Digital Commons Network^™

A Phytochemical Analysis Of Secondary Metabolites In Eupatorium Serotinum, Elise Snow

Theses and Dissertations

Phytochemistry, a subset of Natural Products Chemistry, studies chemically derived products from natural substances. Advances in this field have important applications in medicinal research due to the distinctive and unique properties of natural compounds. All metabolites are produced from the metabolic cycle, which is a pathway that provides energy for the organism. These metabolic compounds vary greatly and are classified based on their function within the organism. Primary metabolites are abundant and contribute to organism growth, development, and maintenance of energy. Secondary metabolites are found in lesser quantity and correlate to natural defense mechanisms. For example, salicylic acid is a …

Molecular Devices For Measuring Weak Solvophobic Interactions And The Development Of Pedagogical Tools For Organic Chemistry Students, Alexander N. Manzewitsch

Theses and Dissertations

The main topics of this dissertation are: 1) the development and discussion of a new molecular balance for measuring alkyl-alkyl interactions in a wide array of organic solvents, 2) the development of linear solvation energy relationships between solvent interaction parameters and solvent accessible surface area (SASA) in CH-arene interactions, and 3) the development of online resources for helping undergraduate students perform organic chemistry mechanisms problems well.

The solvophobic effect, that is the forced association between two solutes due to intermolecular attraction of the solvent molecules, is ubiquitous in organic chemistry and responsible for many significant phenomena thereof. However, there is …

Structural Analysis Of [Ni(Dippe)] Fragment Using Computational Methods, Jennifer L. Sanchez

Theses and Dissertations

The structural analysis of the Nickel (Bisdiisopropylphospino)ethane, also known as [Ni(dippe)H]2, has been heavily studied in our group in collaboration with William D. Jones's group. A computational analysis of the [Ni(dippe)] fragment was performed to determine the structural relationship between the nickel center and its phosphine ligand, due to phosphines having both electronic and steric properties. The reactivity of the Nickel will be most dependent on the dippe ligand. A conformational search generated 244 conformers after a thorough minimization using Molecular Mechanic (MM) calculations where a thorough minimization was performed and then re-minimized using a SEED command until unique conformers …

Gas Phase Structure Characterization Of Host-Guest Systems Using Ion Mobility Spectrometry, Jamir Shrestha

Theses and Dissertations

This dissertation focuses on the investigation of gas-phase characteristics of cucurbituril host-guest systems using ion mobility spectrometry (IMS) and related techniques. Collision cross-sections (CCS) of alkylammonium complexes of cucurbit[n]uril (CB[n]) are measured to understand the allosteric interactions that induce conformational changes in the complex in the presence of metal cations on one of the portals of the cucurbit[6]uril (CB[6]) host. Cationic species on one CB[6] rim sterically force longer linear alkylammonium guests out of the cucurbituril cavity during complex formation. Similarly, rigid cucurbituril-metal complexes were studied using IMS to demonstrate the effect of long-range ion-neutral interactions on the gas phase …

The Chemistry Laboratory Experience Of El Camino Students While In Emergency Remote Teaching Due To The Covid-19 Pandemic, Shaun A. Cook

Theses and Dissertations

Future college environments, including those in chemistry, will entail flexible formats. The pandemic spurred appreciation of the need, and though it has largely passed, adaptability to multiple formats in the future has been a critical part of planning for a rapidly changing future. Experiences during the pandemic will guide pedagogical changes and practices in the future. At El Camino College in Southern California, the chemistry department provided varied laboratory instruction to students during Emergency Remote Teaching. Understanding the experience students had during this extraordinary time is essential. Students who took courses that had an online laboratory course completed a mixed-methods …

Accident Tolerant Fuels Claddings And The Evolution Of Their Surface Characteristics Under Critical Heat Flux, Rajnikant V. Umretiya

Theses and Dissertations

Enhanced Accident Tolerant Fuels (ATFs) systems for light water reactors require higher temperature oxidation resistance in steam environments than the current UO₂ – zirconium fuel system. Investigating the ATF materials’ surface properties is needed as they have evidenced to affect the Critical Heat Flux (CHF), which is an important parameter of the thermal-hydraulic performance required to provide safety margins. In this dissertation, the surface properties of FeCrAl alloys (APMT and C26M), Zircaloy-2, Zircaloy-4, and Cr-coating on Zircaloy-4 substrates produced by Physical Vapor Deposition (PVD) and Cold Spray (CS) were investigated according to their chemistry, topography, and wettability. The static …

Toward Improved Characterization Of Biologically Relevant Isomeric And Isobaric Ions On Mass Spectrometry-Based Platforms, Baku Acharya

