Chemistry Commons^™

Studies Directed Towards The Iridium Catalyzed Synthesis Of New Carbon-Nitrogen Bonds., Maria Lindsay

LSU New Orleans Theses and Dissertations

Amines are ubiquitous in nature and serve a variety of functions in living organisms. Because of this fact amines are of great biological and pharmaceutical interest. The iridium catalyst (pentamethylcyclopentadienyl) iridium dichloride dimer ([Cp*IrCl₂]₂) has been used in a number of ways to synthesize new carbon-nitrogen bonds. These studies were directed toward the development of a method for the iridium catalyzed N-alkylation of alpha-amino acid esters as well as the development of a strategy for synthesis of the natural product 275A.

We have optimized a method for the N-alkylation for alpha-amino acid esters. Using this …

Development Of Luminescent Quantum Dot-Enabled Nano- And Microplatforms For Multiplex Detection Of Biomarkers, Kristen S. Williams

LSU New Orleans Theses and Dissertations

Luminescent semiconductor quantum dots (QDs) are extensively researched for use in biological applications. They have unique optical and physical properties that make them excellent candidates to replace conventional organic dyes for cellular labeling, multiplexing, nucleic acid detection, and as generalized probes. The primary focus of this dissertation was to utilize quantum dots for improvement in immunoassays. Specifically, atherosclerosis biomarkers were detected simultaneously in an effort to demonstrate advances in early detection diagnostics.

Quantum dot-antibody bioconjugates were prepared by encapsulation into mesoporous silica and functionalized with thiol and amine groups to enable bioconjugation. Functionalization of the mesoporous silica quantum dot composites …

Design And Fabrication Of Nanostructures For The Enhancement Of Photovoltaic Devices, Richard M. Prevost Iii

LSU New Orleans Theses and Dissertations

In 2012 the net world electricity generation was 21.56 trillion kilowatt hours. Photovoltaics only accounted for only 0.1 trillion kilowatt hours, less than 1 % of the total power. Recently there has been a push to convert more energy production to renewable sources. In recent years a great deal of interest has been shown for dye sensitized solar cells. These devices use inexpensive materials and have reported efficiencies approaching 12% in the lab. Here methods have been studied to improve upon these, and other, devices. Different approaches for the addition of gold nanoparticles to TiO₂ films were studied. These …

C(Sp2)–H Functionalizations Employing 2-Aminophenyl-1h-Pyrazole As A New Removable Directing Group, Wan-Chen Lee

Master's Theses

2-Aminophenyl-1H-pyrazole (2-APP) was discovered as a novel removable bidentate directing group for copper-mediated aerobic oxidative C(sp2)–H bond amidation and sulfonamidation bearing a wide range of sulfonamides, When Cu(OAc)2 was employed as the copper source, 1,1,3,3-tetramethylguanidine (TMG) as an organic base, the reaction, optimally carried out overnight in DMSO at 80 °C in open air, produced a variety of products in moderate to excellent yields. In addition, C(sp2)–H bond chlorination has been developed by using this auxiliary, employing trichloroacetamide as a new chlorine source. Furthermore, this unprecedented directing group also can assist copper-mediated regio-selective hydroxylation, and ortho-alkynylation/annulation by using Cu(OAc)2 as …

Cancer Cell Spheroids Are A Better Screen For The Photodynamic Efficiency Of Glycosylated Photosensitizers, Patrícia M. R. Pereira, Naxhije Berisha, N.V.S. Dinesh K. Bhupathiraju, Rosa Fernandes, João P.C. Tomé, Charles Michael Drain

Publications and Research

Environmental remediation requires ion-selective polymers that operate under a wide range of solution conditions. In one example, removal of trivalent and divalent metal ions from waste streams resulting from mining operations before they enter the environment requires treatment at acidic pH. The monoethyl ester phosphate ligands developed in this report operate from acidic solutions. They have been prepared on polystyrene-bound ethylene glycol, glycerol, and pentaerythritol, and it is found that intraligand hydrogen bonding affects their metal ion affinities. The affinity for a set of trivalent (Fe(III), Al(III), La(III), and Lu(III)) and divalent (Pb(II), Cd(II), Cu(II), and Zn(II)) ions is greater …

