TEMPLATE POLYMERIZATION

该建议涉及合成网络聚合物的制备， 可以作为催化剂和补充剂， 大分子 模板聚合技术（分子 印迹），涉及单体在其聚合之前的预组织。 聚合，用于产生结合位点，并催化 交联网络聚合物中的活性位点。 印记或模板 分子被设计成在形状上与 底物、过渡态或产物。 催化剂计划是在一个 脱氟化氢反应。 创建底物的策略 结合位点和组织的催化功能，使用 描述了模板聚合方法。 系统性的努力， 提出了通过分子水平工程对催化剂进行“微调”。 该系统为利用模板进行催化剂设计提供了一个范例 聚合法 另外的研究包括一种可聚合形式的 维生素B6的辅因子-底物复合物及其评价 底物特异性和催化活性以及合成 可聚合的TS类似物，其被设计为产生催化位点， 氯酸的重排和对映选择性水解 活性α-氨基酯。 第二部分介绍了分子印迹技术， 用于制备核苷酸碱基的聚合互补物， 寡聚核苷酸。 这些聚合物材料有希望作为 用于序列特异性分离的色谱载体 寡聚核苷酸。

This proposal involves the preparation of synthetic network polymers that can function as catalysts and as complements to biological macromolecules. The technique of template polymerization (molecular imprinting), involving preorganization of monomers prior to their polymerization, is employed to create the binding sites and catalytically active sites in crosslinked network polymers. The imprinting or template molecule is designed to be complementary in shape to either the substrate, transition state, or product. The catalyst program is developed within the context of a dehydrofluorination reaction. The strategy for creation of a substrate binding site and organization of catalytic functionality using the template polymerization approach is described. A systematic effort to "fine tune" the catalyst by molecular level engineering is proposed. This system serves as a paradigm for catalyst design using template polymerization. Additional studies include a polymerizable form of a cofactor-substrate complex of Vitamin B6 and an evaluation of its substrate specificity and catalytic activity and the synthesis of polymerizable TS analogs designed to produce catalytic sites for the rearrangement of chorismic acid and the enantioselective hydrolysis of active alpha-amino esters. In second part of this proposal, molecular imprinting technology will be used to prepare polymeric complements to nucleotide bases and to oligomeric nucleotides. These polymeric materials hold promise as chromatographic supports for the sequence specific separation of oligomeric nucleotides.