两性氨基酸修饰聚偏氟乙烯膜的制备及其血液相容性研究

发布时间：2019-06-24 15:25

【摘要】：作为一种典型的生物材料,聚偏氟乙烯(PVDF)被广泛的应用于血液纯化和过滤。但是,PVDF膜疏水性太强,容易引起蛋白质的非特异性吸附,血液相容性差,因此与血液接触时会诱导血栓形成,使其应用受到限制。接枝改性是常见的改善PVDF膜血液相容性的方法,但是现有的接枝改性只能形成单一的接枝层,因接枝密度使抗蛋白吸附效果和血液相容性有限,本论文尝试用高效便捷的方法在膜表面构建具有复杂结构的两性离子功能层,采用两种不同的方法将两性氨基酸接枝到PVDF膜表面,以改善材料的血液相容性和抗粘污性能。具体如下:(1)利用氢氧化钠乙醇溶液预处理PVDF膜表面引入双键,在此基础上接枝一层交联聚乙二醇水凝胶,然后通过水凝胶层剩余的环氧基团和半胱氨酸的巯基之间的开环反应,在膜表面引入半胱氨酸两性离子。(2)利用氢氧化钠乙醇溶液预处理PVDF膜表面引入双键,再通过ATRP方法在膜表面引入超支化聚乙二醇二甲基丙烯酸酯,最后通过迈克尔加成反应在膜表面接枝上赖氨酸两性离子。通过表面衰减全反射傅里叶变换红外光谱(ATR-FTIR)、X-射线光电子能谱(XPS)、场发射扫描电镜(FESEM)、表面动态水接触角(WCA)和表面电势(Zeta电位)等物理手段表征了改性膜的形貌、结构、润湿性和荷电性。通过静态抗蛋白吸附实验和动态蛋白污染实验对材料的抗生物污染进行了研究。通过体外血小板粘附实验、红细胞粘附实验和抗凝血实验对材料的生物学性能进行了初步研究。结果表明,两性氨基酸成功接枝在PVDF膜表面,接枝改性后PVDF膜亲水性显著提高,具有较好的抗蛋白污染效果,膜材料对血小板和红细胞粘附较少,并且表现出了良好的抗凝血性能。本论文在PVDF膜表面成功接枝了具有良好的抗生物粘附和血液相容性的两性氨基酸离子,为进一步研究两性离子改性分离膜材料提供了可靠的基础。
[Abstract]:As a typical biomaterial, polyvinylidene fluoride (PVDF) is widely used for blood purification and filtration. However, the PVDF membrane is too hydrophobic to cause non-specific adsorption of the protein and poor blood compatibility, so that the formation of thrombus can be induced when the blood is in contact with the blood, and the application thereof is limited. the grafting modification is a common method for improving the blood compatibility of the PVDF membrane, In this paper, a highly efficient and convenient method was used to construct a zwitterionic functional layer with complex structure on the surface of the membrane, and the amphoteric amino acid was grafted onto the surface of the PVDF membrane by two different methods, so as to improve the blood compatibility and anti-fouling performance of the material. The method comprises the following steps: (1) pre-treating the surface of a PVDF membrane with a sodium hydroxide ethanol solution to introduce a double bond, grafting a layer of cross-linked polyethylene glycol hydrogel on the surface of the PVDF membrane, A cysteine zwitterionic is introduced on the membrane surface. (2) the surface of the PVDF membrane is pretreated by using an ethanol solution of sodium hydroxide to introduce a double bond, and then the hyperbranched polyethylene glycol dimethacrylate is introduced on the surface of the membrane by the ATRP method, and finally, the lysine amphoteric ion is grafted on the surface of the membrane by the Michael addition reaction. The morphology and structure of the modified film were characterized by surface-attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscope (FESEM), surface dynamic water contact angle (WCA) and surface potential (Zeta potential). And the wettability and the charge-to-charge property. The anti-biological pollution of the material was studied by the static anti-protein adsorption experiment and the dynamic protein pollution experiment. The biological properties of the materials were studied by the in vitro platelet adhesion experiment, the red blood cell adhesion experiment and the anticoagulant experiment. The results showed that the grafting of the amphoteric amino acid on the surface of the PVDF membrane, the hydrophilicity of the PVDF membrane improved significantly after the graft modification, and the membrane material has better anti-protein pollution effect, and the membrane material has less adhesion to the platelets and red blood cells, and has good anticoagulant performance. This paper has successfully grafted amphoteric amino acid ions with good anti-bioadhesion and blood compatibility on the surface of PVDF membrane, and provides a reliable basis for further study of the zwitterionic modified separation membrane material.
【学位授予单位】：天津工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ051.893

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