Interfaces and surfaces are ubiquitous in the environment. Heterogeneous binding events and reactions control the transport and speciation of dissolved pollutants in groundwater. Many heterogeneous processes occur at mineral oxide/water interfaces, and can be controlled either by the mineral oxide, or organic molecules bound to the surface. The prevalent natural...
Preventing the build-up of indoor pollutants represents an emerging goal in environmental chemistry. Heterogeneous catalysis provides an attractive method of remediating indoor air pollution, but optimization through rational catalyst design requires a detailed understanding of the catalytic surface and surface-pollutant interactions. In this work, a chemical ionization mass spectrometry (CIMS)...
The overarching theme of this thesis is the development of non-natural oligomers for use in biological applications. Chapter I details the synthesis and studies of modified peptide nucleic acid (PNA) oligomers. PNA is a synthetic oligonucleotide mimic that binds to natural nucleic acids with extremely high affinity and specificity, making...
This dissertation describes the invention and development of a new nanolithographic method: On-Wire Lithography (OWL). OWL is a simple, reproducible, and high-throughput procedure for the synthesis and lithographic processing of metal nanowires (i.e. Au, Ag, Pt, Ni, and Cu) that allows researchers to control the morphology and feature size of...
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...