CN116768615A - 一种可响应超声波机械刺激的电活性骨修复材料及其制备方法 - Google Patents
一种可响应超声波机械刺激的电活性骨修复材料及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种可响应超声波机械刺激的电活性骨修复材料及其制备方法，该可响应超声波机械刺激的电活性骨修复材料，由粉体、保护剂、分散剂、塑型剂组成；粉体中磷酸三钙的含量为90～95％，铌酸钾钠的含量为5～10％。本发明的材料烧结成型后能较好保持支架结构，具有较好的机械性能和抗菌效果，且可响应超声波机械刺激，通过压电效应转化为电刺激，可通过电化学反应生成抗菌物质，抑制细菌在材料表面的生长和生物膜的形成，具有很好的抗菌效果，相较于传统骨修复材料具有显著优势。
Description
技术领域
本发明属于生物医用材料技术领域，尤其是涉及一种可响应超声波机械刺激的电活性骨修复材料及其制备方法。
背景技术
磷酸三钙(Calcium Phosphate Tribasic,TCP)是最常见的骨组织工程支架材料之一，具有良好的生物相容性和细胞相容性。将TCP制成的骨修复植入物后，细胞易在由表面黏附、增殖及成骨分化，但同时该植入物表面也会对各种细菌也有较大的吸引力，在将植入物植入体内的手术过程中，容易引起细菌的感染，引起炎症导致种植体周围炎。此外，细菌还会氧化和腐蚀材料，产生金属离子、颗粒和碎片，破坏受感染的植入物表面，最终导致植入失败。一旦发生植入物相关感染，会给患者及家属带来巨大的身心压力和成倍增长的经济负担。
目前已有多种具有抗菌表界面的植入物表面，如抗细菌黏附的表面，释放抗生素、抗菌离子的表面，直接接触抗菌表面等。以上抗菌策略均具有一定的抗菌效果，但仍有许多尚待改进之处，包括骨整合性能低、抗菌寿命短及抗生素耐药性等问题。因此，迫切需要开发出一种具有响应能力的本体抗菌植入材料以实现高效持久的杀菌效果。低强度脉冲超声(low-intensity pulsed ultrasound,LIPUS)可作为一种机械刺激用于激发压电生物材的压电效应，在材料表面富集更多的电荷。含有压电陶瓷的材料能响应LIPUS的机械刺激，进而激发其压电效应，从而产生表面电荷。如表面有BT涂层的智能钛合金植入材料可在LIPUS的作用下促进周围骨组织再生。然而，TCP/BT材料及其协同LIPUS作用的抗菌性能尚未见报道。
铌酸钾钠(K0.5Na0.5NbO3，KNN)是一种具有良好的生物安全性的压电陶瓷材料，属于典型的钙钛矿ABO3型结构，具有居里温度高、介电常数低、压电性能良好和机电耦合系数高等特性。在烧结成型过程中，KNN可通过掺杂其他物质实现特定功能，在骨组织再生方面具有较大的潜力。
中国专利201510047297.1，一种仿生骨植入材料及其制备方法，公开了一种仿生骨植入材料及其制备方法。主要是通过共混分散剂和陶瓷颗粒得到的，其压电相陶瓷占陶瓷颗粒总质量的50-99％，压电相陶瓷占比过高，导致其生物安全性、生物相容性、降解性能不能满足使用需求，而且其也不具备抗菌的作用。
发明内容
本发明的目的在于：针对现有骨组织工程材料体内活性不足，无法有效刺激新组织生成，同时又容易染菌的问题，提供一种可响应超声波机械刺激的电活性骨修复材料。本发明还提供了所述可响应超声波机械刺激的电活性骨修复材料的制备方法。
为了实现上述目的，本发明采取以下技术方案：
一种可响应超声波机械刺激的电活性骨修复材料，由粉体、保护剂、分散剂、塑型剂组成；所述粉体中磷酸三钙的含量为90～95％，铌酸钾钠的含量为5～10％。
进一步的优选所述铌酸钾钠粒径为10～20nm；所述磷酸三钙的粒径为30～100μm。