Regioselective Baeyer–Villiger Oxidation Of Lignin Model Compounds With Tin Beta Zeolite Catalyst And Hydrogen Peroxide, John Adam Jennings, Sean R. Parkin, Eric Munson, Sean Delaney, Julie L. Calahan, Mark Isaacs, Kunlun Hong, Mark Crocker

Chemistry Faculty Publications

Lignin depolymerization represents a promising approach to the sustainable production of aromatic molecules. One potential approach to the stepwise depolymerization of lignin involves oxidation of the benzylic alcohol group in β-O-4 and β-1 linkages, followed by Baeyer–Villiger oxidation (BVO) of the resulting ketones and subsequent ester hydrolysis. Towards this goal, BVO reactions were performed on 2-adamantanone, a series of acetophenone derivatives, and lignin model compounds using a tin beta zeolite/hydrogen peroxide biphasic system. XRD, ¹¹⁹Sn MAS NMR spectroscopy, DRUVS and XPS were used to determine tin speciation in the catalyst, the presence of both framework Sn and extra framework …

The Effect Of Diffusive Transport On Mineral Carbonation In Geologic Carbon Sequestration, Wei Xiong

McKelvey School of Engineering Graduate Student Theses & Dissertations

Geologic carbon sequestration (GCS) is an effective method to mitigate environmental problems due to excessive anthropogenic CO2 emissions. It involves injecting supercritical CO2 into deep geologic formations in which CO2 will ultimately be converted to solid carbonate minerals. Basalt is a promising host rock that is rich in the divalent cations Ca, Mg and Fe that are important for mineral trapping of CO2. Fractures and pores in basalt reservoirs provide substantial surface area for geochemical reactions during carbon sequestration. The transport in fractures and pores is controlled by diffusion. The coupling of diffusive transport and geochemical reactions leads to carbonate …

Mapping Analyte-Signal Relations In Lc-Ms Based Untargeted Metabolomics, Nathaniel Guy Mahieu

Arts & Sciences Graduate Student Theses and Dissertations

The goal of untargeted metabolomics is to profile metabolism by measuring as many metabolites as possible. A major advantage of the untargeted approach is the detection of unexpected or unknown metabolites. These metabolites have chemical structures, metabolic pathways, or cellular functions that have not been previously described. Hence, they represent exciting opportunities to advance our understanding of biology. This beneficial approach, however, also adds considerable complexity to the analysis of metabolomics data - an individual signal cannot be readily identified as a unique metabolite. As such, a major challenge faced by the untargeted metabolomic workflow is extracting the analyte content …

Nuclear Spin Alignment In Optically Pumped Semiconductors, Matthew M. Willmering

Arts & Sciences Graduate Student Theses and Dissertations

Nuclear magnetic resonance (NMR) has shown its ability to be a very informative analytical technique due to the ability to measure very small changes in the energy splittings due to the nuclei’s local environment. However, this ability is hindered by the low sensitivity of the experiment. Many methods have been postulated and implemented to enhance the sensitivity of NMR experiments; one of which is optically pumped NMR (OPNMR). In this dissertation, the usefulness and potential applications of OPNMR are presented. First, a doubly resonant OPNMR probe was fabricated in order to complete more advanced NMR techniques while optically pumping the …

Oxidative C-C Bond Formation Reactivity Of High Valent Nickel And Palladium Complexes, Michael Benjamin Watson

Arts & Sciences Graduate Student Theses and Dissertations

The development of both palladium and nickel catalysis over the past several decades has led to the ability to perform a multitude of C-C coupling, C-Heteroatom coupling, and C-H functionalization reactions. These reactions typically utilize a catalytic cycle involving Pd0/II/IV and Ni0/II. While using these types of catalytic cycles one can create a multitude of different hard to make bonds, it is always important to keep expanding what we view as potential catalytic intermediates to keep developing new cycles capable of new transformations. One such way to expand our knowledge of these catalytic cycles is to look at the oxidation …

