Physical Sciences and Mathematics Commons^™

Tuning Polymeric Chiral Surfactants For Enhanced Enantiomeric Recognition In Micellar Electrokinetic Chromatography, Jepkoech Tarus

LSU Doctoral Dissertations

The research presented in this dissertation involves the synthesis, modification, characterization, and the application of polymeric surfactants in micellar electrokinetic chromatography (MEKC). Sodium undecenoyl-L-Leucinate (L-SUL) was synthesized and modified by use of alkali metal counterions, alcohols, and Triton X-102. Characterization of the modified poly-L-SUL was performed in order to elucidate the structural changes on the surfactants by use of four techniques. While surface tensiometry was used for the determination of the critical micelle concentration (cmc), fluorescence measurements were used for the determination of the polarity of the modified polymeric surfactants. The information about the size of the polymeric surfactants was …

Investigation Of Structure-Property Relationships Of Heavy-Fermion Materials, Robin Macaluso

LSU Doctoral Dissertations

This work focuses on how local structural features influence large effective masses, magnetism, and superconductivity that are yet to be understood in heavy-fermion materials. Three sets of structurally-related materials are discussed in light of dimensionality, layering effects, choice of transition metal, coordination, and structural distortions: LnnMIn3n+2 (Ln = La, Ce; n = 1, 2, ‡; M = Co, Rh, Ir), CePdGa6, and Ce2PdGa12, and CeNiSb3. The LnnMIn3n+2 (n = 1, 2, ‡; Ln = La, Ce; M = Rh, Ir) intergrowth homologous series presents a unique opportunity to study structure-property relationships. LnnMIn3n+2 (Ln = La, Ce; n = 1, 2; …

Protein Aggregation Studies: Inhibiting And Encouraging Β-Amyloid Aggregation, Jed Paul Aucoin

LSU Doctoral Dissertations

This work demonstrates peptide-based aggregation mediation of fibril forming peptides, notably β-amyloid (1-40), Aβ_1-40. To achieve the goals of this work, Aβ_1-40 aggregation was governed by ionic strength, temperature, and pH. After controlling and reproducing Aβ_1-40 aggregate formation (fibrils), each peptide-based aggregation mediator was evaluated for its ability to self-aggregate and to possess surface-active properties. The incorporation of these mediators in Aβ_1-40 solutions changed the surface tension and produced aggregate complexes of mediator and Aβ_1-40. Evidence that Aβ_1-40 fibril formation may be mediated by disorder-to-order transitions has been observed by layer formation …

Applications Of The Titanium Catalyzed Cyclocarbonylation Towards Natural Product Syntheses, Jongtae Yang

LSU Doctoral Dissertations

Recently an efficient methodology, a hetero Pauson-Khand reaction, based on titanium-catalyzed cyclocarbonylation of tethered enals for the general preparation of ¥ã-butyrolactone rings, which are typically embedded in polycyclic systems of many natural products was reported. To demonstrate this new strategy, the total syntheses of the natural products asteriscanolide and ginkgolide were investigated. The first part of this work is dedicated to synthetic efforts toward the total synthesis of asteriscanolide. Approaches highlighted by the [2,3]-Wittig rearrangement, the thermal silyloxy-Cope rearrangement, and a titanium-catalyzed cyclocarbonylation, which is the pivotal step to afford the ¥ã-butyrolactone ring. This study firmly established the utility of …

Microelectrophoresis System Utilizing Conductivity Detection Analyzing Biological Molecues, Michelle Galloway

LSU Doctoral Dissertations

Microfabrication technology has proven to be a valuable tool for creating polymer-based devices utilized in chemical and biochemical assays. Although, reducing the size of the device allows for short analysis times and reduces the reagent demand to ultrasmall volumes (< 1 nanoliter), a resulting consequence is the constraint placed on the limits of detection associated with the detector hardware required for readout. To overcome such constraints, laser-induced fluorescence (LIF) is often employed as a detection method as it provides low detection limits, which approach the single molecule level. Unfortunately, most LIF systems do not offer the benefits of miniaturization, with the detector components (i.e. laser, optics, filters) often times requiring a much larger footprint compared to the device. Another readout strategy that has shown promise for these devices is conductivity detection. Detection can be accomplished using either conventional-size or microfabricated electrodes, which can be integrated on the device. Although conductivity has been commonly used to detect inorganic or small organic species, the potential for detection of biological species has received little attention. In this work, an integrated conductivity detector was developed for the analysis of amino acids, peptides, proteins, and oligonucleotides (double-stranded DNA). Using the detector, mass detection sensitivities in the range of 10^-18 - 10^-21 moles were achieved. To increase the throughput of the system a state-of-the-art, multichannel device with a conductivity array detector was devised. This device, which consists of a 16-channel fluidic network and a printed circuit board, is geared toward automating three-processing steps onto a single fluidic platform including purification, preconcentration and detection for downstream parallel processing.

