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Geometrical And Electronic Structure Of Metal Oxide Nanoparticles On Silica And Alumina, Udaya Indike Rodrigo

LSU Doctoral Dissertations

Recent studies demonstrated nanometer-scale combustion-generated nanoparticles cause demonstrable health effects. It is essential to understand the chemical characteristics of these nanoparticles. Since combustion-generated nanoparticles arise in complex mixtures, we employed a dendrimeric method to generate simpler, more reproducible nanoparticles, which were tethered to fumed silica and alumina to provide surrogates for fly ash. We collected XANES and EXAFS data, which are useful for characterizing disordered mixtures where the metal is a minor component. The effect of particle size on structural properties was studied with copper oxide nanoparticles on fumed silica. XANES data demonstrated copper atoms in the nanoparticles are present …

Synthesis And Characterization Of Red And Near-Infrared Bodipy-Based Fluorophores For Various Biological Applications, Timsy Kaur Uppal

LSU Doctoral Dissertations

ABSTRACT 4,4-Difluoro-3a,4a-diaza-s-indacene, better known as BODIPY® dyes, have attracted considerable attention due to their intriguing physicochemical and spectral properties, including high absorption coefficient, fluorescence quantum yield and good photochemical stability. Despite the recent progress achieved in this field, the synthesis of BODIPY derivatives that absorb and emit in the red- and NIR-region of the electromagnetic spectrum and their application to biomolecular targets, represents a long-standing challenge in BODIPY chemistry. This research work is therefore focused on the synthesis and characterization of red and NIR-emissive BODIPY-based fluorophores for various bioanalytical and biomedical applications. Chapter 1 of this dissertation represents a concise …

Single-Molecule Detection Of Molecular Beacons Generated From Ldr On Thermoplastic Microfluidic Device For Bioanalysis, Zhiyong Peng

LSU Doctoral Dissertations

Current clinical techniques for nucleic acid detection and analysis often involve PCR, lacking adequate specificity or sensitivity to meet the stringent requirements in certain applications. This research aims to develop an innovative molecular assay and the associated hardware to rapidly signal the presence of certain targets using reporter sequence found in their genome without requiring PCR. This assay coupled the sensitivity of single-pair fluorescence resonance energy transfer (spFRET) with the specificity of ligase detection reaction (LDR) to provide near real-time readout of target biomarkers. Heightened concerns on potential bioterrorism threats, such as rapid dissemination of pathogenic bacteria or viruses into …

Chemical Crystallography At The Interface Of Physics, Chemistry, And In Engineering: Structure Determination Of Highly Correlated Extended Solids, Main Group Compounds, Coordination Complexes, And Bioceramics, Gregory Todd Mccandless

LSU Doctoral Dissertations

Multi-disciplinary research is essential to address the major challenges in science, engineering, and medicine. For these three areas, crystallography has played and continues to play a huge role by providing researchers with the means to determine the structure of a compound and relate these to its properties. This dissertation is highly interdisciplinary, focusing on structure determination of complex systems and materials with tailored applications. This work includes the characterization by single crystal and powder X-ray diffraction of intermetallic extended solids, layered metal oxides, inorganic complexes, discrete organic molecules, and bioceramics. These projects range from modeling translational disorder with pseudo-hexagonal symmetry …

Characterizing Dissolved Organic Matter And Cu2+, Zn2+, Ni2+, And Pb2+ Binding In Salt Water And Implications For Toxicity, Rachael L. Diamond

Theses and Dissertations (Comprehensive)

The binding of metal to dissolved organic matter in aquatic environments is important in controlling the bioavailability and potential toxicity of metals such as Zn²⁺, Pb²⁺, Ni²⁺ and Cu²⁺. The purpose of this research is to: (i) quantify binding capacity to different sources of marine organic matter at environmentally relevant concentrations; (ii) test fluorescence quenching and voltammetric method for use in seawater conditions and; (iii) compare predicted speciation parameters with toxicological observations in the same samples.