Apparent Retention Volume Variation With Flow Rate Change In High Performance Liquid Chromatography, Susanne Buntz Erz

Seton Hall University Dissertations and Theses (ETDs)

Recent studies have demonstrated noticeable flow rate dependency of the chromatographic zone retention volume with respect to migration within the empty capillary. This appears to be the result of superposition of asymmetric lateral diffusion and of the laminar flow profile. Although these effects have been studied on empty capillaries, in the presence of the packed column, the retention shift may be insignificant relative to the adsorption-based retention of the analytes. In the case of fast and ultrafast HPLC with short capillary columns, the effect of extra-column caused variation in the analyte retention may constitute an increase of up to 120 …

Study Of Selectivity In Extraction, Separation, And Detection On Drugs Using Gas Chromatography, Anumeha P. Muthal

Seton Hall University Dissertations and Theses (ETDs)

The selectivity of a method is defined by its ability to determine a particular analyte without interference in a complex mixture. Selectivity in gas chromatography (GC) can be obtained at different points in the analysis including the sample preparation, sample introduction, separation on column and detection. In GC, the first dimension of selectivity can be obtained in sample preparation; the second dimension in chromatographic separation and the third dimension in detection. This research focuses on the relationships between selectivity in these different dimensions, studied using some non-steroidal anti-inflammatory drugs, glucocorticoids, fatty acid methyl esters and polycyclic aromatic hydrocarbons. Recent methodologies …

Understanding The Dynamic Process Of Dissolution Using In-Situ Ft-Ir Spectroscopy, Vrushali M. Bhawtankar

Seton Hall University Dissertations and Theses (ETDs)

Dissolution studies provide valuable and critical drug release information (in vitro) that are important for quality control drug development. Using in-situ FT-IR spectroscopy methods has been developed for analyzing and monitoring dissolutions of pharmaceutical APIs. The accuracy of this technique was found to be ± 3% relative to HPLC and UV/Vis Spectroscopy. A dynamic analysis of the dissolution and subsequent hydrolysis of aspirin has been determined by in-situ FT-IR. This technique allows real-time analysis of the behavior of aspirin under simulated physiological conditions (pH 1.2, 4.5, 6.8) as aspirin (1205 cm^-1) and salicylic acid (1388 cm^-1) …

Synthesis Of Pyranobenzopyrans, Sumiea B. Eltayeb

Seton Hall University Dissertations and Theses (ETDs)

Carbohydrates and their derivatives are involved in a wide array of biological processes and are crucial for the survival of living entities. As a result, sugar-based compounds have become attractive scaffolds for drug design. In addition, pyranobenzopyran derivatives have shown promise in the treatment of numerous health conditions such as anticoagulants, antifungal, and anti-inflammatory agents. They have also shown important properties as antibiotics anti-AIDS agents) and antitumor drugs. The main point of our research was to determine and develop a synthetic method for the preparation of pyranobenzopyrans and carbohydrate fused heterocyclic compounds. This was accomplished via a [4+2] cycloaddition reaction …

Mass Spectrometry-Based Structural Analysis Of Photosynthetic Protein Assemblies, Yue Lu

Arts & Sciences Graduate Student Theses and Dissertations

This dissertation focuses on using mass spectrometry-based techniques to study photosynthetic protein assemblies. Photosynthesis is a process that converts light energy into chemical energy, the basis of most life on Earth. The two most crucial protein machineries involved in this process are reaction center and light harvesting complexes. They are usually giant protein complexes with different numbers of co-factors. In a more expanded sense, photosynthesis is not just about the utilization of solar energy, the regulation of light energy is also essential as excess light energy is detrimental to photosynthesis organisms. Again, protein assemblies play an indispensable role in this …

Tissue Damage Quantification In Alzheimer's Disease Brain Via Magnetic Resonance Gradient Echo Plural Contrast Imaging (Gepci), Yue Zhao

