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Organic materials as templates for the formation of mesoporous inorganic materials and ordered inorganic nanocomposites
Hierarchically structured inorganic materials are everywhere in nature. From unicellular aquatic algae such as diatoms to the bones and/or cartilage that comprise the skeletal systems of vertebrates. Complex mechanisms involving site-specific chemistries and precision kinetics are responsible for the formation of such structures. In the synthetic realm, reproduction of even the most basic hierarchical structure effortlessly produced in nature is difficult. However, through the utilization of self-assembling structures or "templates", such as polymers or amphiphilic surfactants, combined with some favorable interaction between a chosen inorganic, the potential exists to imprint an inorganic material with a morphology dictated via synthetic molecular self-assembly. In doing so, a very basic hierarchical structure is formed on the angstrom and nanometer scales. The work presented herein utilizes the self-assembly of either surfactants or block copolymers with the desired inorganic or inorganic precursor to form templated inorganic structures. Specifically, mesoporous silica spheres and copolymer directed calcium phosphate-polymer composites were formed through the co-assembly of an organic template and a precursor to form the desired mesostructured inorganic. For the case of the mesoporous silica spheres, a silica precursor was mixed with cetyltrimethylammonium bromide and cysteamine, a highly effective biomimetic catalyst for the conversion of alkoxysilanes to silica. Through charge-based interactions between anionic silica species and the micelle-forming cationic surfactant, ordered silica structures resulted. The incorporation of a novel, effective catalyst was found to form highly condensed silica spheres for potential application as catalyst supports or an encapsulation media. Ordered calcium phosphate-polymer composites were formed using two routes. Both routes take advantage of hydrogen bonding and ionic interactions between the calcium and phosphate precursors and the self-assembling copolymer template. Some evidence suggests that the copolymer morphology remained in the composite despite the known tendency for calcium phosphates to form highly elongated crystalline structures with time, as is commonly the case for synthetic hydroxyapatites. Such materials have obvious application as bone grafts and bone coatings due, in part, to the osteoconductive nature of calcium phosphate as well as to the mesoporosity generated through the cooperative assembly of the block copolymer and the inorganic. Future work, including potential experiments to determine osteoconductivity of as-prepared composites, is also presented herein.
Inorganic chemistry|Organic chemistry|Polymer chemistry|Materials science
Ziegler, Christopher R, "Organic materials as templates for the formation of mesoporous inorganic materials and ordered inorganic nanocomposites" (2011). Doctoral Dissertations Available from Proquest. AAI3498416.