TEMPLATE POLYMERIZATION

这项提议涉及合成网络聚合物的制备，该网络聚合物 可以作为催化剂和生物的补充 大分子。模板聚合技术(分子 印迹)，涉及单体在其 聚合，用来创建结合位，并催化 交联型网络聚合物中的活性中心。印记或模板 分子被设计成在形状上与 底物、过渡态或产物。 CATALYER计划是在 脱氢氟化反应。制造衬底的策略 使用催化官能团的结合位置和组织 介绍了模板聚合的方法。一项系统性的努力 提出了用分子水平工程对催化剂进行“微调”。 该系统可作为使用模板进行催化剂设计的范例 聚合反应。其他研究包括一种可聚合形式的 维生素B6的辅因子-底物复合体及其评价 底物专一性和催化活性及其合成 可聚合的TS类似物，旨在为 分支酸的重排和对映体选择性的水解 活性的α-氨基酯。 在本提案的第二部分，分子印迹技术将 用于制备核苷酸碱基的聚合物补体并用于 寡聚核苷酸。这些聚合物材料有希望成为 用于序列特异性分离的层析载体 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.