Template copolymerization to control site structure around metal ions: Applications towards sensing and gas storage and release.

摘要

The development of functional materials for sensing and gas storage and release is useful in a number of chemical and biological applications. Investigating function of molecularly imprinted polymers (MIP), often used for these purposes, has relied on circumstantial evidence because direct examination of immobilized sites is not possible. Described in this dissertation is the design, synthesis, characterization and function studies of materials synthesized by template copolymerization methods. Metal ions exhibit unique spectroscopic properties and their utilization makes site examination more feasible. Ligand binding modulates these properties such that the event can be measured by spectroscopy. The metal ion's secondary coordination environment can also be tuned to increase or decrease function of the material.;In Chapter Two the utilization of template copolymerization to immobilize a europium-containing compound for the detection of volatile organic compounds is described. Luminescence of the immobilized complex is quenched in the presence of volatile organic compounds (VOC). The quenching effect is dependent on concentration of VOC and the nature of polymeric host.;Chapters Three and Four describe the development of materials for the photolytic release of nitric oxide (NO). In Chapter Three, a novel manipulation of the immobilized complex is employed to produce binding sites that contain ligands covalently embedded into the host in a position to bind the metal ion upon NO release in order to block rebinding. Incompatible binding affinities of the iron-containing templates made it impossible to study NO photo-release from this material. Second-row transition metals are more compatible with NO binding, and Chapter Four describes a ruthenium salen-containing polymer that releases NO in response to light. Additionally, transfer of NO to a metalloporphyrin and myoglobin has been achieved. This is the first report of photolytic heterogeneous NO transfer by a material.;The design of new materials has let to the development of a novel class of vinyl-substituted ligands. Chapter Five illustrates a new synthetic methodology for the monosubstitution of various beta-diketones. Dialkylated species, which are unable to coordinate metal ions, are often the major product. It was found that using an excess of starting diketone yields monosubstitution exclusively.