Arts & Sciences Graduate Student Theses and Dissertations

Alzheimer’s disease (AD) affected approximately 48 million people worldwide in 2015. Its devastating consequences have stimulated an intense search for AD prevention and treatment. Clinically, AD is characterized by memory deficits and progressive cognitive impairment, leading to dementia. Over the past two to three decades, researchers have found that amyloidbeta (Aβ) plaques and neurofibrillary tau tangles occur during a long pre-symptomatic period (preclinical stage) before the onset of clinical symptoms. As a result, identification of the preclinical stage is essential for the initiation of prevention trials in asymptomatic individuals. Currently, Positron Emission Tomography (PET) imaging with injected 11C or 18F …

Surface Mutation Thr34his Facilitates Purification Of Haemophilus Influenza Carbonic Anhydrase Via Metal Affinity Chromatography, Caroline Foley, Dr. Kathleen Cornely

Chemistry & Biochemistry Student Scholarship

In order to pursue Haemophilus influenza carbonic anhydrase (HICA) as a potential drug target, easy and efficient purification methods must be developed. While immobilized metal affinity chromatography (IMAC) may be used, complications with polyhistidine tags is a concern. Inspired by the endogenous metal affinity of Escherichia coli β-carbonic anhydrase (ECCA), we suggest that the generation of histidine clusters on HICA’s surface will facilitate its purification by metal affinity chromatography without the potential interference of His-tags. Here we investigate the Thr34His mutation as a method to generate metal affinity in HICA. Since Thr34His is located only 5.3 Å away from His32, …

Universal Disorder In Organic Semiconductors Due To Fluctuations In Space Charge, Tzucheng Wu

Physics & Astronomy ETDs

This thesis concerns the study of charge transport in organic semiconductors. These materials are widely used as thin-film photoconductors in copiers and laser printers, and for their electroluminescent properties in organic light-emitting diodes. Much contemporary research is directed towards improving the efficiency of organic photovoltaic devices, which is limited to a large extent by the spatial and energetic disorder that hinders the charge mobility. One contribution to energetic disorder arises from the strong Coulomb interactions between injected charges with one another, but to date this has been largely ignored. We present a mean-field model for the effect of mutual interactions …

Adsorption And Wetting In Model Mesoporous Silicas And In Complex Metal Oxide Catalysts, Karthik Jayaraman

Seton Hall University Dissertations and Theses (ETDs)

The surface of most metal oxides is covered by hydroxyl groups which influence many surface phenomena such as adsorption and wetting, catalysis and surface reactions. Surface chemistry of silica is a subject of exhaustive studies owing to a wide variety of practical applications of silica. In Chapter 1, a brief review of classification, synthesis and characterization of silica is provided. The hydroxylation of silica surface i.e the number of hydroxyl (-OH) groups on the surface is of utmost importance for its practical applications. In Chapter 2, a brief introduction to surface hydration of silica is provided followed by the gas …

Graphene Nanoribbons And Their Polymeric Nanocomposites: Controlled Synthesis, Characterization And Applications, Nada M. Aljehany

Electronic Theses & Dissertations

Carbon based materials are very promising as electrode materials energy generation and storage devices. They have been used for fuel cells, supercapacitors and solar cells. Among the carbon-based materials, graphene is very attractive due to its unique properties such as high electrical conductivity, good mechanical flexibility, large theoretical surface area (2630 m²/g), and high thermal and chemical stability. These unique properties make them very suitable for energy storage applications particularly for supercapacitors. The performance of the graphene as energy storage material could be further improved by growing them in nanoribbon form by unzipping carbon nanotubes. In this thesis, …

High-Resolution Three-Dimensional Nmr Structure Of The Kras Proto-Oncogene Promoter Reveals Key Features Of A G-Quadruplex Involved In Transcriptional Regulation, A. Kerkour, J. Marquevielle, S. Ivashchenko, Liliya A. Yatsunyk, J.-L. Mergny, G. F. Salgado

