Physical Sciences and Mathematics Commons^™

The Paleoecology And Biogeography Of Ordovician Edrioasteroids, Rene Anne Lewis

Doctoral Dissertations

All organisms are subjected to the living and non-living influences of their surroundings. They derive their energy and essential materials, such as sunlight and nutrients, from their environment, sharing their world not only with members of their own species but also with members of other species. These interactions are central to the survival of the organism, forming reciprocating and integrated systems with other members of their environment. Paleoecology uses the fossil record to interpret and reconstruct life habits of past organisms and environments. By examining well-preserved fossil populations we can assess the relationship between the organisms and their surrounding environment, …

Electronic Excitations In Ytio3 Using Tddft And Electronic Structure Using A Multiresolution Framework, William Scott Thornton

Doctoral Dissertations

We performed ab initio studies of the electronic excitation spectra of the ferro- magnetic, Mott-insulator YTiO3 using density functional theory (DFT) and time- dependent density functional theory (TDDFT). In the ground state description, we included a Hubbard U to account for the strong correlations present within the d states on the cation. The excitation spectra was calculated using TDDFT linear response formalism in both the optical limit and the limit of large wavevector transfer. In order to identify the local d-d transitions in the response, we also computed the density response of YTiO3 using a novel technique where the basis …

Homogeneous And Heterogeneous Approaches To 1,2,4-Triazine-Accelerated Copper-Catalyzed Azide-Alkyne Cycloadditions, Ashleigh Lauren Prince

Doctoral Dissertations

Over the last decade, the domain of click chemistry has grown exponentially and has significantly impacted the fields of organic synthesis, medicinal chemistry, molecular biology, and materials science. The ideal model of a click reaction has become the copper-catalyzed azide-alkyne cycloaddition (CuAAC). Inherent limitations of CuAAC, including high temperatures, long reaction times, and difficult purifications, have been minimized by the development of nitrogen-based ligands. Herein, we present a novel application of 1,2,4-triazines by investigating their use as accelerants for CuAAC.

A diverse library of 1,2,4-triazines were synthesized in order to examine the molecular determinants of their catalytic activity. These ligands …

Liquid Extraction Based Surface Sampling: Liquid Microjunction Surface Sampling Probes Coupled With Mass Spectrometry, Matthew John Walworth

Doctoral Dissertations

The direct sampling of analytes from surfaces under atmospheric conditions followed by mass spectrometric analysis is an ever expanding area of scientific research. Atmospheric pressure surface sampling and ionization techniques for mass spectrometry (MS) offer the ability to interrogate samples that could not be studied under vacuum conditions required of more traditional MS surface analysis techniques. The geometry and nature of materials or surfaces that can be analyzed has been greatly expanded as a result. This dissertation characterizes and shows applications of liquid microjunction surface sampling probe (LMJ-SSP) electrospray ionization systems. The presented work compares traditional analytical work flows with …

Petrology And Geochemistry Of Olivine-Bearing Diogenites And A Group Of Paired Howardites, Andrew William Beck

Doctoral Dissertations

Asteroid 4 Vesta, the largest differentiated body in the asteroid belt, is a protoplanet, much like those that accreted to form the Earth. Understanding the geology of Vesta furthers understanding of early differentiation processes that occurred on Earth and helps define igneous processes occurring on other differentiated bodies in the early solar system. Howardite, eucrite and diogenite (HED) meteorites, which are thought to have originated from Vesta, can be analyzed to better understand the geology of that asteroid. Here my colleagues and I investigate the petrology and geochemistry of two groups of HEDs. This work is timely, in that the …

Oceanic-Atmospheric And Hydrologic Variability In Long Lead-Time Forecasting, Abdoul Aziz Oubeidillah

Doctoral Dissertations

Water managers throughout the world are challenged with managing scarce resources and therefore rely heavily on forecasts to allocate and meet various water demands. The need for improved streamflow and snowpack forecast models is of the utmost importance. In this research, the use of oceanic and atmospheric variables as predictors was investigated to improve the long lead-time (three to nine months) forecast of streamflow and snowpack. Singular Value Decomposition (SVD) analysis was used to identify a region of Pacific and Atlantic Ocean SSTs and a region of 500 mbar geopotential height (Z500mb) that were teleconnected with streamflow and snowpack. The …

A Geospatial Based Decision Framework For Extending Marssim Regulatory Principles Into The Subsurface, Robert Nathan Stewart