Information regarding the solubility of copper and copper compounds is important for risk assessment and can be …

Laboratory Methods For The Advancement Of Wastewater Treatment Modeling, Holly E. Gray

Theses and Dissertations (Comprehensive)

To achieve the low levels of total phosphorus required in wastewater treatment plant effluent all chemical forms of phosphorus should be removed. The most refractory phosphorus in terms of removal is so-called “organic phosphorus”. This thesis explores potential relationships between dissolved organic matter and organic phosphorus and methods of removing organic phosphorus from waste water. Fluorescence spectroscopy will be used to characterize dissolved organic matter (DOM) in wastewater. The fluorescent DOM will then be monitored throughout the various wastewater treatment plants to investigate any changes throughout the treatment train. Correlations between fluorophore concentrations (concentrations determined for the different classifications of …

Investigation Of Electroosmotic Flow Dynamics And Reproducibility In Capillary Electrophoresis, Funda Kizilkaya

LSU Doctoral Dissertations

The goal of this dissertation is to investigate electroosmotic flow (EOF) and electric field dynamics during capillary electrophoresis (CE) experiments using methods based on periodic photobleaching of fluorophores added to the separation buffer at nanomolar concentrations. The methods provide time resolved EOF and local electric field information during an experiment, which can be applied to fundamental studies to provide better understanding of CE techniques. The potential of the EOF monitoring method to improve CE migration reproducibility was investigated in Chapter 2. The EOF monitoring method and four other methods from the literature were applied to the same electrophoretic separations, and …

Synthesis, Cellular Studies, And Computational Analysis Of Porphyrin And Bodipy Conjugates With Affinity For Epidermal Growth Factor Receptor, Alecia Michelle Mccall

LSU Doctoral Dissertations

Chapter 1 is a description of the basic fundamental concepts of porphyrins and BODIPYs, (including synthetic methodologies), a general mechanism of the processes of EGFR, and computational concepts that are elaborated upon in future chapters. Chapter 2 is a discussion solely on the porphyrins that were synthesized to be used as fluorophores for EGFR-targeted conjugates, both peptidic and non-peptidic. The porphyrins were primarily synthesized via the Lindsey method as well as by O-alkylation of tetrahydroxy porphyrins. Synthesis of PEG linkages are discussed as well through three methodologies. Chapter 3 is a presentation of the synthesis, characterization, cellular studies, and computational …

Infrared Laser Ablation For Biological Mass Spectrometry, Fan Huang

LSU Doctoral Dissertations

Instrument and technique development and modeling of ionization methods using infrared (IR) laser desorption and ablation for mass spectrometry (MS) analysis of chemical and biochemical samples are described. Infrared lasers are highly efficient at sample removal and post-ablation ionization of materials removed by IR laser can be used to improve ionization efficiency. Fundamental studies of the physical processes in laser ablation mass spectrometry can help elucidate the mechanism. In this research, an infrared/ultraviolet two-laser matrix-assisted laser desorption ionization (MALDI) MS was developed for analysis of biomolecules. An infrared laser was used to ablate a mixture of analyte and matrix, and …

Investigations Into The Role Of Humic Acid In Biomembrane Permeability And The Effects Of Naturally Formed Gold And Silver Nanoparticles On These Interactions, Loice Marklyne Ojwang

LSU Doctoral Dissertations

The mechanism and kinetics of the interaction of humic acids (HAs) with a 1-palmitoyl-2-oleoyl-Sn-glycero-3-phosphatidylcholine (POPC) large unilamellar vesicle (LUV) model biomembrane system were studied by fluorescence spectroscopy. All three HAs studied induced a perturbation to the biomembrane bilayer structure at pH 4.8. Concentration dependence studies revealed that biomembrane perturbation increased with increasing HA concentrations for Suwannee River HA (SWHA) from 0 to 20 mg C/L. For both Leonardite HA (LAHA) and Florida Peat HA (FPHA) aggregation influenced biomembrane perturbation at concentrations above 5 and 7.5 mg C/L, respectively. Temperature studies over the environmentally relevant ranges of 10 to 30 °C …