Chemistry & Biochemistry Faculty Works

Non-canonical base pairing within guanine-rich DNA and RNA sequences can produce G-quartets, whose stacking leads to the formation of a G-quadruplex (G4). G4s can coexist with canonical duplex DNA in the human genome and have been suggested to suppress gene transcription, and much attention has therefore focused on studying G4s in promotor regions of disease-related genes. For example, the human KRAS proto-oncogene contains a nuclease-hypersensitive element located upstream of the major transcription start site. The KRAS nuclease-hypersensitive element (NHE) region contains a G-rich element (22RT; 5′-AGGGCGGTGTGGGAATAGGGAA-3′) and encompasses a Myc-associated zinc finger-binding site that regulates KRAS transcription. The NEH region …

In The Tristate Area Consisting Of Kansas, Missouri, And Oklahoma, A Local And State Level Comparison Of High School Chemistry Prerequisites, High School Chemistry Instructor Preparation, And The Readiness Of A High School Student For College Chemistry, Greg Howard

Electronic Theses & Dissertations

The purpose of this thesis is to create an awareness among secondary and post-secondary instructors as to the student’s preparation in high school Chemistry I and the student’s readiness for General Chemistry I in college for a tristate area consisting of Kansas, Missouri, and Oklahoma. Student preparation in this research included chemistry I course prerequisites, high school chemistry teacher qualifications including preparation, and student exposure to rigorous science and math course patterns in high school as these relate to college readiness.

Data was gathered from a local cohort group consisting of high schools in Southeast Kansas (SEK), Southwest Missouri (SWM), …

Facile Synthesis And Characterization Of Graphene Nanoribbons/Polypyrrole Nanocomposite, Johara A. Al Dream

Electronic Theses & Dissertations

Carbon is present in various forms such as coal, carbon nanotubes, graphene, diamond etc. Among various forms, carbon nanotubes and graphene have attracted considerable research attention due to their high thermal stability, high mechanical strength and electrical conduction. These properties largely depend on synthesis procedure. In this work, we synthesized graphene nanoribbons using carbon nanotubes for nanocomposites with polypyrrole. Chemical oxidation was used to unzip the carbon nanotubes. These graphene nanoribbons were used to fabricate nanocomposites with polypyrrole for energy storage applications. The synthesized nanocomposites were structurally and electrochemically characterized.

The structural characterization was performed using X-ray diffraction, FT-IR, SEM, …

Use Of Decahydrodecaborate As Flame Retardants In Polyurethanes, Austin W. Bailey

Electronic Theses & Dissertations

There is a growing need for non-halogenated flame retardants due to the toxicity and environmental impacts that are exhibited by current ones. The polyurethane industry is one that has expressed a need for flame retardants in many of its industrial and commercial applications. For these reasons, two different decaborate compounds, tetramethyl and tetrabutyl ammonium decahydrodecaborate, were synthesized and incorporated into polyurethane films for testing. The compounds were characterized using Fourier Transform Infrared (FT-IR) spectroscopy, Proton-Nuclear Magnetic Resonance (¹H-NMR) spectroscopy, Carbon-Nuclear Magnetic Resonance (¹³C-NMR) spectroscopy, and Boron-Nuclear Magnetic Resonance (¹¹B-NMR) spectroscopy. The compounds were incorporated …

One-Pot Syntheses And Characterizations Of “Click-Able” Polyester Polymers For Potential Biomedical Applications, James F. Beach Ii

Electronic Theses & Dissertations

In this study, a synthetic polyester polymer was designed using polyethylene glycol, sorbitol, glutaric acid and 4-pentynoic acid as monomers. The synthesis was carried out using standard melt polymerization technique and catalyzed by Novozyme-435, an enzyme suitable for polyesterification of biocompatible compounds. The progress of the reaction was monitored with respect to time and vacuum exposure, with samples being subjected to standard characterization protocols. Polymers with high molecular weight and water solubility were chosen for further modification into folate-functionalized polymeric nanoparticles for targeted drug delivery to cancer cells. This was achieved by employing a solvent diffusion method, wherein the polymer …

