Physical Sciences and Mathematics Commons^™

The Redox Potential Of Ddt: An Environmental Perspective, Anne Lewis, Christopher Cramer, John Bumpus

Presidential Scholars Theses (1990 – 2006)

Due to their low water solubility, the reduction potentials of DDT and dicofol are difficult to determine experimentally. Through computational methods, we calculated the one and two electron reduction potentials for DDT as 0.51 V and 0.67 V, respectively, and those for dicofol were 0.50 V and 0.74 V. This study is significant because we are able to calculate reliable redox potentials that may be utilized to predict chemical behavior and degradation pathways of environmental pollutants. To assess the accuracy of theoretical chemistry, we compared experimental and computational data and examined whether our calculated redox potentials fit with the known …

Transport Analysis In Polymeric Liquids And Films: Investigations In Ionic Mobility Isolation Techniques And Permeability Control, Julia D. Warner

Dissertations, Theses, and Masters Projects

An in situ measurement technique that isolates the mobility of charge carriers is described and analyzed. The technique allows significant improvement over conductivity measurements to monitor changes in the physical properties and state of a material as it cures. This is essential in systems where Ni, the number of charge carriers, cannot be assumed constant such as during cure of epoxies, urethanes and polyimides.;Currently, there is an assumption made in the literature that the number of charge carriers present in a curing material is constant when conductivity is used as an in situ measurement technique to monitor changes in mobility. …

Approaches To The Synthesis Of Novel Triptycene Dendrimers And Hyperbranched Poly(Phenylene Sulfides) And Poly(Phenylene Sulfones), Alfredo Mellace

Seton Hall University Dissertations and Theses (ETDs)

.

Analysis Of Phycotoxin And Mycotoxin, Contaminants In Foods, Using Liquid Chromatography - Mass Spectrometry Techniques, Ana Brana Magdalena

Theses

The impact of phycotoxins and mycotoxins on human and animal health are of important concern for worldwide authorities and the scientific community. Liquid chromatography-mass spectrometry (LC-MS) techniques have been developed, optimised and validated for the analysis of these toxins.

Phycotoxins are potentially toxic substances, which are produced by marine phytoplankton and which may accumulate in shellfish or finfish. Azaspiracid poisoning (AZP) is a recently discovered syndrome that has been implicated in several incidents of human intoxications. A study was undertaken to examine the distribution of azaspiracids (AZA) in scallops {Pecten maximiis) and mussels {Mytiliis edulis). Domoic acid (DA) is an …

Synthetic And Mechanistic Studies Of Poly(Vinyl Chloride) And Some Other Chlorinated Polymers, Xianlong Ge

Dissertations, Theses, and Masters Projects

Unlike vinyl chloride, 1,2-dichloroethylene (DCE) experienced dimerization under free-radical conditions. Chain transfer to DCE by beta-Cl elimination was shown to be the major reason for its nonpolymerization.;During the chlorination of alkyl chlorides with molecular chlorine, the involvement of a bridged intermediate led to the formation of vicinal chlorides as the major products. The yields of geminal chlorides increased significantly in the presence of solvents that form complexes with chlorine atoms, but such solvents also decreased the reactivity of the chlorination. Thus the chlorination of poly(vinyl chloride) (PVC) in the presence of complexing solvents was not a useful method for the …

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

LSU Master's Theses

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

Design, Synthesis, And Applications Of Bio-Derived Crosslinking Monomers For Molecular Imprinting, Martha Sibrian-Vazquez

LSU Doctoral Dissertations

Most of the research in the field of molecular imprinting has been focused on the development of new functional monomers, in order to improve the molecular recognition properties afforded by these materials. The role of the crosslinking monomer has often been overlooked, since it is considered an inert component that only provides a scaffold to support the binding sites. However, the crosslinking monomer represents a high percent (80-90%) of the composition of molecularly imprinted polymers (MIPs), which can have a large influence on the MIPs properties. This research addresses the design, synthesis, and applications of new crosslinking monomers for molecular …

Silica Supported Copper Complexes And Their Biomimetic Activities, Jun Wang

Dissertations, Theses, and Masters Projects

No abstract provided.