Doctoral Dissertations

The Multi-Agency Radiological Site Survey Investigation Manual (MARSSIM) is a regulatory guidance document regarding compliance evaluation of radiologically contaminated soils and buildings (USNRC, 2000). Compliance is determined by comparing radiological measurements to established limits using a combination of hypothesis testing and scanning measurements. Scanning allows investigators to identify localized pockets of contamination missed during sampling and allows investigators to assess radiological exposure at different spatial scales. Scale is important in radiological dose assessment as regulatory limits can vary with the size of the contaminated area and sites are often evaluated at more than one scale (USNRC, 2000). Unfortunately, scanning is …

A Time-And-Space Parallelized Algorithm For The Cable Equation, Chuan Li

Doctoral Dissertations

Electrical propagation in excitable tissue, such as nerve fibers and heart muscle, is described by a nonlinear diffusion-reaction parabolic partial differential equation for the transmembrane voltage $V(x,t)$, known as the cable equation. This equation involves a highly nonlinear source term, representing the total ionic current across the membrane, governed by a Hodgkin-Huxley type ionic model, and requires the solution of a system of ordinary differential equations. Thus, the model consists of a PDE (in 1-, 2- or 3-dimensions) coupled to a system of ODEs, and it is very expensive to solve, especially in 2 and 3 dimensions.

In order to …

Circle Packings On Affine Tori, Christopher Thomas Sass

Doctoral Dissertations

This thesis is a study of circle packings for arbitrary combinatorial tori in the geometric setting of affine tori. Certain new tools needed for this study, such as face labels instead of the usual vertex labels, are described. It is shown that to each combinatorial torus there corresponds a two real parameter family of affine packing labels. A construction of circle packings for combinatorial fundamental domains from affine packing labels is given. It is demonstrated that such circle packings have two affine side-pairing maps, and also that these side-pairing maps depend continuously on the two real parameters.

Adaptive Discontinuous Galerkin Finite Element Methods For A Diffuse Interface Model Of Biological Growth, Andreas C Aristotelous

Doctoral Dissertations

This PhD dissertation concentrates on the development and application of adaptive Discontinuous Galerkin Finite Element (DG-FE) methods for the numerical solution of a Cahn-Hilliard-type diffuse interface model for biological growth. Models of this type have become popular for studying cancerous tumor progression in vivo. The work in this dissertation advances the state-of-the-art in the following ways: To our knowledge the work here contains the first primitive-variable, completely discontinuous numerical implementations of a 2D scheme for the Cahn-Hilliard equation as well as a diffuse interface model of cancer growth. We provide numerical evidence that the schemes above are convergent, with the …

Counting Reducible Composites Of Polynomials, Jacob Andrew Ogle

Doctoral Dissertations

This research answers some open questions about the number of reducible translates of a fixed non-constant polynomial over a field. The natural hypothesis to consider is that the base field is algebraically closed in the function field. Since two possible choices for the base field arise, this naturally yields two different hypotheses. In this work, we explicitly relate the two hypotheses arising from this choice. Using the theory of derivations, and specifically an explicit construction of a derivation with a well-understood ring of constants, we can relate the ranks of the two relative-unit-groups involved, both of which are free Abelian …

Optimal Theory Applied In Integrodifference Equation Models And In A Cholera Differential Equation Model, Peng Zhong

Doctoral Dissertations

Integrodifference equations are discrete in time and continuous in space, and are used to model the spread of populations that are growing in discrete generations, or at discrete times, and dispersing spatially. We investigate optimal harvesting strategies, in order to maximize the profit and minimize the cost of harvesting. Theoretical results on the existence, uniqueness and characterization, as well as numerical results of optimized harvesting rates are obtained. The order of how the three events, growth, dispersal and harvesting, are arranged also affects the harvesting behavior.

Cholera remains a public health threat in many parts of the world and improved …

Modeling And Control For Heave Dynamics Of A Flexible Wing Micro Aerial Vehicle Distributed Parameter System, Lisa M. Kuhn

Doctoral Dissertations

In recent years, much research has been motivated by the idea of biologically-inspired flight. It is a conjecture of the United States Air Force that incorporating characteristics of biological flight into air vehicles will significantly improve the maneuverability and performance of modern aircraft. Although there are studies which involve the aerodynamics, structural dynamics, modeling, and control of flexible wing micro aerial vehicles (MAVs), issues of control and vehicular modeling as a whole are largely unexplored. Modeling with such dynamics lends itself to systems of partial differential equations (PDEs) with nonlinearities, and limited control theory is available for such systems.

