This dissertation describes the use of discrete, self-assembled organic objects as templates for the nucleation and growth of inorganic nanostructures. The self-assembly of two different one-dimensional supramolecular systems is discussed, as is the mineralization of these structures with an inorganic semiconductor (cadmium sulfide) and a magnetic iron oxide (magnetite). By using well-defined, stable organic templates, novel inorganic nanostructures directly related to the template structure are produced.
The dendron rodcoil (DRC) molecules used to create a template have a triblock architecture containing a dendritic head, rigid, rod-like midsection, and flexible, coil-like tail. These amphiphilic molecules self-assemble in various slightly polar organic solvents into ribbon-like objects 10×2 nm cross-section and several microns in length. In some solvents these adopt a twisted helical structure with a fairly regular pitch of ~20 nm.
Twisted DRC ribbons in 2-ethylhexyl methacrylate and ethyl methacrylate were selectively mineralized to produce the first examples of helices of cadmium sulfide (CdS). The coiled morphology and ~50 nm pitch of these structures can be understood in terms of the template structure and periodicity. Single helices of CdS are produced as a result of nucleation and growth along one face of the ribbon template, while double helices of CdS are formed as a result of nucleation and growth on both faces of the twisted DRC ribbons.
Peptide-amphiphile (PA) molecules, used here as templates for CdS and magnetite (Fe₃O₄), contain a hydrophilic peptide sequence and hydrophobic alkyl tail, leading to their aqueous self-assembly into nanofibers. The peptide sequence displayed on the periphery of these fibers can be readily tailored to target different minerals. In one example, PA fibers containing phosphate and acid groups are used to nucleate isolated CdS quantum dots at low Cd²⁺:PA ratios. At higher cadmium concentrations, the fibers become completely encapsulated by CdS. In another example, a histidine-rich PA fiber is used to grow one-dimensional arrays of magnetite nanocrystals. These mimic the onedimensional organization of chains of magnetite in magnetotactic bacter