Quantitative Analysis Of Diepoxybutane Damage Within The Chicken Β-Globin Domain, André M. Pilon

Honors Theses

In industrial polymer and synthetic rubber production facilities, workers are exposed to 1,3-butadiene. This compound is converted in vivo to 1,2,3,4-diepoxybutane (DEB) and has been linked to increased incidences of cancer in these individuals. Carcinogenesis has been attributed to formation of DEB induced DNA interstrand cross-links. Previous studies have demonstrated that DEB cross-links deoxyguanosine residues within 5'-GNC sequences in synthetic DNA, in restriction fragments, and in defined sequence nucleosomes. The current study utilized the polymerase chain reaction (PCR) to examine DEB damage frequencies within nuclear genes, found within "open" regions of chromatin, as compared to regions of unexpressed sequence that …

Resonance Two Photon Ionization Study Of Binary Clusters Of Styrene With Polar Molecules, Hatem Ahmed Mahmoud

Theses and Dissertations

One-color resonance two-photo ionization (R2PI) spectra of mixed clusters of styrene molecule (S) with polar molecules [water (W), methanol (M), ethanol (E), and trifuoroethanol (T)] were measured through the S1←S0 transition of the styrene molecule. The spectra reveal a rapid increase in complexity with the number of polar molecules in the cluster, associated with van der Waal modes and isomeric forms. The spectral shifts of the cluster origins from the S1-S0 transition of the bare styrene molecule reflect the nature of the intermolecular interactions within the binary clusters. The obtained R2PI spectra xv were compared with the spectra of the …

Application Of The Chan-Evans Diaryl Ether Synthesis To The Formation Of Bis(Bibenzyls), Eric Rosenthal

Honors Theses

Alkene (6) was produced in three steps from 3-hydroxybenzaldehyde (8), and 3-bromobenzyl bromide (10). A variety of strategies were employed to synthesize the desired boronic acid (13), but as of this time none have been successful. The synthesis of this boronic acid is necessary to study the feasibility of applying the Chan-Evans copper mediated formation of diaryl ethers to a bis(bibenzyl) synthesis. In seeking to exploit the advantages of the Chan-Evans ether synthesis over the Ullman ether synthesis, we have encountered some of the associated difficulties. The utilization of an arylboronic acid to produce a diaryl ether first requires the …

Synthesis Of Montiporynes A And B, Traci Jenelle Speed

Honors Theses

This thesis reports the first complete synthesis of monriporynes A and B. isomeric diacetylenes that bear α, β unsaturated ketone functionalities. Recently isolated from the stony coral Montipora sp. these compounds are reported to possess in vitro cytotoxic activity against several human solid tumor cells. We have synthesized both isomers in three simple steps. In the first step, l-iodononyne was prepared by reacting 1-nonyne with N-iodosuccinimide and a catalytic amount of silver nitrate. This iodoalkyne was then coupled with propargyl alcohol using copper iodide as the catalyst to give 2,4dodecadiynyl alcohol. Finally, the diacetylenic alcohol was subjected to the Swern …

Sedimentological And Plant Taphonomic Evaluation Of The Early Middle Devonian Trout Valley Formation, Jonathan Allen

Honors Theses

The Trout Valley Formation of Emsian-Eifelian age, outcropped in Baxter State Park, Maine, consists offluvial and coastal deposits preserving early land plants. Massive, crudely bedded conglomerate represents deposits of proximal braided channels on an alluvial fan complex. Lithic sandstone bodies in channel-form geometries represent deposits of river channels draining the Acadian highlands whereas associated siltstones represent overbank deposits, intertidal flats, and tidal channels. Localized lenticular quartz arenites represent nearshore shelf bar deposits that were storm influenced. The majority of plant assemblages preserved mainly in siltstone lithologies are allochthonous and parautochthonous, with only one autochthonous assemblage identified in the sequence. Plant …

Double Stranded Dna-Binding Studies Of Potential Rhodium(Ll) Antitumor Complexes, Amity Elizabeth Burr

Honors Theses

In 1952, Dwyer and coworkers began testing a series of metal complexes for potential inhibition of cancer cell proliferation in animals.[l] The complexes tested were unsuitable for such studies due to their high toxicity. Therefore, no further work was done on the project. However, in 1965, Rosenberg and coworkers revisited the possibility of potential metal-based drugs. Serendipitously, they discovered that cis-diamminedichloroplatinum(lI) (cisplatin) inhibits cell division in E. coli.[2] Further studies of this and other platinum compounds revealed inhibition of tumor cell lines sarcoma 180 and leukemia LI2l0 in mice.[l] Cisplatin was approved by the Food and Drug Administration in 1970 …

Mechanistic Studies On Chlorinated Polymeric Systems, Jing Zhang

Dissertations, Theses, and Masters Projects

No abstract provided.

