Chemistry Commons^™

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; …

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 …

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 …

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 …

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 …

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 …

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 …

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 …

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) …

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 …

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.

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 …

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 …

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. …

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 …

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 …

Review Of The Final Frontier, Michael F. Russo

Faculty Publications

No abstract provided.

Design And Synthesis Of Handles For Solid-Phase Peptide Synthesis And Convergent Peptide Synthesis, Jose Giraldes

LSU Doctoral Dissertations

The recent popularity of methods for solid-phase peptide synthesis that use the 9-fluorenylmethyloxycarbonyl (Fmoc) group for N^α-amino protection has created a need for compatible anchoring linkages and handles. In an effort to develop mild new methods for use in solid-phase peptide synthesis (SPPS), a new ferrocene containing linker or “handle”, the 1’1-ferrocenyl carboxaldehyde handle was designed, synthesized, characterized and tested. This linker is analogous to those commercially available and developed by Barany. The ferrocenyl amine linker(FAL) releases C-terminal peptide amides upon acidolysis. Since the FAL handle is acid labile it is compatible with Fmoc and N^α-dithiasuccinoyl …

Synthesis, Characterization, And Application Of Water-Soluble Chiral Calix[4]Arene Derivatives In Spectroscopy And Capillary Electrokinetic Chromatography, Kim Hamilton

LSU Doctoral Dissertations

This dissertation is an account of the synthesis, characterization, and application of novel water-soluble chiral calixarenes in spectroscopy and capillary electrophoresis. It is divided into four sections. The first part describes the synthesis and nuclear magnetic resonance (NMR) characterization of four p-t-butylcalix[4]arenes bearing L-amino acid moieties on their lower rims (CX4-AA). The structure and conformation of the derivatives have been determined using one- and two-dimensional NMR techniques. Proton and carbon-13 spectra show that the derivatives are tetra-substituted and adopt a cone conformation. The preparation and characterization of silica-bonded calixarene stationary phases for capillary electrochromatography is also reported in Chapter 2. …

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 …

The Roles Of Silanes As Coupling Reagents And In Deoxygenative Alkylations, Andrea S. Dupre

LSU Master's Theses

Silane reagents play important roles in many areas of organic synthesis. This is primarily due to the ability of silanes to bond to more ligands than the traditional four to become hypervalent (i.e. penta- or hexavalent). This hypervalency causes the silicon center to become more Lewis Acidic and causes the formation of carbon nucleophiles from organosilane ligands. These nucleophiles have been used to perform many cross-coupling reactions with organohalide reagents. The research presented in this thesis reports the utility of silane reagents in cross-coupling reactions of Grignard reagents with alkyl halides. This cross coupling was desirable because the silane should …

Design And Synthesis Of Constrained Dipeptide Units For Use As Β-Sheet Promoters, Umut Oguz

LSU Doctoral Dissertations

The study of factors promoting beta-sheet formation has recently gained interest due to the suspected involvement of beta-sheets in brain degenerative diseases such as Alzheimer's disease (AD), Creutzfeldt-Jacob disease (CJD) and bovine spongiform encephalopathy. Understanding beta-sheet formation and the factors that stabilize beta-sheet structure may serve as a basis for future drug design. The extended structure of a beta-sheet can be stabilized by constrained amino acid analogs that are pre-organized to adopt the extended conformation. In this dissertation using innovative synthetic organic chemistry methods, two dipeptide units are designed and synthesized that are constrained to form the extended conformation and …

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 …

Diffusion Of A Rodlike Virus In Complex Solutions, Randall Charles Cush

LSU Doctoral Dissertations

Entanglement phenomena in concentrated polymer solutions remain an interesting and challenging problem. It is still unclear how entanglement onset affects polymer chain motion at small distance scales. One way to study such motion is to follow the diffusion of a probe particle while increasing the concentration of the polymer. Many such studies have been done using probes ranging from linear and star polymers to various colloidal particles; however, relatively few studies have used rodlike probes. Rodlike probes are potentially more interesting due to the added information that may be gained by following rotational as well as translational diffusion. The anisotropic …

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 …

Genome Analysis: Mutation Analysis Using Near Infrared Laser-Induced Fluorescence (Nir-Lif) And Single Molecule Detection In Microfluidic Devices, Musundi Ben Wabuyele

LSU Doctoral Dissertations

A number of genotyping methods have been developed for mutation analysis, each of which has its own unique advantage. DNA amplification via polymerase chain reaction (PCR) provides an unlimited supply of material for subsequent genetic analysis even in case where only a single copy of the DNA molecule is present in the sample. Research presented in this dissertation first examines the efficiency of in vitro amplification of single copy DNA with subsequent sequencing analysis of PCR product. The PCR products (amplicons) were investigated for possible alteration, distortions or mutations due to the amplification process. The sequencing data for single copy …

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 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). …