本发明中所述保护剂的质量为粉体总量的1～3％。所述保护剂为氧化钙、氧化铁、氧化铝中的一种或任意几种的混合，所述保护剂的粒径为10～20nm。
本发明中的保护剂可有效防止铌酸钾钠在烧结过程中与磷酸三钙之间的反应，减少副产物的形成，同时还使烧结后的压电组织致密，晶粒尺寸增大，大幅降低材料体系中压电材料的用量，使生物安全性和生物相容性大幅提升。
本发明中，所述粉体与分散剂的质量体积比为(2.0～3.0)g:1ml。
所述分散剂为聚甲基丙烯酸铵水溶液、聚乙烯醇水溶液、聚羧酸钠盐水溶液中的一种或任意几种的混合，所述分散剂的浓度为30～60g/L。
本发明中，所述塑型剂与分散剂的质量体积比为(0.1～0.5)g:1/ml。所述塑型剂为甲从纤维素、乙华纤维素、起乙基纤维素中一种或任意几种的混合。
本发明一种可响应超声波机械刺激的电活性骨修复材料的制备方法，包括以下步骤：
S1、配置好分散剂，再向其中加入粉体，超声混合均匀，得磷酸三钙/铌酸钾钠混合物；
S2、在步骤S1得到的磷酸三钙/铌酸钾钠混合物中加入塑型剂，搅拌混匀后，脱泡，抽真空，得浆料；
S3、将步骤S2中得到的浆料通过模具成型，得毛坯；
S4、将步骤S3所得毛坯进行煅烧后得到支架；
S5、将步骤S4煅烧后的支架进行极化即可。
本发明步骤S1中，所述超声混合的温度为50～60℃，超声时间为15～30min。
步骤S2中，混匀和脱泡过程的转速为1500～2500rpm，搅拌时间为5～10min。
步骤S4中，煅烧分为3个阶段，第一阶段的工艺温度为300～500℃，升温速率为0.5～2℃/min；第二阶段的工艺温度为700～900℃，升温速率为1～3℃/分钟；第三阶段的工艺温度为900～1100℃，升温速率为1～3℃/分钟。
所述步骤S5中，极化的条件为具体方法为：在煅烧后的毛坯上下表面涂覆一层银电极；在1～6Kv/mm，80～130℃的条件下反应20～40min；极化完成后除去材料表面银电极，清洗干燥即可。
本发明中的一种可响应超声波机械刺激的电活性骨修复材料在LIPUS刺激下具有较高的安全性。同时本材料因为含较低浓度的压电陶瓷，成分与天然骨组织更接近，生物相容性更好。
与现有技术相比，本发明的有益效果为：
1、本发明一种可响应超声波机械刺激的电活性骨修复材料，烧结成型后能较好保持支架结构，具有较好的机械性能和抗菌效果。
2、本发明制备的骨修复材料可使用超声波进行机械刺激，通过压电效应转化为电刺激，可通过电化学反应生成抗菌物质，抑制细菌在材料表面的生长和生物膜的形成，具有很好的抗菌效果，相较于传统骨修复材料具有显著优势。
附图说明
图1为金黄色葡萄球菌在各组材料上12h后MTT检测结果；
图2为mBMSCs在各组材料上增殖情况。
具体实施方式
下面结合具体实施例对本发明作进一步的说明，但并不局限于此。
实施例
本实施例中一种可响应超声波机械刺激的电活性骨修复材料由以下步骤制备得到：
S1、在10L分散剂中加入粉体(铌酸钾钠和磷酸三钙)，粉体的总添加量和分散剂的质量体积比为2.5g/ml，再加入粉体总量1％重量的氧化钙(保护剂)，混合均匀，在60℃的温度下、超声30min，得到的磷酸三钙/铌酸钾钠混合物；
S2、在步骤S1的得到的磷酸三钙/铌酸钾钠混合物中加入与分散剂的质量体积比为0.1g/ml的甲从纤维素(塑型剂)，经2000rmp混匀脱泡5min，之后抽真空去除残余气泡；
S3、将步骤S2中得到的浆料通过模具成型，得毛坯；
S4、将步骤S3所得毛坯室温干燥24h后，在400℃(升温速率为1℃/min)下烧结1h以去除有机质，然后在900℃温度下(升温速率为3℃/min)煅烧2h得到支架。
