Jagiellonian University, Doctoral School of Exact and Natural Sciences, Łojasiewicza 11, 30-348 Kraków, Poland.
Jagiellonian University, Faculty of Physics, Astronomy and Applied Computer Science, Smoluchowski Institute of Physics, Łojasiewicza 11, 30-348 Kraków, Poland.
ACS Biomater Sci Eng. 2023 Nov 13;9(11):6256-6272. doi: 10.1021/acsbiomaterials.3c00917. Epub 2023 Oct 24.
The fabrication of multifunctional, thermoresponsive platforms for regenerative medicine based on polymers that can be easily functionalized is one of the most important challenges in modern biomaterials science. In this study, we utilized atom transfer radical polymerization (ATRP) to produce two series of novel smart copolymer brush coatings. These coatings were based on copolymerizing 2-hydroxyethyl methacrylate (HEMA) with either oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or -isopropylacrylamide (NIPAM). The chemical compositions of the resulting brush coatings, namely, poly(oligo(ethylene glycol) methyl ether methacrylate--2-hydroxyethyl methacrylate) (P(OEGMA--HEMA)) and poly(-isopropylacrylamide--2-hydroxyethyl methacrylate) (P(NIPAM--HEMA)), were predicted using reactive ratios of the monomers. These predictions were then verified using time-of-flight-secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The thermoresponsiveness of the coatings was examined through water contact angle (CA) measurements at different temperatures, revealing a transition driven by lower critical solution temperature (LCST) or upper critical solution temperature (UCST) or a vanishing transition. The type of transition observed depended on the chemical composition of the coatings. Furthermore, it was demonstrated that the transition temperature of the coatings could be easily adjusted by modifying their composition. The topography of the coatings was characterized using atomic force microscopy (AFM). To assess the biocompatibility of the coatings, dermal fibroblast cultures were employed, and the results indicated that none of the coatings exhibited cytotoxicity. However, the shape and arrangement of the cells were significantly influenced by the chemical structure of the coating. Additionally, the viability of the cells was correlated with the wettability and roughness of the coatings, which determined the initial adhesion of the cells. Lastly, the temperature-induced changes in the properties of the fabricated copolymer coatings effectively controlled cell morphology, adhesion, and spontaneous detachment in a noninvasive, enzyme-free manner that was confirmed using optical microscopy.
基于聚合物的多功能、温敏平台的制造，这些聚合物可以很容易地进行功能化，是现代生物材料科学中最重要的挑战之一。在这项研究中，我们利用原子转移自由基聚合（ATRP）来制备两种新型智能共聚物刷涂层。这些涂层是通过共聚 2-羟乙基甲基丙烯酸酯（HEMA）与聚乙二醇甲基醚甲基丙烯酸酯（OEGMA）或异丙基丙烯酰胺（NIPAM）来制备的。利用单体的反应比来预测所得刷涂层的化学组成，即聚（聚乙二醇甲基醚甲基丙烯酸酯-2-羟乙基甲基丙烯酸酯）（P（OEGMA-HEMA））和聚（异丙基丙烯酰胺-2-羟乙基甲基丙烯酸酯）（P（NIPAM-HEMA））。然后使用飞行时间二次离子质谱（ToF-SIMS）和 X 射线光电子能谱（XPS）验证这些预测。通过在不同温度下测量水接触角（CA）来研究涂层的温敏性，发现这是由低临界溶液温度（LCST）或高临界溶液温度（UCST）或消失转变驱动的转变。观察到的转变类型取决于涂层的化学组成。此外，通过改变其组成可以很容易地调整涂层的转变温度。使用原子力显微镜（AFM）对涂层的形貌进行了表征。为了评估涂层的生物相容性，我们使用了皮肤成纤维细胞培养物，结果表明，没有一种涂层表现出细胞毒性。然而，细胞的形状和排列受到涂层化学结构的显著影响。此外，细胞的活力与涂层的润湿性和粗糙度相关，这决定了细胞的初始附着。最后，所制备的共聚物涂层的性质在温度诱导下的变化以非侵入性、无酶的方式有效控制了细胞形态、粘附和自发脱落，这一点通过光学显微镜得到了证实。