In …

A Characterization Of Ramsey Graphs For R(3,4), Nicholas M. Richardson

Doctoral Dissertations

The Ramsey number R(ω, α) is the minimum number n such that every graph G with |V(G)| ≥ n has an induced subgraph that is isomorphic to a complete graph on ω vertices, Kω, or has an independent set of size α, Nα. Graphs having fewer than n vertices that have no induced subgraph isomorphic to K ω or Nα form a class of Ramsey graphs, denoted ℜ(ω, α). This dissertation establishes common structure among several classes of Ramsey graphs and establishes the complete list of ℜ(3, 4).

The process used to …

A Numerical Method For Studying Thermal Deformation In 3d Double-Layered Thin Films With Imperfect Interfacial Thermal Contact Exposed To Ultrashort-Pulsed Lasers, Runzhou Liu

Doctoral Dissertations

Micro heat transfer induced by Ultrashort-pulsed lasers is an important research topic in mechanical engineering and material science. In order to apply ultrashort-pulsed lasers successfully, studying the thermal deformation in double-layered thin films with imperfect thermal interfacial contact induced by ultrashort-pulsed lasers is important for preventing thermal damage. For the ultrashort-pulsed laser, the thermal damage is different from that caused by the long-pulsed lasers, and ultrafast cracks occur after heating.

This dissertation presents a new finite difference method for investigating the thermal deformation in a 3D gold-chromium thin film with imperfect interfacial thermal contact exposed to ultrashort-pulsed lasers. The method …

Improving The Accuracy Of The Generalized Fdtd-Q Scheme For Solving The Linear Time-Dependent Schrödinger Equation, James John Elliot Iii

Doctoral Dissertations

This dissertation improves the accuracy of the Generalized Finite Difference Time Domain (FDTD) scheme by determining a differential operator that is capable of achieving reasonable accuracy when used to obtain even-order derivatives up to order fourteen. The Generalized FDTD scheme is an explicit, scheme used to solve the time-dependent Schrödinger equation, and being an explicit scheme, it must utilize a carefully devised ratio of the temporal step to the spatial step to maintain numerical stability. This ratio is called the mesh ratio, and the Generalized FDTD scheme allows this ratio to be significantly relaxed. As the mesh ratio increases, the …

A Characterization Of Ramsey Graphs For R(3,4), Nicholas M. Richardson

Doctoral Dissertations

The Ramsey number R(ω, α) is the minimum number n such that every graph G with |V(G)| ≥ n has an induced subgraph that is isomorphic to a complete graph on ω vertices, Kω, or has an independent set of size α, Nα. Graphs having fewer than n vertices that have no induced subgraph isomorphic to K ω or Nα form a class of Ramsey graphs, denoted ℜ(ω, α). This dissertation establishes common structure among several classes of Ramsey graphs and establishes the complete list of ℜ(3, 4).

The process used to …

Remote Sensing Of Sediments And Volatiles On The Martian Surface And Terrestrial Analog Sites, Craig James Hardgrove

Doctoral Dissertations

The role of water and volatiles in the solar system is of critical interest in planetary science. Evidence for the past action of water or direct observation of water on a planetary body can indicate the potential to harbor life and is critical to human exploration of the solar system. We study two very different remote sensing techniques that address the issue of identifying water-related processes on the surface of other planetary bodies, and in particular, Mars. The first technique, combined thermal infrared and visible imaging, has been used extensively on Mars for determining the thermal inertia of surface materials. …

Advances In Seismic First-Arrival Tomography, David Paul Gaines

Doctoral Dissertations

Seismic first-arrival tomography is a technique currently experiencing a renaissance in popularity due to the simplicity of implementation and promising results for delineating a variety of subsurface targets. The purpose of this study is to investigate seismic first-arrival tomography in a variety of settings and applications, and thus to provide a solid framework for future work. The study largely consists of two separate themes, hydrogeophysics and low-velocity anomaly detection. Hydrogeophysics is an emerging field whereby measured geophysical properties are used as proxies for physical properties of the subsurface. This study represents one of the first high-resolution hydrogeophysical investigations in the …

The Elucidation Of Stationary Phase Treatment Effects In Enantiomeric Separations, Joel Garrett Putnam

Doctoral Dissertations

Acid/base modifiers are sometimes used as additives in the elution on columns packed with amylose tris(3,5-dimethylphenylcarbamate) stationary phase to separate enantiomers. When modifiers are removed from the mobile phase, the stationary phase is affected in ways that are not understood because of the lack of systematic studies, making the scale-up of preparative separations difficult to predict. Once a column has been exposed to these modifiers, the selectivity of certain pairs of enantiomers may change, for the better or the worse. Numerous pairs of molecules affected by this phenomenon are listed in the literature. Five pairs of these molecules were chosen, …

