Thermoresponsive, Pyrrolidone‐Based Antifouling Polymer Brushes
Thermoresponsive, Pyrrolidone‐Based Antifouling Polymer Brushes
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DOI：
10.1002/admi.202101717
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发表时间：
2022-01
影响因子：
5.4
通讯作者：
L. W. Teunissen;Andriy R. Kuzmyn;F. Ruggeri;Maarten M. J. Smulders;H. Zuilhof
中科院分区：
文献类型：
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作者：
L. W. Teunissen;Andriy R. Kuzmyn;F. Ruggeri;Maarten M. J. Smulders;H. Zuilhof
通常，使用热响应性聚合物对表面进行改性是使用聚(N-异丙基丙烯酰胺)(聚(NIPAM))。然而，由于丙烯酰胺本身的聚合特性不可控，将聚(NIPAM)与第二聚合物整合以获得更复杂的共聚结构已被证明是具有挑战性的。本研究通过表面引发原子转移自由基聚合(SI-ATRP)合成了N-(2-甲基丙烯酰氧乙基)吡咯烷酮(NMEP)，并在控制条件下以二氧化硅为底物进行聚合，制备了热敏性聚(NMEP)电刷。通过用低聚(乙二醇甲基醚)甲基丙烯酸酯重新引发聚(NMEP)刷子得到两嵌段共聚物刷子，证明了刷子的活性。在广泛的表征之后，这些聚(NMEP)刷的可逆热响应行为被用相控AFM形貌测量在水溶液环境中显示出来。这些测量表明，在27℃时，聚(NMEP)刷子被溶解，并从表面延伸出去，而在60℃时，聚合物是不溶的，以折叠的构象存在。最后，为了研究聚(NMEP)刷子在生物医疗设备中的潜在应用，使用石英晶体耗散监测微天平(QCM-D)测试了涂层在含有BSA、纤维蛋白原或10%稀释人血清的水介质中的防污性能。这些测量显示出非常好的防污性能，即使暴露在10%稀释的人血清中也是如此。
Commonly, modification of surfaces with thermoresponsive polymers is performed using poly(N‐isopropylacrylamide) (poly(NIPAM)). However, integration of poly(NIPAM) with a second polymer to obtain more complex copolymer structures has proven challenging due to inherently poorly controllable polymerization characteristics of acrylamides. In this study, (N‐(2‐methacryloyloxyethyl)pyrrolidone (NMEP) is synthesized and polymerized under controlled conditions from silicon oxide substrates via surface‐initiated atom transfer radical polymerization (SI‐ATRP) to produce thermoresponsive poly(NMEP) brushes. The livingness of the brushes is demonstrated by reinitiation of poly(NMEP) brushes using oligo(ethylene glycol) methyl ether methacrylate to obtain diblock copolymer brushes. Following extensive characterization, the reversible thermoresponsive behavior of these poly(NMEP) brushes is demonstrated using phase‐controlled AFM topography measurements in an aqueous liquid environment. These measurements indicate that at 27 °C the poly(NMEP) brushes are solvated and extend away from the surface, whereas at 60 °C the polymers are insoluble and reside in a collapsed conformation. Finally, to investigate the potential applicability of poly(NMEP) brushes in biomedical devices, the antifouling properties of the coating are tested in aqueous media containing BSA, fibrinogen, or 10% diluted human serum using quartz crystal microbalance with dissipation monitoring (QCM‐D). These measurements reveal very good antifouling properties, even when exposed to 10% diluted human serum.