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The study of ferritin includes a rich history of discoveries and scientific progress. Initially, the composition of ferritin was determined. Soon, it was shown that ferritin is a spherical, hollow protein. Eventually, over several decades of research, the structure and some function of this interesting protein was elucidated. However, the ferritin field was not completely satisfied. Today, for example, researchers are interested in refining the details of ferritin function, in discovering the role of ferritin in a variety of diseases, and in using ferritin for materials chemistry applications. The work presented in this dissertation highlights the progress that we have made in each of these three areas: 1) Mechanistic studies: The buffer used during horse spleen ferritin iron loading significantly influences the mineralization process and the quantity of iron deposited in ferritin. The ferrihydrite core of ferritin is crystalline and ordered when iron is loaded into ferritin in the presence of imidazole buffer. On the other hand, when iron is loaded into ferritin in the presence of MOPS buffer, the ferrihydrite core is less crystalline and less ordered, and a smaller amount of total iron is loaded in ferritin. We also show that iron can be released from the ferritin core in a non-reductive manner. The rate of Fe3+ release from horse spleen ferritin was measured using the Fe3+-specific chelator desferoxamine. We show that iron release occurs by three kinetic events. 2) Disease studies: In order to better understand iron disruption during disease states, we performed in vitro assays that mimicked chronic kidney disease. We tested the hypothesis that elevated levels of serum phosphate interrupted normal iron binding by transferrin and ferritin. Results show that phosphate competes for iron, forming an iron(III)-phosphate complex that is inaccessible to either transferrin or ferritin. Ferritin samples separated from the iron(III)-phosphate complex shows that as the phosphate concentration increases, iron loading into ferritin decreases. 3) Materials chemistry studies: Anion sequestration during ferritin core reduction was studied. When the core of horse spleen ferritin is fully reduced using formamidine sulfinic acid, a variety of anions, including halides and oxoanions, cross the protein shell and enter the ferritin interior. Efforts have been made to use ferritin to control the concentration of anions for reactions. In addition, the native ferrihydrite mineral core of ferritin is a semi-conductor capable of catalyzing oxidation/reduction reactions. Light can photo-reduce AuCl4- to form gold nanoparticles (AuNPs) with ferritin as a photocatalyst. The mechanism of AuNP formation using ferritin as a photocatalyst was examined. From this work, we propose that the ferrihydrite core of ferritin photo-reduces; the mineral core dissolves into a soluble iron(II) mineral. The iron(II) then re-oxidizes, and a new mineral forms that appears to be the new photocatalyst, as the lag phase is significantly decreased with this new mineral form of ferritin.

In chapter I Photo-retro-Diels-Alder (PrDA) reactions of a variety of Diels Alder (DA) adducts were studied. Experimental results showed that the photoreactivity (quantum yield) depends on the electron-donating ability of the diene component and the electronwithdrawing ability of the dienophile component. The mechanism was studied by trapping the reaction intermediate, O2 quenching and femtosecond time-resolved absorption spectroscopy. All the results support a mechanism that involves a charge-separated intermediate generated from a singlet excited state. The PrDA reaction may find applications in photoresponsive materials, photolithography, drug delivery and mechanistic research. Chapter II shows two applications of the PrDA reaction. The first, being the formation of the 2 nd -ring DA adduct together with the central-ring adduct in a reaction of pentacene and tetracyanoethylene (TCNE) at room temperature. DFT calculations showed that the difference between the free energy of the two isomers is about 3.9 kcal/mol. Photo- and thermally induced isomerization between the central-ring adduct and the 2nd -ring adduct were studied in solutions and in polymer films. In solution, the less stable 2nd -ring adduct can be completely converted to the more stable central-ring adduct either thermally or photochemically, but the reverse transformation does not occur. In a polymer matrix, isomerization can be photochemically induced in both directions at different wavelengths, which results in a photoswitchable system. Formation of pentacene in the photochemical experiments was also observed, which supports an isomerization process involving a photoretro-Diels Alder (PrDA) reaction. iv The second application was the design and synthesis of a polymer with an anthracene diketone moeity which could undergo a PrDA reaction which should result in significant conductivity changes. Although the synthesis of this type of polymer was unsuccessful during this study, we still believe in the theoretical soundness of the synthesis and utility of this type of polymer. Chapter IV undertakes the study of a class of photoacids which are based on a merocyanine core. These photoacids have been studied and characterized using UV-Vis spectroscopy and the pH of two photoacids have been shown to decrease by 2.0 units upon irradiation with blue light. In addition, the relaxation times of these photoacids have been studied in water and ethanol. We have taken one step further and synthesized and characterized three polymers which have a photoacid moeity in them. These polymers respond to visible light reversibly in solution and in solid state.

Molecular oxygen in its lowest electronically excited state plays an important roll in the field of chemistry. This excited state is often referred to as singlet oxygen and can be generated in a photosensitized process under one- or two-photon excitation of a photosensitizer. It is particularly useful in the field of photodynamic cancer therapy (PDT) where singlet oxygen formation can be used to destroy cancerous tumors. The use of two-photon activated photosensitizers possesses great potential in the field of PDT since near-IR light is used to activate the sensitizer, resulting in deeper penetration of light into biological tissue, less photobleaching of the sensitizer, and greatly improved resolution of excitation. The synthesis and photophysical characterization of new fluorene-based photosensitizers for efficient singlet oxygen production were investigated. The spectral properties for singlet oxygen production were measured at room temperature and 77 K. Two-photon absorption (2PA) cross-sections of the fluorene derivatives were measured by the open aperture Z-scan method. The quantum yields of singlet oxygen generation under one- and two-photon excitation (Φ∆ and 2PAΦ∆, respectively) were determined by the direct measurement of singlet oxygen luminescence at ≈ 1270 nm. The values of Φ∆ were independent of excitation wavelength, ranging from 0.6 - 0.9. The singlet oxygen quantum yields under two-photon excitation were 2PAΦ∆ ≈ ½Φ∆, indicating that the two processes exhibited the same mechanism of singlet oxygen production, independent of the mechanism of photon absorption.

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