Physical Sciences and Mathematics Commons^™

Design, Synthesis, And Applications Of Bio-Derived Crosslinking Monomers For Molecular Imprinting, Martha Sibrian-Vazquez

LSU Doctoral Dissertations

Most of the research in the field of molecular imprinting has been focused on the development of new functional monomers, in order to improve the molecular recognition properties afforded by these materials. The role of the crosslinking monomer has often been overlooked, since it is considered an inert component that only provides a scaffold to support the binding sites. However, the crosslinking monomer represents a high percent (80-90%) of the composition of molecularly imprinted polymers (MIPs), which can have a large influence on the MIPs properties. This research addresses the design, synthesis, and applications of new crosslinking monomers for molecular …

Synchrotron Radiation As A Probe Of Chemical Information Using Novel Experimental Configurations, George Farquar

LSU Doctoral Dissertations

Determination of chemical information with synchrotron radiation is an area of great scientific interest, and expanding the range of available techniques is the topic of this dissertation. The experimental methods described herein allows for a significant advancement of the availability of subtle chemical information. This dissertation uses ionizing radiation to study three chemical systems. First, the l=3 shape resonance in CO is investigated using a cryogenically cooled gas jet. Shape resonant effects have been studied for many years. Previously, this was accomplished on the vibrational structure of molecules with a limited ability to determine the rotational substructure effects. A dramatic …

Solid-Phase Dna Sequencing Reactions Performed In Micro-Capillary Reactors And Solid-Phase Reversible Immobilization In Microfluidic Chips For Purification Of Dye-Labeled Dna Sequencing Fragments, Yichuan Xu

LSU Doctoral Dissertations

The research presented in this dissertation involves micro-capillary reactors for solid phase DNA sequencing, the identification of dye terminator sequencing fragments with time-resolved methods, and purification of dye-labeled DNA fragments using solid- phase reversible immobilization in microfluidic chips. Solid-phase micro-reactors have been prepared for DNA sequencing applications using slab gel electrophoresis. A PCR product was immobilized to the interior wall of a fused-silica capillary tube via a biotin-streptavidin linkage. Solid-phase sequencing was carried out in micro-capillary reactors using a four-lane, single color dye primer chemistry strategy. The read length was found to be 589 bases. The complementary DNA fragments generated …

Characterization Of Native And Bypass Human Coronary Artery Plaque Deposits From The Same Heart: Investigation Of The Chemical Form Of Calcium In Human Coronary Artery Plaque Deposits, Serigne Thiam

LSU Doctoral Dissertations

Gradual deposits of lipids, proteins, and calcium on the coronary arterial walls cause atherosclerosis, leading to blockage of the blood flow and possible heart attack. Despite many studies, the mechanism underlying these processes remains unclear. In this research, differences between native and bypass plaque deposits from the same heart were examined. In addition, the crystalline and the amorphous plaques within these native and bypass vessels were characterized. The techniques used to characterize the deposits included inductively coupled plasma mass spectrometry (ICPMS), solid-state nuclear magnetic resonance (NMR), high performance liquid chromatography (HPLC), etc. The results from the ICPMS technique showed that …

Synthesis, Characterization, And Applications Of Novel Pseudostationary Phases In Micellar Capillary Electrophoresis For Separation Of Chiral And Archiral Compounds H[Electronic Resource], Cevdet Akbay

LSU Doctoral Dissertations

The research presented in this dissertation involves the synthesis, characterization, and the use of novel surfactants, including both micelles and vesicles, as pseudostationary phases in micellar capillary electrophoresis (MCE) for the separation of achiral and chiral compounds. Separation of environmental pollutants such as 2 to 6-ring polycyclic aromatic hydrocarbons (PAHs) was achieved using poly(sodium undecylenic sulfate). A baseline separation of all 16 PAHs was possible for the first time in MCE by a single-surfactant system. In addition, a surfactant with a phosphated head group, i.e., di(2-ethylhexyl)phosphate (DEHP), was also introduced as a novel pseudostationary phase for separation of 21 weakly …

The Ligase Detection Reaction: The Evolution Of A Mutation Detection Strategy, Hannah D. Farquar

LSU Doctoral Dissertations

Early detection of genetic mutations is important for control of diseases such as cancer and Alzheimer's. Early detection requires methods that detect small amounts of mutated DNA in very large amounts of normal or wild type DNA. One method to detect mutated DNA is the ligase detection reaction (LDR). Since its inception LDR has evolved greatly from a simple detection reaction after PCR amplification to PCR/RE/LDR, a scheme which uses nucleoside base analogs in PCR to convert wild type sequences to sequences containing restriction endonuclease (RE) sites which can then be cleaved leaving only mutant sequences for detection by LDR. …

Artificial Peptides Containing Ca,A- Disubstituted Amino Acids: Synthesis, Conformational Studies, And Application As Β-Strand Mimics, Yanwen Fu

