Chemistry Commons^™

Novel Aromatic Ion–Pairs: Synergy Between Electrostatics And Π-Face Aromatic Interactions, Pramod Prasad Poudel

Theses and Dissertations--Chemistry

This dissertation focuses on the design and study of charged aromatic molecules where weak π-π interactions synergize with electrostatic interactions to enhance the overall interaction between aromatic moieties. Each chapter investigates some aspect of this hypothetical synergy between electrostatics and π-face aromatic cohesion.

The first chapter unveiled the importance of electrostatics in the intramolecular stacking of flexible aromatic molecular templates 1-2Br and 2a. While our previous studies found dicationic molecular template 1-2Br to have intramolecular π-stacking between electron poor pyridinium and electron rich xylylene moieties, no such stacking interaction was observed in the neutral analog 2a.

Chapter two systematically …

Investigation Of The Critical Residues At The C-Terminus Of The E.Coli Periplasmic Chaperone, Sura, Brent Ferrell

Theses and Dissertations--Chemistry

SurA is a molecular chaperone in the periplasm of E.coli and has been implicated in the maturation of outer membrane proteins (OMPs). SurA consists of four domains, but only two of them, namely the N and C-­terminal domains, are necessary for chaperone function. Very little is known about which residues drive the interaction between the N and C-­termini that facilitates normal activity. We mutated several conserved residues on the C-terminus and generated additive truncations to observe the effects of each on the fitness of the cell. We found one mutation E(408):A was sufficient to reduce SurA activity by 3-­fold, but …

Development Of Novel Chemical Tools For Proteasome Biology & A New Approach To 1-Azaspirocyclic Ring System, Lalit Kumar

Theses and Dissertations--Chemistry

The proteasome, a multiprotease complex, is clinically validated as an anticancer target by the FDA approval of bortezomib and carfilzomib for the treatment of multiple myeloma. The emergence of resistance to proteasome inhibitors however remains a major clinical challenge. Recently, distinct types of proteasomes termed ‘intermediate proteasomes’, which contain unconventional mixtures of catalytic subunits, have been implicated with drug resistance of tumor cells. In elucidating the role of intermediate proteasomes in drug resistance, a crucial step is to unequivocally determine the subunit composition of intermediate proteasomes in cells. With this in mind, the goal of the studies reported in this …

Spectroscopic Detection And Characterization Of Jet-Cooled Transient Molecules, Mohammed Gharaibeh

Theses and Dissertations--Chemistry

Transient molecules are of great importance due to their critical role as intermediates in the semiconductor industry, in upper atmosphere reactions, and in astrochemistry. In the present work, reactive intermediates were produced in the laboratory by applying an electric discharge through a suitable precursor gas mixture and studied by means of their laser-induced fluorescence and emission spectra.

The band systems of and have been studied in detail. The energy levels of both isotopologues were fitted with a Renner-Teller model, and the isotope relations have been used to test the validity of the derived parameters.

The A²Π_u - …

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 …

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.

Quantitative Analysis Of Co-Enzyme A In A Plant Tissues And Cancer Biomarkers In Urine Samples By Using Capillary Electrophoresis And Liquid Chromatography-Mass Spectrometry, Yongqing Jiang

Doctoral Dissertations

"Despite continuous effort and progress in cancer detection and therapy, cancer remains one of our greatest health concerns because of its low survival rate and rapid incidence increase. One reason for this is the late detection and therefore pre-cancer diagnosis is crucial. In pre-cancer studies, cancer biomarkers become significant because of the useful information it contains such as possible cancer type and stage. Separation and detection technique plays an important role in cancer biomarker identification.

