Zou Wen, Qin Hui, Shi Wenbin, Sun Shudong, Zhao Changsheng
College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University , Chengdu 610065, People's Republic of China.
Langmuir. 2014 Nov 18;30(45):13622-30. doi: 10.1021/la502343c. Epub 2014 Nov 7.
In this study, we provide a new method to modify poly(ether sulfone) (PES) membrane with good biocompatibility, for which diazotized PES (PES-N2(+)) membrane is covalently coated by a negatively charged copolymer of sodium sulfonated poly(styrene-alt-maleic anhydride) (NaSPS-MA). First, aminated PES (PES-NH2) is synthesized by nitro reduction reaction of nitro-PES (PES-NO2), and then blends with pristine PES to prepare PES/PES-NH2 membrane; then the membrane is treated with NaNO2 aqueous solution at acid condition; after surface diazo reaction, surface positively charged PES/PES-N2(+) membrane is prepared. Second, poly(styrene-alt-maleic anhydride) (PS-alt-MA) is synthesized, then sulfonated and treated by sodium hydroxide solution to obtain sodium sulfonated (PS-alt-MA) (NaSPS-MA). Finally, the negatively charged NaSPS-MA copolymer is coated onto the surface positively charged PES/PES-N2(+) membrane via electrostatic interaction; after UV-cross-linking, the linkage between the PES-N2(+) and NaSPS-MA changes to a covalent bond. The surface-modified PES membrane is characterized by FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS) analyses, and surface zeta potential analyses. The modified membrane exhibits good hemocompatibility and cytocompatibility, and the improved biocompatibility might have resulted from the existence of the hydrophilic groups (sodium carboxylate (-COONa) and sodium sulfonate (-SO3Na)). Moreover, the stability of the modified membrane is also investigated. The results indicated that the modified PES membrane using negatively charged copolymers had a lot of potential in blood purification fields and bioartificial liver supports for a long time.
在本研究中，我们提供了一种制备具有良好生物相容性的聚醚砜（PES）膜的新方法，即通过静电相互作用，将磺化聚（苯乙烯-马来酸酐）钠（NaSPS-MA）的带负电荷共聚物共价包覆在重氮化PES（PES-N2(+)）膜上。首先，通过硝基聚醚砜（PES-NO2）的硝基还原反应合成胺化聚醚砜（PES-NH2），然后与原始聚醚砜共混制备PES/PES-NH2膜；接着将该膜在酸性条件下用亚硝酸钠水溶液处理；经过表面重氮化反应，制备出表面带正电荷的PES/PES-N2(+)膜。其次，合成聚（苯乙烯-马来酸酐）（PS-alt-MA），然后磺化并用氢氧化钠溶液处理，得到磺化聚（苯乙烯-马来酸酐）（NaSPS-MA）。最后，通过静电相互作用将带负电荷的NaSPS-MA共聚物包覆在表面带正电荷的PES/PES-N2(+)膜上；紫外光交联后，PES-N2(+)与NaSPS-MA之间的连接转变为共价键。通过傅里叶变换红外光谱（FT-IR）、X射线光电子能谱（XPS）分析和表面zeta电位分析对表面改性的PES膜进行表征。改性膜表现出良好的血液相容性和细胞相容性，亲水性基团（羧酸钠（-COONa）和磺酸钠（-SO3Na））的存在可能导致生物相容性得到改善。此外，还研究了改性膜的稳定性。结果表明，使用带负电荷共聚物改性的PES膜在血液净化领域和生物人工肝支持方面具有长期的巨大潜力。
