Ojha Umaprasana, Feng Dingsong, Chandekar Amol, Whitten James E, Faust Rudolf
Department of Chemistry, University of Massachusetts Lowell, One University Avenue, Lowell, Massachusetts 01854, USA.
Langmuir. 2009 Jun 2;25(11):6319-27. doi: 10.1021/la9000768.
Peptide surface modification of poly[(methyl methacrylate-co-hydroxyethyl methacrylate)-b-isobutylene-b-(methyl methacrylate-co-hydroxyethyl methacrylate)] P(MMA-co-HEMA)-b-PIB-b-P(MMA-co-HEMA) triblock copolymers with different HEMA/MMA ratios has been accomplished using an efficient synthetic procedure. The triblock copolymers were reacted with 4-fluorobenzenesulfonyl chloride (fosyl chloride) in pyridine to obtain the activated polymers [poly{(methyl methacrylate-co-fosyloxyethyl methacrylate)-b-isobutylene-b-(methyl methacrylate-co-fosyloxyethyl methacrylate)}] P(MMA-co-FEMA)-b-PIB-b-P(MMA-co-FEMA), with an activating efficiency of 80-90%. The resulting polymers were soluble in chloroform, and their solutions were used to coat thin uniform films with a predetermined thickness on smooth steel surfaces. The presence of reactive activating groups on the film surface was confirmed by X-ray photoelectron spectroscopy (XPS), dye labeling, and confocal laser scanning microscopic studies. Activation of the triblock copolymer films was also achieved under heterogeneous conditions in polar (acetonitrile) and nonpolar (hexanes) media. The extent of activation was controlled by varying the dipping time and polarity of the medium. Peptide attachment was accomplished by immersing the coated steel strips into aqueous buffer solution of Gly-Gly or GYIGSR. XPS and solubility studies revealed successful attachment of peptides to the polymer surface. Virtually all remaining activating groups were successfully replaced in the subsequent step by a treatment with Tris(hydroxymethyl)amino methane in a buffered methanol/water mixture.
采用一种高效的合成方法,对具有不同甲基丙烯酸羟乙酯/甲基丙烯酸甲酯(HEMA/MMA)比例的聚[(甲基丙烯酸甲酯-共-甲基丙烯酸羟乙酯)-b-异丁烯-b-(甲基丙烯酸甲酯-共-甲基丙烯酸羟乙酯)]P(MMA-共-HEMA)-b-PIB-b-P(MMA-共-HEMA)三嵌段共聚物进行了肽表面修饰。三嵌段共聚物在吡啶中与4-氟苯磺酰氯(氟磺酰氯)反应,以80%-90%的活化效率得到活化聚合物[聚{(甲基丙烯酸甲酯-共-氟磺酰氧基乙基甲基丙烯酸酯)-b-异丁烯-b-(甲基丙烯酸甲酯-共-氟磺酰氧基乙基甲基丙烯酸酯)}]P(MMA-共-FEMA)-b-PIB-b-P(MMA-共-FEMA)。所得聚合物可溶于氯仿,其溶液用于在光滑钢表面涂覆具有预定厚度的均匀薄膜。通过X射线光电子能谱(XPS)、染料标记和共聚焦激光扫描显微镜研究证实了薄膜表面存在反应性活化基团。在极性(乙腈)和非极性(己烷)介质的非均相条件下,三嵌段共聚物薄膜也实现了活化。通过改变浸渍时间和介质极性来控制活化程度。通过将涂覆的钢带浸入甘氨酰甘氨酸或GYIGSR的水性缓冲溶液中来完成肽的附着。XPS和溶解性研究表明肽成功附着在聚合物表面。在随后的步骤中,通过在缓冲的甲醇/水混合物中用三(羟甲基)氨基甲烷处理,几乎所有剩余的活化基团都被成功取代。