The research detailed in this dissertation is focused on the use of biomolecules (i.e., peptides and proteins) to form non-biologically produced materials under mild reaction conditions (i.e, neutral pH, aqueous solutions, and room temperature). The peptides utilized in the studies detailed in this dissertation were identified through the screening of single crystal rutile TiO2 substrates or Ge powder with a phage-displayed peptide library. Twenty-one peptides were identified which possessed an affinity for Ge. Those peptides possessing a basic isoelectric point as well as hydroxyl- and imidazole-containing amino acid residues were found to be the most effective in precipitating amorphous germania from an alkoxide precursor. The phage-displayed peptide library screening of TiO2 substrates yielded twenty peptides. The titania formation activity of these peptides was found to correlate with the number of positive charges they carried. The titania materials generated by the library-identified and designed peptides were found to be composed of amorphous titania as well as <10 nm anatase and/or monoclinic TiO2 crystallites. Four recombinant proteins, derived from the amino acid sequences of proteins (silaffins) associated with biosilicification in diatoms, were also investigated for titania precipitation activity. The two most basic of these recombinant silaffins, rSil1L and rSilC, were able to induce the formation of titania. The titania precipitates generated by rSil1L were found to be similar to those produced by the phage-displayed library identified peptides. The second recombinant silaffin, rSilC, was found to produce hollow spheres of titania, which, following dehydration, were observed to transform into larger, solid spheres composed of radially aligned columns of rutile TiO2. The highly repetitive nature of the rSilC s amino acid sequence is believed to be responsible for the differences in TiO2 polymorph generated by the different recombinant silaffins and peptides. This dissertation also details research conducted on the formation of titania utilizing rSilC conjugated to synthetic and biogenic silica surfaces. These silica surfaces were functionalized with a newly developed drendritic growth technique. The dendritic functional-group amplification process was demonstrated to increase the loading of hexahisitidine tagged proteins on silica surfaces by more than 40%, as compared to traditional immobilization procedures.

Thesis (Ph. D.)--Materials Science and Engineering, Georgia Institute of Technology, 2008. / Committee Chair: Sandhage, Kenneth; Committee Co-Chair: Kröger, Nils; Committee Co-Chair: Naik, Rajesh; Committee Member: Hud, Nicholas; Committee Member: Marder, Seth.

Thesis (M. S.)--Materials Science and Engineering, Georgia Institute of Technology, 2008. / Committee Chair: Sandhage, Kenneth H.; Committee Co-Chair: Snyder, Robert L.; Committee Member: Sanders, Thomas H.

Diatoms possess characteristics such as abundance, diversity, and high reproductivity, which make their nano-structured frustules (diatom frustules) attractive for a wide range of applications. To overcome the limitation of their silica based frustule composition, diatom frustules have been converted into a variety of materials including silicon, silicon carbide, silver, gold, palladium and carbon in the present study. The compositions and the extent of shape preservation of the replicas are examined and evaluated with different characterization methods such as X-ray diffraction, SEM, TEM and FTIR analyses. These replicas still retained the complex 3D structures and nano-scaled features of the starting diatom frustules. Some properties and possible applications of converted materials are explored and the kinetics and thermodynamics related to the successful replications (conversions) are also studied and discussed.

BaSIC, which stands for Bioclastic and Shape-preserving Inorganic Conversion, is shape-preserving chemical conversion process of biological (or man-made) silica structures for producing complex 3-D microscale structures. This dissertation reports the BaSIC reaction of halide gases (i.e., TiF4, ZrF4, and ZrCl4) with 3-D silica structures, (i.e., diatom frustules, silicified direct-write assembly scaffolds, and Stöber silica spheres) to produce titania and zirconia replicas of the original 3-D structures. The kinetics of reaction of silica with titanium tetrafluoride gas is analyzed by using a novel HTXRD reaction chamber, nitrogen adsorption, and transmission electron microscope (TEM). The crystal structure and the temperature-induced phase transformation (from the room temperature hexagonal R-3c structure to the higher temperature cubic Pm3m structure) of polycrystalline TiOF2 that was synthesized through metathetic reaction of silica with TiF4(g) is reported. Additionally, potential applications of the converted titania diatom frustules (i.e., as a fast micron-sized ethanol sensor, and as a pesticide hydrolyzing agent) are also demonstrated in this work.

Numerous organisms produce ornately detailed inorganic structures (often known as shells) with features on length scales from the nanoscale to the microscale. One organism, commonly referred to as a diatom, originates from algae and is found throughout the oceans on Earth. These diatoms possess skeletal structures, frustules, made from silicon dioxide. This chemical makeup limits the number of possible applications for which these structures can be used. Using a series of gas displacement reactions, these frustules can be converted to other useful materials, such as magnesium oxide and titanium dioxide, while maintaining the features of the frustule template. In the current research, silicon dioxide frustules were converted to titanium dioxide replicas using method previously devised by our group. The titanium dioxide replicas were subjected to a hydrothermal reaction by exposing the replicas to an aqueous basic solution containing barium hydroxide to form barium titanate and barium strontium titanate replicas. The effects of reaction temperature, time, and solution composition on extent of conversion were examined. The conventional method of converting titanium dioxide to barium titanate, using a convection heating oven, was compared with a microwave assisted heating method to study the advantages of using microwave heating over convection heating.