| 引用本文: | 李胜飞,夏一夫,张涛.不同亲疏水性聚合物刷的生物防污性能[J].中国表面工程,2024,37(6):391~400 |
| LI Shengfei,XIA Yifu,ZHANG Tao.Biological Antifouling Properties of Polymer Brushes with Different Hydrophilic and Hydrophobic Properties[J].China Surface Engineering,2024,37(6):391~400 |
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| 摘要: |
| 聚合物刷是指大分子链通过物理作用力或共价键牢固地束缚在基材上，并具有可定义功能化的刷状结构，多用于表面防污改性。然而，系统地对不同链长和官能团类型的聚合物刷在防污能力方面的评价工作依然较少。通过表面引发零价铜介导的可控自由基聚合（SI-Cu0 CRP）制备一系列不同侧链结构的甲基丙烯酸酯类聚合物刷（如亲水性的寡聚乙二醇类、烷基类和疏水性的含氟类），并利用红外光谱（IR）和接触角（CA）表征其结构和表面性质。此外，使用耗散型石英晶体微天平（QCM-D）原位监测聚合物刷界面的蛋白质粘附，并通过荧光蛋白浸泡试验模拟蛋白质的非特异性吸附。结果表明：聚合物刷的侧链长度决定了其界面的水合能力，如聚（寡聚乙二醇）甲醚甲基丙烯酸酯-n20 （pOEGMA-n20）的 CA 仅为 39.6°±0.5°；长侧链结构的亲水性聚合物刷更易形成水合界面，抗蛋白吸附能力远高于疏水性聚合物刷界面（低至 1.7 ng / cm2 ）；多氟长链结构的疏水性界面可以在动态流速下构建出一个空气层，通过减少蛋白质与材料表面的接触而展现出一定的防污能力。研究结果系统分析了聚合物刷侧链长度和官能团对其界面防污性能的影响，为聚合物刷改性的防污涂层提供参考依据。 |
| 关键词: 聚合物刷 生物防污 表面引发零价铜介导的可控自由基聚合(SI-Cu0 CRP) 耗散型石英晶体微天平(QCM-D) 侧链长度 水合界面 空气层 |
| DOI：10.11933/j.issn.1007-9289.20231229004 |
| 分类号:TG156；TB114 |
| 基金项目:国家自然科学基金（52003279，52005491）；浙江省重点研发计划项目（2023C01089）；浙江省领军型创新创业团队（2021R01005） |
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| Biological Antifouling Properties of Polymer Brushes with Different Hydrophilic and Hydrophobic Properties |
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LI Shengfei，XIA Yifu，ZHANG Tao
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Key Laboratory of Advanced Marine Materials, Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences, Ningbo 315201 , China
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| Abstract: |
| Polymer brushes are a class of functionalized brush-like structures with macromolecular chains firmly tethered to the substrate through physical forces or covalent bonds, which are widely used for surface antifouling because their chain lengths and types of functional groups can be customized. However, limited research has been performed on the intrinsic relationship between the chain length, functional group type, and antifouling performance. The preparation of these functional polymer brushes is highly dependent on versatile surface-initiated controlled radical polymerization (SI-CRP) strategies. In this study, a series of methacrylate polymer brushes with different side-chain structures (hydrophilic oligo(ethylene glycol), alkyl groups, and hydrophobic fluorinated polymers) were prepared by surface-initiated zero-valent copper-mediated controlled radical polymerization (SI-Cu0 CRP), and the relationship between these brushes and their antifouling properties was explored. The thicknesses of the polymer brushes were recorded by scanning probe microscopy (SPM), where the poly(oligo(ethylene glycol) methyl ether methacrylate)-n20 (pOEGMA-n20) brush thickness reached 265 nm after 180 min of polymerization. The structure and surface properties of polymer brushes were characterized by infrared (IR) spectroscopy and contact angle (CA). The CA of poly(2-(perfluorooctyl)ethyl methacrylate) (pF-17) has been significantly increased to 122.8°±0.2°from 39.6°±0.5°of pOEGMA-n20, which suggests that the side-chain length and functional groups of the polymer brush determines its interfacial hydration capacity. To understand the antifouling properties of the polymer brushes across the flow interface, the protein adhesion behavior was monitored in situ by the quartz crystal microbalance with dissipation (QCM-D). Among hydrophilic pOEGMA brushes, the hydration capacity of the interface was proportional to its protein adsorption resistance, such as the protein adhesion content of pOEGMA-n20 brush (39.6°±0.5°) was only 1.7 ng / cm2 , while that of pOEGMA-n1 brush (66.6°±0.3°) was up to 31.88 ng / cm2 . Unlike hydrophilic brushes, the antifouling properties of hydrophobic brushes are highly dependent on air layers at the flow interface. The protein adhesion content of pF-17 was 256.3 ng / cm2 , higher than 301.7 ng / cm2 of poly(2,2,2-trifluoroethyl methacrylate) (pF-3). Notably, the poly(1H,1H-heptafluorobutyl methacrylate) (pF-7) brush with asurface wettability between the pF-3 and the pF-17 brushes, has a protein adhesion content of 363 ng / cm2 , which is mainly attributed to the unstable air layer at the interface. Compared to hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) brushes and hydrophobic fluorinated brushes, the antifouling properties of alkyl brushes remain higher than fluorinated brushes regardless of being at mediocre surface properties, which are more favorable to the hydration layer theory, and the poly(methyl methacrylate) (pMMA) brush with a CA of 73.9°±0.1°only adhered to 3.26 ng / cm2 of the protein. To investigate the protein adhesion kinetics, the adhesion content of the pOEGMA-n20 brush surface at different concentrations of bovine serum albumin (BSA) was monitored by QCM-D. The protein adhesion content of the pOEGMA-n20 brush surface was only 6.8 ng / cm2 despite the BSA solubility being as high as 5 mg / mL. Finally, based on the fluorescent protein immersion experiments, the nonspecific adsorption of proteins was simulated under steady-state conditions. From the analysis of the optical images recorded by fluorescence microscopy, the hydrophilic polymer brush interface showed extremely high antifouling performance, especially the superhydrophilic pOEGMA-n20 brush. However, the interface of the most hydrophobic pF-17 brush had a high protein content, which was mainly attributed to the air layer between the hydrophobic interface and the liquid being difficult to construct in a static environment, leading to more protein deposition (higher than that of the substrate without modification by the polymer brush). This investigation systematically analyzes the effects of the polymer brush side-chain length and functional groups on the interfacial antifouling properties and provides a reference for polymer brush-modified antifouling coatings. |
| Key words: polymer brush biological antifouling surface-initiated Cu0 -mediated controlled radical polymerization (SI-Cu0 CRP) quartz crystal microbalance with dissipation (QCM-D) side-chain length hydration layer air layer |