Sonogashira Coupling Routes To Ortho-Alkynl-And- Fused-Ring Sydnones, Andrew John Weisner

Browse all Theses and Dissertations

In the present work, suitably functionalized arylsydnones were used to synthesize a variety of ortho-alkynyl sydnones both as potential precursors to novel sydnoquinolines and to provide non-linear optical (NLO) species of interest to Wright-Patterson Air Force Base (WPAFB). The versatile intermediate, 3-(2-(trimethylsilylethynyl)phenyl)sydnone, was prepared in good yield by the coupling of 3-(2-iodophenyl)sydnone with trimethylsilyl acetylene under Sonogashira conditions. From this intermediate, several ortho-alkynyl sydnones were prepared via a one-pot desilylation with tetrabutylammonium fluoride and Sonogashira coupling with para-substituted aryl iodides. In addition, a three-reaction-in-one-pot procedure was developed to access some of these species directly from 3-(2- iodophenyl)-sydnone. Subsequent reaction of …

The Synthesis Of 2-(1-Indenyl)-Phenol: A Potential Ligand For Metallocene Polymerization Catalysts; And, Ω-Iodoalkyl(Methyl) Malonate Esters: Synthesis And Application In Bioconjugate Chemistry, Sara E. Bendler

Masters Theses

Chapter I:

Metallocene catalysis is an important division of polymerization chemistry. The design of appropriate ligands for metallocene catalysts has focused on stereochemical control and structural diversity. The synthesis of the potential ligand 2-(1-indenyl)-phenol has been developed. Indenyl phenol ligands offer advancements over cyclopentadienyl ligands because the steric and electronic properties of the catalyst could be tailored to suit individual polymerization reactions. 2-(1-Indenyl)-phenol was synthesized with an overall yield of 4% and characterized with ¹H NMR and ¹³C NMR.

Chapter II:

A large percentage of breast malignancies overexpress the nuclear estrogen receptor (ER) protein. Binding to nuclear receptors …

Investigation Of Model Cell Membrane Disruption Via Fluorescence And Light Scattering Techniques, Imara Charles

Seton Hall University Dissertations and Theses (ETDs)

.

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

LSU Doctoral Dissertations

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

Synchrotron Radiation As A Probe Of Chemical Information Using Novel Experimental Configurations, George Farquar

LSU Doctoral Dissertations

Determination of chemical information with synchrotron radiation is an area of great scientific interest, and expanding the range of available techniques is the topic of this dissertation. The experimental methods described herein allows for a significant advancement of the availability of subtle chemical information. This dissertation uses ionizing radiation to study three chemical systems. First, the l=3 shape resonance in CO is investigated using a cryogenically cooled gas jet. Shape resonant effects have been studied for many years. Previously, this was accomplished on the vibrational structure of molecules with a limited ability to determine the rotational substructure effects. A dramatic …

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

LSU Doctoral Dissertations

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

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

LSU Doctoral Dissertations

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

Solid-Phase Dna Sequencing Reactions Performed In Micro-Capillary Reactors And Solid-Phase Reversible Immobilization In Microfluidic Chips For Purification Of Dye-Labeled Dna Sequencing Fragments, Yichuan Xu

LSU Doctoral Dissertations

The research presented in this dissertation involves micro-capillary reactors for solid phase DNA sequencing, the identification of dye terminator sequencing fragments with time-resolved methods, and purification of dye-labeled DNA fragments using solid- phase reversible immobilization in microfluidic chips. Solid-phase micro-reactors have been prepared for DNA sequencing applications using slab gel electrophoresis. A PCR product was immobilized to the interior wall of a fused-silica capillary tube via a biotin-streptavidin linkage. Solid-phase sequencing was carried out in micro-capillary reactors using a four-lane, single color dye primer chemistry strategy. The read length was found to be 589 bases. The complementary DNA fragments generated …