Coenzyme A (CoA) facilitates more than 100 chemical reactions in cells. Because of its low abundance accumulated in cells, it is critical to develop a …

Investigation Of Biomarkers For Noninvasive Early Diagnosis Of Cancer, Sanjeewa Bandara Gamagedara

Doctoral Dissertations

"Cancer is the second leading cause of death worldwide, and deaths from cancer worldwide are projected to continue rising, with an estimated 12 million deaths in 2030. Cancer occurs when cells in a part of the body begin to grow out of control. It develops very rapidly, and early diagnosis offers a greater chance of successful treatment and a higher survival rate. Biomarkers are good potential tools for early diagnosis. The main hypothesis of this study is that the levels of certain metabolites present in human urine can indicate the current or future behavior of cancer. Therefore, these studies focused …

Part I: Quantitative Determination Of Total Corrosive Sulfur In Mineral Insulating Oils And Technical Liquids; Part Ii: Development And Validation Of A Broad Spectrum Microbial Disinfectant, Kyle Rodney Anderson

Doctoral Dissertations

"Part one of this dissertation deals with the development and validation of a test method for determination of total corrosive sulfur in mineral insulating oils other technical oils. The method involved reaction of corrosive sulfur compounds in oils with finely divided copper at temperatures ≥ 110 °C. The reaction yielded cuprous sulfide (Cu₂S), Cu₂S was then oxidized to cupric sulfate (CuSO₄), which was determined as sulfate with ion chromatography. The method offers a quantitative assessment of corrosive sulfur compounds in oils and eliminates ambiguities associated with the international standard methods for corrosive sulfur in mineral insulating oils and other technical …

Electrodeposition And Electrochemical Reduction Of Epitaxial Metal Oxide Thin Films And Superlattices, Zhen He

Doctoral Dissertations

"The focus of this dissertation is the electrodeposition and electrochemical reduction of epitaxial metal oxide thin films and superlattices. The electrochemical reduction of metal oxides to metals has been studied for decades as an alternative to pyrometallurgical processes for the metallurgy industry. However, the previous work was conducted on bulk polycrystalline metal oxides. Paper I in this dissertation shows that epitaxial face-centered cubic magnetite (Fe₃O₄) thin films can be electrochemically reduced to epitaxial body-centered cubic iron (Fe) thin films in aqueous solution on single-crystalline Au substrates at room temperature. This technique opens new possibilities to produce special epitaxial metal/metal oxide …

Organic And Composite Aerogels Through Ring Opening Metathesis Polymerization (Romp), Dhairyashil Mohite

Doctoral Dissertations

"Aerogels are open-cell nanoporous materials, unique in terms of low density, low thermal conductivity, low dielectric constants and high acoustic attenuation. Those exceptional properties stem from their complex hierarchical solid framework (agglomerates of porous, fractal secondary nanoparticles), but they also come at a cost: low mechanical strength. This issue has been resolved by crosslinking silica aerogels with organic polymers. The crosslinking polymer has been assumed to form a conformal coating on the surface of the skeletal framework by covalent bridging elementary building blocks. However, "assuming" is not enough: for correlating nanostructure with bulk material properties, it is important to know …

Chelating Compounds As Potential Flash Rust Inhibitors And Melamine & Aziridine Cure Of Acrylic Colloidal Unimolecular Polymers (Cups), Jigar K. Mistry

Doctoral Dissertations

Waterborne coatings on ferrous substrates usually show flash rusting which decreases the adhesion of the coating and the corrosion products can form a stain. Chelating compounds were investigated as potential flash rust inhibitors. Compounds being evaluated include amine alcohols, diamines and sulfur containing amines. A new corrosion inhibitor 2,5-bis(thioaceticacid)-1,3,4-thiadiazole (H2ADTZ) was synthesized and its performance characteristics were evaluated. It was noted that the observed structure of 1,3,4-thiadiazolidine-2,5-dithione (also known as 2,5-dimercapto-1,3,4-thiadiazole (DMTD or DMcT)) has been previously reported in three different tautomeric forms including -dithiol and -dithione. The relative stability of each form as well as the synthesis and characterization …

X-Ray Crystallography For The Study Of Nickel And Iron Salicylaldimines, Carla Schmiesing Eribal