Analytical Separations Using Packed And Open-Tubular Capillary Electrochromatography, Constantina P. Kapnissi

LSU Doctoral Dissertations

The goal of the research reported in this dissertation is to develop packed and open-tubular capillary electrochromatographic methods for improved achiral and chiral separations of various classes of analytes. The first part of this research involves the separation of seven benzodiazepines by the use of the packed mode of capillary electrochromatography (CEC) and a 40 cm packed bed of Reliasil 3 μm C₁₈ stationary phase. Optimal conditions were established by varying the mobile phase, the amount of organic modifier, the buffer concentration, the applied voltage, and the column temperature. The second part of this research focuses on the open-tubular …

Synthesis And Antibacterial Assessment Of Water-Soluble Hydrophobic Chitosan Derivatives Bearing Quaternary Ammonium Functionality, Mrunal R. Thatte

LSU Doctoral Dissertations

Chitosan is a naturally occurring, bio-degradable, non-toxic, non-allergenic bio-polysaccharide derived from chitin, found in abundance in nature. Studies aimed at deriving newer applications of chitosan are hence of interest. Among these, one of the focuses of investigations is aimed at excellent antimicrobial activity demonstrated by chitosan. In this context, certain quaternary ammonium derivatives of chitosan have been shown in the past to be highly effective antibacterial materials. In the present study, substituted chitosan derivatives were synthesized and further quaternized using Quat-188 to produce water soluble derivatives at neutral pH. The antibacterial assessments of the quaternized derivatives of substituted chitosan were …

Spectroscopic Investigation Of Nitrogenase: Epr And Mcd Studies Of The Femo Cofactor And The P-Cluster, Robyn B. Broach

LSU Doctoral Dissertations

Little is known about substrate binding and reduction of nitrogenase. EPR spectroscopy is used here to observe intermediate states generated by different substrates. Two different spin states (S=3/2 and S=1/2) were exhibited for each substrate, which may result from different binding of the substrate to the cofactor (side-on or terminal binding) or the difference of the substrate binding to either Fe or Mo of the cofactor. Parallel studies were performed on a variant MoFe protein, alpha-195^Gln, which exhibited different signals from the wild-type suggesting that the substituted amino acid maybe necessary to reach some mechanistic states that the …

Spectroscopic And Synthetic Studies Relating To A Dirhodium Hydroformylation Catalyst, Petia Gueorguieva Gueorguieva

LSU Doctoral Dissertations

The main goal of this dissertation research was to further study and characterize our bimetallic hydroformylation catalyst, rac-[Rh₂(nbd)₂(et,ph-P4)](BF₄)₂, and to fully identify the catalytically inactive mono- and dirhodium complexes formed upon fragmentation of the catalyst under hydroformylation conditions. Various in situ NMR methods such as 1D ¹H and ³¹P, and 2D COSY, HMBC, and HMQC were employed and indicated the formation of the key catalyst, [rac-Rh₂H₂(μ-CO)₂(CO)₄(et,ph-P4)]²⁺, 4, and a number of other Rh-phosphine species on and off the catalytic cycle. …

Comparison Studies Of The Mechanistic Formation Of Polyhalogentaed Dibenzo-P-Dioxins And Furans From The Thermal Degradation Of 2-Bromophenol And 2-Chlorophenol, Catherine Spearing Evans

LSU Doctoral Dissertations

Emissions of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and polybrominated dibenzo-p-dioxins and furans (PBDD/Fs) from hazardous waste incinerators, and many other sources for combustion have been considered environmentally hazardous and a major health threat. Recently, a growing number of materials containing brominated hydrocarbons, commonly used flame retardants, have been disposed in municipal and hazardous waste incinerators. This results in the increased potential for formation of PBDD/Fs and other hazardous combustion by-products. In contrast to chlorinated hydrocarbons, the reactions of brominated hydrocarbons have been studied only minimally. In fact, studies have shown that brominated phenols form higher yields of PBDD/Fs than the …

Dynamics Of Complex Polymer Solutions: Putting Diffusion To Work And Exploring Rigid Rod Diffusion, Garrett John Doucet

LSU Doctoral Dissertations

This dissertation is concerned with random coil and rodlike polymer diffusion in complex solutions. The development of fluorescence photobleaching recovery, FPR, as a technique to determine polymer molecular weight distributions by measuring the diffusion distribution and converting it to a molecular weight distribution using a calibration curve is first covered. Fluorescently tagged probes were individually dissolved in polymer solutions at negligible amounts and measured with FPR to construct the calibration curve of self-diffusion vs. molecular weight. Once calibration curves were constructed, bimodal distributions were separated using the matrices corresponding to the calibration curves. The diffusion of the probes and separation …

Synthesis And Characterization Of Superparamagnetic Silica--Homopolypeptide Composite Particles, Sibel Turksen

