TEMPLATE POLYMERIZATION

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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.