Yang Qian, Hu Meng-Xin, Dai Zheng-Wei, Tian Jing, Xu Zhi-Kang
Institute of Polymer Science and Key Laboratory of Macromolecule Synthesis and Functionalization (Ministry of Education), Zhejiang University, Hangzhou 310027, P. R. China.
Langmuir. 2006 Oct 24;22(22):9345-9. doi: 10.1021/la0610598.
Increasingly, carbohydrate-protein interactions are viewed as important mechanisms for many biological processes such as blood coagulation, immune response, viral infection, inflammation, embryogenesis, and cellular signal transfer. However, the weak affinity of the interactions and the structural complexity of carbohydrates have hindered efforts to develop a comprehensive understanding of carbohydrate functions. Fortunately, synthetic polyvalent glycoligands give us a chance to reveal the nature of these biological processes. In this work a sugar-containing monomer (alpha-D-allyl glucoside (AG)) was grafted onto polypropylene microporous membrane (PPMM) by UV-induced graft polymerization to generate a glycosylated porous surface for the first time. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy were employed to confirm the glycosylation. Water contact angle measurement was used to evaluate the hydrophilicity change of the surfaces before and after the graft polymerization of AG. It was found that the grafting density increased reasonably with the increase of AG monomer concentration, and then this increase slowed when the AG concentration exceeded 80 g/L. At the same time a 20-25 min UV irradiation was enough for the grafting polymerization. The photoinitiator concentration also influenced the grafting density obviously, and there was an optimal concentration of the photoinitiator for the grafting process. The water contact angle of the polyAG-tethered membrane surface decreased from 149 degrees to 80 degrees with the increase of grafting density from 0 to 187.76 microg/cm2, which indicated a hydrophilic variation of the membrane surface by the grafting of AG. Results also indicated that the surface-grafted polyAG chains showed weak interaction with Con A when the grafting density was low. However, when the sugar density exceeded 90 microg/cm2, the binding affinity increased dramatically which was the due to the "glycoside cluster effect".
碳水化合物 - 蛋白质相互作用日益被视为许多生物过程的重要机制,如血液凝固、免疫反应、病毒感染、炎症、胚胎发育和细胞信号传递。然而,这些相互作用的弱亲和力以及碳水化合物的结构复杂性阻碍了人们全面理解碳水化合物功能的努力。幸运的是,合成多价糖配体为我们揭示这些生物过程的本质提供了机会。在这项工作中,首次通过紫外线诱导接枝聚合将含糖类单体(α - D - 烯丙基葡萄糖苷(AG))接枝到聚丙烯微孔膜(PPMM)上,以产生糖基化多孔表面。采用傅里叶变换红外光谱、X射线光电子能谱和扫描电子显微镜来确认糖基化。通过测量水接触角来评估AG接枝聚合前后表面亲水性的变化。发现接枝密度随着AG单体浓度的增加而合理增加,当AG浓度超过80 g/L时,这种增加减缓。同时,20 - 25分钟的紫外线照射足以进行接枝聚合。光引发剂浓度也明显影响接枝密度,并且在接枝过程中存在光引发剂的最佳浓度。随着接枝密度从0增加到187.76 μg/cm²,聚AG接枝膜表面的水接触角从149度降至80度,这表明通过AG接枝,膜表面发生了亲水性变化。结果还表明,当接枝密度较低时,表面接枝的聚AG链与伴刀豆球蛋白A表现出弱相互作用。然而,当糖密度超过90 μg/cm²时,结合亲和力急剧增加,这是由于“糖苷簇效应”。