Thesis (Ph.D.)--Brown University, 2008. / Vita. Advisor : Edward Hawrot. Includes bibliographical references.

Thesis (Ph. D.) -- California Institute of Technology, 2010. / Title from home page (viewed 03/04/2010). Advisor and committee chair names found in the thesis' metadata record in the digital repository. Includes bibliographical references.

Thesis (Ph. D.)--University of Virginia, 2001. / Includes bibliographical references (leaves 123-140). Also available online through Digital Dissertations.

Thesis (Ph. D.)--Oregon State University, 2010. / Printout. Includes bibliographical references (leaves 173-189). Also available on the World Wide Web.

Thesis (Ph. D.)--University of Texas at Austin, 2001. / Vita. Includes bibliographical references (leaves 148-173). Available also in a digital version from Dissertation Abstracts.

Thesis (Ph. D.)--University of Texas at Austin, 2001. / Vita. Includes bibliographical references (leaves 190-204). Available also in a digital version from Dissertation Abstracts.

Anion Binding has recently emerged as an important field of study due to the role these small inorganic species play in a plethora of biological processes. Chapter 1 of this thesis describes the biological relevance and scientific justifications for studying the ability of synthetic molecules to transport or extract anions under interfacial conditions. This chapter also serves to underscore the need to study both the thermodynamics and kinetics of anion binding as achieved using synthetic receptors. Methods for determining the thermodynamics of ion recognition are well-developed, and many equilibrium analyses of supramolecular binding events have been reported; however, the kinetics of such interactions are often neglected. Chapter 2 details the author's efforts to address this deficiency with respect to anion-binding and reports progress towards quantitative kinetic analyses of the interaction between cyclo[8]pyrrole (C8), an expanded porphyrin, and two test anions. It has been determined that stopped-flow analysis can provide on and off-rates, as well as activation parameters not accessible through thermodynamic means. Initial flash photolysis kinetic studies have also revealed that C8 has the potential to act as a photosensitizing agent through electron donation. This work is presented in Chapter 3, wherein the author discusses the construction of novel donor-acceptor dyads based on C8. As detailed in this chapter, time-resolved optical analyses have confirmed that photoinduced electron transfer occurs under conditions of photoexcitation and that the lifetime of the charge separated state is approximately 300 [mu]s. Finally, Chapter 4 describes a comprehensive set of spectroscopic work conducted by the author involving porphyrin and porphycenes that have a RuCp* (Cp*: pentamethylcyclopentadienyl) fragment either coordinated to the central porphyrinic core or directly attached to the "[pi]-face" of the macrocycle. These systems display unique intramolecular electron transfer properties that are ascribed to the metallated-porphyrin core acting as an electron acceptor, as opposed to a donor as is normally observed with porphyrins. / text

I present the characterization and applications of a technique to modify the surface of the conducting polymer, polypyrrole, via a novel, 12-amino acid peptide, THRTSTLDYFVI (T59). This peptide non-covalently binds to the chlorine-doped conducting polymer polypyrrole, allowing it to be used in tethering molecules to polypyrrole for uses such as a scaffold for the treatment of peripheral nerve injury or in surface coatings of neural recording electrodes. I have quantified the binding of this peptide as well as investigating the mechanism of the binding. The equilibrium constant of the binding interaction of PPyCl and the T59 peptide was found through a binding assay to be 92.6 nM, and the off rate was found to be approximately 2.49 s⁻¹, via AFM force spectroscopy. The maximum observed surface density of the peptide was 1.27 +/- 0.42 femtomoles/cm². Furthermore, my studies suggest that the eighth residue, aspartic acid, is the main contributor of the binding, by interacting with the partially positive charge on the backbone of polypyrrole. I have demonstrated practical applications of the technique in the successful modification of a PPyCl surface with the laminin fragment IKVAV, as well as the so-called stealth molecule poly(ethylene glycol) (PEG). A subcutaneous implant study was performed to confirm that the T59 peptide did not induce any significant reaction in vivo. Significantly, the conductivity of a PPyCl surface was unaffected by this surface modification technique. / text

This dissertation examines the social and scientific factors which fostered the inclusion of strength training as an adjunct to sport preparation programs. It utilizes Thomas Kuhn's theory of "paradigm shift," outlined in his 1962 treatise The Structure of Scientific Revolutions, to describe how strength training went from an activity perceived as harmful and deleterious to sport, to one which is now considered an indispensable component of optimal performance. In the late-nineteenth and early-twentieth centuries physicians, physiologists, and physical educators theorized that the body operated under the constraints of fixed capacities. Increased demands by one component of the body necessarily robbed nourishment from other parts. Under this paradigm, increased muscular strain posed a risk to other organ systems and was advised against. Through a thorough exploration of the scientific literature, this work demonstrates the evolution of the understanding of physiology which precipitated the displacement of the old paradigm. In addition to scientific literature, popular magazines are also utilized because of their importance in the erosion of the old paradigm and in laying the groundwork for the acceptance of the current paradigm of strength training as an adjunct to athletic performance. Moreover, this work discusses the importance of the Second World War, the Cold War, and the Olympics in hastening the demise of the belief that strength training was physically and athletically harmful. The number of athletes training with weights in the United States dramatically increased in the 1950s and the pace accelerated through the 1960s. The endorsement of the new paradigm was cemented with the hiring of specialists in strength training who went on to create their own literature and sponsor their own research. Completion of the paradigm shift is evident in the contemporary ubiquity of weight training which is performed for nearly all sports, all age groups, year-round, often in highly specialized facilities and overseen by individuals certified as strength and conditioning or performance-enhancement specialists. / text

Over the last decade, the classic organic donor tetrathiafulvalene (TTF) has emerged as an important functionality in supramolecular systems and complex ligand chemistry. Due to synthetic advances, TTF is no longer a moiety strictly limited to the area of charge transfer salts in material science. In fact, many complex systems incorporating the electron rich donor system are known. More can be imagined. This doctoral dissertation describes the author's journey in designing, synthesizing, and studying various compounds in which the TTF moiety serves a practical purpose, oftentimes giving known molecules new functions. The reported findings have led to a greater understanding of anion binding effects on TTF-containing anion receptors, the use of transition metals to pre-organize [pi]-faces for through-space donor-acceptor interactions, and the introduction of actinide species to tetrathiafulvalene ligands. The first Chapter provides a brief introduction and a short history of TTF chemistry. It also provides an overview describing the fundamental properties of TTF compounds, including TTF dimeric behavior and redox properties. Chapter 2, as the major focus of this dissertation, details the use of a flexible TTF-modified macrocyclic ligand, which upon metallation can effectively preorganize two TTF units to interact when oxidized. Specifically, a new way to stabilize the through-space mixed-valence TTF dimer, in which a transition metal can affect the degree of interaction between the two TTF units, is described. The mixed-valence TTF species in question could see use as components in molecular machines and could play an important role as molecular organic conductors, and discussions along these lines are included in this chapter. These mixed valence complexes were investigated by spectroscopic (¹H-NMR, UV-Vis NIR titrations, and EPR analysis) and X-ray single crystallographic analyses involving both the neutral and oxidized products. Chapter 3 introduces the synthesis, characterization, and electrochemistry of the first TTF-ligand to form a complex with an actinide cation. Chapter 4 details the synthesis, binding studies and X-ray single crystallographic analyses of a TTF-based electrochemical sensor for dihydrogen phosphate anion detection. Experimental procedures and characterization data are reported in Chapter 5. / text