Milatz Roland, Duvigneau Joost, Vancso Gyula Julius
Department of Materials Science and Technology of Polymers, University of Twente, Enschede 7522 NB, The Netherlands.
DPI, P.O. Box 902, Eindhoven 5600 AX, The Netherlands.
ACS Omega. 2024 Aug 23;9(36):38153-38159. doi: 10.1021/acsomega.4c03428. eCollection 2024 Sep 10.
Polydopamines (PDA) are a popular class of materials and promising candidates as adhesives for new fastening techniques. PDA layers can be formed on a wide range of substrates in various environments. Here, we present a novel method for functionalizing PDA-based copolymer films by using click chemistry. These copolymers adhere strongly to various surfaces and simultaneously have active groups that allow the attachment of functional groups. We discuss the coupling of two types of chitosan and a rhodamine B dye molecule to the alkyne groups of the copolymers by employing click reactions. Azidopropyl methacrylate (AzMA), methyl methacrylate (MMA), and dopamine methacrylamide (DOMA) are copolymerized and codeposited with (3-aminopropyl)triethoxysilane on silicon wafers, polyethylene (PE), and polytetrafluoroethylene (PTFE). AzMA provides the surfaces with azides for use in click reactions, MMA functions to control the polymer as a nonfunctional diluent, whereas DOMA provides adhesion, as well as cross-linking groups. After codeposition, the dyes are grafted to the copolymer to illustrate the ability of the films to link functional groups covalently. Fourier transform infrared spectroscopy confirms the successful click reaction in solution, and atomic force microscopy shows the surface morphologies following grafting. Fluorescence microscopy provides evidence of successful grafting. As an example of a possible application, layers exhibiting antifouling properties are prepared. Chitosan grafted to PE is tested for antifouling performance. These functionalized layers show nonspecific inhibition of protein adsorption. We find that chitosan can lower the adsorption of fluorescein-labeled bovine serum albumin (BSA) protein by more than 90% for the best performing fluorescein-labeled BSA protein and by more than 90% for the best-performing layer. These results demonstrate the viability of our PDA-based copolymers for surface functionalization through click chemistry grafting at challenging adhesion to surfaces.
聚多巴胺（PDA）是一类广受欢迎的材料，有望成为新型紧固技术的粘合剂。PDA层可以在各种环境中的多种基材上形成。在此，我们提出一种通过点击化学对基于PDA的共聚物薄膜进行功能化的新方法。这些共聚物能牢固地粘附在各种表面上，同时具有可连接官能团的活性基团。我们讨论了通过点击反应将两种壳聚糖和一种罗丹明B染料分子与共聚物的炔基进行偶联。甲基丙烯酸叠氮丙酯（AzMA）、甲基丙烯酸甲酯（MMA）和甲基丙烯酰胺多巴胺（DOMA）在硅片、聚乙烯（PE）和聚四氟乙烯（PTFE）上与（3-氨丙基）三乙氧基硅烷进行共聚和共沉积。AzMA为表面提供用于点击反应的叠氮化物，MMA作为非功能性稀释剂来控制聚合物，而DOMA则提供粘附力以及交联基团。共沉积后，将染料接枝到共聚物上以说明薄膜共价连接官能团的能力。傅里叶变换红外光谱证实了溶液中点击反应的成功，原子力显微镜显示了接枝后的表面形态。荧光显微镜提供了成功接枝的证据。作为一个可能应用的例子，制备了具有防污性能的层。测试了接枝到PE上的壳聚糖的防污性能。这些功能化层显示出对蛋白质吸附的非特异性抑制。我们发现，对于性能最佳的荧光素标记牛血清白蛋白（BSA）蛋白，壳聚糖可将其吸附降低90%以上，对于性能最佳的层，壳聚糖可将其吸附降低90%以上。这些结果证明了我们基于PDA的共聚物通过点击化学接枝实现表面功能化以及在具有挑战性的表面附着力方面的可行性。
