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Investigation Into The Dirhodium-Catalyzed Hydroformylation Of 1-Alkenes And Preparation Of A Novel Tetraphosphine Ligand, Alexandre R. Monteil Jan 2006

Investigation Into The Dirhodium-Catalyzed Hydroformylation Of 1-Alkenes And Preparation Of A Novel Tetraphosphine Ligand, Alexandre R. Monteil

LSU Doctoral Dissertations

The reaction of the tetraphosphine ligand rac-et,ph-P4 (et,ph-P4 = PEt2CH2CH2(Ph)PCH2P(Ph)CH2CH2PEt2) with 2 equiv. of [Rh(nbd)2]+ (nbd = norbornadiene) generates [rac-Rh2(nbd)2(et,ph-P4)]2+, which is the precursor to a highly active and regioselective hydroformylation catalyst system. The “key” catalyst species generated under H2/CO pressure has been proposed to be the dihydrido complex [rac-Rh2H2(ì-CO)2(et,ph-P4)]2+, and represents one of the most dramatic example of homobimetallic …


Simulating Protein Evolution Via Thermodynamic Models, Yanlong Xu Jan 2006

Simulating Protein Evolution Via Thermodynamic Models, Yanlong Xu

LSU Doctoral Dissertations

Natural proteins are results of evolution and they need to maintain certain thermodynamic stabilities in order to carry out their biological functions. By simulating protein evolution based on thermodynamic rules, we could reconstruct the evolution trajectory and analyze the evolutionary dynamics of a protein population, and further understand the protein sequence-structure-function relationship. In this study, we have used both a simplified lattice model and a high-resolution atomic model to simulate protein evolution processes. With the lattice model, we have investigated general theoretical questions about how protein structural designability would affect protein evolution, particularly how it would affect protein recombination and …


Influence Of Surface Chemistry On The Aggregation Of Beta Amyloid Peptide, Mariah Joan Wooldridge Mcmasters Jan 2006

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 Jan 2006

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 …


Two-Dimensional And High-Throughput Electrophoretic Separation Of Proteins Using Polymeric Microchips, Hamed Shadpour Jan 2006

Two-Dimensional And High-Throughput Electrophoretic Separation Of Proteins Using Polymeric Microchips, Hamed Shadpour

LSU Doctoral Dissertations

A major task in proteomics is to identify proteins from a biological sample using two-dimensional (2-D) separation prior to mass spectrometry of peptides generated via proteolytic digestion of the proteins. For 2-D separations, microfluidic devices are superior to bench top and capillary-based systems since they potentially provide higher separation efficiencies due to the minimal dead volumes produced during peak transfer between the two separation dimensions. In addition, fast separations can be envisioned because the column lengths are typically shorter in microfluidic platforms without scarifying peak capacity. High-throughput capabilities are extremely desirable for many types of bio-analytical analyses, such as understanding …


Multianalyte Detection Of Breast Cancer By Fabrication Of Hybridmicroarrays On Polymer-Based Microanalytical Devices, Suying Wei Jan 2006

Multianalyte Detection Of Breast Cancer By Fabrication Of Hybridmicroarrays On Polymer-Based Microanalytical Devices, Suying Wei

LSU Doctoral Dissertations

Breast cancer is one of the most common and fatal cancer diseases that affect women worldwide. As is true with most other cancer diseases, early detection of breast cancer is very crucial for proper medical treatment because treatment of advanced breast cancer will be much more difficult and inconsistent. Screening and testing of breast cancer biomarkers, either genetic or proteomic, are among techniques used for diagnosis of breast cancers. Nevertheless, none of the biomarkers is by itself sensitive and selective enough for diagnosis of breast cancer, and thus, multi-analyte assays towards detection of multiple breast cancer biomarkers from different classes …


Fabrication, Characterization And Properties Of Hiercchically Ordered Nanocomposites, Avinash Dundigalla Jan 2006

Fabrication, Characterization And Properties Of Hiercchically Ordered Nanocomposites, Avinash Dundigalla