Design, Synthesis, Characterization, And Application Of Peptides As Different Medical Treatment, Krystal Renee Fontenot

LSU Doctoral Dissertations

A peptide is defined, as a molecule that contains less than fifty amino acids; anything larger is a protein. Peptides are important molecules because they have diverse uses. Peptides were utilized in two ways: 1) Peptide bioconjugates containing a fluorescent porphyrin or phthalocyanine macrocycle were designed and investigated, with or without a PEG moiety for selective targeting of the epidermal growth factor receptor (EGFR). 2) Amyloid aggregating mitigating peptides (AAMPs) was synthesized and investigated containing polar amino acids, MiniPEGs, and/or ααAAs that have the ability to inhibit and disrupt Amyloid Beta (Aβ). The peptide bioconjugates containing a porphyrin or phthalocyanine …

Ionic Materials For Applications In Sensing And Optoelectronics, Sergio L. De Rooy

LSU Doctoral Dissertations

Organic salts consist of bulky anions and/or cations whose properties can be tailored for specific purposes. Ionic liquids (ILs) are (semi)organic salts with melting points below 100 ºC. They typically exhibit neglible vapor pressures, high thermal stability, wide liquidus range, and tunable solubility. Moreover specific functions can be built into their respective ions. The first part of the dissertation involves discussions of chiral ionic liquids with additional protic, magnetic, and magneto-luminescent properties, respectively. In addition to their enantioselective sensing capabilities, the ILs may find use in chiral separations and catalysis. The second part of the dissertation involves discussions of fluorescent …

Investigations Into The Role Of Natural Organic Matter As An Interface Between Aquatic Organisms And Environmental Pollutants, Caroline Lillian Schneider

LSU Doctoral Dissertations

The impact of the continuous pollution of freshwater environments by multiple pollutants has not been well-studied. The goal of this research was to evaluate the toxicity of several modern pollutants in a model environment. The prokaryotic, unicellular blue-green algae Synechocystis WT6803 and the eukaryotic, multicellular Utterbackia imbecillis mussel larvae were studied along with Suwannee River natural organic matter (NOM). The toxicity response of the blue-green algae Synechocystis sp. was measured through changes in growth rates. The inorganic pollutant silver nanoparticles (0.044 μM) were toxic. Gold nanoparticles did not affect the growth rate. The addition of 15 mg/L NOM partially inhibited …

Design And Analysis Of Cloaked Fluorophores For Rapid Detection And Visualization Of Cancer Cells Containing Nad(P)H:Quinone Oxidoreductase-1, William Silvers

LSU Doctoral Dissertations

The development of fluorogenic substrates for real-time tumor cell detection has led to a vastly expanding field for personal oncology. Fluorophores have been studied as appendages to larger scaffolds leading to accumulation of these dyes in tumor cells or their surrounding environment, taking advantage of tumor anatomy. A new class of fluorophores has been developed in which the dye is an active participant in the mechanism of cancer cell detection. These dyes have been conjugated such that their fluorescence has been eliminated or altered and will undergo a change to reveal their fluorescent signal upon activation by a mechanism that …

Syntheses And Characterization Of Water-Soluble Phythalocyanines For Diagnosis And Treatment Of Cancer, Benson Getenga Ongarora

LSU Doctoral Dissertations

Ongarora, Benson Getenga, B.S., Moi University, 2005 Doctor of Philosophy, Fall Commencement, 2012 Major: Chemistry Syntheses and Characterization of Water-Soluble Phthalocyanines for Diagnosis and Treatment of Cancer Dissertation directed by Professor M.Graҫa H. Vicente Pages in dissertation, xi. Words in abstract, 251. ABSTRACT Chapter 1 describes the general properties of phthalocyanines, synthesis of metallo-phthalocyanines, their photophysical features and their uses. The concepts of PDT and targeted therapeutics are also introduced. Chapter 2 describes the syntheses, characterization, photophysical studies and biological evaluation of cationic phthalocyanines. The trimethylaminophenoxy substituted phthalocyanines were synthesized through statistical condensation method, which gave a statistical mixture of …

Development Of Innovative Stationary Phases For Chiral And Protein Separations In Open Tubular Capillary Electrochromatography, Leonard Moore, Jr.