S5、将步骤S4所得支架上下表面涂覆一层银电极，并在5Kv/mm，120℃，条件下极化30min；极化完成后除去支架表面银电极，清洗干燥即得。
其中：
粉体由10％的铌酸钾钠和90％的磷酸三钙混合而成；铌酸钾钠的粒径为10nm；磷酸三钙粉体的粒径为100μm；
分散剂为聚乙烯醇水溶液和聚羧酸钠盐水溶液按1∶1的比例混合配置而成，其浓度为50g/L。
对比例
对比例1
对比例1中骨修复材料由以下步骤制备得到：
S1、在10L分散剂中加入粒径为100μm的磷酸三钙，磷酸三钙的总添加量和分散剂的质量体积比为2.5g/ml，再加入磷酸三钙1％含量的氧化钙(保护剂)，混合均匀，60℃温度下，超声30min，得到混合物；
S2、在步骤S1的得到的混合物中加入与分散剂的质量体积比为0.1g/ml的甲从纤维素(塑型剂)，经2000rmp混匀脱泡5min，之后抽真空去除残余气泡；
S3、将步骤S2中得到的浆料通过模具成型，得毛坯；
S4、将步骤S3所得毛坯室温干燥24h后，在400℃(升温速率为1℃/min)下烧结1h以去除有机质，然后在900℃温度下(升温速率为3℃/min)煅烧2h得到支架。
S5、将步骤S4所得支架上下表面涂覆一层银电极，并在5Kv/mm，120℃，条件下极化30min；极化完成后除去支架表面银电极，清洗干燥即得。
其中，对比例1使用的分散剂组成和实施例中相同。
对比例2
对比例2中骨修复材料的制备方法与实施例不同之处在于，对比例2使用的粉体中铌酸钾钠和磷酸三钙的含量均为50％；其余步骤、材料的选择及工艺条件均与实施例相同。
应用例
材料及主要试剂、仪器：
金黄色葡萄球菌(齐源生物)；大鼠骨髓间充质干细胞(赛业)；
Thermo3001酶标仪(赛默飞世尔科技(中国)有限公司)，Axio Imager M2m金相显微镜(卡尔蔡司)。
1.抗菌能力测试
将金黄色葡萄球菌悬浮在PBS溶液中，配置得到106CFU/mL的浓度用于抗菌试验。灭菌后的材料置于48孔板中，取实施例制备的材料分为三组，并分别命名为Blank、TCP/KNN、TCP/KNN/LIPUS组，将对比例1和对比例2分别命名为TCP、TCP/H-KNN/LIPUS组，将细菌悬液分别滴加到实施例TCP/KNN、TCP/KNN/LIPUS组和对比例TCP、TCP/H-KNN/LIPUS组中的每个材料表面(其中Blank是在实施例的制备的材料中没有添加细菌以作为的空白对照)，将5组材料置于37℃孵育12h。孵育期间每间隔4h对TCP/KNN/LIPUS组和TCP/H-KNN/LIPUS组进行一次LIPUS刺激。12h后将材料取出置于另一新48孔板内，每孔加200μL MTT(5mg/ml)，35℃培养20min后每孔加入DMSO 100μL，振荡10min，检测570nm处的吸光度值，检测结果如图1所示，图中测出的吸光度值越低，说明材料的抗菌效果越好。
由图1可以看出，实施例TCP/KNN组的材料相比于对比例1只添加TCP的材料具有更好抗菌效果，TCP/KNN/LIPUS组和TCP/H-KNN/LIPUS组制备得到的电活性骨修复材料在LIPUS刺激条件下，能显著抑制金黄色葡萄球菌在支架表面的生长。说明本发明制得的电活性骨修复材料是可以响应超声波机械刺激的，且在LIPUS刺激条件下抗菌效果更加明显。
其中，LIPUS刺激条件为：频率1.5MHz；强度120mW/cm2；工作时间800μs，停止时间200μs；5min/次。
2.细胞毒性测试
