Chemistry Commons^™

Influence Of Surface Chemistry On The Aggregation Of Beta Amyloid Peptide, Mariah Joan Wooldridge Mcmasters

LSU Doctoral Dissertations

Alzheimer's disease is a progressive neurological ailment affecting 4.5 million aging Americans. The disease is characterized by the presence in the brain of self-assembled fibrils consisting of beta amyloid protein (Aβ). Soluble Aβ protein is present in normal human cerebrospinal fluid, but it is unclear what makes the protein aggregate into insoluble plaques. There is evidence that the Aβ fibril assembly is affected by interactions with biological surfaces, such as neuronal membranes. Here, surfaces consisting of self-assembled alkanethiol monolayers with different end groups were used to test the effect of surface chemistry on the structure and morphology of aggregates formed …

Infrared Laser Desorption/Ionization Mass Spectrometry: Fundamental And Applications, Mark Little

LSU Doctoral Dissertations

This dissertation on infrared laser desorption/ionization mass spectrometry encompasses fundamental studies of the desorption/ionization process and direct-from-gel laser desorption/ionization applications. Understanding of the fundamentals behind desorption and ionization can lead to improvements in the technique and to new applications. Experiments aimed at advancing this goal are wavelength studies and two-laser infrared/ultraviolet matrix-assisted laser desorption/ionization experiments. The direct-from-gel laser desorption/ionization application in which infrared laser desorption/ionization of analytes directly ionized after gel electrophoretic separation will also be presented. Protein and peptide standards were used as test analytes and the infrared lasers used were a 10.6 micrometers carbon-dioxide laser and a mid-IR …

Synthesis, Crystal Growth, Magnetic And Transport Properties Of Ln-M-X (Ln=Lanthanide, M=Transition Metal, X=In, Ga) Compounds, Willa Maria Williams

LSU Doctoral Dissertations

ABSTRACT This dissertation focuses on the structural stability, magnetic and transport properties of ternary lanthanide compounds grown using indium and gallium flux. Single crystals of TbRhIn5 were synthesized using indium flux. TbRhIn5 is isostructural to the well known LnnMIn3n+2 (n = 1, 2, ∞; Ln = La, Ce; M = Rh, Ir) and adopts the HoCoGa5 structure type and crystallizes in the space group P4/mmm, Z = 1. Lattice parameters are a = 4.6000(6) Å and c = 7.4370(11) Å, V = 157.29(6) Å3. A sharp antiferromagnetic transition is observed at TN = 48 K for TbRhIn5. Single crystals of …

Applications Of Titanium-Mediated Reductive Coupling And Cyclocarbonylation Reactions Toward Natural Product Synthesis, Maria A. Appeaning

LSU Doctoral Dissertations

Previous work in our laboratory has demonstrated not only a synthetic value of tandem reductive cyclization - carbonylation reactions in the preparation of complex molecules but also the interesting stereoselectivity observed therein. The first part of this work employs the titanium-mediated cyclocarbonylation of tethered dienals for the synthesis of prostaglandin analogues, in particular PGF_2α and methyl jasmonate. Based on this hetero Pauson-Khand strategy, we have established an efficient racemic route to both the prostaglandin and the methyl jasmonate core skeletons. Moderate to excellent selectivities with regard to the hetero Pauson-Khand reaction were observed in both cases. The second part …

Synthesis, Characterization And Properties Of Cooper(Ii) Beta-Diketonate Macrocycles, Sylvester Burton

LSU Doctoral Dissertations

This dissertation deals with the synthesis and properties of multidentate β-diketone ligands and their transition-metal complexes. (1) We prepared two bis(β-diketones), C₁BAH₂ and p-XBAH₂ (see sketch below), determined their crystal structures, and studied their reactions with copper(II). We envisioned that they would form macrocyclic complexes with 3-6 metal atoms. In both cases, although the initial products are soluble, as expected for the desired molecular products, we were unable to isolate well-behaved molecular solids. In the case of C₁BAH₂, this may be because the cyclic product requires an unusual combination of conformations of …

Crystal Growth And The Search For Highly Correlated Ternary Intermetallic Antimonides And Stannides, Evan Lyle Thomas

LSU Doctoral Dissertations

This dissertation describes the crystal growth, chemical structures, and efforts made towards the understanding of the physical properties of novel ternary rare-earth intermetallics, which may display signature behavior such as superconductivity, heavy fermion behavior, intermediate valence, and/or large magnetoresistance. To address the problem of correlating these characteristics with structural features, several ternary antimony- and tin-containing phases, Ln-T-X (Ln = lanthanide; T = Co, Ni, Pd; X = Sn, Sb), have been synthesized in single crystalline form by metallic flux-growth methods and characterized by X-ray diffraction. The antimonide compounds LnNi1-xSb2 (Ln = Y, Gd-Tb, Er, Yb), alpha, beta-LnNiSb3 (Ln = La, …

