The work of this dissertation was aimed at synthesizing new types of nanoparticle-DNA conjugates, investigating their chemical and physical properties, and exploring their biodiagnostic applications. Chapters Two and Three describe the synthesis of new types of nanoparticle-DNA conjugates: (1) silver nanoparticle-DNA conjugates (DNA-Ag NPs) and (2) 2-nm gold nanoparticle-DNA conjugates...
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...
The electronic properties of various transparent conducting oxide (TCO) surfaces are probed electrochemically via self-assembled monolayers (SAMs). A novel graftable probe molecule having a tethered trichlorosilyl group and a redox-active ferrocenyl functionality (Fc(CH2)4SiCl3) is synthesized for this purpose. On as-received ITO, saturation coverage by a close-packed monolayer having of 6.6...
Magnetic resonance imaging (MRI) is a technique widely used in both clinical and experimental settings to produce high-resolution images of opaque living organisms without utilizing ionizing radiation. Currently, MR imaging is augmented by contrast agents; however, these small molecule Gd(III) chelates are confined to extracellular and vascular regions of the...
N-Heterocyclic carbene catalysis has recently emerged as an important field in organic chemistry. Two new strategies have been developed to advance the use of N-heterocyclic carbenes (NHCs) as Lewis-base organic catalysts. The first approach utilizes NHCs to catalyze the generation of homoenolates and the conjugated Breslow intermediate is added to...
Chapter 1 describes the homopolymerization of styrene and the copolymerization of ethylene and styrenic comonomers mediated by the single-site bimetallic "constrained geometry catalysts" (CGCs), (µ-CH2CH2-3,3'){(η5-indenyl)[1-Me2Si(tBuN)](TiMe2)}2 [EBICGC(TiMe2)2; Ti2], (µ-CH2CH2-3,3'){(η5-indenyl)[1-Me2Si(tBuN)](ZrMe2)}2 [EBICGC(ZrMe2)2; Zr2], (µ-CH2-3,3'){(η5-indenyl)[1-Me2Si(tBuN)](TiMe2)}2 [MBICGC(TiMe2)2; C1-Ti2], and (µ-CH2-3,3'){(η5-indenyl)[1-Me2Si(tBuN)](ZrMe2)}2 [MBICGC(ZrMe2)2; C1-Zr2], in combination with the borate activator/cocatalyst Ph3C+B(C6F5)4- (B1). Under identical styrene homopolymerization conditions,...
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 work presented in this thesis describes investigations into linear and nonlinear optical properties of two-dimensional silver nanoparticle arrays. The linear optical measurements - extinction measurements were performed on two-dimensional square arrays of L-shaped silver nanoparticles fabricated by electron beam lithography in order to study the effect of dipole coupling...
Two new methods have been developed employing silicon-containing molecules in novel organic transformations. The first strategy utilizes Lewis base-activation of triethoxysilylalkynes to deliver mild acetylide nucleophile equivalents. The second approach involves the use of enolate additions to acylsilanes to generate β-silyloxy homoenolate intermediates.
Lewis base-catalyzed activation of triethoxysilylalkynes promotes the...
This dissertation focuses on the utilization of two coordination chemistry-based synthetic approaches, which provide the ability to rapidly and quantitatively assemble sophisticated supramolecular cofacial porphyrin complexes. Significantly, by adopting a coordination chemistry-based approach, the porphyrin-porphyrin interactions can be regulated in situ via the addition or removal of chemical effector molecules....