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...
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...
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 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...
Copper serves as a cofactor for many proteins and enzymes involved in important biological processes, but at the same time, excessive copper is toxic to cell. Thus, the intracellular copper concentration must be tightly controlled such that copper is provided to essential enzymes but does not accumulate to toxic levels....
The early transition metal oxide fluoride molecular anions with the general formula [MOxF6-x]n- with x = 1 for M = V5+, Nb5+, Ta5+ (n = 2) and x = 2 for M = Mo6+, W6+ (n = 2) feature distorted octahedral coordinations, that arise from electronic dπ pπ metal oxide...
The work presented here describes investigations into the interaction of resonant molecules with metallic nanoparticles by localized surface plasmon resonance (LSPR) spectroscopy. The contents of this thesis include the study of the coupling mechanism between molecular resonance and plasmon resonance from experimental and theoretical perspectives and applications of this mechanism...
Particulate methane monooxygenase (pMMO) is a membrane-bound metalloenzyme that oxidizes methane to methanol in methanotrophic bacteria. The nature of the pMMO active site and the overall metal content are controversial, with spectroscopic and crystallographic data suggesting the presence of a mononuclear copper center, a dinuclear copper center, a trinuclear center,...
Nanoscale materials are demonstrating new properties and promising applications with each passing day. The fabrication of ever more complex and precise nanomaterials represents a continuing drive in the fields of physics, chemistry, and biology. Template-based approaches provide an attractive method of producing new inaccessible materials by modifying and confining older...
My thesis focuses on the design and synthesis of lanthanide coordination complexes as Zn(II)-responsive magnetic resonance imaging (MRI) contrast agents. These agents produce an increase in MR intensity upon binding of Zn(II) through water modulation to Gd(III) chelates. To this end, several Zn(II)-responsive contrast agents have been synthesized and studied...
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...
The biological antagonism between copper and molybdenum, first observed when cattle developed copper deficiencies after ingesting high levels of plant-born molybdenum, is currently being used in humans to treat two conditions: Wilson's Disease as well as several forms of metastatic cancer. There is surprisingly little known about the interaction of...
The promise of a clean, renewable, and abundant energy supply make the efficient conversion of solar energy to electricity a compelling scientific and societal goal. In the following chapters, I will describe my efforts to advance one class of photovoltaic technology, dye-sensitized solar cells, by demonstration and characterization of unexplored...
Magnetic resonance imaging (MRI) is an advanced imaging modality that is experiencing increasing popularity in clinical and experimental settings. MRI enjoys the benefit of high-resolution, the use of non-ionizing radiation, and the ability to distinguish between soft tissues. MR imaging is enhanced with the use of Gd3+ chelated contrast agents;...
Au nanoprisms are a new type of inorganic nanoparticle that is particularly interesting because these particles can be made in high yield, are composed of a metal with well known surface chemistry, exhibit strong, architecture and environment-sensitive optical features, and have well-defined crystallographic facets. All of these features make Au...
The safe and efficient storage of hydrogen is possibly the chief obstacle to its use as a fuel on a large scale. Metal-organic frameworks (MOFs) are well poised to provide unique solutions to hydrogen storage, and gas storage in general, a result of their crystalline, porous networks that present the...
The new binuclear organo-zirconium and -titanium metal complexes {2,7-di-[(2,6diisopropylphenyl)imino]-1,8-naphthalenediolato group 4 metal complexes {1,8-(O)2C10H4-2,7[CH=N(2,6-iPr2C6H3)]2}Zr2Cl6(THF)2 (FI2-Zr2) and {1,8-(O)2C10H4-2,7-[CH=N(2,6-
i 2 t
Pr2C6H3)]2}Ti2Cl6(THF)2 (FI -Ti2) are compared to the mononuclear analogues {3- Bu-2(O)C6H3CH=N(2,6-iPr2C6H3)}ZrCl3(THF) (FI-Zr1) and {3-tBu-2-(O)C6H3CH=N(2,6-
i
Pr2C6H3)}TiCl3(THF) (FI-Ti1), respectively, in ethylene polymerization and ethylene + olefin copolymerization processes. The comonomers studied...
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...
This work is a research effort aimed at understanding the mechanisms of single-molecule surface-enhanced Raman spectroscopy (SMSERS). In the decade since its discovery in 1997, the role of resonance Raman (RR) enhancement, the origin of blinking, and the properties of the hot spot formed at the junction of two nanoparticles...
π-Conjugated oligomeric and polymeric semiconductors have been the focus of intense research over the past few decades as alternatives to inorganic semiconductors for low-cost electronic applications such as organic field-effect transistors (OFETs). These materials enable vapor- or solution-phase fabrication of large-area, light-weight electronic devices, and are compatible with plastic substrates...