This thesis describes the synthesis and characterisation of phosphonium aryloxides, amides and phosphides. These compounds have been formed via the deprotonation of organic acids [of the type ROH, and R(_2)X, where X = NH, PH, R = aryl group] by basic phosphonium ylidic species [R(_3)PX, X = CH(_2,) C(Me)H, C(Ph)H, NH] in mixtures of hydrocarbon (toluene) and/or polar (acetonitrile, thf) solvents. All of these compounds contain both acidic CHs and 'naked' anions which promote extensive hydrogen bonding. Chapter 1 provides an outline of the fields of ylidic chemistry and hydrogen bonding. In Chapter 2, general experimental methods are described. Chapter 3 records all experimental results pertaining to this work. Here preparation of starting materials is documented, followed by an account of the synthesis and characterisation of twenty-three compounds. For all compounds melting point measurements, (^1)H NMR, (^31)P NMR, infrared spectra, and elemental analysis are recorded. Discussion of these results is documented in Chapters 4 to 7. Where possible, solid-state structures for compounds obtained by single crystal X-ray diffraction (nineteen structures) and single crystal neutron diffraction (two structures) are included. Chapter 4 discusses simple phosphonium aryloxide salts, while Chapter 5 is concerned with related phosphonium amides and phosphides. Chapter 6 deals with an extension of this work involving multifiinctional organic acids. Finally, Chapter 7 discusses unexpected results resulting from the work described in Chapter 6.

The main goal of this thesis was to explore the role of H-bonding interactions in ferrocene peptide conjugates at the molecular and supramolecular level. With the help of detailed spectroscopic and crystallographic studies, the intermolecular association of a range of conjugates was studied and described here. It was shown that C-terminal modifications directed the supramolecular assembly. In the case of Fc[CO-Gly-Val-OH]2, the C-terminal carboxylate group directed intermolecular interactions, causing formation of a supramolecular architecture that was characterized by large solvent-filled hydrophobic channels. In the absence of this directional group, as was the case in Fc[CO-Leu-Val-OMe]2 extended β-sheets were formed. Hierarchical self-assembly of disubstituted ferrocene peptide conjugates possessing Gly-Val-Phe and Gly-Val-Phe-Phe peptide substituents gave rise to nano- and micro-sized assemblies. Spontaneous self-assembly of Fc-peptides through intra-and intermolecular hydrogen bonding interactions induced supramolecular building blocks, which further associated to fibers, large fibrous crystals, and twisted ropes. Next, intermolecular H-bonding interactions were studied using a surface-based approach. A fragment of the amyloid-beta (Aβ) peptide was bound to a gold surface through a C-terminal Cys. Various aspects of the peptide film were examined using different electrochemical and surface analytical techniques. The interaction of Congo red and of Lys-Leu-Val-Phe-Phe with the immobilized Aβ fragment was studied using electrochemical methods, showing responses that indicated intermolecular interactions. This surface approach was used to probe the interaction of a series of ferrocene peptides (Fc-CO-Leu-Val-Phe-Phe-OX and Fc-CO-Lys(Boc)-Leu-Val-Phe-Phe-OX with X=H and Me) with the surface-bound Aβ fragment. Biomolecular interactions between Fc-peptides and the Aβ-modified surface were studied by electrochemical methods. The current response of the Fc redox process was modulated by the interaction with the Aβ-modified surface.

Thesis (Ph. D.)--University of Nevada, Reno, 2006. / "December, 2006." Includes bibliographical references (leaves 120-123). Online version available on the World Wide Web. Library also has microfilm. Ann Arbor, Mich. : ProQuest Information and Learning Company, [2006]. 1 microfilm reel ; 35 mm.

Thesis--University of California, Berkeley, 1959. / Includes bibliographical references (p. 74-76).

Thesis (Ph. D.)--University of Nevada, Reno, 2008. / "December 2008." Includes bibliographical references (leaves 201-211). Online version available on the World Wide Web.

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