Theses and Dissertations

Mass spectrometry has frequently been employed in the analysis of biologically relevant molecules; however, mass spectrometry alone may not always be sufficient for the differentiation and characterization of isomeric and isobaric ions. In this work, infrared multiple photon dissociation (IRMPD) spectroscopy and ion mobility spectrometry (IMS) were evaluated as complementary techniques for the characterization and separation of isomeric and isobaric ions of biological relevance. In the first project, analysis of experimental IRMPD spectroscopy data shows that this technique is useful in the differentiation of hydroxyproline isomers. Absorption bands allow for the differentiation of three isomeric species: 1640 cm-1 (trans-4-hydroxyproline), 1718 …

Computational Chemistry Investigation Of Gas-Phase Structures, Infrared Spectroscopy, And Dissociation Pathways Of Isomeric Molecules, Widana Kaushalya

Theses and Dissertations

While chemical isomers typically have distinct properties, differentiating between them is often an analytical challenge, especially for mass spectrometric methods. Infrared multiple photon dissociation (IRMPD) spectroscopy and ion mobility spectrometry (IMS) can be useful in analysis of such isomeric compounds; however, experimental results alone do not directly provide in-depth structural information. In this thesis, computational chemistry is first used to explain experimental results and understand the conformational preference of the gas phase ions formed from the lithiation of cis-3, cis-4 and trans-4 hydroxyproline isomers and then used in a predictive manner to evaluate IRMPD spectroscopy and IMS as potential paths …

Fundamental Understanding Of Plasma Discharge Formation In Liquid And Multiphase Configurations Through Multiphysics Modeling, Ali Charchi Aghdam

Theses and Dissertations

During the last two decades, non-thermal plasma discharges in and in contact with liquids have received significant attention due to their wide range of applications including chemical analysis, medical, water treatment, fuel processing, etc. Despite the tremendous interest and advances attained in the experimental studies, modeling efforts providing a comprehensive understanding of the underlying physicochemical processes are limited. There is still no unified theory on plasma formation in dense medium and various theories have been proposed such as the presence of bubbles and tunneling which are topics of debate. In the first part of this study, a mathematical model is …

Computational Studies Of High-Oxidation State Main-Group Metal Hydrocarbon C-H Functionalization, Clinton R. King

Theses and Dissertations

High-oxidation state main-group metal complexes are potential alternatives to transition metals for electrophilic C-H functionalization reactions. However, there is little known about how selection of the p-block, main-group metal and ligand impact C-H activation and functionalization thermodynamics and reactivity. Chapter 2 reports density functional theory (DFT) calculations used to determine qualitative and quantitative features of C-H activation and metal-methyl functionalization energy landscapes for reaction between high-oxidation state d10s0 InIII, TlIII, SnIV, and PbIV carboxylate complexes with methane. While the main-group metal influences the C-H activation barrier height in a periodic manner, the carboxylate ligand has a much larger quantitative impact …

The Effectiveness Of Google Classroom In The Self-Contained Chemistry Classroom, Steven J. Gross

Theses and Dissertations

The purpose of this exploratory investigation was to ascertain the effectiveness of Google Classroom in the self-contained Chemistry classroom in terms of student turning in of assignments, student performance on summative assessment, student satisfaction with the use of Google Classroom, student contribution to class discussion in terms of frequency and quality, and the student acceptance of Google Classroom as a system of technology. Results suggest increased growth on summative assessments, turning in of assignments, and less regression in turning in of assignments with the implementation and use of Google Classroom. Results also suggest that the student population performs better through …

Studies On Regulation Of Dihydrotestosterone Binding To And Releasing From The Androgen Receptor, Tahyra M. Resto Santos

Theses and Dissertations

The androgen receptor (AR) is a nuclear receptor that responds to testosterone and 5α-dihydrotestosterone (DHT) by modulating gene expression in a variety of cells, including prostate and muscle tissues. Studies of small molecule interaction with AR have shown diphenyl compounds inhibiting through a binding site labeled Binding Function 3 (BF3). The goal of this research is to analyze the interaction of the BF3 site with DDT and related compounds. Amino acids that are exposed on the surface of the BF3 that might interact with different compounds were mutated. Mutant proteins were tested experimentally for their impact on the inhibition the …

Structure-Activity Relationship Studies Of Synthetic Cathinones And Related Agents, Rachel A. Davies

Theses and Dissertations

Synthetic cathinones and related agents represent an international drug abuse problem, and at the same time an important class of clinically useful compounds. Structure-activity relationship studies are needed to elucidate molecular features underlying the pharmacology of these agents. Illicit methcathinone (i.e., MCAT), the prototype of the synthetic cathinone class, exists as a racemic mixture. Though the differences in potency and target selectivity between the positional and optical isomers of synthetic cathinones and related agents have been demonstrated to have important implications for abuse and therapeutic potential, the two MCAT isomers have never been directly compared at their molecular targets: the …

