Physical Sciences and Mathematics Commons^™

Towards Completely Automated Glycan Synthesis, Matteo Panza

Dissertations

Carbohydrates are ubiquitous both in nature as biologically active compounds and in medicine as pharmaceuticals. Although there has been continued interest in the synthesis of carbohydrates, chemical methods require specialized knowledge and hence remain cumbersome. The need for development of rapid, efficient and operationally simple procedures has come to the fore. This dissertation focuses on the development of a fully automated platform that will enable both experts and non-specialists to perform the synthesis of glycans. Existing automated methods for the synthesis of oligosaccharides are highly sophisticated, operationally complex, and require significant user know-how. By contrast, high performance liquid chromatography (HPLC) …

Recover Data In Sparse Expansion Forms Modeled By Special Basis Functions, Abdulmtalb Mohamed Hussen

Dissertations

In data analysis and signal processing, the recovery of structured functions (in terms of frequencies and coefficients) with respect to certain basis functions from the given sampling values is a fundamental problem. The original Prony method is the main tool to solve this problem, which requires the equispaced sampling values.

In this dissertation, we use the equispaced sampling values in the frequency domain after the short time Fourier transform in order to reconstruct some signal expansions, such as the exponential expansions and the cosine expansions. In particular, we consider the case that the phase of the cosine expansion is quadratic. …

Chemical Synthesis Of Oligosaccharides From Human Milk, Mithila Dulanjalee Bandara Weerasooriya Mudiyanselage

Dissertations

Human milk oligosaccharides (HMO) are a family of structurally related glycans that are highly abundant in breast milk. Oligosaccharide fraction is the third largest solid component in human milk after lactose and lipids. There is an accumulating evidence that HMO can provide significant benefits to the breast-fed infants. However, understanding of the exact HMO functions is still incomplete due to the lack of individual compounds in sufficient quantities. Therefore, development of expeditious strategies for the chemical synthesis of HMO has been increasingly important. Among all the methods available for oligosaccharide synthesis, armed-disarmed strategy introduced by Fraser-Reid is based on chemoselective …

A Computational Study Of Sleep And The Hemispheres Of The Brain, Tera Ashley Glaze

Dissertations

Sleep and sleep cycles have been studied for over a century, and scientists have worked on modeling sleep for nearly as long as computers have existed. Despite this extensive study, sleep still holds many mysteries. Larger and more extensive sleep-wake models have been developed, and the circadian drive has been depicted in numerous fashions, as well as incorporated into scores of studies. With the ever-growing knowledge of sleep comes the need to find more ways to examine, quantify, and define it in the context of the most complex part of the human anatomy – the brain. Presented here is the …

Capabilities And Limitations Of The Spin Hamiltonian Formalism In Single Molecule Magnets, Philip Ferko

Dissertations

The rational design of molecular magnetic materials is an ongoing effort involving physics, materials science, and chemistry. A common approach to design of complexes and interpretation of magnetic data is the spin Hamiltonian formalism. In this approach, magnetic data is interpreted through constants extracted from the parameterization of data. In design, certain structural motifs are pursued, rationalized by the minimization or maximization of terms in the spin Hamiltonian. In this work, monometallic complexes were prepared to simplify magnetic behavior and allow the examination of specific factors that influence single molecule magnetism like coordination geometry, ligand identity, symmetry, and spin-orbit coupling. …

Enhancing Scalability In Genetic Programming With Adaptable Constraints, Type Constraints And Automatically Defined Functions, George Gerules

Dissertations

Genetic Programming is a type of biological inspired machine learning. It is composed of a population of stochastic individuals. Those individuals can exchange portions of themselves with others in the population through the crossover operation that draws its inspiration from biology. Other biologically inspired operations include mutation and reproduction. The form an individual takes can be many things. It, however, is represented most of the time as a computer program. Constructing correct efficient programs can be notoriously difficult. Various grammar, typing, function constraint, or counting mechanisms can guide creation and evolution of those individuals. These mechanisms can reduce search space …

Decoding The History Of The Early Solar System Using Comet Volatile Compositions, Nathan Roth

Dissertations

Understanding the evolution of the solar system, as well as its current volatile content, requires knowledge of the initial conditions present in the solar nebula. As some of the first objects to accrete in the solar nebula, cometary nuclei are among the most primitive remnants of solar system formation, and their present-day volatile composition likely reflects the composition and conditions where (and when) they formed. As such, the volatile compositions of cometary nuclei may serve as "fossils" of solar system formation. High-resolution near-infrared spectroscopy offers a valuable tool for sampling the primary volatile (i.e., ices subliming directly from the nucleus) …

High Resolution Near-Infrared/Visible Intracavity Laser Spectroscopy Of Small Molecules, Jack Harms

Dissertations

Intracavity laser spectroscopy has been used to study the electronic structure of several small molecules. The molecules studied as part of this dissertation include germanium hydride (GeH), copper oxide (CuO), nickel chloride (NiCl), platinum fluoride (PtF), platinum chloride (PtCl), and copper hydroxide (CuOH). This work encompasses five peer-reviewed publications and two submitted manuscripts.

Application Of The Picoloyl Group In Carbohydrate Chemistry, Michael Mannino

Dissertations

Stereocontrol of glycosylation reactions is a constant struggle in the field of synthetic carbohydrate chemistry. The application of the picoloyl (Pico) substituent can offer numerous stereocontrolling avenues. The most popular application is the Hydrogen-bond-mediated Aglycone Delivery (HAD) method that provides excellent selectivity in the glycosylation of a variety of sugar substrates. The HAD method relies on the formation of an intermolecular hydrogen bond between the nitrogen atom of the Pico substituent on the glycosyl donor with the hydroxyl group of the glycosyl acceptor. This interaction provides a facial preference for the nucleophilic attack and hence provides powerful stereocontrol for the …