LSU Doctoral Dissertations

Protein biomarkers in bodily fluids can lead to an indication of the onset of a disease. Due to low abundance of the biomarker at early stages of the disease and other protein interferences, detection may be challenging. Therefore, in order to achieve more selective protein separations, the development of a novel stationary phase has been investigated. Moreover, novel methods to apply polysaccharides as stationary phases were developed for protein separations as well as chiral separations. The initial discussions in this dissertation commences with the use of novel zwitterionic lysine-based molecular micelles as a coating for open tubular capillary electrochromatography (OT-CEC) …

Detection And Characterization Of Environmentally Persistent Free Radicals (Epfrs) In Soils And Sediments From Superfund Sites, Albert Leo N. Dela Cruz

LSU Doctoral Dissertations

Environmentally persistent free radicals (EPFRs) from combustion-generated PM have been demonstrated to form via reactions of molecular precursors with redox-active transition metals at 150-500C thermal reactions in a few seconds reaction times. While ambient temperatures are much lower, soils/sediments contain similar transition metals, and reaction times of contaminants in soils/sediments are years, rather than seconds. This questions whether EPFRs could be formed at ambient temperatures in soils/sediments from Superfund sites that are contaminated with hazardous materials. Superfund soils contaminated with PCP from Georgia and Montana, and sediments contaminated with PAHs from Washington. Using EPR spectroscopy, EPFR concentrations and structural assignments …

Total Synthesis Of A Virotoxin And Analogs For Conformational Studies, Benson Jumba Edagwa

LSU Doctoral Dissertations

This dissertation describes the first total synthesis of alloviroidin in trace amounts, along with that of three analogs containing L-proline (Pro), trans-3-hydroxyproline (3-Hyp) or cis-4-hydroxyproline (4-hyp) residue substituting for 2,3-trans-3,4-trans-dihydroxyproline in the natural product. We report herein an efficient strategy that provides a dipeptide containing a (2S,4S)-4,5-dihydroxyleucine (dihyLeu) residue, including a diastereoselective dihydroxylation. Nα-Carbobenzyloxy-(2S)-4,5-dehydroleucine was coupled with valine ethyl ester to give a dipeptide that was subjected to a Sharpless asymmetric dihydroxylation to introduce the diol. The relative configuration at C4 was assigned as S by X-ray crystallography after derivatization as an α-amino-γ-lactone hydrochloride salt. The preparation of the 2-(methylsulfonyl)tryptophan …

Atr-Ftir Studies On The Kinetics Of Dimethylarsinic Acid (Dma) Surface Complexation With Iron(Oxyhydr)Oxides, Julia Tofan-Lazar Miss

Theses and Dissertations (Comprehensive)

Dimethylarsinic acid (DMA) is an organoarsenical compound that, along with monomethylarsonic acid, poses a health and an environmental risk, and a challenge to the energy industry. Little is known about the surface chemistry of DMA at the molecular level with materials relevant to geochemical environments and industrial sectors. The surface chemistry of phosphorus and arsenic compounds in their organic and inorganic forms is of great interest due to its role in controlling their transport, bioaccessibility and speciation. This thesis reports the first in-situ and surface-sensitive rapid kinetic studies on the adsorption and desorption of DMA to and from Fe-(oxyhydr)oxide films …

Synthesis And Investigation Of The Liquid Crystalline Properties Of Polycyclic Aromatic Hydrocarbons, Joseph A. Paquette

Theses and Dissertations (Comprehensive)

In this thesis, the synthesis and liquid crystalline properties of a series of novel substituted dibenz[a,c]anthracenes is reported. Specifically, a series of hexaalkoxydibenz[a,c]anthracenes were prepared and found not to exhibit a mesophase. In contrast, when substituents are introduced on the aromatic core, columnar mesophases are observed over broad temperature ranges. A series substituted derivatives was prepared and their mesomorphic properties compared. In general, electron-withdrawing substituents promote broad mesophase temperature ranges, as do larger substituents. The liquid crystalline phase is a result of the electronic effects, size and shape of the substituents in the 10 and 13 positions.