Thermally Robust Ald And Silver Nanocube Based Plasmonic Probe For High Temperature And Microfluidic Sers Measurement, Joshy Francis John

Doctoral Dissertations

Raman spectroscopy is normally a non-destructive, highly selective technique that has become an ubiquitous tool for analytical chemists. One of the primary limitations of Raman spectroscopy, however, is the relatively low cross-section of the technique. With signal enhancements relative to normal Raman scattering as high as 1011, the ultra-trace detection of adsorbates down to the single molecule level has been achieved with SERS. Despite the dramatic improvement in the sensitivity and the high selectivity afforded by the SERS method, the acceptance of SERS as a general analytical tool has been hindered by a lack of stability and reproducibility in the …

Thermo- And Ph-Sensitive Hydrophilic Block Copolymers: Synthesis, Micellization, Gelation, And Application, Thomas G. O'Lenick

Doctoral Dissertations

This dissertation presents the synthesis of a series of thermo- and pH-sensitive hydrophilic block copolymers and the study of their solution behavior in water. By incorporating a small amount of weak acid or base groups into the thermosensitive block(s) of a hydrophilic block copolymer, the LCST of the thermosensitive block(s) can be modified by changing the solution pH. Accordingly, the critical micellization temperature (CMT) and the sol-gel transition temperature (Tsol-gel) of the block copolymer in water can be tuned. Chapter 1 describes the synthesis of thermo- and pH-sensitive poly(methoxydi(ethylene glycol) methacrylate-co-methacrylic acid)-b-PEO-bpoly( methoxydi(ethylene glycol) methacrylate co-methacrylic acid) and the study …

Surface-Enhanced Raman Scattering: Substrate Development And Applications In Analytical Detection, Deepak Bhandari

Doctoral Dissertations

To advance the capabilities of surface-enhanced Raman scattering (SERS), we developed a silver modified polypropylene filter (AgPPF) substrate which acts as a pseudo stationary phase in harvesting SERS signatures of so called "phytochemical estrogens" and other environmentally significant chemicals. To augment electron beam lithography (EBL) in SERS research, we also introduced an interesting nanotransfer printing (nTP) technique which could circumvent the low throughput and extremely high resolution (< 10 nm) limitations of EBL in designing advanced SERS substrates. In our study, a nominal average thickness of 10 nm silver on the polypropylene microfiber produced nanoglobules of less than 100 nm in diameter. This noble metal nanoroughened layer allowed AgPPF to serve as a SERS active substrate, onto which the noted endocrine disrupting chemicals were passed through and harvested. The intense, multifeatured vibrational Raman spectra of very rarely SERS studied chemical species collected indicates the potential for useful detection via this approach of creating SERS substrates. AgPPF substrates were also used in characterizing the adsorption behavior of hydroxyl complexes of uranium. Interestingly, hydroxyl group on the uranium complexes showed slow sorption kinetics on the nanostructured silver surfaces. Understanding the adsorption behavior of aqueous solution of uranium on nanostructured silver surfaces has opened up the possibilities of SERS detection of these environmental and non-proliferation concerned species without any surface modifications. nTP is a high resolution printing technique and relies on interfacial chemistries to control the transfer of thin metal film from a "stamp" to a "substrate". In our research, high-aspect-ratio AutoCAD designed nanopatterns were created on silicon wafers using e-beam lithography and reactive ion etching. Silicon relief pillars based stamps were then used to integrate a variety of nanostructures on different dielectric materials. Thus created nanopatterns have shown their promise to hold their inherent SERS activity. For its simplicity, cost-effectiveness, and ease of operation, this hyphenated nTP-SERS technique is impressive in the selection of suitable supporting-films for better SERS enhancements and also to manipulate gap between nanodiscs (gap-plasmonic SERS effect).

