Synthesis and evaluation of molecularly imprinted polymers (MIPs) for the selective recognition of biomolecules

Molecular imprinting is a process by which highly selective binding sites can be created for various compounds in a crosslinked polymer network. This dissertation comprises research efforts towards the synthesis and evaluation of various molecularly imprinted polymers (MIPs).; After a brief introduction to molecular imprinting and its applications, Chapter I discusses the development of a MIP for oligonucleotides such that recognition can take place in an aqueous environment. The results of this study show that imprinting of nucleotides and oligonucleotides can be performed using acrylamide hydrophilic monomers using mixtures of methanol and water as the porogen. MIPs synthesized in this fashion can successfully be used to perform selective binding in an aqueous media.; Chapter 2 discusses the development of several fluorescent ‘trifunctional’ monomers for the introduction of stimuli responsive binding sites in MIPs. We developed and synthesized three types of monomers that incorporate the template (imprinting molecule), a fluorescent probe and a polymerizable olefin in the same molecule, thus locating the probe in proximity to the MIP binding site. These fluorescent functional monomers are compatible with the free radical polymerization conditions necessary for molecular imprinting, and the template molecule can be cleaved from polystyrene polymers using these monomers.; The incorporation of these fluorescent monomers in crosslinked imprinted polymers, and the analysis of their ability to behave as chemosensors for cholesterol is described in Chapter 3. The synthesis and evaluation of a series of MIPs with varying types of fluorescent trifunctional monomers and differing types of crosslinking monomers is discussed. This study demonstrates that a fluorescent probe in close proximity to a binding site can be affected by the incoming analyte; however, additional studies need to be performed to develop a fluorescent MIP that would be of practical use in the field.; In Chapter 4, we explore the known affinity of fluorinated compounds for other fluorinated groups and examine whether this fluorine-fluorine interaction could be used to create selective MIPs for small fluorinated molecules. We have found that the imprinting effect of small fluorinated molecules on a fluorinated polymer did not result in enhanced binding of the template.; Finally, Chapter 5 is a literature review of combinatorial and computational approaches that have been employed to select an optimal MIP formulation for a targeted analyte. The use of MIPs in the combinatorial field, specifically their use for screening libraries of small molecules, is also discussed.