We also synthesized …

Resonant Inelastic X-Ray Scattering Of Methyl Chloride At The Chlorine K Edge, L. El Khoury, Loic Journel, Renaud Guillemin, Stephane Carniato, Wayne C. Stolte, T. Marin, Dennis W. Lindle, Marc Simon

Chemistry and Biochemistry Faculty Research

We present a combined experimental and theoretical study of isolated CH3Cl molecules using resonant inelastic x-ray scattering (RIXS). The high-resolution spectra allow extraction of information about nuclear dynamics in the core-excited molecule. Polarization-resolved RIXS spectra exhibit linear dichroism in the spin-orbit intensities, a result interpreted as due to chemical environment and singlet-triplet exchange in the molecular core levels. From analysis of the polarization-resolved data, Cl 2px, y and 2pz electronic populations can be determined.

Thomson-Resonant Interference Effects In Elastic X-Ray Scattering Near The Cl K Edge Of Hcl, Stephane Carniato, P. Selles, Loic Journel, Renaud Guillemin, Wayne C. Stolte, L. El Khoury, T. Marin, Faris Gel'mukhanov, Dennis W. Lindle, Marc Simon

Chemistry and Biochemistry Faculty Research

We experimentally observed interference effects in elastic x-ray scattering from gas-phase HCl in the vicinity of the Cl K edge. Comparison to theory identifies these effects as interference effects between non-resonant elastic Thomson scattering and resonant Raman scattering. The results indicate the non-resonant Thomson and resonant Raman contributions are of comparable strength. The measurements also exhibit strong polarization dependence, allowing an easy identification of the resonant and non-resonant contributions.

2- Bromophenyl Salicylate, Donovan Thompson, Sierra Mitchell, Kevin Clarke, Kerry Sarden, Karelle Aiken

Chemistry: Faculty Publications (1990-2023)

2-Bromophenyl salicylate is synthesized from 2-benzyloxybenzoic acid in two steps. The final compound has been characterized by IR,¹H-NMR, ¹³C-NMR and HRMS. The melting point for 2-bromophenyl salicylate is provided.

A General Synthesis Of Bis-Indolylpiperazine-2,5-Diones, Stephen N. Crooke, Christine Whitlock

Chemistry: Faculty Publications (1990-2023)

The one-pot synthesis of three dragmacidin derivatives is reported. Sarcosine anhydride (4) is brominated and immediately reacted with the corresponding indole to produce the products, namely 3,6-bis(5′-methoxy-3′-indolyl)-1,4-dimethylpiperazine-2,5-dione (1), 3,6-bis(7′-methyl-3′-indolyl)-1,4-dimethylpiperazine-2,5-dione (2) and 3,6-bis-(6′-chloro-3′-indolyl)-1,4-dimethylpiperazine-2,5-dione (3), which are characterized by ¹H-NMR.

Synthesis Of \Alpha-Aminonitriles Catalyzed By Montmorillonite K10 In The Presence Of Dicationic Phosphonium Salt In Water Under Ultrasonic Effect, Çi̇ğdem Yildirim, Çi̇ğdem Yolaçan, Feray Aydoğan

Turkish Journal of Chemistry

The synthesis of \alpha-aminonitriles was successfully accomplished by the 1-pot 3-component reaction of several aldehydes with (S)-\alpha-phenylethylamine and sodium cyanide in water in the presence of montmorillonite K10 and dicationic phosphonium salt under ultrasonic effect with good yields and moderate diastereoselectivities.

Synthetic Access To Benzazolyl (Pyrazoles, Thiazoles, Or Triazoles), Bakr Fathy Abdelwahab, Hanan Ahmed Mohamed

Turkish Journal of Chemistry

This review surveys data published in recent years on the synthesis of benzazoles linked directly with pyrazoles, thiazoles, or triazoles. Some of the commercial applications are mentioned.

