Key Laboratory of Biomedical Polymers of Ministry of Education, College of Chemistry and Molecular Science , Wuhan University , Wuhan 430072 , P. R. China.
College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials , Luoyang Normal University , Luoyang 471022 , P. R. China.
Langmuir. 2018 Sep 18;34(37):11101-11109. doi: 10.1021/acs.langmuir.8b02584. Epub 2018 Sep 10.
In this paper, a series of amphiphilic diblock polymers of poly(hydroxyethylacrylamide)- b-poly(1H,1H-pentafluoropropyl methacrylate) (PHEAA- b-PFMA) were grafted from silicon wafer via surface-initiated atom transfer radical polymerization (SI-ATRP). Surface wettability and chemical compositions of the modified surfaces were characterized by contact angle goniometer and X-ray photoelectron spectroscopy (XPS) respectively. Molecular weight and polydispersity of each block were measured using gel permeation chromatography (GPC). The topography and the microphase separation behavior of PHEAA- b-PFMA surfaces were investigated by atomic force microscope (AFM). The results show that only when the grafting density (σ) and thickness of PHEAA brush were in the range of 0.9-1.3 (chain/nm) and 6.6-15.1 nm, respectively, and the ratio of PFMA/PHEAA varied from 89/42 to 89/94, could the diblock copolymer phase separate into nanostructures. Further, the antiprotein adsorption performance of the modified surfaces against BSA, fibrinogen, and lysozyme was studied. The results indicated the modified surfaces could reduce the protein adsorption compared to the pristine silicon wafer. For Fibrinogen, the antiadsorption effect of PHEAA- b-PFMA-modified surfaces with microphase segregation was better than that of corresponding PHEAA modified surfaces. The results provide further evidence that surface composition and microphase segregation of fluorinated moieties of block copolymer brushes significantly impact protein adsorption behaviors.
本文通过表面引发原子转移自由基聚合（SI-ATRP）将一系列亲水性两嵌段聚合物聚（羟乙基丙烯酰胺）-b-聚（1H，1H-全氟丙基甲基丙烯酸酯）（PHEAA-b-PFMA）接枝到硅片上。分别采用接触角测角仪和 X 射线光电子能谱（XPS）对改性表面的润湿性和化学成分进行了表征。采用凝胶渗透色谱（GPC）分别测定了各嵌段的分子量和多分散性。采用原子力显微镜（AFM）研究了 PHEAA-b-PFMA 表面的形貌和微相分离行为。结果表明，只有当接枝密度（σ）和 PHEAA 刷的厚度分别在 0.9-1.3（链/nm）和 6.6-15.1nm 的范围内，且 PFMA/PHEAA 的比例在 89/42 到 89/94 之间时，两嵌段共聚物才能分相成纳米结构。进一步研究了改性表面对 BSA、纤维蛋白原和溶菌酶的抗蛋白吸附性能。结果表明，与原始硅片相比，改性表面能减少蛋白质的吸附。对于纤维蛋白原，具有微相分离的 PHEAA-b-PFMA 改性表面的抗吸附效果优于相应的 PHEAA 改性表面。结果进一步证明了氟代嵌段共聚物刷的表面组成和微相分离对蛋白质吸附行为有显著影响。
