CN112358317A - 一种医用骨再生修复纳米生物陶瓷材料及其制备方法与应用 - Google Patents

一种医用骨再生修复纳米生物陶瓷材料及其制备方法与应用 Download PDF

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CN112358317A
CN112358317A CN202011309699.1A CN202011309699A CN112358317A CN 112358317 A CN112358317 A CN 112358317A CN 202011309699 A CN202011309699 A CN 202011309699A CN 112358317 A CN112358317 A CN 112358317A
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repair
ceramic
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calcium phosphate
bone regeneration
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吕玉光
张琳琳
吴江
张国梁
任恒鑫
李俏
程雨晴
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Jiamusi University
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Abstract

本发明公开了一种医用骨再生修复纳米生物陶瓷材料及其制备方法与应用，所述材料由掺杂Ag的纳米氧化锌粉体和双相磷酸钙陶瓷制成，其中：掺杂Ag的纳米氧化锌粉体中，Zn2+和Ag+的摩尔比为2~4:1；双相磷酸钙陶瓷为由羟基磷灰石和β‑磷酸三钙两相成分构成的陶瓷，羟基磷灰石和β‑磷酸三钙的质量比为1:1~3。本发明构建了具有协同可控释放Ag和ZnO功能的多孔磷酸钙纳米陶瓷微球，多孔球形磷酸钙纳米陶瓷颗粒具有优异的骨缺损修复能力，进而达到诱导感染性骨缺损组织再生修复和长效抗菌的目的，为实现抗菌药物的高效装载提供了可能。