Integrating Micro-Scale Separations To Matrix Assisted Laser Desorption And Ioniation Time Of Flight Mass Spectrometry (Maldi-Tof-Ms) For Protein Analysis, Harrison K. Musyimi

LSU Doctoral Dissertations

This dissertation describes the integration of micro-scale separations to matrix assisted laser desorption and ionization time-of-flight mass spectrometry (MALDI TOF MS) for protein analysis. MALDI MS provides unsurpassed accurate mass measurements of intact bio-molecules, for example peptides and proteins, which in turn generate high molecular specificity enabling the identity, function and structure of these molecules to be characterized. However, in order to realize the full potential of MS in proteomic studies, integrated sample processing on automated and high throughput platforms is required to address the complexity, diversity and the dynamic range of proteomic analysis. The work described here contributes towards …

Direct Detection Of Homocysteine And Syntheses Of Lanthanide Complexes As Biosensors, Weihua Wang

LSU Doctoral Dissertations

At elevated levels, homocysteine (Hcy) is a risk factor for cardiovascular diseases and Alzheimer’s disease. It’s also implicated in a number of other diseases such as neural tube defects, pregnancy complications, and renal failures. The monitoring of Hcy levels in plasma is of current concern. To date, the biochemical mechanism by which Hcy is involved in disease states is unclear. Herein, we describe highly selective colorimetric methods for the direct determination of Hcy. Inexpensive, commercially available materials are reported. The results show potential application for the detection of Hcy in human blood plasma. Additionally, new HPLC postcolumn detection methods for …

Characterization Of A Modified Poly(Propylene Imine) Dendrimer Host System, Amy D. Morara

LSU Doctoral Dissertations

The research in this dissertation focuses on the design of a novel redox-responsive host system that has the ability to encapsulate guest molecules. The host at hand is a tri(ethylene oxide), TEO, pyrrole-terminated PPI dendrimer that possesses water-solubility as a result of the presence of the TEO chains on the pyrrole groups and redox-responsive activity from the pyrrole groups after their oligomerization. The pyrrole moieties at the periphery of the dendrimer exhibit the ability to be oligomerized by oxidation chemistry, and this is shown to aid in the retention and egress of guest molecules located within the dendrimer interior. These …

Analytical Separations Using Polymetric Surfactants, Mary Waithira Kamande

LSU Doctoral Dissertations

The goal of the research presented in this dissertation is to develop effective analytical methods for the separation of both achiral and chiral analytes using polymeric surfactants. Three analytical techniques are employed to accomplish this objective: open-tubular capillary electrochromatography (OT-CEC), open-tubular capillary electrochromatography coupled to mass spectrometry (OT-CEC/MS), and micellar affinity gradient focusing (MAGF). This research work presents novel application of polymeric surfactants that contributes to improved separations of difficult to separate analytes. The first part focuses on the application of an achiral polyelectrolyte multilayer (PEM) coating using OT-CEC. The PEM coating consisting of the cationic polymer poly (diallyldimethylammonium chloride), …

An Evaluation Of The Enantiomeric Recognition Of Amino Acid Based Polymeric Surfactants And Cyclodextrins Using Spectroscopic And Chromatographic Methods, Bertha Cedillo Valle

LSU Doctoral Dissertations

The scope of this dissertation is to explore the enantiomeric recognition properties of amino acid based polymeric surfactants using a combination of analytical techniques including chromatographic and spectroscopic methods. Chapter 1 includes an introduction to chirality and chiral separations using capillary electrophoresis. Using cyclodextrin modified micellar electrokinetic chromatography (CD-MEKC), the enantioseparation of three binaphthyl derivatives using native alpha- and beta-cyclodextrins in combination with various diastereomers of chiral polymeric surfactants (PS) was examined. A reversal of enantiomeric order was observed with the enantiomers of (1,1 S-binaphthyl-2,2 S-diamine (BNA) and (1,1 S-binaphthol (BOH) due to a competition between the two chiral selectors …

Hydrophobic Guar Gum Derivatives Prepared By Controlled Grafting Processes For Hydraulic Facturing Applications, Ahmad Bahamdan

LSU Doctoral Dissertations

The synthesis of new water soluble guar gum derivatives is described. Introduction of polyalkoxyalkyleneamide grafts to guar gum or hydroxyopropyl guar was achieved in a three step process: carboxymethylation with sodium chloroacetate, esterification with dimethyl sulfate and amidation with a series of polyalkoxyalkylene-amines. The process steps were followed using infrared spectroscopy; the grafted guar derivatives were characterized using FT-IR and ¹H NMR. A series of hydroxypropyl guar derivatives with degrees of carboxymethylations ranging from 0.15-0.25 were modified with polyalkoxyalkyleneamines with molecular weights ranging from 300-3000. The ratio of oxypropylene to oxoethylene units in the polyalkoxyalkyleneamines was varied from 9/1 …