Doctoral Dissertations

"X-ray diffraction of single crystals has developed dramatically over the last century by combining fundamental theories of light, diffraction, and statistics to generate the complete, geometric structure of molecules. The quality of the resulting X -ray structure data are reported in R₁ < 5%, wR2 < 12% and a goodness of fit value of one. This technique was applied specifically to the evaluation of the spin crossover (SCO) compound [Fe(salpm)₂]BF₄ʺ0.5EtOH and how the molecule's geometry changed during a two-step thermal LS-HS conversion. The crystal structure was measured at 100,175,225, and 296 K to yield final R₁ values of 0.047, 0.054, 0.051, and 0.058, respectively. The coordination bond lengths show the spin transitions occur between 100-175K at one crystallographically unique Fe and between 175-225K at the other Fe site. No strong long range interactions are found, suggesting a gradual spin transition. Reaction ofNi(Nalkyl-sal)₂ complexes with Ni(N0₃)₂ form either nickel dimeric, [Ni₃(Rsal)(N0₃)(MeOH)]₂ or trinuclear complexes, Ni₃(Rsal)₄(N0₃)₂. The binuclear complexes, with orthogonal bridging ligands, show overall ferromagnetic interactions. The crystal structures for Ni₃(Rsal)₄(N0₃)₂ from methyl to benzyl were solved and indicate no steric restriction on formation for the series. The trinuclear compounds form an isosceles triangle of metal atoms with the isopropyl analog showing an overall antiferromagnetic interaction with J=+11.386 and J23=-13.891. Lastly, xanthene spirolactam derivatives were structurally analyzed to determine binding modes for their selective and sensitive (µM) detection of metals Cr³⁺, Fe³⁺, Ni²⁺, Co²⁺ and the nerve gas mimic, dichlorophosphate"--Abstract, page iii.

Nano-Particles Induced Oxidative Stress In Immortalized Human Brain Endothelial Cells, Xinsheng Zhang

Doctoral Dissertations

"Nanoparticles are engineered structure with at least one dimension of 100 nanometers or less. These materials are increasingly being used for commercial purposes such as catalyst, semiconductor, cosmetics, microelectronic, and drug carrier. However, the toxicological impact of these materials has not yet been studied in detail, thereby limiting their use. In our present study, we use human brain endothelial cell line as a blood-brain barrier (BBB) model to investigate if two kinds of nanoparticles [ 1). Diesel exhaust particles (DEPs) and 2). single wall carbon nanotube (CNT) ] induced oxidative stress in cell model. Our studies showed that DEPs or …

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 …

Studies Of A Dirhodium Tetraphosphine Catalyst For Hydroformylation And Aldehyde-Water Shift Catalysis, Aaron Rider Barnum

LSU Doctoral Dissertations

Research into the dirhodium tetraphosphine catalyst precursor [rac-Rh2(nbd)2(et,ph-P4)](BF4)2 shows it is capable of forming a highly active and regioselective hydroformylation catalyst in situ when using an acetone or acetone/water solvent. Hydroformylation experiments (using 1-hexene), FT-IR studies, and acid-base studies were performed to better understand the various complexes of the dirhodium catalyst cycle. These studies lead to the newly proposed catalyst mechanism when performed in an acetone/water solution, using the monocationic [rac-Rh2(H)(µ-CO)2(CO) (et,ph-P4)]+ as the proposed active catalyst complex for hydroformylation. For the conversion of 1-hexene to heptanal, it is capable of performing an initial rate of 30 turnovers per min, …

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 …

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 …

A Simple Approach For Synthesis, Characterization And Bioactivity Of Bovine Bones To Fabricate The Polyurethane Nanofiber Containing Hydroxyapatite Nanoparticles, Faheem A. Sheikh, M. A. Kanjwal, Javier Macossay-Torres, N. A. M. Barakat, H. Y. Kim

