Theoretical analysis of DNA bridge-mediated electron transfer (ET) led to the proposal that photoinduced ET might occur via either superexchange or hopping mechanisms. Electron transfer has been proposed to occur via a superexchange mechanism at short distances and via a hopping mechanism at longer distances. However, a crossover in mechanism...
The first section of this thesis focuses on applications of DNA-modified gold nanoparticles (AuNPs) while the second part addresses the fundamental properties that arise from conjugating DNA to inorganic AuNPs. Two types of applications are discussed. The first application utilizes the colorimetric properties of AuNPs to screen duplex and triplex...
This thesis consists of the synthesis and photophysical characterization of chlorophyll- and porphyrin- based multichromophore arrays designed for the purpose of studying energy and charge transfer therein. The first series of arrays consists of donor-acceptor dyads in which various arylene diimide electron acceptors are attached through a phenyl group to...
The porphyrazines (pzs), a class of porphyrin derivatives, have shown potential as therapeutic and imaging agents due to a combination of their near-IR absorbance/fluorescence and their enhanced chemical flexibility. Cell viability/proliferation assays and fluorescence microscopy were carried out in both tumor and normal cells to characterize the biological activity of...
The [(salen)CrCl + LB] catalyst system was found to be a highly active catalyst system for the [aziridine + CO<sub>2</sub>] coupling reaction, and exhibited a marked preference for the formation of 5-substituted oxazolidinone product, especially in the absence of cocatalyst. The activity of this catalyst system is optimized by modifying...
A catalytic, multi-component coupling reaction for the synthesis of nitrogen-containing heterocycles has been developed, via the reaction of an imine, &#945;-diazoester and unsaturated coupling partner in the presence of a copper(I) or rhodium(II) transition metal catalyst with excellent diastereo-selectivities and high yields. The transition metal-catalyzed decomposition of a diazo compound...
In Chapter 1, a series of "constrained geometry" organoactinide complexes, (CGC)An(NMe)2 (CGC = Me2Si(h5-Me4C5)(tBuN); An = Th, 1; U, 2), prepared via efficient in situ, two-step protodeamination routes in good yields and high purity, is presented. Both 1 and 2 are quantitatively converted to the neutrally charged, solvent-free dihalides (1-Cl2,...
The utilization of hydrofluoric acid for the preparation of silver vanadium oxide fluorides has been advanced for the synthesis of Ag<sub>4</sub>V<sub>2</sub>O<sub>6</sub>F<sub>2</sub> and Ag<sub>3</sub>VO<sub>2</sub>F<sub>4</sub>. Silver-rich metal oxide fluorides are important battery cathode materials due to the high reduction potential of silver vs. Li, which is made even higher by the incorporation...
The need for readily synthesized scaffold architectures to build monodisperse, high molar mass mobility modifiers or "drag-tags" in end-labeled free solution electrophoresis (ELFSE) led to the development of a novel class of multivalent molecular tools. Poly-N-substituted glycines (peptoids) were created with evenly spaced amino groups as branching points along the...
Organic light emitting diodes (OLEDs) are fabricated and characterized on anodes modified by a variety of surface treatments. OLED performance response is correlated to the treatment conditions with current-voltage (I-V) measurements and impedance spectroscopy. Small-scale OLED arrays are fabricated using a novel shadow mask approach and are characterized with electrical...