LSU Doctoral Dissertations

The objectives of this research are to study the structure, morphology and properties of poly(ethylene-oxide) (PEO)-clay nanocomposites using various imaging techniques. Optical Microscopy, Scanning Electron Microscopy, Environmental Scanning Electron Microscopy and Atomic Force Microscopy are used to image structures on all length scales. Complementary scattering experiments are discussed along with preliminary differential scanning calorimetry and Fourier Transform Infrared spectroscopy results. In particular we investigated the multilayered structures of PEO-Laponite and PEO-Montmorillonite multilayered films made from solution. The shear orientation of a polymer-clay network in solution combined with simultaneous solvent evaporation leads to supramolecular multilayer formation in the film. The resulting …


Characterization Of Beta-Amyloid Peptide Aggregation And Acceleration With Non-Fibrillar Forming Peptide-Based Mediators, Nadia J. Edwin Jan 2006

Characterization Of Beta-Amyloid Peptide Aggregation And Acceleration With Non-Fibrillar Forming Peptide-Based Mediators, Nadia J. Edwin

LSU Doctoral Dissertations

Protein aggregation occurs under many circumstances, from the dynamic assembly of tubulin to form microtubules, the aggregation of actin into filaments, as well as plaque formation by amyloid precipitation. One important requirement in studying the mechanism of amyloid aggregation is the ability to monitor the growth kinetics over a wide range in size scales (10 nm to microns) with time that spans microseconds to seconds. Understanding the mechanisms of the aggregation may then lead to improved design of drugs to help control or suppress the aggregation process. In this dissertation, the physical characterization of the â-amyloid peptide and its interaction …


Mcd And Magnetization Studies On Nifb/Nifz Minus Molybdenum Iron Protein From Azotobacter Vinelandii, Marcia S. Cotton Jan 2006

Mcd And Magnetization Studies On Nifb/Nifz Minus Molybdenum Iron Protein From Azotobacter Vinelandii, Marcia S. Cotton

LSU Master's Theses

This study reports a characterization of the iron-sulfur clusters of the MoFe protein expressed by the nifBnifZ deletion strain of A. vinelandii. VT-MCD spectroscopic and magnetization analysis of as-isolated ΔnifBΔnifZ MoFe protein were undertaken. VT-MCD spectra of as-isolated ΔnifBΔnifZ MoFe protein contains bands remarkably similar to those seen in as-isolated ΔnifH MoFe protein, assigned to arise from an [4Fe-4S]+ cluster. The low-temperature magnetization curve of as-isolated ΔnifBΔnifZ MoFe protein reveals the MCD spectra bands stem from an S = ½ spin system with diamagnetic contributions of some other species. As-isolated ΔnifBΔnifZ MoFe protein is compared with as-isolated ΔnifH MoFe …


Syntheses And Biological Evaluation Of Water Soluble Carboranylporphyrins For Application In Boron Neutron Capture Therapy, Vijay Gottumukkala Jan 2006

Syntheses And Biological Evaluation Of Water Soluble Carboranylporphyrins For Application In Boron Neutron Capture Therapy, Vijay Gottumukkala

LSU Doctoral Dissertations

The goal of the research presented in this dissertation is to develop novel water soluble carboranylporphyrins that can deliver therapeutic dosage of boron specifically to tumors for application in boron neutron capture therapy. In order to accomplish this goal novel water soluble tetra(nido-carboranyl)porphyrin and the octa(nido-carboranyl)porphyrin with high boron contents are synthesized by the condensation of the carborane substituted benzaldehyde with the pyrrole under acidic conditions. These porphyrins are made water soluble by the deboronation of the closo-carboranes to afford the corresponding amphiphilic nido-carborane cages. The low cytotoxicity, high cellular uptake and intracellular localization of these carboranylporphyrins in tumor cells …


Use Of Atomic Force Microscopy To Study A Molecular Micelle As An Anionic Polymer For Polyelectrolyte Multilayer Deposition On Polymeric Substrates, Angela Nakeeta Douglas Jan 2006