Synthetic Development And Application Of Compounds With Biological Relevance, Jeffery Caleb Clark

LSU Doctoral Dissertations

Nature has provided a vast number of compounds that have medicinal application. The use of these compounds provided by nature however, is limited by the amount of a specific compound that nature provides. The synthesis of these molecules and their derivatives provides an even greater number of compounds for biological screening. Various pyrroles, the heterocyclic building blocks of porphyrins, can be prepared synthetically over several steps. The implementation of carboranes on pyrrole rings intrinsically provides substrates that can be converted into porphyrins bearing carborane substituents. The condensation of these carboranylpyrroles with carboranylaldehydes provides carboranylporphyrins bearing a higher order of carborane …

The Stereoselective Synthesis Of The Butyrolactone-Bridged [8-5-5] Tricyclic Ring Systems Of (+/-)-Asteriscanolide Via The Titanium-Mediated Hetero-Pauson-Khand Reaction, Mohamed G. Sherriff

LSU Doctoral Dissertations

The stereoselective construction of the tricyclic ring system of asteriscanolide from cyclooctadiene has been achieved. The synthesis involves two main steps; the synthesis of the aldehyde precursor(5)and the titanium-mediated cabocyclization of 5 to make the three rings of 43 stereoselectively.

Shear Induced Orientation In Polymer-Clay Solutions And Their Influence On The Structure In Multilayered Films, Matthew Michael Malwitz

LSU Doctoral Dissertations

The influence of shear on viscoelastic solutions of poly(ethylene oxide) (PEO) and clay (Cloisite, CNA) was investigated by rheology and small angle neutron scattering (SANS) under shear. These measurements determined the shear-induced orientation of the clay and the polymer as well as their relaxation behavior after cessation of shear. Comparison of PEO-CNA solutions (~100 nm diameter platelets) to previously studied PEO-Laponite gels (~30 nm diameter platelets) found that the orientation of CNA platelets occurs at much lower shear rates. Additionally, the relaxation times were much longer for CNA platelets than for Laponite platelets. From these solutions and gels, multilayered nanocomposite …

Separation And In Situ Catalytic Testing Of A Dirhodium Tetraphosphine Catalyst, Bobby Lloyd Barker

LSU Doctoral Dissertations

Attempts to study the asymmetric hydroformylation abilities of [rac-Rh₂(nbd)₂(et,ph-P4)](BF₄)₂ were made through the separation of the enantiomers of et,ph-P4 using a chiral HPLC column. Efforts were also made to optimize the NiCl₂ separation chemistry for the methyl analogue of et,ph-P4 for use in asymmetric hydroformylation. A study of hydroformylation of olefins using [rac-Rh₂(nbd)₂(et,ph-P4)](BF₄)₂ in ionic liquids was also performed, leading directly to the important (and unexpected) effect of increased hydrogen pressure on [rac-Rh₂(nbd)₂(et,ph-P4)](BF₄)₂ in the acetone/water system to …

Synthesis, Characterization And Application Of Polymeric Surfactants In Micellar Electrokinetic Chromatography: Use Of Ionic Liquids As Modifiers, Simon M. Mwongela

LSU Doctoral Dissertations

The goal of the research presented in this dissertation is to synthesize, characterize, and apply a novel chiral amino acid-based surfactant and achiral sulfate-based surfactants for the effective separations of chiral and achiral compounds in micellar electrokinetic chromatography (MEKC). The first part of this research involves novel synthesis, characterization, and application of polysodium oleyl-L-leucyl-valinate (poly-L-SOLV) for the separation of chiral compounds in MEKC. Surface tensiometry, proton nuclear magnetic resonance, infrared spectroscopy, densitometry and analytical ultracentrifugation were used as the characterization techniques. Optimal MEKC separating conditions were established by varying surfactant concentration, buffer concentration and pH, applied voltage, and capillary temperature. …

Characterization Of Aged Polymer Modified Asphalt Cements For Recycling Purposes, Codrin Daranga

LSU Doctoral Dissertations

Since polymer modified asphalt cement (PMAC) has been employed for a decade, the lifetime and wear on some of these pavements is reaching a stage where resurfacing is necessary. This research focuses on the characterization of aged polymer modified asphalt cements (PMAC) to evaluate their potential for recycling. A styrene-butadiene-styrene tri-block (SBS) polymer modified asphalt cement was selected and characterized using standard asphalt binder qualification techniques, i.e., the Superpave PG protocol. We developed a procedure to characterize the relative concentration of polymer in asphalt cements by gel permeation chromatography (GPC). Infrared spectrographic, thermogravimetric and rheological techniques were used to identify …

