海洋壳寡糖配位分子印迹聚合物的合成及识别性能研究

With the purpose of finding the functional materials which can effectively separate the marine chitooligosaccharide monomers with degree of polymerization n=4-9 in aqueous solution, this project will combine the principle of molecular imprinting with the theory of coordination chemistry together and proceed from the molecular structure characteristics of marine chitooligo- saccharide monomers. The model of bimetallic coordinative molecularly imprinted polymers that can specifically recognize chitooligosaccharide molecules will be constructed by inducting the metal coordinate bond molecular recognition mode with designing and clipping the function monomers. With the photopolymerization process, an orienting series of bimetallic coordinative molecularly imprinted polymers that can specifically recognize marine chitooligosaccharide monomers with different degree of polymerization will be synthesized. Sequentially these polymers' recognition and separate efficiency on various marine chitooligosaccharide monomers will be evaluated. The recognition mechanism of these polymers, and the synergistic effect between the coordination and noncovalent interactions such as hydrogen bond and van der waals force in aqueous solution during the molecular recognition process will be studied. Finally the materials of coordinative molecularly imprinted polymers with high separate efficiency and large treatment capacity will be available, which will open a new way to produce highly purified marine chito- oligosaccharide monomers in aqueous solution on a large scale. This project will have not only an important academic value, but also a broad prospect. It will be of great practical significances to the development and utilization of marine resources in the blue economic zone of Shandong Peninsula.

本项目以寻找能够在水溶液中有效分离聚合度n = 4-9的海洋壳寡糖单体的功能材料为目标，将分子印迹原理与配位化学理论相结合，从海洋壳寡糖单体分子结构特点出发，通过对功能单体的设计与剪裁引入金属配位键分子识别模式，构筑对壳寡糖分子专一识别的双金属配位分子印迹聚合物模型；采用光引发聚合工艺，定向合成一系列对不同聚合度的海洋壳寡糖单体具有特异性识别的双金属配位分子印迹聚合物；测定这些配位分子印迹聚合物对壳寡糖单体的识别性能；考察其对不同海洋壳寡糖单体的分离效果；研究水溶液中配位作用与氢键及范德华力等非共价作用在分子识别过程中的协同效应；探讨配位分子印迹聚合物对海洋壳寡糖单体的识别机理；从中筛选出分离度高、处理容量大的配位分子印迹聚合物材料，开辟从水溶液中规模化制备高纯度的海洋壳寡糖单体新途径。该项目不仅有重要学术价值，而且应用前景广阔，对山东半岛蓝色经济区海洋资源开发具有十分重要的现实意义。

海洋壳寡糖因其结构独特、并与内源性寡糖有很多结构相似性，在生物医药和农业等领域具有极为广泛的应用前景，其研究与开发已成为糖化学和糖生物学领域的热点课题之一。目前，国内外市场对不同聚合度的壳寡糖单体产品的需求潜力巨大。然而，由于壳寡糖单体之间物理化学性质和化学结构的差异性小，常规的分离提取技术难以实现其规模化制备，导致海洋壳寡糖单体“纯度低、产量小、价格贵”，成为制约其应用开发的技术瓶颈。为此，本项目以寻找能够在水溶液中有效分离聚合度n = 4~9的海洋壳寡糖单体的功能材料为目标，将分子印迹原理与配位化学理论相结合，从海洋壳寡糖单体的分子结构出发，设计合成了含有酚羟基和羧基的两类不对称N,N’-双(取代)草酰胺类桥联配体，在金属离子存在下，使其与海洋壳寡糖分子上氨基识别位点配位组装，构筑了双金属配位识别模型；采用悬浮聚合法定向合成一系列对不同聚合度的海洋壳寡糖单体具有特异性识别的双金属配位分子印迹聚合物(MIP)微球树脂；测定了这些MIP微球树脂对壳寡糖单体的识别性能；考察了其对壳寡糖单体的分离效果；研究了水溶液中配位作用与氢键和范德华力等非共价作用在分子识别过程中的协同性；探讨了海洋壳寡糖分子与功能单体之间的识别机理。从中筛选出分离度高、处理容量大的MIP分离材料，实现了从水溶液中规模化制备高纯度的海洋壳寡糖单体的研究目标。.该项目首次将分子印迹技术用于海洋壳寡糖单体的分离，提出了规模化制备海洋壳寡糖单体的新思路；构筑的具有双金属配位键识别和非共价键识别协同效应的配位分子印迹聚合物，为解决水溶液中规模化制备海洋壳寡糖单体提供了关键技术，开辟了规模化制备高纯度的海洋壳寡糖单体新途径。已发表SCI收录论文28篇，研究结果具有重要学术价值；其相关成果的进一步开发与转化对于海洋资源的开发利用具有重要的现实意义和广阔的应用前景，可望取得显著地经济和社会效益。