Development of Separation Material for Saccharide on the Basis of Surface Imprinting Procedure

糖类的识别和分离一直是近年来人们关注的焦点。硼酸是实现这一目的的有力工具，因为它可以与糖形成稳定的配合物（环酯），特别是与含有顺式二醇基团的糖。另一方面，合成聚合物制成的微球已成为功能材料发展的热点。在本工作中，我们制备了表面带有苯硼酸基团的聚合物微球，并对其进行了表征。以乙烯、丙烯酸丁酯和间丙烯酰胺苯硼酸为原料，采用乳液聚合法制备了聚合物微球。通过加入甲基乙基酮使微球在碱性水悬浮液中膨胀，使树脂中的苯硼酸位点以电离形式迁移到水-有机界面。由于分子结构不同，d -葡萄糖与微球结合，而1-甲基- α - d -葡萄糖苷与微球不结合。d -葡萄糖的吸附是通过苯硼酸段与d -葡萄糖的顺式二醇基形成络合物（酯）来实现的。虽然对印迹结构的引入进行了一些初步的实验和理论计算，但我们还没有得到具有良好再现性的特定结构的印迹微球。然而，这些数据和计算为理解苯硼酸修饰微球的化学行为以及制备糖印迹结构的操作参数提供了线索。该材料预计可用于分离和浓缩含有顺式二醇基团的生物成分，例如，糖蛋白和核蛋白、核酸以及糖类。

Recognition and separation of saccharides have been the focus of much recent attention. Boronic acid is a powerful tool for this purpose since it can form a stable complex (cyclic ester) with saccharides, especially with those comprising a cis-diol group. On the other hand, microspheres from synthetic polymers have become of interest in functional materials development. In the present work, we have prepared polymer microspheres having phenylboronic acid groups on their surface and carried out their characterizations. The polymer microspheres were prepared by emulsion polymerization of stirene, butyl acrylate, and m-acrylamidophenylboronic acid. The microsphere was swollen in an alkaline aqueous suspension by adding methylethylketone so that phenylboronic acid sites in the resin would migrate out to the aqueous-organic interface in their ionized forms. D-Glucose was bound onto the microsphere while 1-methyl-alpha-D-glucoside was not, due to their different molecular structures. The adsorption of D-glucose was performed by complex (ester) formation between phenylboronic acid moiety and cis-diol group of D-glucose. Although some preliminary experiments and theoretical calculations were performed for introduction of the imprinting structure, we have not yet got the imprinted microspheres for a specific structure of saccharide with a good reproducibility. However, the data and calculations give a clue in understanding the chemical behaviors of phenylboronic acid-modified microspheres as well as the operational parameters in the preparation of saccharide-imprinted structures. The material is expected to be useful for separation and concentration of biological constituents comprising a cis-diol group, e.g., glyco-and nucleo proteins, nucleic acids as well as saccharides.