Use Of Atomic Force Microscopy To Study A Molecular Micelle As An Anionic Polymer For Polyelectrolyte Multilayer Deposition On Polymeric Substrates, Angela Nakeeta Douglas

LSU Master's Theses

Polyelectrolyte multilayers (PEMs) have been used as stationary phases for various chiral and achiral separations in open-tubular electrochromatagraphy (OT-CEC). However, the physical characteristics of PEMs are not well understood. The production of PEM coatings involves flowing alternating rinses of positive and negative charged polyelectrolytes onto a surface. Although PEMs are typically deposited on fused silica capillaries, there is growing interest to use this approach in conjunction with microchip devices to enhance separation characteristics. Since microchips are fabricated using polymeric substrates, the deposition of PEMs on these substrates needs to be examined. The study reported in this thesis uses atomic force …


Synthesis, Characterization And Properties Of Cooper(Ii) Beta-Diketonate Macrocycles, Sylvester Burton Jan 2006

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 …


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 Jan 2006

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 Jan 2006

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 …


Applications Of Titanium-Mediated Reductive Coupling And Cyclocarbonylation Reactions Toward Natural Product Synthesis, Maria A. Appeaning Jan 2006

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 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 …


Ab Initio Molecular Dynamics Simulations Of Methylaluminoxane (Mao) Synthesis By Hydrolysis Of Trimethylaluminum, Lacramioara Negureanu Jan 2006

Ab Initio Molecular Dynamics Simulations Of Methylaluminoxane (Mao) Synthesis By Hydrolysis Of Trimethylaluminum, Lacramioara Negureanu

LSU Doctoral Dissertations

MAO is the co-catalyst in the metallocene catalytic systems, which are widely used in single site olefin polymerization due to their high stereoselectivity. To date, the precise structure of MAO, the particular compound or compounds catalytically active in MAO, have eluded researchers. MAO, a white amorphous powder, is not a good sample for a direct spectroscopic characterization, and its NMR spectra are broad and almost featureless. Many structural models have been proposed but none are generally accepted. In the first part of this work the MAO formation mechanism was addressed. Molecular dynamics simulations at MP2 configuration interaction theory level have …


Development Of Analytical Techniques For The Analysis Of Submicron Particles And Protein Aggregates, Yohannes H. Rezenom Jan 2006

Development Of Analytical Techniques For The Analysis Of Submicron Particles And Protein Aggregates, Yohannes H. Rezenom

LSU Doctoral Dissertations

The goal of the research presented in this dissertation is to develop analytical techniques for the analysis of heterogeneous mixtures of submicron particles and protein aggregates. In Chapter 2, a simple and reproducible technique for constructing perfectly aligned gaps in fused-silica capillaries has been developed for postcolumn reagent addition with capillary electrophoresis (CE) to take advantage of laser-induced fluorescence (LIF) detection. This technique uses laser ablation with a Nd:YAG laser to create gaps of 14.0 ¡Ó 2.2 ƒÝm. These structures have been used for reagent addition for postcolumn derivatization with LIF detection and have been tested for the separation of …


Application Of Polymeric Microfluidic Devices For Separation Of Single-Stranded Dna, Shawn Llopis Jan 2006

Application Of Polymeric Microfluidic Devices For Separation Of Single-Stranded Dna, Shawn Llopis

LSU Doctoral Dissertations

Microsystems targeted for DNA sequencing, especially those focused on electrophoretic separations, are rapidly proving their viability to genomic research, mimicking the progress made when capillary electrophoresis developed from miniaturizing slab gel electrophoresis techniques. Being the more recent electrophoretic separation platform, the commercial availability of microchip electrophoresis devices remains relatively limited. To this extent, high-aspect ratio microstructures formed in thermo plastics have been developed using rapid fabrication methods from molding tools designed for mass replication of high-aspect ratio microfeatures. In this work, the choice and compatibility of poly(methylmethacrylate) (PMMA) – the primary substrate for DNA separations in this work – was …


