Schönemann Eric, Laschewsky André, Wischerhoff Erik, Koc Julian, Rosenhahn Axel
Department of Chemistry, University Potsdam, Karl-Liebknecht-Str. 24-25, 14476 Potsdam-Golm, Germany.
Fraunhofer Institute of Applied Polymer Research IAP, 14476 Potsdam-Golm, Germany.
Polymers (Basel). 2019 Jun 8;11(6):1014. doi: 10.3390/polym11061014.
Films of zwitterionic polymers are increasingly explored for conferring fouling resistance to materials. Yet, the structural diversity of polyzwitterions is rather limited so far, and clear structure-property relationships are missing. Therefore, we synthesized a series of new polyzwitterions combining ammonium and sulfate groups in their betaine moieties, so-called poly(sulfabetaine)s. Their chemical structures were varied systematically, the monomers carrying methacrylate, methacrylamide, or styrene moieties as polymerizable groups. High molar mass homopolymers were obtained by free radical polymerization. Although their solubilities in most solvents were very low, brine and lower fluorinated alcohols were effective solvents in most cases. A set of sulfabetaine copolymers containing about 1 mol % (based on the repeat units) of reactive benzophenone methacrylate was prepared, spin-coated onto solid substrates, and photo-cured. The resistance of these films against the nonspecific adsorption by two model proteins (bovine serum albumin-BSA, fibrinogen) was explored, and directly compared with a set of references. The various polyzwitterions reduced protein adsorption strongly compared to films of poly(butyl methacrylate) that were used as a negative control. The poly(sulfabetaine)s showed generally even somewhat higher anti-fouling activity than their poly(sulfobetaine) analogues, though detailed efficacies depended on the individual polymer-protein pairs. Best samples approach the excellent performance of a poly(oligo(ethylene oxide) methacrylate) reference.
两性离子聚合物薄膜在赋予材料抗污染性能方面正受到越来越多的探索。然而,到目前为止,聚两性离子的结构多样性相当有限,并且缺少明确的结构-性能关系。因此,我们合成了一系列新型聚两性离子,其甜菜碱部分结合了铵基和硫酸根基团,即所谓的聚(磺酸甜菜碱)。它们的化学结构系统地变化,单体带有甲基丙烯酸酯、甲基丙烯酰胺或苯乙烯基团作为可聚合基团。通过自由基聚合获得了高摩尔质量的均聚物。尽管它们在大多数溶剂中的溶解度非常低,但盐水和低级氟化醇在大多数情况下是有效的溶剂。制备了一组含有约1摩尔%(基于重复单元)反应性甲基丙烯酸二苯甲酮的磺酸甜菜碱共聚物,旋涂在固体基材上并进行光固化。研究了这些薄膜对两种模型蛋白(牛血清白蛋白-BSA、纤维蛋白原)非特异性吸附的抗性,并与一组参考物直接比较。与用作阴性对照的聚(甲基丙烯酸丁酯)薄膜相比,各种聚两性离子大大降低了蛋白质吸附。聚(磺酸甜菜碱)通常比其聚(磺基甜菜碱)类似物表现出更高的抗污染活性,尽管具体效果取决于个别聚合物-蛋白质对。最佳样品接近聚(聚(环氧乙烷)甲基丙烯酸酯)参考物的优异性能。