将灭菌后的TCP/KNN、TCP/KNN/LIPUS、TCP、TCP/H-KNN/LIPUS组4组材料分别置于48孔板中，每孔接种2×104个mBMSCs细胞。将TCP/KNN/LIPUS和TCP/H-KNN/LIPUS组材料在细胞接种24h后按照1次/天的频率进行LIPUS刺激。培养1、4、7天后，检测细胞在各组材料上的增殖情况(检测450nm处的吸光度值)，结果如图2所示，图中测出的吸光度值越高，说明细胞在各组材料上的增殖数量越多。
根据图2可知，本实施例制得的TCP/KNN组材料上的mBMSCs细胞增长速率相对于对比例TCP和TCP/H-KNN/LIPUS组要快，说明本发明制备的电活性骨修复材料可以很好的促进mBMSCs在支架上的增殖，KNN含量过高的H-KNN/LIPUS组对mBMSCs细胞增长速率造成了一定的影响；而TCP/KNN/LIPUS材料上的mBMSCs细胞增长速率最快，说明LIPUS刺激可进一步的促进mBMSCs在支架上的增殖，即本发明制备的电活性骨修复材料是可积极响应超声波机械刺激的。
Claims (10)
1.一种可响应超声波机械刺激的电活性骨修复材料，其特征在于由粉体、保护剂、分散剂、塑型剂组成；所述粉体中磷酸三钙的含量为90～95％，铌酸钾钠的含量为5～10％。
2.根据权利要求1所述的可响应超声波机械刺激的电活性骨修复材料，其特征在于所述保护剂的质量为粉体总量的1～3％；所述粉体与分散剂的质量体积比为(2.0～3.0)g:1ml；所述塑型剂与分散剂的质量体积比为(0.1～0.5)g:1/ml。
3.根据权利要求2所述的可响应超声波机械刺激的电活性骨修复材料，其特征在于所述保护剂为氧化钙、氧化铁、氧化铝中的一种或任意几种的混合，所述保护剂的粒径为10～20nm。
4.根据权利要求2所述的可响应超声波机械刺激的电活性骨修复材料，其特征在于所述分散剂为聚甲基丙烯酸铵水溶液、聚乙烯醇水溶液、聚羧酸钠盐水溶液中的一种或任意几种的混合，所述分散剂的浓度为30～60g/L。
5.根据权利要求2所述的可响应超声波机械刺激的电活性骨修复材料，其特征在于所述塑型剂为甲从纤维素、乙华纤维素、起乙基纤维素中一种或任意几种的混合。
6.一种权利要求1至5中任一项所述的可响应超声波机械刺激的电活性骨修复材料的制备方法，其特征在于包括以下步骤：
S1、配置好分散剂，再向其中加入粉体，超声混合均匀，得磷酸三钙/铌酸钾钠混合物；
S2、在步骤S1得到的磷酸三钙/铌酸钾钠混合物中加入塑型剂，搅拌混匀后，脱泡，抽真空，得浆料；
S3、将步骤S2中得到的浆料通过模具成型，得毛坯；
S4、将步骤S3所得毛坯进行煅烧后得到支架；
S5、将步骤S4煅烧后的支架进行极化即可。
7.根据权利要求6所述的可响应超声波机械刺激的电活性骨修复材料的制备方法，其特征在于步骤S1中，所述超声混合的温度为50～60℃，超声时间为15～30min。
8.根据权利要求6所述的可响应超声波机械刺激的电活性骨修复材料的制备方法，其特征在于所述步骤S2中，混匀和脱泡过程的转速为500～2500rpm，搅拌时间为5～10min。
9.根据权利要求6所述的可响应超声波机械刺激的电活性骨修复材料的制备方法，其特征在于所述步骤S4中，煅烧分为3个阶段，第一阶段的工艺温度为300～500℃，升温速率为0.5～2℃/min；第二阶段的工艺温度为700～900℃，升温速率为1～3℃/分钟；第三阶段的工艺温度为900～1100℃，升温速率为1～3℃/分钟。
10.根据权利要求6所述的可响应超声波机械刺激的电活性骨修复材料的制备方法，其特征在于所述步骤S5中，极化的具体方法为：在煅烧后的毛坯上下表面涂覆一层银电极；在1～6Kv/mm，80～130℃的条件下反应20～40min；极化完成后除去材料表面银电极，清洗干燥即可。
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