Surfaces and interfaces, which are ubiquitous in the environment, control the mobility,speciation, and ultimate fate of groundwater species. The presented work provides insight into the interfacial behavior of three environmental pollutants: hexavalent chromium, oxytetracycline, and morantel. Model surfaces are employed for these studies, including (1-102) α-Al<sub>2</sub>O<sub>3</sub> and a carboxylic acid-terminated...
Okilactomycin and chrolactomycin are antitumor antibiotics isolated in 1987 and 2001, respectively. These tetracyclic natural products possess a unique 6-5 fused tetrahydropyrone-butyrolactone. The spirocenter is part of a highly functionalized cyclohexene ring, which together with the aforementioned 6-5 system compose the core of these molecules. A six carbon, 1,3-dialkyl-substituted carbon...
Metal oxide surfaces are generally recognized as active substrates for many catalytic reactions. Density Functional Theory (DFT) has been found as a useful computational tool to investigate the geometry, energy, electronic structure of reactive oxide surfaces and their interaction with small molecules and fragments. In this thesis, primary efforts have...
Small molecule organic materials based on perylene- and naphthalene- diimide are synthesized and characterized for use as semiconductor thin films in organic field-effect transistors. The orbital energetics of the materials are investigated via electrochemical, spectroscopic, and computational techniques. The thin film solids are characterized by x-ray diffraction techniques and surface...
Direct dynamics quasiclassical trajectory (QCT) calculations are performed to study the dynamics of model atom + polyatom reactions. In the first part of this thesis, we examine adiabatic dynamics of H/O reaction with simple alkanes, CD4 and C2H6. Overall good agreement with state-of-the-art experiments shows that the molecular motion is...
This dissertation covers the synthesis and study of peptide nucleic acids (PNAs), specifically, derivatives of PNA containing amine-bearing sidechains or cyclopentane portions. PNAs are non-natural nucleic acids that have far reaching potential in therapeutics and nucleic acid detection. Despite immense potential and widespread application, improving on the design and applications...
Alkenylsilanes of varying chain lengths are investigated as simultaneous chain transfer agents + comonomers in organotitanium-mediated olefin polymerization processes. Ethylene + alkenylsilane polymerizations were carried out with activated Me2Si(Me4C5)(NtBu)TiMe2 and (-CH2CH2-3,3'){(5-indenyl )[1-Me2Si(tBuN)]}2Ti2Me4 precatalysts. Alkenylsilane incorporation levels follow the trend C8H15SiH3 < C6H11SiH3 ≈ C4H7SiH3 < C3H5SiH3. Long-chain branching levels versus...
Nanoplasmonics is an emerging branch of photonics that studies the optical properties of noble metals. Nanostructured noble metal materials, which can strongly interact with light and support various plasmon modes, are exceptional candidates for nanophotonic devices. This work describes the latest advances in the fabrication of ordered silver nanoparticles or...
The work presented here describes investigations into the optical properties of single silver nanoparticles. The contents of this thesis are divided into two parts: (1) single nanoparticle localized surface plasmon resonance (LSPR) spectroscopy and sensing and (2) approaches to combining LSPR spectroscopy with atomic force and transmission electron microscopies. Part...
The work presented in this dissertation is centered on experimental efforts to maximize the sensitivity of surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS) toward their application in ultrasensitive nanoscale chemical analysis. The work focuses on fundamental studies of the plasmonic properties of silver nanostructures, and how those properties...