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Articles 481 - 510 of 619

Full-Text Articles in Chemistry

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 …


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 …


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 …


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 …


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 …


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 …


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 …


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 …


An Investigation Of Modified Superconductivity Through Structural Alteration Of Mgcni3 And Mgb2, Nathan L. Henderson Apr 2005

An Investigation Of Modified Superconductivity Through Structural Alteration Of Mgcni3 And Mgb2, Nathan L. Henderson

Honors Capstones

No abstract provided.


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. …


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 …


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 …


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), …


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 …


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 …


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 …


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.


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 …


Naturally-Derived Porphyrin And Chlorin Photosensitizers For Photodynamic Therapy, Jodie Angela Hargus Jan 2005

Naturally-Derived Porphyrin And Chlorin Photosensitizers For Photodynamic Therapy, Jodie Angela Hargus

LSU Master's Theses

In oncologic applications of photodynamic therapy (PDT), the discriminating localization of porphyrin-type compounds in solid tumors is exploited for the selective ablation of neoplastic tissue with minimal destruction and irritation to normal tissue. PDT is a locoregional, binary cancer therapy in which a photosensitizer—light-activated drug—absorbs light of an appropriate wavelength and excites to the singlet state. This photosensitizer in the excited singlet state can undergo an internal transition to the excited triplet state, a relatively long-lived and high-energy species that transfers its excess energy to molecular oxygen. Molecular oxygen subsequently excites from the stable triplet state to the highly reactive …


Linear Versus Cyclic Inorganic/Organic Hybrid Oligomeric Molecules, Christopher Roland Sparrow Jan 2005

Linear Versus Cyclic Inorganic/Organic Hybrid Oligomeric Molecules, Christopher Roland Sparrow

LSU Master's Theses

The synthesis of the new aryl bis(β-diketone) ligand m-phenylenebis(acetylacetone) (m-pbaH2) allowed for complexation with copper(II) to form a 4-membered ring Cu4(m-pba)4. An alternate route, via a phospholene adduct, was implemented after difficulties in preparing the ligand via an azo sulfide conversion from m-phenylenediamine. The connection of two m-pba ligands coordinated to a Cu(II) metal ion causes a distortion along the axial position of the metal center. The pore has a diameter of (Cu-----Cu = 14.317 Å) when viewing opposite metal centers. An open coordination site along Cu(II) axial position may facilitate host-guest binding interactions. The concave shape of the host …


The Importance Of Size And Shape In Imprinted Polymers, Jason Campbell Jan 2005

The Importance Of Size And Shape In Imprinted Polymers, Jason Campbell

LSU Master's Theses

The existence of shape selectivity in non-covalent molecularly imprinted polymers has been proven using molecular probes. A series of amines varying with different structural motifs and secondary amines with different sized side chains were imprinted, and binding evaluated by HPLC for each amine on polymers imprinted with similar amines. Trends in the binding relationships revealed two major contributions of cavity structure on selectivity afforded by molecularly imprinted polymers (MIPs). First, sterics play a dominant role in cases where a molecules structure is too big too fit into an imprinted site formed from a smaller template molecule. Second, molecular structures that …


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, …


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 …


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 …


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 …


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.


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 …


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 …