Description

一种医用骨再生修复纳米生物陶瓷材料及其制备方法与应用
技术领域
本发明属于医用材料制备技术领域，涉及一种医用骨再生修复纳米生物陶瓷材料及其制备方法与应用。
背景技术
生物陶瓷（Bioceramies）是指用作特定的生物或生理功能的一类陶瓷材料，即直接用于人体或与人体相关的生物、医用、生物化学等的陶瓷材料。广义讲，凡属生物工程的陶瓷材料统称为生物陶瓷。做为生物陶瓷材料，需具备如下条件：（1）生物相容性；（2）力学相容性；（3）与生物组织有优异的亲和性；（4）抗血栓；（5）灭菌性并具有很好的物理、化学稳定性。
生物陶瓷材料可分为生物惰性陶瓷、生物活性陶瓷和生物复合材料三类。生物陶瓷材料因其与人的生活密切相关，故一直倍受材料科学工作者的重视。磷酸钙陶瓷如磷酸三钙（TCP）和羟基磷灰石（HA）是常用人工骨替代材料，由羟基磷灰石、氟磷灰石、磷酸三钙和碳酸磷灰石等磷酸钙盐或其复合物构成的生物陶瓷。Ca/P原子比和材料结构决定其表面是否具有生物活性或生物可吸收性。骨诱导性磷酸钙陶瓷材料是由羟基磷灰石和β-磷酸三钙两相成分构成的陶瓷，其化学组成与骨组织的无机成分相似。目前体内外研究表明双相磷酸钙陶瓷除具有良好的生物相容性、生物活性、骨传导性以外，还具有骨诱导性，因此有望成为理想的骨替代材料。
发明内容
本发明的目的是提供一种医用骨再生修复纳米生物陶瓷材料及其制备方法与应用，通过陶瓷物相组分、工艺参数的控制来调控陶瓷表面纳米空心管的形貌尺寸，以构建最佳的载药位点。结合先进的材料表征技术、细胞及分子生物学技术研究表明，本发明制备的纳米ZnO-Ag生物陶瓷材料对金葡萄球菌和大肠杆菌具有良好的抗菌活性。
本发明的目的是通过以下技术方案实现的：
一种医用骨再生修复纳米生物陶瓷材料，由掺杂Ag的纳米氧化锌粉体和双相磷酸钙陶瓷制成，其中：掺杂Ag的纳米氧化锌粉体中，Zn2+和Ag+的摩尔比为2~4:1，优选摩尔比为3:1；双相磷酸钙陶瓷为由羟基磷灰石和β-磷酸三钙两相成分构成的陶瓷，羟基磷灰石和β-磷酸三钙的质量比为1:1~3，优选质量比为1:2。
一种上述医用骨再生修复纳米生物陶瓷材料的制备方法，包括如下步骤：
步骤一、双相磷酸钙陶瓷坯体的制备：
采用湿法工艺通过控制钙磷比直接得到自然形成的双相磷酸钙粉末羟基磷灰石/β-磷酸三钙，具体制备步骤如下：
选择硬脂酸为大孔造孔剂，双氧水为微孔造孔剂，聚乙烯醇为黏结剂，选择纳米级HA和纳米级β-TCP 粉末为原材料，按照质量比为羟基HA ：β-TCP：造孔剂：聚乙烯醇：双氧水=1: 1~3: 0.5~1.5:0.5~1.5 : 0.1~0.3: 0.1~0.3混料比例，加压成型制得陶瓷坯体，烘干过夜去残留过氧化氢及硬脂酸；
步骤二、骨再生修复纳米生物陶瓷材料制备：
将掺杂Ag的纳米氧化锌粉体和双相磷酸钙陶瓷混合，在1000~1200℃烧结成形，制得骨再生修复纳米生物陶瓷材料，其可用于骨缺损组织再生修复。
相比于现有技术，本发明具有如下优点：
（1）构建了具有协同可控释放Ag和ZnO功能的多孔磷酸钙纳米陶瓷微球；
（2）多孔球形磷酸钙纳米陶瓷颗粒具有优异的骨缺损修复能力，进而达到诱导感染性骨缺损组织再生修复和长效抗菌的目的，为实现抗菌药物的高效装载提供了可能。
附图说明
图1为Ag-ZnO扫描电子显微镜下的结构；
图2为纳米生物陶瓷材料颗粒形貌；
图3为梯度ZnO-Ag/CS/LST纳米生物陶瓷材料及其梯度释放LST和纳米ZnO-Ag协同抗菌的示意图，CS：壳聚糖，LST：葡萄球菌酶。
具体实施方式
下面结合实施例对本发明的技术方案作进一步的说明，但并不局限于此，凡是对本发明技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，均应涵盖在本发明的保护范围中。
实施例1、纳米ZnO-Ag的制备：
步骤1：量取50ml、0.2mol/L硝酸锌水溶液和一定量的掺杂Ag离子的硝酸溶液（即：将Ag的硝酸盐溶解在2mol/L的硝酸中）加入锥形瓶中。
步骤2：磁力搅拌下均匀滴加0.5mol/L(NH4)2CO3溶液，得到沉淀，陈化12h。
步骤3：离心分离，将得到的沉淀用去离子水洗涤三次，用无水乙醇洗涤三次后，真空70 ℃干燥4小时得到前驱体，再放入管式电阻炉中400 ℃退火4小时，即得掺杂Ag的纳米氧化锌粉体，其中：Zn和Ag二种离子的摩尔比为3:1。
实施例2、双相磷酸钙陶瓷坯体的制备：
本实施例中，双相磷酸钙陶瓷为由羟基磷灰石和β-磷酸三钙两相成分构成的陶瓷，其生物活性高于羟基磷灰石陶瓷。本实施例采用湿法工艺通过控制钙磷比直接得到自然形成的双相磷酸钙粉末羟基磷灰石/β-磷酸三钙，具体制备步骤如下：
选择硬脂酸为大孔造孔剂，体积分数30%双氧水为微孔造孔剂，5%聚乙烯醇为黏结剂，选择纳米级HA 和纳米级β-TCP 粉末为原材料，并将二者以HA/β-TCP =1: 2 的质量比混合。按照羟基HA ：β-TCP：造孔剂：聚乙烯醇：双氧水= 1: 2: 1: 1: 0.2: 0.2（质量比）混料比例，2MPa加压成型制得陶瓷坯体，烘干过夜去残留过氧化氢及硬脂酸。
实施例3、骨再生修复纳米生物陶瓷材料制备：
将纳米ZnO-Ag粉体和磷酸钙陶瓷坯体质量比为1: 3, 在1100℃烧结成形，制得骨再生修复纳米生物陶瓷材料。
实施例4、骨再生修复纳米生物陶瓷材料的应用
综合运用场发射扫描电镜、X-射线衍射分析仪、比表面积仪、电感耦合等离子体光谱仪等先进仪器设备对骨再生修复纳米生物陶瓷材料的表面及断面形貌、相组成、元素分布、微孔分布等材料特征及纳米ZnO-Ag的释放行为进行表征和分析，同时应用酶联免疫吸附方法对溶葡萄球菌酶（LST）装载量和释放行为进行定量分析。
由图1所示Ag-ZnO的电子显微镜扫描图可知，合成的样品粒径大小颗粒比较均匀，团聚现象不明显。Ag-ZnO样品平均粒径大小约为30 nm，粒径大小同Scherrer公式的预测值基本相符合。纳米生物陶瓷材料颗粒形貌如图2所示。由图3可知，本实施例采用海藻酸钠凝胶法结合双氧水发泡法成功构建了纳米生物陶瓷材料颗粒，陶瓷颗粒具有良好的球形度、三维贯通的孔隙结构且纳米级的晶粒尺寸，将纳米生物陶瓷材料颗粒植入兔下颌临界尺寸（9mm）骨缺损进行修复评价，发现植入100天后骨缺损有良好的再生修复效果，在缺损区域及材料内部都有大量新生骨组织的生成。纳米生物陶瓷材料颗粒优异的骨缺损修复能力，为材料的构建和感染性骨缺的再生修复奠定了良好的基础。

