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PHEAA-b-PFMA刷修饰表面的相分离行为及抗蛋白吸附研究
PHEAA-b-PFMA Brush Modified Surfaces:the Microphase Separation Behavior and Resistance to Protein Adsorption
【作者】 张晓红;
【导师】 刘传军;
【作者基本信息】 武汉大学 , 高分子化学与物理, 2018, 硕士
【摘要】 非特异性蛋白吸附给生物医用材料如植入体、医疗器械及生物传感器的应用带来了严峻挑战,它们通常会降低医疗器械的性能或引起植入材料的排异反应和细菌感染。近二十年来,利用表面改性的方法来抵抗和调节非特异性蛋白吸附被广泛地发展和应用。其中,聚合物刷作为一种表面修饰方法由于具有种类多、相对容易修饰及生物相容性较好等优点,被越来越多地用在抵抗非特异性蛋白吸附的材料改性中。根据表面性质不同,聚合物刷可分为亲水性、疏水性和低表面能三类。从结构和成分上划分,它们修饰的表面又分为单一的和复杂的。在本论文中,我们将具有亲水性抗生物黏附性能的聚合物和低表面能的氟化物相结合,利用表面引发原子转移自由基聚合(SI-ATRP)的方法,制备了一系列两亲性嵌段聚合物(PHEAA-b-PFMA)刷修饰的硅表面。探讨了这些嵌段聚合物刷在硅基底表面的微相分离行为和抗蛋白吸附效果。论文第一章概述常见的利用表面改性来抵抗蛋白吸附的策略和研究。基于表面改性方法和材料的表面性质,我们将从抗蛋白吸附表面修饰方法和抗蛋白吸附表面材料两方面来归类总结和介绍。在第二章节中,我们利用SI-ATRP制备了一系列PHEAA和PHEAA-b-PFMA刷修饰的硅表面,随后探讨了影响PHEAA-b-PFMA在硅片基底上发生微相分离的条件参数。当PHEAA刷的厚度、植入密度、PHEAA/PFMA的聚合度之比在6.6-15.1 nm、0.9-1.3(chain/nm2)和 89/42-89/94 范围时,得到的 PHEAA-b-PFMA刷才能在修饰基底上微相分离成蠕虫状结构。最后,我们选择BSA、Fibrinogen、Lysozyme和IgG作为模型蛋白探究了这些聚合物刷修饰表面的抗蛋白吸附性能。对比空白硅片,大部分修饰的表面均表现出了抗白吸附性能,且随着聚合物分子量增加,效果增强。对于Fibrinogen,PHEAA-b-PFMA形成的相分离表面(无论尺寸大小)的抗吸附效果比对应PHEAA好。而含氟单元的引入对其它几种蛋白的抗蛋白吸附效果影响不大。
【Abstract】 Nonspecific protein adsorption brings severe challenge to biomaterials,such as implant materials,medical device,and biosensors.The adsorbent nonspecific protein on biomaterials surface usually leads decreased performance of medical device and increased rejection reaction or bacterial infection of implant materials.In recent two decades years,surface modification as an effective method is extensively developed and applied in regulating and resisting the interaction between proteins and surfaces.There are a number of strategies for surface modification.Among them,polymer brush as a surface modification method attract much attention due to its diversity,easy modification,and good biocompatibility.According to the difference of surface property,surfaces modified by polymer brush can be divided into the hydrophilic,hydrophobic,and low surface energy.From the point of the structure and component,the modified surfaces can also be divided into homogeneous and heterogeneous.Compared to the homogeneous polymer brush modified surfaces,the latter generously possesses the more high efficiency and long term anti-protein adsorption performance.In this paper,we fabricated a serial of amphiphilic block copolymers brush(PHEAA-b-PFMA)modified silicon surfaces via successive surface-initiated atom transfer radical polymerization(SI-ATRP).And then we investigated the microphase separation behavior and anti-protein adsorption performance of the block copolymer brush modified silicon wafers.In chapter 1,we mainly introduced and summarized the strategies,as well as the common polymers for resisting proteins adsorption.According to the surface structure and chemical composition,we overviewed the methods and materials used in surface modification.In chapter 2,we synthesized a series of PHAA and PHEAA-b-PFMA brush modified silicon wafers via SI-ATRP and then studied the effect of parameters on the microphase separation behavior of PHEAA-b-PFMA.Only when the grafting density(σ),thickness of PHEAA brush,and the ratio of PFMA/PHEAA were in the range of 0.9-1.3(chain/nm2),6.6-15.lnm and 89/42-89/94,could PHEAA-b-PFMA phase separate into worm-like structure.Finally,we chose BSA,Fibrinogen,Lysozyme and IgG as the model proteins to investigate the anti-adsorption performance of PHEAA and PHEAA-b-PFMA modified surfaces.The results indicated that most of the modified surfaces could obviously reduced the protein adsorption compared to the pristine silicon wafers.And with the increase of molecular weight,the antifouling performance increased.For Fibrinogen,the anti-adsorption effect of PHEAA-b-PFMA modified surfaces with both separated sizes were better than corresponding PHEAA.However,there was no obviously enhanced anti-adsorption performance after the introduction of fluorine containing units in PHEAA-b-PFMA for other proteins.