Enantioselective Syntheses And Chemical Investigations Of Plant-Derived Bioactive Volatile Compounds, Anne Marie Sauer

LSU Doctoral Dissertations

Research, inspired by nature, provides ample opportunity for discovery, ingenuity, and creative endeavor. For these reasons, the work and accomplishments presented herein focus on the total syntheses and related investigations of a variety of natural product derivatives, specifically (+)-nootkatone and jasmone. While the former consists of several independent projects: (a) an enantioselective synthetic route to (+)-nootkatone and derivatives, (b) examination of the valencane ring system, (c) determination of the absolute configuration of (+)-nootkatone, and (d) rearrangements of various sesquiterpenoid derivatives; the latter focuses on the construction ofƒndelta, epsilon-unsaturated carbonyl compounds, hetero Pauson-Khand substrates, via [3,3]-sigmatropic rearrangements.

Capillary And Microchip Gel Electrophoresis Using Multiplexed Fluorescence Detection With Both Time-Resolved And Spectral-Discrimination Capabilities: Applications In Dna Sequencing Using Near-Infrared Fluorescence, Li Zhu

LSU Doctoral Dissertations

Increasing the information content obtainable from a single assay and system miniaturization has continued to be important research areas in analytical chemistry. The research presented in this dissertation involves the development of a two-color, time-resolved fluorescence microscope for the acquisition of both steady-state and time-resolved data during capillary and microchip electrophoresis. The utility of this hybrid fluorescence detector has been demonstrated by applying it to DNA sequencing applications. Coupling color discrimination with time-resolved fluorescence offers increased multiplexing capabilities because the lifetime data adds another layer of information. An optical fiber-based fluorescence microscope was constructed, which utilized fluorescence in near-IR region, …

Detection Of Biologically Important Molecules, Kyukwang Kim

LSU Doctoral Dissertations

Anions play important roles in biological systems. The design of anion sensors has been of great interest. The selective detection of a specific anion is particularly challenging. In the first chapter, I describe the synthesis of a TBS-protected fluorescein dye (1.1) and its use for the selective detection of fluoride. Solutions of 1.1 either in DCM or in aqueous media at physiological pH show the excellent selectivity towards fluoride to afford color formation while solutions of other interfering anions remain colorless. The monitoring of homocysteine (Hcy) and cysteine (Cys) levels is important since they are biomarkers associated with Alzheimer’s and …

Molecular Recognition And Its Underlying Mechanisms In Molecularly Imprinted Polymers, Ryan Simon

LSU Doctoral Dissertations

Molecular recognition in molecularly imprinting polymers (MIPs) is governed by two mechanisms: pre-organization of functional groups and shape specificity of the binding site. While pre-organization of functional groups has been studied extensively, shape specificity of the binding site has not been rigorously explored. The goal of this research is to determine the influence of shape specificity on molecular recognition in MIPs (Chapter 2). Once shape selectivity was proven to play a vital role in molecular recognition, it was important to determine if pre-organization of functional groups or shape specificity was the dominating factor in determining molecular recognition in the binding …

Infrared And X-Ray Spectroscopic Studies Of The Copper(Ii) Oxide Mediated Reactions Of Chlorinated Aromatic Precursors To Pcdd/F, Steven L. Alderman

LSU Doctoral Dissertations

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) are toxic compounds produced in combustion systems such as incinerators, and their emissions are an important environmental issue. Chlorinated phenols and benzenes form PCDD/F through heterogeneous reactions following adsorption onto fly-ash surfaces. Current research implicates transition metals in promoting formation of phenoxyl radicals that react to form PCDD/F, although this has not been studied extensively. This objective of this work is to better understand PCDD/F formation from chlorinated aromatic precursors. Using 2 chlorophenol as a model PCDD/F precursor and silica as a fly-ash surrogate, time-dependent chemisorption of 2 chlorophenol onto silica was studied in situ …

Synthesis Of Symmetric And Asymmetric Water-Soluble Porphyrin Derivatives, Caroline Owendi Ongayi

LSU Doctoral Dissertations

Novel symmetric and asymmetric water-soluble tetrabenzoporphyrin are synthesized in relatively good yields. These compounds are synthesized by the condensation of butanopyrrole with several aldehydes that contain masked water solubilizing groups followed by metal insertion, oxidation and demetallation and deprotection of the masked solubilizing groups. The biological evaluation (in vitro and in vivo) studies are described in addition to the photophysical evaluations of the corresponding compounds. A novel versatile route to the syntheses of novel free-bases and metallo-benzoylbiliverdin is discussed. The treatment of metal free-dodecasubstituted porphyrin with sodium nitrite and trifluoroacetic acid at room temperature in the presence of oxygen affords …

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.

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 …

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 …

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 …