Quantum Dot Metrics For Preparative Chemistry And Fluorescence Applications, Yi Shen

Theses and Dissertations

Colloidal semiconductor quantum dots (QDs) are considered to be a promising candidate for bio-imaging and solar cells because of their extraordinary photo-physical properties. The ultimate goal of this dissertation is to design a reliable matrix and a reproducible method to prepare QDs-based biocompatible probe for fluorescence applications. Synthesis of quantum dots requires a large amount of ligands to improve the stability at high temperature. However, for further application and surface modification of QDs, excess ligands must be removed. In this dissertation, I will first describe using gel permeation chromatography (GPC) as a media to purify different types of QDs. A …

Stream Energy Impacting Sediment Transport Through Low-Gradient Agricultural Streams, Paula Jane Pryor

Theses and Dissertations

Water quality can be severely impacted by increased sediment transport, particularly agriculturally-dominated systems like those found in central Illinois. Many low-gradient sediment studies focus on the fine material transported in suspension. However, coarse-material transport can be equally important for understanding sediment loads to surficial reservoirs for local drinking water. To address a general gap in knowledge of coarse-sediment transport through agricultural streams, seasonal changes and watershed differences in sediment transport were examined in a low-gradient system. This was accomplished through the installation of bedload traps, scour-fill markers, and bank erosion pins at two streams, Six Mile Creek and Money Creek …

Non-Conventional Approaches To Syntheses Of Ferromagnetic Nanomaterials, Dustin M. Clifford

Theses and Dissertations

The work of this dissertation is centered on two non-conventional synthetic approaches to ferromagnetic nanomaterials: high-throughput experimentation (HTE) (polyol process) and continuous flow (CF) synthesis (aqueous reduction and the polyol process). HTE was performed to investigate phase control between Fe_xCo_1-x and Co_3-xFe_xO_y. Exploration of synthesis limitations based on magnetic properties was achieved by reproducing M_s=210 emu/g. Morphological control of Fe_xCo_1-x alloy was achieved by formation of linear chains using an H_ext. The final study of the Fe_xCo_1-x chains used DoE to …

Synthesis And Utility Of Bis-Urea Macrocycles As Nanoreactors And As Ligands For Metal Organic Materials, Sahan R. Salpage

Theses and Dissertations

“Supramolecular chemistry” powered by non-covalent interactive forces forms the crux in the area of host-guest chemistry. Supramolecular assemblies often have different chemical and physical properties than that of its individual molecular entities and are used to develop novel functional materials. Our expertise involves making functional materials from macrocycles, which contain two urea groups and two rigid C shaped spacer groups. These individual macrocyclic components can self-assemble through hydrogen bonding and other non-covalent interactions to form porous supramolecular assemblies that can be used as confined reaction environments and as ligands to synthesize novel metal organic materials.

This dissertation focuses on studying …

Surface Chemistry And Transport Properties Of Ii-Vi Semiconductor Nanowires, Pravin Paudel

Theses and Dissertations

Semiconductor nanowires have been widely studied due to their unique properties such as width comparable to critical length-scales, high aspect ratio, and high carrier mobility. These unique properties make them a suitable candidate for various optical and electronic devices like photovoltaics, photodetectors, and field effect transistors. The nanowire surface plays an important role in the performance of these devices because of their high surface to volume ratio. The larger surface area of nanowires may provide better charge separation than planar heterostructures in photovoltaics by providing shorter distance to move for carrier before separation, however, presence of surface states may lead …

Elaboration And Design Of Α7 Nachr Negative Allosteric Modulators, Osama I. Alwassil

Theses and Dissertations

α7 Neuronal nicotinic acetylcholine receptors are one of two major classes of receptors responsible for cholinergic neurotransmission in the central nervous system. The existence of α7 neuronal nAChRs in different regions of the nervous system suggests their involvement in certain essential physiological functions as well as in disorders such as Alzheimer’s disease (AD), drug dependence, and depression. This project was aimed toward the discovery and development of small–molecule arylguanidines that modulate α7 nAChR function with improved subtype-selectivity through an allosteric approach. Identifying the required structural features of these small molecules allowed optimization of their negative allosteric modulator (NAM) actions at …

Kinetic Experimental And Modeling Studies On Iron-Based Catalysts Promoted With Lanthana For The High-Temperature Water-Gas Shift Reaction Characterized With Operando Uv-Visible Spectroscopy And For The Fischer-Tropsch Synthesis, Basseem Bishara Hallac