Functional Promiscuity Of The Cog0720 Family, Gabriela Phillips, Laura L. Grochowski, Shilah Bonnett, Huimin Xu, Marc Bailly, Crysten Haas-Blaby, Basma El Yacoubi, Dirk Iwata-Reuyl, Robert H. White, Valérie De Crécy-Lagard

Chemistry Faculty Publications and Presentations

The biosynthesis of GTP derived metabolites such as tetrahydrofolate (THF), biopterin (BH4), and the modified tRNA nucleosides queuosine (Q) and archaeosine (G⁺) relies on several enzymes of the Tunnel-fold superfamily. A subset of these proteins include the 6-pyruvoyl-tetrahydropterin (PTPS-II), PTPS-III, and PTPS-I homologs, all members of the COG0720 family, that have been previously shown to transform 7,8-dihydroneopterin triphosphate (H₂NTP) into different products. PTPS-II catalyzes the formation of 6-pyruvoyltetrahydropterin in the BH₄ pathway. PTPS-III catalyzes the formation of 6-hydroxylmethyl-7,8-dihydropterin in the THF pathway. PTPS-I catalyzes the formation of 6-carboxy-5,6,7,8-tetrahydropterin in the Q pathway. Genes of these …

Elucidation Of B-N And B-P Stretching Vibrations Using Raman Spectroscopy And Electronic Structure Calculations, Dana Nicole Reinemann

Honors Theses

Boron-nitrogen (B-N) and boron-phosphorus (B-P) dative bond stretching vibrational frequencies were studied using vibrational spectroscopic methods and electronic structure calculations. There has been a great controversy over the assignment of B-N dative bond vibrational frequencies for many years with a range of inconsistent assignments in the literature. The B-N dative bond stretching frequency in N-methyliminodiacetic acid (MIDA) esters was analyzed here using infrared, Raman, and surface enhanced Raman spectroscopic methods and compared to the results of electronic structure calculations employing the MP2 and M06-2X methods with a triple zeta basis set. The mode including the B-N stretching motion proved to …

Synthesis, Characterization, And Antimicrobial Activity Of A New Pyrimidine Schiff Base And Its Cu(Ii), Ni(Ii), Co(Ii), Pt(Ii), And Pd(Ii) Complexes, Mehmet Gülcan, Mehmet Sönmez, İsmet Berber

Turkish Journal of Chemistry

A new Schiff base, {1-[(5-bromo-2-hydroxy-benzylidene)- amino]-4-phenyl-2-thioxo-1,2-dihyro-pyrimidin-5-yl}-phenyl-methanone, was synthesized from N-amino pyrimidine-2-thione and 5-bromsalicylaldehyde. Metal complexes of the Schiff base were prepared from acetate salts of Cu(II), Ni(II), Co(II), Pd(II), and PtCl_2 in methanol. The chemical structures of the Schiff base ligand and its metal complexes were confirmed by spectroscopic analysis. All of the compounds were evaluated for their antimicrobial against 4 gram-positive bacteria, 1 gram-negative bacterium, and 3 yeast strains. The Schiff base and the Cu(II) and Co(II) complexes showed good biological activity against all tested bacteria and yeast strains.

Dna-Carbon Nanotubes Composites As Gene Sensors, Hugo Alarcon

Open Access Theses & Dissertations

Carbon fullerenes are unusually structured molecules with robust mechanical and electronic properties. Their versatility is astounding; envisioned applications range from field emission displays to impregnated metal composites, battery storage media, and nanoelectronic devices. The combination of simple constituency, diverse behavior, and ease of fabrication makes these materials a cornerstone topic in current research.

This work describes experiments conducted on nanotubes using Dynamic light scattering (DLS). The aim is to detect cluster formation from individual carbon nanotube (CNT) solutions using a nanotube DNA binding sequence and a secondary recognizing complementary DNA sequence to bind neighboring CNTs. Dynamic Light Scattering is an …