅拌半个小时得到均匀溶液。
3)将所得混合溶液注入模具中，冷却至室温，
具体方式为：将混合溶液注入两片玻璃板与一个橡胶圈构成的模具中，避光冷却至室温。
4)进行紫外光辐照，得到琼脂/PAAc-PAAm-Fe3+双网络水凝胶。
具体方式为：将稍成型的单体在紫外光中辐照1.5小时，得到琼脂/PAAc-PAAm-Fe3+双网络水凝胶关节软骨。
下面结合具体实施例对本发明作进一步详述。
实施例1
以琼脂的物质的量与丙烯酸和丙烯酰胺的物质的量之和的比为1:35，铁离子的物质的量为丙烯酸物质的量的0.5％的比例制备溶液。先配制0.05mol/L的琼脂溶液，水浴温度95℃搅拌4小时溶解，随后配置AAc、AAm、Fe(NO3)3·9H2O、MBAA(0.0054g)、KA(0.0051g)溶液，避光搅拌0.5小时，再将其加入琼脂溶液中搅拌0.5小时，得到均匀溶液。将所得混合溶液注入玻璃模具中，冷却至室温，再进行紫外光辐照1.5小时，得到琼脂/PAAc-PAAm-Fe3+双网络水凝胶关节软骨。与纯琼脂水凝胶7MPa相比，压缩模量提高85％左右，自修复性能可实现，完全自修复时间为2天，摩擦系数为0.09。
实施例2
以琼脂的物质的量与丙烯酸和丙烯酰胺的物质的量之和的比为1:50，铁离子的物质的量为丙烯酸物质的量的0.75％的比例制备溶液。先配制0.05mol/L的琼脂溶液，水浴温度95℃搅拌4小时溶解，随后配置AAc、AAm、Fe(NO3)3·9H2O、MBAA(0.0077g)、KA(0.0073g)溶液，避光搅拌0.5小时，再将其加入琼脂溶液中搅拌0.5小时，得到均匀溶液。将所得混合溶液注入玻璃模具中，冷却至室温，再进行紫外光辐照1.5小时，得到琼脂/PAAc-PAAm-Fe3+双网络水凝胶关节软骨。与纯琼脂水凝胶相比，压缩模量提高98％左右，自修复性能可实现，完全自修复时间为3天，摩擦系数为0.1。
实施例3
以琼脂的物质的量与丙烯酸和丙烯酰胺的物质的量之和的比为1:75，铁离子的物质的量为丙烯酸物质的量的1％的比例制备溶液。先配制0.05mol/L的琼脂溶液，水浴温度95℃搅拌4小时溶解，随后配置AAc、AAm、Fe(NO3)3·9H2O、MBAA(0.0116g)、KA(0.0110g)溶液，避光搅拌0.5小时，再将其加入琼脂溶液中搅拌0.5小时，得到均匀溶液。将所得混合溶液注入玻璃模具中，冷却至室温，再进行紫外光辐照1.5小时，得到琼脂/PAAc-PAAm-Fe3+双网络水凝胶关节软骨。与纯琼脂水凝胶相比，压缩模量提高118％左右，自修复性能可实现，完全自修复时间为7天，摩擦系数为0.077。
对比例1
以琼脂的物质的量与丙烯酸和丙烯酰胺的物质的量之和的比为1:20，铁离子的物质的量为丙烯酸物质的量的1％的比例制备溶液。先配制0.05mol/L的琼脂溶液，水浴温度95℃搅拌4小时溶解，随后配置AAc、AAm、Fe(NO3)3·9H2O、MBAA(0.0031g)、KA(0.0029g)溶液，避光搅拌0.5小时，再将其加入琼脂溶液中搅拌0.5小时，得到均匀溶液。将所得混合溶液注入模具中，冷却至室温，再进行紫外光辐照1.5小时，得到琼脂/PAAc-PAAm-Fe3+双网络水凝胶关节软骨。与纯琼脂水凝胶相比，压缩模量仅提高40％左右，自修复时间为2天，摩擦系数为0.3。
对比例2
以琼脂的物质的量与丙烯酸和丙烯酰胺的物质的量之和的比为1:100，铁离子的物质的量为丙烯酸物质的量的0.5％的比例制备溶液，先配制0.05mol/L的琼脂溶液，水浴温度95℃搅拌4小时溶解，随后配置AAc、AAm、Fe(NO3)3·9H2O、MBAA(0.0154g)、KA(0.00146g)溶液，避光搅拌0.5小时，再将其加入琼脂溶液中搅拌0.5小时，得到均匀溶液。将所得混合溶液注入玻璃模具中，冷却至室温，再进行紫外光辐照1.5小时，得到琼脂/PAAc-PAAm-Fe3+双网络水凝胶关节软骨。与纯琼脂水凝胶相比，压缩模量提高98％左右，自修复时间为14天，未完全修复，表面仍有裂纹，摩擦系数为0.08。
Claims (6)
1.基于琼脂的自修复仿生低摩擦水凝胶关节软骨的制备方法，其特征在于，具体步骤如下：
在丙烯酸、丙烯酰胺单体和Fe3+的混合溶液中加入交联剂N,N'-亚甲基双丙烯酰胺与光引发剂α-酮戊二酸，混合均匀后，95℃～100℃下加入到琼脂水溶液中，搅拌均匀后注入模具中，冷却至室温，紫外光辐照，得到琼脂/PAAc-PAAm-Fe3+双网络水凝胶关节软骨；其中，所述的丙烯酸和丙烯酰胺的总摩尔量与琼脂的摩尔比为35：1～75:1，铁离子的摩尔量为丙烯酸摩尔量的0.5％～1％。
2.根据权利要求1所述的制备方法，其特征在于，所述的琼脂水溶液的浓度为0.05～0.1mol/L。
3.根据权利要求1所述的制备方法，其特征在于，所述的丙烯酸与丙烯酰胺的摩尔比为1：3。
4.根据权利要求1所述的制备方法，其特征在于，所述的Fe3+溶液为硝酸铁溶液。
5.根据权利要求1所述的制备方法，其特征在于，所述的N,N'-亚甲基双丙烯酰胺与α-酮戊二酸加入的摩尔量为丙烯酸和丙烯酰胺的总摩尔量的0.1％～0.5％。
6.根据权利要求1所述的制备方法，其特征在于，所述的紫外光辐照时间为1.5h。
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