基于多巴胺改性纳米复合水凝胶的制备和性能

doi:10.11901/1005.3093.2023.342

材料研究学报

2024, Vol. 38

Issue (4): 269-278 DOI: 10.11901/1005.3093.2023.342

研究论文

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基于多巴胺改性纳米复合水凝胶的制备和性能

王仲楠(

), 郭慧, 母悦山

北京交通大学机械与电子控制工程学院北京 100044

Preparation and Properties of Nanocomposite Hydrogel with Dopamine Modification

WANG Zhongnan(

), GUO Hui, MU Yueshan

School of Mechanical, Electronic and Control Engineering, Beijing Jiaotong University, Beijing 100044, China

引用本文:

王仲楠, 郭慧, 母悦山. 基于多巴胺改性纳米复合水凝胶的制备和性能[J]. 材料研究学报, 2024, 38(4): 269-278.
Zhongnan WANG, Hui GUO, Yueshan MU. Preparation and Properties of Nanocomposite Hydrogel with Dopamine Modification[J]. Chinese Journal of Materials Research, 2024, 38(4): 269-278.

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摘要:

分别在酸性和碱性条件下用多巴胺修饰纳米羟基磷灰石制备纳米粒子改性的复合水凝胶并研究其性能，结果表明：多巴胺能在纳米羟基磷灰石表面生成氧化膜，且改性纳米粒子中的苯环与两性离子水凝胶高分子链形成共价键结合。同时，在酸性条件下多巴胺能提高纳米羟基磷灰石的分散性进而提高两性离子水凝胶的热稳定性(323℃才发生分解)，也能提高水凝胶的网络结构强度(储能模量为2.7 MPa)和内耗能力(损耗因子为0.041)。而且，酸性纳米复合水凝胶的抗压能力达到11.66 MPa，比纯PSBMA两性离子水凝胶提高了32倍。这表明，酸性纳米复合水凝胶的结构特点和力学性能与天然软骨相似。

关键词 ：高分子材料, 纳米复合水凝胶, 力学性能, 多巴胺改性, 纳米羟基磷灰石

Abstract：

Zwitterionic hydrogel is one of the most promising cartilage repair and replacement materials with good biocompatibility and anti-bacteria adhesion properties. However, there is a certain gap involving in mechanical properties compared to natural cartilage, which greatly limits its practical application. Herein, the nano-hydroxyapatite was modified with dopamine by acid, and alkali conditions respectively to obtain a nanoparticle-modified composite hydrogel. It is found that an oxide film could form on the surface of nano hydroxyapatite modified by dopamine, and the benzene ring in the modified nano particles is combined to form a covalent bond with the zwitterionic hydrogel polymer chain. Meanwhile, dopamine improves the dispersity of nano-hydroxyapatite by acidic condition, thereby enhancing the thermal stability of zwitterionic hydrogel (decomposing until 323^oC), as well as its network structure strength (energy storage modulus of 2.7 MPa) and internal friction capacity (loss factor of 0.041). Moreover, the compressive strength of acid nanocomposite hydrogel arrives at 11.66 MPa, which is 32 times higher than that of pure PSBMA zwitterionic hydrogel. Thus, the structural characteristics and mechanical properties of acid nanocomposite hydrogels are similar to those of natural cartilage, which provides a significant reference for the design and preparation of bionic materials.

Key words： polymer material nanocomposite hydrogel mechanical properties dopamine modification nano hydroxyapatite

收稿日期: 2023-07-12

ZTFLH:

TQ174

基金资助:北京交通大学人才基金(2022XKRC009);国家自然科学基金(51905296)

通讯作者: 王仲楠，副教授，E-mail：zhn.wang@bjtu.edu.cn，研究方向为机械设计理论与微纳米技术

Corresponding author: WANG Zhongnan, Tel: 18845616596, E-mail: zhn.wang@bjtu.edu.cn

作者简介: 王仲楠，男，1984年生，博士

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图1 D@H改性后的红外光谱、拉曼光谱、XRD谱以及改性纳米粒子干燥后的粉末图示

图2 水凝胶的表面颜色和在空气中静置后表面颜色的变化、水凝胶溶胀后静置在空气中颜色的变化、水凝胶的微观结构以及水凝胶的红外光谱

图3 水凝胶组分结构和纳米复合水凝胶合成机理的图示

图4 水凝胶的基本理化性质

图5 添加剂含量不同的水凝胶的储能模量G′和耗散模量G″随角速度ω的变化、DA与HA质量比不同的纳米复合水凝胶储能模量G′和耗散模量G″随角速度ω的变化、添加剂含量不同的水凝胶的应力松弛实验结果、DA与HA质量比不同的纳米复合水凝胶的应力松弛实验结果、添加剂含量不同的水凝胶的损耗因子tan δ和归一化松弛模量G、DA与HA质量比不同的水凝胶的损耗因子tan δ和归一化松弛模量G以及TD@H-GE纳米复合水凝胶的粘附性

图6 添加剂不同的水凝胶的压缩断裂实验结果和DA与HA质量比不同的纳米复合水凝胶的压缩断裂实验结果

图7 几种水凝胶的压缩循环实验结果

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