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

LSU Doctoral Dissertations

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

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

LSU Doctoral Dissertations

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

Characterization Of Native And Bypass Human Coronary Artery Plaque Deposits From The Same Heart: Investigation Of The Chemical Form Of Calcium In Human Coronary Artery Plaque Deposits, Serigne Thiam

LSU Doctoral Dissertations

Gradual deposits of lipids, proteins, and calcium on the coronary arterial walls cause atherosclerosis, leading to blockage of the blood flow and possible heart attack. Despite many studies, the mechanism underlying these processes remains unclear. In this research, differences between native and bypass plaque deposits from the same heart were examined. In addition, the crystalline and the amorphous plaques within these native and bypass vessels were characterized. The techniques used to characterize the deposits included inductively coupled plasma mass spectrometry (ICPMS), solid-state nuclear magnetic resonance (NMR), high performance liquid chromatography (HPLC), etc. The results from the ICPMS technique showed that …

Chlorobenzenes And Chloronitrobenzenes Interaction With Iron (O), Manuel Alejandro Serratos

Masters Theses

Degradation of chlorobenzene, dichlorobenzenes and chloronitrobenzenes (ClB, x-Cl2B and x-ClNO2B) was tested by trying to make them react with metallic iron, Fe (0), in water solvent.

The experiments consisted of optimizing the parameters of the reactions (like minimum mass of iron needed) and analytical detection conditions. Analytical techniques used were gas and liquid chromatography (GC and HPLC), mass spectrometry (MS) and UV-Vis spectroscopy.

No substances other than the initial ClB and x-Cl2B were detected in their tests with Fe (0) after shaking for periods of up to three days, although 10%weight average decreases in concentration were observed.

The ClNO2B isomers …

Synthesis And Characterization Of A Polypyridyl Ru(Ii)-Alloxazine Complex For Adsorption On Tio2-Coated Ito Electrodes, Manisha A. Patel

Masters Theses

TiO₂-coated conducting glass electrodes can be modified by attachment of redox-active molecules to the TiO₂ surface. This thesis describes the synthesis and characterization of a polypyridyl Ru(II) complex that can be covalently bound to a TiO₂ surface through the carboxylate groups of 2,2'-bipyridine-4,4' -dicarboxylic acid, H₂dcbpy. In addition, the bound complex contains a redox-active alloxazine derivative, pptd, which is capable of 2e^-/2H⁺ transfers. Thus the TiO₂-coated electrode is modified with a transition metal complex capable of shuttling H-atoms to substrates in solution. Synthesis of the PF₆^- salt …

Phosphido-Bridged Complexes Linked By Unsaturated Phosphines, Yong Liu

Masters Theses

Di(p-tol)phosphido-bridged complexes, (OC)₄M[μ-P(p-tol)₂]₂M(CO)₄ (M = Mo, W), have been synthesized for the first time. These have been obtained from the reaction of (OC)₅MP(p-tol)₂H with BuLi, followed by air oxidation. The choice of solvent is very important as the intermediate anion, [(OC)₅MP(p-tol)₂] is unstable in THF. An ideal solvent for these preparations is CH₃OCH₂CH₂OCH₃ (monoglyme) from which yields of 68% and 76% were realized for the tungsten and molybdenum complexes, respectively. …

Dmap As A Catalyst For Carbon Acylation: Elucidation Of Mechanistic Pathway, Including Spectral Characterization Of The Putative Reactive Intermediate, Jagadish K. Boppisetti

Masters Theses

3-Phenylbenzofuranone, when deprotonated with sodium hydride, forms an extended enolate system which, when treated with excess alkyl chloroformates, affords only oxygen-acylated products, as opposed to the usually desired carbon-functionalized derivatives. It was discovered that such molecules, when treated with a catalytic amount of 4- (N, N-dimethylamino)pyridine (DMAP), rearrange quantitatively to the carbon acylated isomers.

These migrations, which are accompanied by a deep blue color, are proposed to involve a reactive intermediate. This intermediate, which is postulated as an ion pair charge transfer (IPCT) complex, has been closely studied in order to gain a better understanding of the …