Claims (6)

1.一种医用骨再生修复纳米生物陶瓷材料，其特征在于所述材料由掺杂Ag的纳米氧化锌粉体和双相磷酸钙陶瓷制成，其中：掺杂Ag的纳米氧化锌粉体中，Zn2+和Ag+的摩尔比为2~4:1；双相磷酸钙陶瓷为由羟基磷灰石和β-磷酸三钙两相成分构成的陶瓷，羟基磷灰石和β-磷酸三钙的质量比为1:1~3。
2.根据权利要求1所述的医用骨再生修复纳米生物陶瓷材料，其特征在于所述Zn2+和Ag+的摩尔比为3:1。
3.根据权利要求1所述的医用骨再生修复纳米生物陶瓷材料，其特征在于所述羟基磷灰石和β-磷酸三钙的质量比为1:2。
4.一种权利要求1-3任一项所述医用骨再生修复纳米生物陶瓷材料的制备方法，其特征在于所述方法包括如下步骤：
步骤一、双相磷酸钙陶瓷坯体的制备：
采用湿法工艺通过控制钙磷比直接得到自然形成的双相磷酸钙粉末羟基磷灰石/β-磷酸三钙；
步骤二、骨再生修复纳米生物陶瓷材料制备：
将掺杂Ag的纳米氧化锌粉体和双相磷酸钙陶瓷混合，在1000~1200℃烧结成形，制得骨再生修复纳米生物陶瓷材料。
5.根据权利要求4所述的医用骨再生修复纳米生物陶瓷材料的制备方法，其特征在于所述双相磷酸钙陶瓷坯体的具体制备步骤如下：
选择硬脂酸为大孔造孔剂，双氧水为微孔造孔剂，聚乙烯醇为黏结剂，选择纳米级HA和纳米级β-TCP 粉末为原材料，按照质量比为羟基HA ：β-TCP：造孔剂：聚乙烯醇：双氧水=1: 1~3: 0.5~1.5:0.5~1.5 : 0.1~0.3: 0.1~0.3混料比例，加压成型制得陶瓷坯体，烘干过夜去残留过氧化氢及硬脂酸。
6.一种权利要求1-3任一项所述医用骨再生修复纳米生物陶瓷材料在骨缺损组织再生修复中的应用。
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