Porous Inorganic-Organic Materials Based On Beta-Diketone Ligands, Yixun Zhang Jan 2006

Porous Inorganic-Organic Materials Based On Beta-Diketone Ligands, Yixun Zhang

LSU Doctoral Dissertations

Synthesis and characterization of porous inorganic-organic materials have been studied mainly on two linear β-diketone multifunctional ligands: pyridine based pyacH and isocyanide based HacphNC. As a known ligand, the preparation of pyacH has been improved with higher yield. When pyacH reacts with Fe and Al metal salts, trigonal metal β-diketonate building blocks M(pyac)3 are produced. When pyacH reacts with zinc acetate, both trans and cis Zn(pyac)2 are produced, both isomers were isolated and characterized by single-crystal X-ray crystallography. Solutions of the trigonal building block Fe(pyac)3 generate various crystal structures on reaction with AgNO3 in CH3CN. When the concentration of AgNO3 …


Self-Assembly And Its Inhibition In Bolaform Amphiphilic Dendrimers, Jirun Sun Jan 2006

Self-Assembly And Its Inhibition In Bolaform Amphiphilic Dendrimers, Jirun Sun

LSU Doctoral Dissertations

Self-assembly is scientifically interesting, technologically important, and sometimes life-threatening. A striking example: Alzheimer’s disease is caused by the self-assembly of the â-amyloid fragment of amyloid precursor protein. Such natural amphiphiles normally are very expensive and complicated to isolate. Synthetic mimics that are much cheaper and easier to prepare can facilitate the development of efficient characterization methods, even as they suggest new materials science applications. Two-directional arborols are synthetic bolaform amphiphilic dendrimers. They dissolve in hot water and form reversible gels at room temperature. Bundles of fibrils, which are made by self-assembly of arborols, are found in the gels. The properties …


Structural Characterization Of Poly(Heterocycles) Formed Using Oxidative Methods, Rebecca Marie Brauch Jan 2006

Structural Characterization Of Poly(Heterocycles) Formed Using Oxidative Methods, Rebecca Marie Brauch

LSU Doctoral Dissertations

This research focused on elucidation of structural information for conducting polymer systems using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The structure of conducting polymer systems has been found to directly influence their physical properties. Poly(pyrrole) and poly(thiophene) are two of the most widely studied conducting polymers due to their high electrical conductivity, stability in the doped state, low toxicity, and current/potential applications. The purpose of this research was to apply MALDI-TOF MS to heterocyclic conducting polymers, specifically those of pyrrole and thiophene, to investigate structural properties of these polymers, with the specific aim of determining end group and …


Investigation Of The Structure In Electrodeposited Nanostructured Co/Cu Alloys, Multilayers, And Cofe/Cu Multilayered Nanowires, Erick Jamal Lawson Jan 2006

Investigation Of The Structure In Electrodeposited Nanostructured Co/Cu Alloys, Multilayers, And Cofe/Cu Multilayered Nanowires, Erick Jamal Lawson

LSU Master's Theses

Since the discovery of giant magnetoresistance (GMR) in electrodeposited nanostructured magnetic multilayers and multilayered nanowires, there has been interest throughout the scientific world in the fabrication and characterization of these materials. Magnetic multilayers in the form of thin films can be used as magnetoresistive sensors in the magnetic data storage industry. Arrays of nanowires have the potential for applications in perpendicular ultra-high density data storage and biosensors. Wire-shaped magnetic multilayered nanowires have been shown to exhibit GMR in the so called “current perpendicular-to plane” configuration (CPP-GMR). GMR of multilayers and multilayered nanowires have been investigated in several systems that include …


Synthesis, Crystal Growth, Magnetic And Transport Properties Of Ln-M-X (Ln=Lanthanide, M=Transition Metal, X=In, Ga) Compounds, Willa Maria Williams Jan 2006

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 …


Crystal Growth And The Search For Highly Correlated Ternary Intermetallic Antimonides And Stannides, Evan Lyle Thomas Jan 2006

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, …