LSU Doctoral Dissertations

Short peptides containing C^α,α-dipropylglycine (Dpg) at alternating sequence positions were synthesized and examined for conformational behavior. Peptide assembly was performed using Fmoc-solid-phase chemistry where the coupling with PyAOP could be significantly enhanced at elevated temperature. Circular dichroism (CD) and NMR conformational studies revealed that incorporation of Dpg residues induced folded structures into peptides. It was observed that Dpg residues adopted helical conformation in a helix-promoting sequence. The resulting helical structure was comprised of consecutive β-turns whose structure was stabilized by salt bridge in aqueous solution. In this study, the preparation of sterically and polyfunctional C^α,α-disubstituted amino …

Electronic And Structural Properties Of Rare Gas Cation Clusters, Jose Alejandro Gascon

LSU Doctoral Dissertations

We study structure and ground and excited state properties of rare gas cation clusters, Rg⁺_N, for N=3-60. The main goal is to understand how the positive charge is delocalized over the cluster and the relationship between cluster geometry and delocalization. He⁺_N, Ar⁺_N, and Xe⁺_N are selected as representatives of the rare gas elements. We perform Monte Carlo simulations to obtain finite temperature properties of the energy spectrum. The Hamiltonian of the system is based on a semi-empirical model whose parameters are obtained through the fitting of experimental and calculated …

Synthesis And Study Of New Materials For The Visual Detection Of Biomolecules, Ming He

LSU Doctoral Dissertations

The visual determination of saccharides has been of interest for well over a century. Sugars are a relatively challenging class of compounds to analyze. They exhibit great structural similarity as well as transparency in the visible region. The sensing of specific saccharides could aid the monitoring of disease or industrial fermentation products. Herein I present new methods allowing for simple and rapid visual detection of sialic acid, fructose and a homologous series of prototypical neutral oligosaccharides, the linear maltodextrins, containing up to seven glucose residues. The new methods allow for selective color detection of fructose in a large excess of …

Peroxynitrite-Mediated Oxidations: Nitration And Nitrosation, Rachel Bolzan

LSU Doctoral Dissertations

Using a direct ultraviolet second-derivative spectroscopy method, three peroxynitrite preparative methods were investigated for the nitrite and nitrate present either as impurities or produced during peroxynitrite decomposition: (I) ozonation of azide, reaction of hydrogen peroxide with (II) isoamyl nitrite and (III) nitrous acid. The oxidation of morpholine by peroxynitrite in the presence and absence of added carbonate gives N-nitromorpholine and N-nitrosomorpholine. Nitration and nitrosation of morpholine are catalyzed by low levels of CO₂; however, excess CO₂ dramatically reduces the yields of nitrosation but not nitration, and the combined yields of the products are about the same under …

Mode Specific Photoionization Dynamics In Polyatomic Molecules, Gerald Jeffery Rathbone

LSU Doctoral Dissertations

The work presented in this dissertation presents new work on polyatomic photoionization. In these investigations, the broad range behavior of both allowed and forbidden vibrational modes in linear triatomic systems were studied to understand mode specific aspects of photoionization. The current study is made possible by the experimental strategy of exploiting high resolution photoelectron spectroscopy and the high brightness of third generation synchrotron radiation sources. The data is taken typically tens of eV’s past the ionization potential. The strategy that I employ is to probe alternative vibrational modes which are frequently affected differently following resonant ionization. Such vibrationally resolved data …

Capillary And Microdevice Electrophoretic Tools For Genetic Analyses: Heteroduplex Analysis For Tuberculosis Drug Susceptibility And Ligase Detection Reaction For Colorectal Cancer Detection, Gloria Thomas

LSU Doctoral Dissertations

The traditional format of electrophoresis, the slab gel, is quickly being replaced by capillary and microdevice platforms, which offer improvements in cost, resolution, speed, quantitation and automation in genetic analyses. These techniques also employ a variety of separation matrices while the slab gel is limited to agarose and polyacrylamide. The research presented here explores the use of these electrophoretic formats for the detection of single nucleotide mutations using two genetic models associated with human disease. Slab gel based heteroduplex analysis (HDA), a popular mutation scanning method, uses a specially designed universal heteroduplex generator (UHG) containing controlled variation to enhance the …

Precursors For Copper Chemical Vapor Deposition, Muna Bufaroosha

LSU Doctoral Dissertations

The main objective of this study was to synthesize precursors that are capable of producing copper films of high quality by chemical vapor deposition (CVD). We investigated some copper(I) and copper(II) complexes as precursors for chemical or photochemical vapor deposition. In chapter 2, we synthesized a series of Cu(hfac)₂(amine) adducts, where hfac^- is hexafluoroacetylacetonate and the amines are: dimethylamine, isopropylamine, allylamine, pyrrolidine, and piperidine. The efficiency of these adducts compared to Cu(hfac)₂(H₂O) as Cu-CVD precursors was examined under hydrogen. We found that among these amine adducts, Cu(hfac)₂(allylamine)₂ gave the best …