Sulfurization Of Nanostructured Cobalt Oxide For Energy Storage Applications, Samiyah Fahad Aloqayli

Electronic Theses & Dissertations

Development of energy storage devices with high energy performance, power density, fast charge-discharge capability and long cyclability is needed to meet the increasing demand for energy, power and environmental protection in our daily life. Supercapacitors have great potential in future energy storage devices with magnificent properties. Recently, researchers have shown great progress for the improvement of supercapacitor performance by fabrication of nanostructured transition metal chalcogenides materials. One of the main objectives of this thesis is to synthesize nanostructured cobalt oxide and then converte them to cobalt sulfide using a facile hydrothermal method. The synthesized cobalt oxide and cobalt sulfide were …

Biowaste Derived Rigid Polyurethane Foams And Supercapacitors: A Renewable And Sustainable Alternative For Petrochemicals, Charith K. R. Akurana Gamaralalage

Electronic Theses & Dissertations

Bio-based polyol for rigid polyurethane (PU) foams and porous structured carbon as an electrode material for supercapacitors were synthesized from readily available biowaste precursor (orange peel) as an alternative to currently used petroleum-based starting materials. Synthesized bio-based polyols were characterized using FTIR, GPC, hydroxyl number, and viscosity measurements. These analyses indicated that intended bio-based polyol was obtained via thiol-ene chemistry with a high yield. Rigid PU foams prepared from bio-based polyol exhibited density around 35 kg/m³, maintained a regular cell structure with uniform cell distribution, closed cell content over 90%, and excellent compressive strength of ~230 kPa, suggesting …

Molecularly Targeted Nanomedicine: Role Of Hsp90 Inhibitor And Sophorolipids In The Treatment Of Lung Cancer, Shuguftha Naz Ms

Electronic Theses & Dissertations

Lactonic sophorolipids (LSL) are a class of enzymatically modified glycolipids known to have HDAC inhibition activity and anticancer properties. Ganetespib (GT), an Hsp90 inhibitor, is known for its superior antitumor activity in several K-RAS mutant Non-Small-Cell Lung Cancer (NSCLC) cells. In this study, a new anti-oxidant nanoplatform is formulated using the combination of these two drugs, LSL and GT, in order to target both HDAC inhibition and Hsp90 signaling pathways in NSCLC. Nanoceria (NC) is an excellent redox platform will be specifically used to supplement the therapeutic potency of these drugs in the effective treatment of NSCLC. We hypothesized that …

Synthesis And Characterization Of Molybdenum Sulfide And For Hydrogen Evolution Reaction And Supercapacitor Applications, Zhuo Wang

Electronic Theses & Dissertations

To meet the constantly rising requirement of energy other than traditional fossil fuel and environment protection, it is a perfect time to development low cost, and efficient materials for clean energy production. Hydrogen generation by water splitting is one of the cleanest ways to produce cheaper energy. Hydrogen evolution reaction (HER) is one of the key steps in water splitting process. Ideally, the thermodynamic potential for HER should be at 0 V (vs. SHE). However, without an efficient catalyst, this reaction occurred at higher potential, called overpotential. A good HER catalyst is needed to lower the overpotential and hence to …

Real-Time Atomistic Observation Of Structural Phase Transformations In Individual Hafnia Nanorods, Bethany M. Hudak, Sean W. Depner, Gregory R. Waetzig, Anjana Talapatra, Raymundo Arroyave, Sarbajit Banerjee, Beth S. Guiton

Chemistry Faculty Publications

High-temperature phases of hafnium dioxide have exceptionally high dielectric constants and large bandgaps, but quenching them to room temperature remains a challenge. Scaling the bulk form to nanocrystals, while successful in stabilizing the tetragonal phase of isomorphous ZrO₂, has produced nanorods with a twinned version of the room temperature monoclinic phase in HfO₂. Here we use in situ heating in a scanning transmission electron microscope to observe the transformation of an HfO₂ nanorod from monoclinic to tetragonal, with a transformation temperature suppressed by over 1000°C from bulk. When the nanorod is annealed, we observe with …