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Theses/Dissertations

Chemistry

LSU Doctoral Dissertations

2005

Articles 1 - 16 of 16

Full-Text Articles in Physical Sciences and Mathematics

An Evaluation Of The Enantiomeric Recognition Of Amino Acid Based Polymeric Surfactants And Cyclodextrins Using Spectroscopic And Chromatographic Methods, Bertha Cedillo Valle Jan 2005

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 …

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Shear Induced Orientation In Polymer-Clay Solutions And Their Influence On The Structure In Multilayered Films, Matthew Michael Malwitz Jan 2005

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 …

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Synthetic Development And Application Of Compounds With Biological Relevance, Jeffery Caleb Clark Jan 2005

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 …

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Characterization Of A Modified Poly(Propylene Imine) Dendrimer Host System, Amy D. Morara Jan 2005

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 …

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Infrared And X-Ray Spectroscopic Studies Of The Copper(Ii) Oxide Mediated Reactions Of Chlorinated Aromatic Precursors To Pcdd/F, Steven L. Alderman Jan 2005

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 …

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Analytical Separations Using Polymetric Surfactants, Mary Waithira Kamande Jan 2005

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), …

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Characterization Of Aged Polymer Modified Asphalt Cements For Recycling Purposes, Codrin Daranga Jan 2005

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 …

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Detection Of Biologically Important Molecules, Kyukwang Kim Jan 2005

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 …

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Hydrophobic Guar Gum Derivatives Prepared By Controlled Grafting Processes For Hydraulic Facturing Applications, Ahmad Bahamdan Jan 2005

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 …

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Synthesis Of Symmetric And Asymmetric Water-Soluble Porphyrin Derivatives, Caroline Owendi Ongayi Jan 2005

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 …

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Enantioselective Syntheses And Chemical Investigations Of Plant-Derived Bioactive Volatile Compounds, Anne Marie Sauer Jan 2005

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.

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Separation And In Situ Catalytic Testing Of A Dirhodium Tetraphosphine Catalyst, Bobby Lloyd Barker Jan 2005

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 …

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Synthesis, Characterization And Application Of Polymeric Surfactants In Micellar Electrokinetic Chromatography: Use Of Ionic Liquids As Modifiers, Simon M. Mwongela Jan 2005

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. …

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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 Jan 2005

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.

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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 Jan 2005

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, …

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Molecular Recognition And Its Underlying Mechanisms In Molecularly Imprinted Polymers, Ryan Simon Jan 2005

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 …

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