Synthesis of boronic acid-immobilized monodispersed porous polymer resins using a templating polymerization technique, and their application to packings for separation of saccharides

采用模板聚合技术合成硼酸固定单分散多孔聚合物树脂及其在糖类分离填料中的应用

• 批准号: 15550077
• 负责人: KITAHARA Keiichi
• 金额: $ 2.24万
• 依托单位: Tokyo Medical University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550077/
• 关键词: analysis of saccharides; boronic acid immobilized monodispersed polymer resins; templating polymerization; HPLC; Evaporative Light Scattering Detector; solid phase extraction; glycolipids; glycoproteins; ボロン酸結合型単分散コポリマーゲル; 単分散フェニルボロン酸コポリマーゲル

Boronic acids form stable cyclic esters with cis-diols of saccharides, and therefore are used in the separation of nucleosides, nucleotides, and glycated proteins such as a glycated hemoglobin. In these investigations boronic acids covalently bound to carriers such as silica gel. and polymer resins were used for the separation. However, pH range of silica gel packed column has been limited by the unstability in alkaline solution. On the other hand, the nonuniformity in particle size of the polymer resins is unavoidable in the conventional preparation method, and lowers the resolution efficiency of a chromatographic column.For separation of saccharides and glycoconjugates, we prepared two types of monodispersed boronic acid immobilized porous styrene-divinylbenzene copolymer particles using a polymerization method based on a templating technique. The polymer particles with 5 μ m particle size was used as the stationary phase for high-performance liquid chromatography. The results of HPLC separation of aldohexoses and aldopentoses revealed that ribose, talose and idose were retained in boronic acid immobilized polymer resins in the pH range of 1.3 〜 11.9. These saccharides exist considerably as a furanose form in an aqueous solution, and therefore, a furanose form probably plays important role in the complex formation between a boronoic acid and saccharides. On the other hand, the solid phase extraction by the polymer particles with 20 μ m particle size was applied to glucose, talose and ganglioside G^<M1>. However no retention with these compounds was observed. This result shows that higher extent of immobilization with boronic acid groups on the polymer surface was required for the solid phase extraction.

硼酸与顺式二醇形成稳定的环酯，因此用于分离核苷、核苷酸和糖化蛋白质如糖化血红蛋白。在这些研究中，硼酸共价结合到载体如硅胶上。并使用聚合物树脂进行分离。但硅胶填充柱在碱性溶液中的不稳定性限制了其pH范围。为了分离多糖和糖缀合物，采用基于模板技术的聚合方法制备了两种单分散硼酸固定化苯乙烯-二乙烯苯共聚物多孔粒子。采用粒径为5 μ m的聚合物颗粒作为高效液相色谱固定相。己醛糖和戊醛糖的HPLC分离结果表明，在pH 1.3 ~ 11.9的范围内，核糖、塔罗糖和艾杜糖被保留在硼酸固定化聚合物树脂中。这些糖在水溶液中以呋喃糖形式大量存在，因此，呋喃糖形式可能在硼酸和糖之间的络合物形成中起重要作用。另一方面，将粒径为20 μ m的聚合物颗粒用于葡萄糖、塔罗糖和神经节苷脂G^的固相萃取<M1>。然而，未观察到这些化合物的保留。该结果表明，固相萃取需要在聚合物表面上更高程度地固定硼酸基团。

项目成果

北原 恵一: "シリカゲルを鋳型とするボロン酸結合型単分散ポリマーゲルの合成と糖分離用カラム充填剤への応用"第65回分析化学討論会講演要旨集. (2004)

Keiichi Kitahara：“以硅胶为模板合成硼酸键合单分散聚合物凝胶及其在糖分离柱填充材料中的应用”第 65 届分析化学研讨会摘要（2004 年）。