Pop-Georgievski Ognen, Rodriguez-Emmenegger Cesar, Pereira Andres de Los Santos, Proks Vladimír, Brynda Eduard, Rypáček František
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, v.v.i., Heyrovsky sq. 2, 162 06 Prague, Czech Republic.
J Mater Chem B. 2013 Jun 14;1(22):2859-2867. doi: 10.1039/c3tb20346h. Epub 2013 May 7.
In this study, we propose a substrate-independent biomimetic modification route for the creation of antifouling polymer brushes. This modification route consists of the formation/deposition of a biomimetic polydopamine anchor layer followed by a well-controlled surface-initiated atom transfer radical polymerization of antifouling polymer brushes initiated by 2-bromo-2-methylpropanoyl groups covalently attached to the hydroxyl and amine groups present in the anchor layer. In this way, we synthesized polymer brushes of methoxy- and hydroxy-capped oligoethylene glycol methacrylate, 2-hydroxyethyl methacrylate and carboxybetaine acrylamide. Spectroscopic ellipsometry (SE) indicated well-controlled polymerization kinetics of the brushes, thus the thickness of the ultra-thin films could be precisely tuned at a nanometer scale. The covalent structure and organization of the brushes grown from the polydopamine anchor layer were accessed by infrared reflection-adsorption spectroscopy (IRRAS) while the change in hydrophilicity caused by the presence of the brush was determined by dynamic water contact angle measurements. Surface plasmon resonance as well as ex situ IRRAS and SE measurements were applied to investigate the adsorption of model protein solutions and undiluted human blood plasma to the brushes. The biomimetic brushes completely suppressed the fouling from single protein solutions and reduced the fouling from plasma to less than 3% from the fouling measured on bare gold surfaces. The proposed modification procedure is non-destructive and does not require any chemical pre-activation or the presence of reactive groups on the substrate surface. Contrary to other antifouling modifications the coating can be performed on various classes of substrates and preserves its properties even in undiluted blood plasma. This work offers a promising technology for the facile fabrication of different surface-based biotechnological and biomedical devices able to perform tailor-made functions while resisting the fouling from the complex biological media where they operate.
在本研究中,我们提出了一种与基底无关的仿生修饰路线,用于制备防污聚合物刷。该修饰路线包括形成/沉积仿生聚多巴胺锚定层,随后通过共价连接到锚定层中存在的羟基和胺基上的2-溴-2-甲基丙酰基引发的表面引发原子转移自由基聚合反应,对防污聚合物刷进行精确控制。通过这种方式,我们合成了甲氧基封端和羟基封端的聚乙二醇甲基丙烯酸酯、甲基丙烯酸2-羟乙酯和羧基甜菜碱丙烯酰胺的聚合物刷。光谱椭偏仪(SE)表明刷的聚合动力学得到了良好控制,因此可以在纳米尺度上精确调节超薄膜的厚度。通过红外反射吸附光谱(IRRAS)研究了从聚多巴胺锚定层生长的刷的共价结构和排列,同时通过动态水接触角测量确定了刷的存在引起的亲水性变化。应用表面等离子体共振以及非原位IRRAS和SE测量来研究模型蛋白溶液和未稀释的人血浆在刷上的吸附。仿生刷完全抑制了单一蛋白溶液的污垢形成,并将血浆污垢降低至裸金表面污垢的3%以下。所提出的修饰方法是非破坏性的,不需要任何化学预活化或基底表面存在反应性基团。与其他防污修饰方法不同,该涂层可以在各种类型的基底上进行,并且即使在未稀释的血浆中也能保持其性能。这项工作为简便制造不同的基于表面的生物技术和生物医学设备提供了一种有前景的技术,这些设备能够执行定制功能,同时抵抗其所处复杂生物介质的污垢。