表面纳米化和GelMA修饰对钛合金生物学性能的影响研究

钛及其合金（以下简称“钛合金”）具有优异的力学性能、化学稳定性和良好的生物相容性，已成为临床上骨种植体的主要材料。然而，钛合金是生物惰性材料，不能促进种植体周围的骨再生，且不具备抗菌能力，导致其临床失效率较高。因此，赋予钛合金种植体良好的骨诱导能力，提高种植体与周围骨组织的结合能力（骨整合）并预防细菌感染是种植体长期保持稳定的关键。光热疗法（Photothermal therapy, PTT）和光动力疗法（Photodynamic therapy, PDT）因具有高效杀菌且不产生细菌耐药性等优点，有望实现安全高效地抗菌。然而，目前常用的PTT和PDT材料因与基底材料的结合强度不高及光敏剂毒性等问题，很难实现在种植体表面的应用。针对上述问题，本文利用水热技术在钛合金表面原位构建氧化钛纳米结构，通过改变工艺参数来调控纳米结构，从而赋予种植体表面近红外光吸收性能。研究了氧化钛纳米结构和光吸收的关系，纳米结构在近红外辐照下的体外抗菌性能。此外，利用甲基丙烯酸酐化明胶（Methacrylate Gelatin, GelMA）对氧化钛纳米结构进行修饰，利用其表面丰富的官能团吸附抗菌药物羧苄青霉素钠（Carbenicillin disodium, CID）和促骨整合的药物姜黄素（Curcumin, Cur），评价了涂层的体外抗菌性能及促成骨相关细胞增殖等生物学性能。本文的主要研究内容和结论如下：

1、钛合金表面氧化钛纳米结构光吸收性能的调控及生物学性能评价。利用水热技术在钛合金表面原位构建氧化钛纳米结构，通过调控实验参数，实现对纳米结构的调控，考察纳米结构和光吸收的关系。通过紫外-可见光-近红外光吸收光谱筛选出具有近红外光吸收的纳米结构，利用扫描电子显微镜、拉曼光谱仪和水接触角测试仪对纳米结构进行表征。结果表明该纳米结构主要由锐钛矿和金红石相构成，纳米结构的形成改善了钛合金表面润湿性。体外抗菌实验表明，纳米结构在近红外光下（808 nm，1.13 W/cm²）照射10 min后对金黄色葡萄球菌具有良好的抗菌能力，同时该纳米结构能够促进MC3T3-E1细胞的增殖，表明该纳米结构具有良好的生物相容性。

2、GelMA对钛合金表面纳米结构的修饰及其生物学性能评价。选择具有近红外光吸收的纳米结构（0.18 M HCl，180 ℃，4 h），在其表面吸附一层GelMA，利用GelMA表面丰富的官能团吸附抗菌药物羧苄青霉素钠以及促成骨功能的药物姜黄素和地塞米松。利用红外光谱和荧光染色等手段证明该纳米结构对GelMA具有较强的吸附能力，扫描电镜结果表明吸附GelMA不会掩盖纳米结构特征。体外抗菌实验表明，吸附羧苄基青霉素钠的纳米结构表面（TiO₂/GelMA-CID）对金黄色葡萄球菌具有显著的抗菌性能，同时体外细胞实验表明其对MC3T3-E1细胞无显著毒性。此外，吸附姜黄素和地塞米松的GelMA修饰的纳米结构表面对成骨细胞的增殖具有一定影响。此结果说明GelMA修饰的纳米氧化钛表面可为药物装载提供良好的平台。

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