LSU Doctoral Dissertations

Hierarchical construction and characterization of core-shell composite particles of interest are presented. The research described shows interest in new types of polymers that provide chirality and responsiveness which have been ignored for so long. The general synthetic design described in this document can be readily used as a model for other systems. Core-shell composite systems of interest consist of silica or silica-coated cobalt cores grafted with a homopolypeptide shell, mostly poly(epsilon-carbobenzyloxy-L-lysine) or poly(gamma-benzyl-L-glutamate). Core particles were decorated with amino groups through a silylation reaction. The amino groups initiated the polymerization (with attachment) of N-carboxyanhydride (NCA) monomers, resulting in a homopolypeptide …

New Insights Into The Binding Site Formation And The Performance Of Molecularly Imprinted Polymers, Hyunjung Kim

LSU Doctoral Dissertations

Molecularly imprinted polymers (MIPs) are finding important applications in the field of separation science, catalysis, sensor, and immunoassays. To optimize the performance of the MIPs, it is essential to understand the underlying mechanism of the process. This research focuses on understanding binding site formation and performance, and improvement of the MIPs. Chapter 1 introduces the concept of the MIPs, and binding isotherm and affinity distribution of heterogeneous binding sites in the MIPs. Chapter 2 describes fundamental studies conducted to understand the binding site formation of the MIPs. The number of binding sites (N) and the number average association constant (Kn) …

Synthesis, Characterization And Study Of Novel Reagents For The Detection Of Saccharides And Amino Acids, Nadia Nadette St. Luce

LSU Doctoral Dissertations

The design of synthetic receptors for the recognition and sensing of saccharides and amino acids is currently a major challenge. This is due to inherent structural similarity and a lack of chromophoric or fluorophoric properties of these compounds. The synthesis and study of novel detection agents for bioactive molecules as well as mechanistic studies are presented herein. The elucidation of the mechanism by which tetraarylboronic acid resorcinarene interact with sugar molecules and promote a solution color change is explored. This vast collaborative study, reveals that DMSO solutions of boronic acid functionalized resorcinarene macrocycles afford visual color changes upon heating or …

Attachment Of Oligonucleotide Probes To Polymer Biochips And Its Application For The Detection Of Point Mutations, Yun Wang

LSU Doctoral Dissertations

This dissertation is on the fabrication of polymer-based microfluidic arrays for the detection of genetic mutations. Poly(methyl methacrylate) was chosen as one of the polymer substrate materials due to its low background noise, low adsorption of biomolecules, and low assembly temperature. The surface modification of polymer substrates for covalent attachment of oligonucleotide probes, the construction of fluidic channels/arrays, and hybridization kinetics will be covered. As an example of the application, point mutation detection using immobilized arrays constructed in microfluidic devices will be demonstrated. The PMMA surface was derivatized with N-lithioethylenediamine solution to introduce amine groups, which were utilized for the …

The Syntheses Of Novel Indicators And Materials For Chiral Separation, Rolanda Johnson

LSU Doctoral Dissertations

The colorimetric properties of resorcinarene solutions had not been fully investigated since von Baeyer's initial synthesis. We find that the solutions containing resorcinarene macrocycles develop color upon heating or standing. In the presence of saccharides, these solutions exhibit significant color changes which are readily observable by visual inspection. We determined that the solution color is due to macrocycle ring opening and oxidation. The optical responses to saccharides are due to complexation of the sugar with the acyclic chromophores. We have applied these mechanistic insights towards the challenging problems of the visual detection of saccharides and other important biologically analytes. In …

Electronic Structural Investigations Of Bi- And Polymetallic Complexes Using Quantum Mechanical Methods, Zakiya Sheni Wilson

LSU Doctoral Dissertations

Understanding the dynamics influencing chemical reactivity is essential for properly exploiting matter into more useful purposes. In that manner, computational chemistry is a tool frequently used to study chemical properties at the most intimate level, i.e. the single molecule.

With this work, we probe the chemistry governing a variety of multi-faceted bi- and polymetallic compounds. To date our research consists of four major projects: bimetallic rhodium-catalyzed hydroformylation and aldehyde-water shift hydrocarboxylation catalysis; a novel linear M-H-M interaction in a bridged bis(dialkylphosphino)methane complex of nickel; and CeBe₁₃, a heavy fermion conductor. Computational investigations on these systems allow us to …

Synthesis, Separation And Reactivities Of Multidentate Phosphine Ligands And Investigation Into Dirhodium Hydroformylation And Hydrocarboxylation Catalysis, David Aubry

LSU Doctoral Dissertations

A dirhodium homogeneous hydroformylation catalyst based on a tetraphosphine ligand, rac-Et₂PCH₂CH₂P(Ph)CH₂P(Ph)CH₂CH₂PEt₂, rac-et,ph-P4, is under investigation. The ligand synthesis produces a racemic mixture and a facile and efficient method of separation of the racemic and meso diastereomers was achieved through reaction of et,ph-P4 with two equivalents of NiCl₂ in EtOH to yield an almost quantitatively isolable precipitate of meso-Ni₂Cl₄(et,ph-P4) and the soluble rac-Ni₂Cl₄(et,ph-P4). Subsequent cyanolysis of these complexes liberates the et,ph-P4 ligand, and the …