3D打印强韧两性离子聚碳酸酯聚氨酯半月板替代物用于改善软骨磨损  

3D-printed tough zwitterionic polycarbonate polyurethane meniscus substitute ameliorates cartilage abrasion

作　　者：吴阳 张倩 杨徐轩 张晓平 聂雄峰 肖萌 姚远 徐子扬 刘文广 Yang Wu;Qian Zhang;Xuxuan Yang;Xiaoping Zhang;Xiongfeng Nie;Meng Xiao;Yuan Yao;Ziyang Xu;Wenguang Liu(School of Materials Science and Engineering,Tianjin Key Laboratory of Composite and Functional Materials,Tianjin University,Tianjin 300350,China)

机构地区：[1]School of Materials Science and Engineering,Tianjin Key Laboratory of Composite and Functional Materials,Tianjin University,Tianjin 300350,China

出　　处：《Science China Materials》2023年第9期3744-3756,共13页中国科学（材料科学（英文版）

基　　金：supported by the National Key Research and Development Program (2018YFA0703100)。

摘　　要：开发同时满足韧性、抗疲劳性和润滑性等多种体内需求的半月板替代物仍面临巨大挑战.本文首先通过磺基甜菜碱二醇、聚碳酸酯二醇和六亚甲基二异氰酸酯之间的反应合成两性离子聚氨酯的预聚物,并通过己二酸二酰肼对两性离子聚氨酯预聚物进行扩链,制得多重氢键交联的两性离子超分子聚氨酯.通过调节硬段中的氢键和水环境下的水合作用,引入的两性离子侧基可以显著提高聚氨酯弹性体的韧性、可打印性和润滑性.通过熔融沉积成型3D打印技术可以在无需任何后处理的前提下,定制兼具强韧性和润滑性的两性离子聚氨酯半月板支架.在溶胀平衡状态下, 3D打印的两性离子聚氨酯结构的杨氏模量为16.87±2.00 MPa,韧性为19.90±5.94 MJ m^(-3),撕裂能为12.51±1.57 kJ m^(-2),且耐疲劳性优异.将3D打印两性离子聚氨酯半月板替代物植入兔膝关节12周,体内结果表明其能够有效减轻软骨表面磨损的问题.Developing a meniscus substitute that meets high in vivo demands of toughness,anti-fatigue,and lubrication remains a great challenge.Herein,a zwitterionic polyurethane(PU)prepolymer is synthesized through the reaction of sulfobetaine-based diol,polycarbonate diol,and hexamethylene diisocyanate.The zwitterionic PU prepolymer is then chain-extended by adipic acid dihydrazide to form multiple hydrogen-bonded crosslinked zwitterionic supramolecular polyurethane.By regulating the hydrogen bonds in the hard segment and hydration under the aqueous environment,the introduced zwitterionic side group can significantly enhance the toughness,printability,and lubrication of PU elastomer.By using the fused deposition modeling three-dimensional(3D)printing technology,the zwitterionic PU meniscus scaffold with robustness,toughness and lubrication was customized without any other post-treatment.In swelling equilibrium,the printed zwitterion-PU construct demonstrates Young’s modulus of 16.87±2.00 MPa,toughness of 19.90±5.94 MJ m^(−3),tear energy of 12.51±1.57 kJ m^(−2),and excellent fatigue resistance.The 3D-printed zwitterionic PU meniscus replacement is implanted into the rabbits’knee joint for 12 weeks with the in vivo result demonstrating an appealing capability to efficiently alleviate the cartilage surface wear.

关 键 词：己二酸二酰肼 聚碳酸酯二醇 聚氨酯弹性体 耐疲劳性 水合作用 两性离子 3D打印 聚碳酸酯聚氨酯 

分 类 号：R318[医药卫生—生物医学工程]