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

In the present study, we had introduced polyurethane (PU) nanofibers that contain hydroxyapatite (HAp) nanoparticles (NPs) as a result of an electrospinning process. A simple method that does not depend on additional foreign chemicals had been employed to synthesize HAp NPs through the calcination of bovine bones. Typically, a colloidal gel consisting of HAp/PU had been electrospun to form nanofibers. In this communication, physiochemical aspects of prepared nanofibers were characterized by FE-SEM, TEM and TEM-EDS, which confirmed that nanofibers were well-oriented and good dispersion of HAp NPs, over the prepared nanofibers. Parameters, affecting the utilization of the prepared nanofibers in …

Bismuth Nitrate-Induced Microwave-Assisted Expeditious Synthesis Of Vanillin From Curcumin, Debasish Bandyopadhyay, Bimal K. Banik

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Background: Curcumin and vanillin are the two useful compounds in food and medicine. Bismuth nitrate pentahydrate is an economical and ecofriendly reagent.

Method: Bismuth nitrate pentahydrate impregnated montmorillonite KSF clay and curcumin were subjected to microwave irradiation.

Results: Microwave-induced bismuth nitrate-promoted synthesis of vanillin from curcumin has been accomplished in good yield under solvent-free condition. Twenty-five different reaction conditions have been studied to optimize the process.

Conclusion: The present procedure for the synthesis of vanillin may find useful application in the area of industrial process development.

Ultrasound-Assisted Aza-Michael Reaction In Water: A Green Procedure, Debasish Bandyopadhyay, Sanghamitra Mukherjee, Luis C. Turrubiartes, Bimal K. Banik

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

The conjugate addition of amines to conjugated alkenes (commonly known as aza-Michael reaction) constitutes a key step for the synthesis of various complex natural products, antibiotics, α-amino alcohols and chiral auxiliaries. Ultrasound-induced addition of several amines to α, β-unsaturated ketones, esters and nitriles has been carried out very efficiently in water as well as under solvent-free conditions. No catalysts or solid supports have been used in this method. Remarkable enhancement of reaction rate has been observed in water under ultrasound-induced method. This environmentally benign procedure has provided clean formation of the products with better selectivity.

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 …

Spontaneous Cooperative Assembly Of Replicative Catalytic Rna Systems, Nilesh Vaidya

Dissertations and Theses

The RNA World hypothesis proposes a period of time during the origins of life in which RNA molecules were the only source of both genotypes and phenotypes. Although a vast amount of evidence has been obtained in support of this hypothesis, a few critical demonstrations are lacking. A most crucial one is a demonstration of self-replication of RNA molecule from prebiotic soup. Previously in the Lehman laboratory, it has been demonstrated that a 198-nucleotide molecule derived from the Azoarcus group I intron can self-assemble from up to four fragments of RNA via recombination. Furthermore, the covalent full-length molecules are catalytically …

Biosynthesis Of Marineosin, A Spiroaminal Undecylprodiginine Natural Product, Shaimaa Mohamed Salem

Dissertations and Theses

Marineosins A and B are two spiroaminal-ring containing tripyrrole compounds isolated from the marine actinomycete, Streptomyces CNQ-617, and were found to possess potent and selective cytotoxic activity against leukemia and melanoma. Marineosins belong to the prodiginines class of natural products, examples of which are undecylprodiginine and streptorubin B. Unlike marineosins, prodiginines structures are characterized by the presence of fully conjugated tripyrrole nucleus linked to an alkyl chain (that lacks any oxygen). Cyclic prodiginines arise from an oxidative cyclization of the alkyl chain onto the tripyrrole, a step catalyzed by Rieske-oxygenase like enzymes such as RedG. The biosynthesis of prodiginines is …

Understanding The Emission From Semiconductor Nanoparticles, Beth Ann Manhat

Dissertations and Theses

This dissertation describes the synthesis and characterization of fluorescent semiconductor nanoparticles (NPs) in order to optimize their biomedical utility for imaging and sensing applications. While both direct and indirect bandgap semiconductor NPs have been studied, control over their emission properties vary. Quantum confinement (QC), which primarily controls the emission wavelength of nanosized semiconductors, dictates that as the size of semiconductor NPs decrease, the magnitude of the bandgap increases, resulting in changes in the observed emission wavelength: smaller NPs have a larger bandgap, and thus a bluer emission. However, surface, interfacial, or shell defects can act as non-radiative or radiative recombination …