Synthesis And Properties Of Novel Macrocycles And Related Chromophoric Benzenoid Compounds, Jorge O. Escobedo Cordova

LSU Doctoral Dissertations

The synthesis and properties of some macrocyclic compounds of interest are presented. Resorcinarenes with functionalized conjugated rigid rods made of oligo-p-phenylenes would lead to an entirely new class of functional, soluble, well-defined architectures impacting a variety of multidisciplinary research efforts. The general synthetic design described in this document could be readly extrapolated to include other electronic systems such as heteroaromatics and polyenes. An extensive collaborative study of chromophore formation in resorcinarene solutions is also described here. The study reveals that upon oxidation, the reversible conversion to acyclic precursors occur first, and then these precursors undergo oxidation to quinoid-type compounds (xanthenes). …

Fabricating Microfluidic Devices In Polymers For Bioanalytica Applications, Sean M. Ford

LSU Doctoral Dissertations

The research presented in this document focuses on the fabrication, characterization and application of microfluidic systems fabricated in poly(methyl methacrylate) (PMMA) with the emphasis focused on the fabrication processing steps. Microfluidic devices were produced in PMMA using X-ray lithography. The fabrication methods investigated were sacrificial mask, polyimide membrane mask and embossing techniques. PMMA microfluidic devices fabricated using X-ray lithography were characterized using scanning electron microscopy (SEM) and optical microscopy, while analytical techniques such as electroosmotic flow determination, separations, and fluorescent microscopy were used to characterize fluid transport in these devices. A novel method for the heat annealing of PMMA to …

X-Ray Spectroscopy Of Geometrically Constrained Systems, Edward Earl Doomes

LSU Doctoral Dissertations

Hard X-rays (2 KeV or greater) are used as spectroscopic tools in the characterization of chemical systems. X-ray absorption near edge structure (XANES) spectroscopy is used to characterize multiple groups of chemicals in a systematic fashion. This thesis focuses on chemical systems that in some context have geometrical constraints on their structure. They include self-assembled n-alkanethiol monolayers that are tethered to silver substrates, cyclic sulfides, and (Bis(diphenylphosphino) alkane tetracarbonyl metal complexes. The study of n-alkanethiol monolayers on Ag(111) contains the first observation in the literature of an anomalous resonance in the 18 carbon monolayer. A new interpretation of a subthreshold …

The Synthesis Of Deuterated Arylamine Dna Adducts For Use In The Development Of An Isotope Dilution Lc/Ms/Ms Method, Philip Dmitri Olsen

LSU Doctoral Dissertations

Polycyclic aromatic amines (arylamines) are a class of chemical carcinogens that are prevalent in environmental and industrial settings. In order to study the mechanism of their toxicity a quantitative and qualitative detection method was developed to measure the C8-adenine adducts of benzidine and 2-aminofluorene in DNA samples. To do this a novel synthetic method using a palladium catalyst was developed to prepare authentic and deuterated arylamine adducts to serve as standards. These standards were then used to develop a high performance liquid chromatography, electrospray, tandem mass spectrometry, isotope dilution, detection method. To demonstrate the validity of this method two spike …

Analysis Of Inorganic Materials Using Advanced Nmr And Nqr Techniques, Anthony Adrian Mrse

LSU Doctoral Dissertations

Several advanced solid-state nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) techniques have been applied to inorganic materials of commercial interest. The specific techniques applied to each system were chosen to solve specific obstacles which impeded the flow of industrial science.

First, the dispersion of brominated flame retardants in polymers is monitored using pulsed ⁸¹Br NQR (nuclear quadrupole resonance) techniques. The NQR spectrometer consists of a homemade NMR console and an automatically tuned loop-gap resonator probe. The two factors which affect the ⁸¹Br NQR transition frequencies of brominated aromatics are: electron-donating and withdrawing substituents on the ring …

Analysis Of Near-Infrared Dye-Labeled Sanger Sequencing Fragments With Gel Electrophoresis Using The Time-Resolved Flourescence Lifetime Indentification Methods, Suzanne Jeanel Lassiter

LSU Doctoral Dissertations

The research presented in this dissertation involves the identification of sequencing fragments with time-resolved methods. For this application, near-infrared heavy-atom tricarbocyanine dyes were developed in our laboratory, which can be excited with a single laser and emission collected using a single detection channel. The dyes have four spectroscopically unique, but relatively short lifetimes that can be altered by the intramolecular heavy-atom they contain. The work described here involves the optimization of dye-primer chemistry for preparing Sanger sequencing reactions for longer reads and the optimization of the separation matrix for capillary gel electrophoresis that produces favorable statistical analysis of the aforementioned …