Use Of Remote Sensing, Hydrologic Tree-Ring Reconstructions, And Forecasting For Improved Water Resources Planning And Management, Cody Lee Moser

Doctoral Dissertations

Uncertainties were analyzed in three areas (remote sensing, dendroclimatology, and climate modeling) relevant to current water resources management. First, the research investigated the relationships between remotely sensed and in situ Snow Water Equivalent (SWE) datasets in three western U.S. basins. Agreement between SWE products was found to increase in lower elevation areas and later in the snowpack season. Principal Components Analysis (PCA) revealed two distinct snow regions among the datasets and Singular Value Decomposition (SVD) was used to link both data products with regional streamflow. Remotely sensed SWE was found to be sufficient to use in statistically based forecast models …

Wind Regimes In Complex Terrain Of The Great Valley Of Eastern Tennessee, Kevin Ray Birdwell

Doctoral Dissertations

This research was designed to provide an understanding of physical wind mechanisms within the complex terrain of the Great Valley of Eastern Tennessee to assess the impacts of regional air flow with regard to synoptic and mesoscale weather changes, wind direction shifts, and air quality. Meteorological data from 2008–2009 were analyzed from 13 meteorological sites along with associated upper level data. Up to 15 ancillary sites were used for reference. Two-step complete linkage and K-means cluster analyses, synoptic weather studies, and ambient meteorological comparisons were performed to generate hourly wind classifications. These wind regimes revealed seasonal variations of underlying physical …

Algorithms For Advection On Hybrid Parallel Computers, James Buford White Iii

Doctoral Dissertations

Current climate models have a limited ability to increase spatial resolution because numerical stability requires the time step to decrease. I describe initial experiments with two independent but complementary strategies for attacking this "time barrier". First I describe computational experiments exploring the performance improvements from overlapping computation and communication on hybrid parallel computers. My test case is explicit time integration of linear advection with constant uniform velocity in a three-dimensional periodic domain. I present results for Fortran implementations using various combinations of MPI, OpenMP, and CUDA, with and without overlap of computation and communication. Second I describe a semi-Lagrangian method …

Adaptation And Stochasticity Of Natural Complex Systems, Roy David Dar

Doctoral Dissertations

The methods that fueled the microscale revolution (top-down design/fabrication, combined with application of forces large enough to overpower stochasticity) constitute an approach that will not scale down to nanoscale systems. In contrast, in nanotechnology, we strive to embrace nature’s quite different paradigms to create functional systems, such as self-assembly to create structures, exploiting stochasticity, rather than overwhelming it, in order to create deterministic, yet highly adaptable, behavior. Nature’s approach, through billions of years of evolutionary development, has achieved self-assembling, self-duplicating, self-healing, adaptive systems. Compared to microprocessors, nature’s approach has achieved eight orders of magnitude higher memory density and three orders …

Holocene Climate And Environmental History Of Laguna Saladilla, Dominican Republic, Maria Anne Caffrey

Doctoral Dissertations

Stratigraphic analyses of lacustrine sediments provide powerful tools for reconstructing past environments. The records that result from these analyses are key to understanding present-day climate mechanisms and how the natural environment may respond to anthropogenic climate change in the future. This doctoral dissertation research investigates climate and environmental history at Laguna Saladilla (19° [degrees] 39' N, 71° [degrees] 42' W; ca. 2 masl), a large (220 ha) lake along the north coast of Hispaniola. I reconstructed changes in vegetation and environmental conditions over the mid to late Holocene based on pollen, microscopic charcoal, and diatoms in an 8.51 m sediment …

The ‘Helper’ Phenotype: A Symbiotic Interaction Between Prochlorococcus And Hydrogen Peroxide Scavenging Microorganisms, James Jeffrey Morris

Doctoral Dissertations

The unicellular cyanobacterium Prochlorococcus is the numerically dominant photosynthetic organism throughout the temperate and tropical open oceans, but it is difficult to grow in pure cultures. We developed a system for rendering spontaneous streptomycin-resistant mutants of Prochlorococcus axenic by diluting them to extinction in the presence of “helper” heterotrophic bacteria, allowing them to grow to high cell concentrations, and then killing the helpers with streptomycin. Using axenic strains obtained in this fashion, we demonstrated that Prochlorococcus experiences a number of growth defects in dilute axenic culture, including reduced growth rate, inability to form colonies on solid media, and higher incidence …

Fluorescent Receptors For Biomolecules, Chi-Linh Do-Thanh

Doctoral Dissertations

The development of synthetic receptors capable of high-affinity complexation of biologically relevant analytes in competitive solvent systems represents an ongoing challenge in molecular recognition. Anion recognition is particularly problematic, which is significant since numerous biological processes are regulated by anions, such as those resulting from phosphorylation. In this dissertation, we present the design and synthesis of a fluorescent sensor containing two cyclen groups that are preorganized to form a binding cleft for anion complexation. The receptor design includes a rigid acridine backbone, which is also exploited for fluorescence signal transduction. Furthermore, click chemistry is employed to facilitate receptor synthesis, and …