This thesis focuses on the use of biomolecular assemblies for creating materials with novel properties. Several aspects of biomimetic materials have been investigated, from fundamental studies on membrane shaping molecules to the integration of biomolecules with inorganic materials. Triply periodic minimal surfaces (TPMS) are mathematically defined surfaces that partition space and present a large surface area in a confined space. These surfaces have analogues in many physical systems. The endoplasmic reticulum (ER) can form intricate structures and it acts as a replica for the wing scales of the butterfly C. rubi, which is characterized by electron microscopy and reflectometry. It was shown to contain a photonic crystal and an analogue to a TPMS. These photonic crystals have been replicated in silica and titania, leading to blue scales with replication on the nanometer scale. Replicas analyzed with left and right handed polarized light are shown be optically active. A macroporous hollow core particle was synthesized using a double templating method where a swollen block copolymer was utilized to create polyhedral nanofoam. Emulsified oil was used as a secondary template which gave hollow spheres with thin porous walls. The resulting material had a high porosity and low thermal conductivity. The areas of inorganic materials and functional biomolecules were combined to create a functional nanoporous endoskeleton. The membrane protein ATP synthase were incorporated in liposomes which were deposited on nanoporous silica spheres creating a tight and functional membrane. Using confocal microscopy, it was possible to follow the transport of Na+ through the membrane. Yop1p is a membrane protein responsible for shaping the ER. The protein was purified and reconstituted into liposomes of three different sizes. The vesicles in the 10-20 nm size range resulted in tubular structures. Thus, it was shown that Yop1p acts as a stabilizer of high curvature structures. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 3: Submitted. Paper 4: Submitted. Paper 5: Submitted.</p>

The generation of nanostructured assemblies with complex (three-dimensional, 3D) self-assembled morphologies and with complex (multicomponent) tailorable inorganic compositions is of considerable technological and scientific interest. This research demonstrates self-assembled 3D organic templates of biogenic origin can be converted into replicas comprised of numerous other functional nanocrystalline inorganic materials. Nature provides a spectacular variety of biologically-assembled 3D organic structures with intricate, hierarchical (macro-to-micro-to-nanoscale) morphologies. Morphology-preserving chemical conversion of such readily available, structurally complex templates will provide a framework for chemical conversion of synthetic organic templates and, potentially, production of organic/inorganic composites. Four research thrusts are detailed in this dissertation. First, chemical conversion of a nanostructured bioorganic template into a multicomponent oxide compound (tetragonal BaTiO₃ via layer-by-layer surface sol-gel coating and subsequent morphology-preserving microwave hydrothermal processing was demonstrated. Second, photoluminescence was imparted to bioorganic template structures through morphology-preserving chemical conversion to exhibit both the dramatic change in properties such processing can provide, and the potential utility of chemically transformed templates in anti-counterfeiting / authentication applications. Third, the reaction mechanism(s) for morphology-preserving microwave hydrothermal conversion of TiO₂ to BaTiO₃, were studied with the aid of Au inert markers on single crystal rutile TiO₂. Finally, constructive coating techniques (SSG) and moderate temperature (< 500C) heat treatments were utilized to modify and replicate structural color and were coupled with deconstructive focused ion beam microsurgery to prepare samples for microscale structure/property interrogation. Specifically, the effects of coating thickness and coating composition on reflection spectra of structurally colored templates were examined. Also, the effects of the replacement of natural material with higher index of refraction inorganic materials on optical properties were studied. The three processing research thrusts constituting chapters 1, 2 and 4 take advantage of moderate temperature processing to ensure nanocrystalline materials, either for shape preservation or to prevent scattering in optical applications. The research thrust presented in chapter 3 examines hydrothermal conversion of TiO₂ to BaTiO₃, not only to identify the reaction mechanism(s) involved in hydrothermal conversion under morphology-preserving conditions, but also to introduce inert marker experiments to the field of microwave hydrothermal processing.

Stereocomplex poly(methyl methacrylate) (PMMA) fibers for the purpose of reinforcing PMMA materials were developed. These kinds of composites are known as "self-reinforced" composites. We were successful in producing stereocomplex PMMA fibers with three different methods - wet spinning, gel spinning and electrospinning. Gel spinning and electrospinning produced the most crystalline fibers. Steroecomplex PMMA fibers were further shown to be resistant to high temperature and also to hot monomer solvent during bulk polymerization. We further describe our efforts in characterization, replication and mimicry of structural color features of butterflies and beetles. We have developed a simple method of characterizing the bidirectional reflectance distribution function of microscopic objects such as butterfly wing scales. We used this method to characterize nanometer sized structural color features resulting from the replication of butterfly Morpho rhetenor, mimickry of butterfly Papilio palinurus and also the native structural color features of iridescent beetle Chrysina gloriosa, which were shown to be cholesteric focal conic defects lined on the surface.

In this research, a new technique for modeling periodic structures in the finite-difference time-domain (FDTD) method is developed, and the technique is applied to the study of structural color in insects. Various recent supplements to the FDTD method, such as a nearly-perfect plane-wave injector and convolutional perfectly matched layer boundary condition, are used. A method for implementing the FDTD method on a parallel, distributed-memory computer cluster is given. To model a periodic structure, a single periodic cell is terminated by periodic boundary conditions (PBCs). A new technique for incorporating PBCs into the FDTD method is presented. The simplest version of the technique is limited to two-dimensional, singly-periodic geometries. The accuracy is demonstrated by comparing to independent results calculated with a frequency-domain, mode-matching method. The periodic FDTD method is then extended to the more general case of three-dimensional, doubly-periodic problems. This extension requires additional steps and imposes new limitations. The computational cost and limitations of the method are presented. Certain species of butterflies exhibit structural color, which is caused by quasi-periodic structures on the scales covering the wings. Numerical experiments are performed to develop a technique for modeling quasi-periodic structures using the periodic FDTD method. The observed structural color of butterflies is then calculated from the electromagnetic data using colorimetric theory. Three types of butterflies are considered. The first type are from the Morpho genus. These are typically a brilliant, almost metallic, blue color. The second type is the Troides magellanus, which exhibits an interplay of structural and pigmentary color, but the structural color is only visible near grazing incidence. The final type is the Ancyluris meliboeus, which exhibits iridescence on the ventral side. For all cases, the effects of changing the dimensions of various structural elements are considered. Finally, some earlier work on the design of TEM horn antennas is presented. The TEM horn is a simple and popular antenna, but only limited design information is available in the literature. A parametric study was performed, and the results are given. A complete derivation of the characteristic impedance of the basic antenna is also presented.

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