Evaluation Of The Performance Of Non-Covalent Molecular Mechanical Models For Zn2+ And Mg2+ Metal Ions, Maria Magdalena Kamm

Master's Theses

Computer simulations using molecular dynamics (MD) on classical molecular mechanical

(MM) interatomic potentials can provide valuable information and quantitative

predictions about these systems. In MD calculations binding free energies of ions to

host molecules can be studied if correct ion solvation free energies in aqueous solution

are obtained. However, no MM models exist that parametrize various Zn2+ and

transition metals consistently and consider both structural and thermodynamic data

simultaneously.

The first part of our work focused on MD free energy perturbation (FEP) simulations

to derive MM interaction parameters for Zn2+ and Mg2+ ions in aqueous

solution. To obtain these parameters …

In Situ And Ex Situ Studies Of Molybdenum Thin Films Deposited By Rf And Dc Magnetron Sputtering As A Back Contact For Cigs Solar Cells, K. P. Aryal, H. Khatri, R. W. Collins, S. Marsillac

Electrical & Computer Engineering Faculty Publications

Molybdenum thin films were deposited by rf and dc magnetron sputtering and their properties analyzed with regards to their potential application as a back contact for CIGS solar cells. It is shown that both types of films tend to transition from tensile to compressive strain when the deposition pressure increases, while the conductivity and the grain size decreas. The nucleation of the films characterized by in situ and real time spectroscopic ellipsometry shows that both films follow a Volmer-Weber growth, with a higher surface roughness and lower deposition rate for the rf deposited films. The electronic relaxation time was then …

Magnetic And Orbital Orders Coupled To Negative Thermal Expansion In Mott Insulators, Ca2ru1-Xmxo4 (M = 3d Transition Metal Ion), Tongfei Qi

Theses and Dissertations--Physics and Astronomy

Ca₂RuO₄ is a structurally-driven Mott insulator with a metal-insulator (MI) transition at T_MI = 357K, followed by a well-separated antiferromagnetic order at T_N = 110 K. Slightly substituting Ru with a 3d transition metal ion M effectively shifts T_MI and induces exotic magnetic behavior below T_N. Moreover, M doping for Ru produces negative thermal expansion in Ca₂Ru_1-xM_xO₄ (M = Cr, Mn, Fe or Cu); the lattice volume expands on cooling with a total volume expansion ratio reaching as high as 1%. The onset of the …

Improved Potential Energy Surface Of Ozone Constructed Using The Fitting By Permutationally Invariant Polynomial Function, M. Ayouz, Dmitri Babikov

Chemistry Faculty Research and Publications

New global potential energy surface for the ground electronic state of ozone is constructed at the complete basis set level of the multireference configuration interaction theory. A method of fitting the data points by analytical permutationally invariant polynomial function is adopted. A small set of 500 points is preoptimized using the old surface of ozone. In this procedure the positions of points in the configuration space are chosen such that the RMS deviation of the fit is minimized. New ab initio calculations are carried out at these points and are used to build new surface. Additional points are added to …

Recent Applications Of The Simple Hydrocarbon Cyclooctatetrene As A Starting Material For Complex Molecule Synthesis, Kevin W. Glaeske, William A. Donaldson

Chemistry Faculty Research and Publications

Cyclooctatetraene [COT], a simple non-aromatic cyclic polyene, is capable of undergoing a variety of oxidation and cycloaddition reactions to afford polycyclic structures. In addition, complexation of COT or the cycloaddition products with transition metals facilitates bond formation. Recent developments in the reactivity of COT and application to the synthesis of naturally occurring and non-naturally occurring compounds is reviewed.