Yang Jintao, Zhang Mingzhen, Chen Hong, Chang Yung, Chen Zhan, Zheng Jie
College of Materials Science & Engineering, Zhejiang University of Technology , 18th Chaowang Road, Hangzhou 310014, P. R. China.
Biomacromolecules. 2014 Aug 11;15(8):2982-91. doi: 10.1021/bm500598a. Epub 2014 Jul 8.
Numerous biocompatible antifouling polymers have been developed for a wide variety of fundamental and practical applications in drug delivery, biosensors, marine coatings, and many other areas. Several antifouling mechanisms have been proposed, but the exact relationship among molecular structure, surface hydration property, and antifouling performance of antifouling polymers still remains elusive. Here this work strives to provide a better understanding of the structure-property relationship of poly(N-hydroxyalkyl acrylamide)-based materials. We have designed, synthesized, and characterized a series of polyHAAA brushes of various carbon spacer lengths (CSLs), that is, poly(N-hydroxymethyl acrylamide) (polyHMAA), poly(N-(2-hydroxyethyl)acrylamide) (polyHEAA), poly(N-(3-hydroxypropyl)acrylamide) (polyHPAA), and poly(N-(5-hydroxypentyl)acrylamide) (polyHPenAA), to study the structural dependence of CSLs on their antifouling performance. HMAA, HEAA, HPAA, and HPenAA monomers contained one, two, three, and five methylene groups between hydroxyl and amide groups, while the other groups in polymer backbones were the same as each other. The relation of such small structural differences of polymer brushes to their surface hydration and antifouling performance was studied by combined experimental and computational methods including surface plasmon resonance sensors, sum frequency generation (SFG) vibrational spectroscopy, cell adhesion assay, and molecular simulations. Antifouling results showed that all polyHAAA-based brushes were highly surface resistant to protein adsorption from single protein solutions, undiluted blood serum and plasma, as well as cell adhesion up to 7 days. In particular, polyHMAA and polyHEAA with the shorter CSLs exhibited higher surface hydration and better antifouling ability than polyHPMA and polyHPenAA. SFG and molecular simulations further revealed that the variation of CSLs changed the ratio of hydrophobicity/hydrophilicity of polymers, resulting in different hydration characteristics. Among them, polyHMAA and polyHEAA with the shorter CSLs showed the highest potency for surface hydration and antifouling abilities, while polyHPenAA showed the lowest potency. The combination of both hydroxyl and amide groups in the same polymer chain provides a promising structural motif for the design of new effective antifouling materials.
为了在药物递送、生物传感器、海洋涂料及许多其他领域实现广泛的基础和实际应用，人们已开发出众多生物相容性防污聚合物。虽然已经提出了几种防污机制，但防污聚合物的分子结构、表面水化性质和防污性能之间的确切关系仍不清楚。在此，本研究致力于更好地理解基于聚（N-羟烷基丙烯酰胺）材料的结构-性能关系。我们设计、合成并表征了一系列具有不同碳间隔长度（CSL）的聚HAAA刷，即聚（N-羟甲基丙烯酰胺）（聚HMAA）、聚（N-（2-羟乙基）丙烯酰胺）（聚HEAA）、聚（N-（3-羟丙基）丙烯酰胺）（聚HPAA）和聚（N-（5-羟戊基）丙烯酰胺）（聚HPenAA），以研究CSL对其防污性能的结构依赖性。HMAA、HEAA、HPAA和HPenAA单体在羟基和酰胺基之间分别含有一个、两个、三个和五个亚甲基，而聚合物主链中的其他基团彼此相同。通过结合实验和计算方法，包括表面等离子体共振传感器、和频产生（SFG）振动光谱、细胞粘附试验和分子模拟，研究了聚合物刷这种微小结构差异与其表面水化和防污性能的关系。防污结果表明，所有基于聚HAAA的刷对来自单一蛋白质溶液、未稀释血清和血浆中的蛋白质吸附以及细胞粘附均具有高达7天的高度表面抗性。特别是，具有较短CSL的聚HMAA和聚HEAA表现出比聚HPMA和聚HPenAA更高的表面水化和更好的防污能力。SFG和分子模拟进一步表明，CSL的变化改变了聚合物的疏水/亲水性比例，导致不同的水化特性。其中，具有较短CSL的聚HMAA和聚HEAA表现出最高的表面水化和防污能力，而聚HPenAA表现出最低的能力。同一聚合物链中羟基和酰胺基的组合为设计新型高效防污材料提供了一个有前景的结构基序。