Theses and Dissertations

The structural and functional roles of lanthana in unsupported iron-based catalysts for the high-temperature water-gas shift reaction and Fischer-Tropsch synthesis were investigated. The performance of the catalysts with varying lanthana contents was based on their activity, selectivity, and stability. With regard to the former reaction, extent of reduction of the iron in Fe2O3/Cr2O3/CuO/La2O3 water-gas shift catalysts is a key parameter that was characterized using UV-visible spectroscopy. Minor addition of lanthana (<0.5 wt%) produces more active and stable catalysts apparently because it stabilizes the iron-chromium spinel, increases the surface area of the reduced catalysts, enhances the reduction of hematite to the magnetite active phase, and facilitates the adsorption of CO on the surface of the catalyst modeled by an adsorptive Langmuir-Hinshelwood mechanism. Statistical 95% confidence contour plots of the adsorption equilibrium constants show that water adsorbs more strongly than CO, which inhibits the reaction rate. A calibration curve that correlates the oxidation state of surface iron domains to normalized absorbance of visible light was successfully generated and applied to the water-gas shift catalysts. UV-visible studies indicated higher extent of reduction for surface Fe domains for the catalysts promoted with 1 wt% of lanthana and showed potential to be a more convenient technique for surface chemistry studies than X-ray absorption near edge spectroscopy (XANES). Lanthana addition to iron-based Fischer-Tropsch catalysts enhances the olefin-to-paraffin ratio, but decreases their activity, stability, and selectivity to liquid hydrocarbons. Adding lanthana at the expense of potassium reduces the water-gas shift selectivity and enhances the activity and stability of the catalysts. Finally, a model that simulates heat and mass transfer limitations on the particle scale for the Fischer-Tropsch reaction applicable at lab-scale suggests optimal operating and design conditions of 256°C, 30 bar, and 80 mirons are recommended for higher selectivity to liquid hydrocarbons. The model considers pressure drop, deactivation, pore diffusion, film heat transfer, and internal heat transfer when solving for the optimal conditions, and maps them as functions of design variables. This model can be up-scaled to provide guidance for optimal design of commercial-size reactors.

Molecular Dynamics Simulations Of Pure Polytetrafluoroethylene Near Glassy Transition Temperature For Different Molecular Weights, Rawan Al-Nsour

Theses and Dissertations

Fluoropolymers are employed in countless end-user applications across several industries. One such fluoropolymer is polytetrafluoroethylene. This research is concerned with studying and understanding the thermal behavior of polytetrafluoroethylene. Such understanding is critical to predict its behavior in diverse service environments as the polymer ages and for allowing bottom up design of improved polymers for specific applications.

While a plethora of experiments have investigated the thermal properties of polytetrafluoroethylene, examining these properties using molecular dynamics simulations remains in its infancy. In particular, the current body of molecular dynamics research on polytetrafluoroethylene has primarily focused on studying polytetrafluoroethylene phases, its physical nature, …

Advances In The Electrodeposition Of Aluminum From Ionic Liquid Based Electrolytes, Kirt Leadbetter

Theses and Dissertations

Aluminum plating is of considerable technical and economic interest because it provides an eco-friendly substitute for cadmium coatings used on many military systems. However, cadmium has been determined to be a significant environmental safety and occupational health (ESOH) hazard because of its toxicity and carcinogenic nature. Furthermore, the cost of treating and disposing of generated wastes, which often contain cyanide, is costly and is becoming prohibitive in the face of increasingly stringent regulatory standards. The non-toxic alternative aluminum is equivalent or superior in performance to cadmium. In addition, it could serve to provide an alternative to hexavalent chromium coatings used …

Identification And Differentiation Of Tier 1 Bacterial Agents Using Gas Chromatography-Mass Spectrometry, Dan Li

Theses and Dissertations

A simple method was developed for detection and differentiation of five Tier 1 bacterial agents, including Bacillus anthracis, Francisella tularensis, Yersinia pestis, Burkholderia pseudomallei and Burkholderia mallei as well as their closely related near neighbors by gas chromatography-mass spectrometry (GC-MS). Generally, different classes of compounds can be used as biomarkers for biowarfare agent detection, including nucleic acids (i.e., DNA or RNA), proteins (i.e., antibodies), carbohydrates (i.e., sugars), lipopolysaccharides, lipids (i.e., fatty acids) and small molecules. One-step thermochemolysis (TCM) was developed to provide GC-MS detectable biomarker signatures, including sugars, fatty acids and small molecules. Solid phase micro-extraction (SPME) was used for …

Designing Direct And Indirect Factor Xa Inhibitors, Rami Al-Horani

Theses and Dissertations

Anticoagulants are the basis for treatment and prevention of thrombotic diseases. The currently available medicines are associated with a wide range of adverse reactions that mandates developing new anticoagulants. Several lines of evidence support the superiority of factor Xa (FXa) as a promising target to develop novel anticoagulants. This work focuses on the design of direct and indirect FXa inhibitors using an interdisciplinary approach. As indirect FXa inhibitors, a focused library of tetrasulfated N–arylacyl tetrahydroisoquinoline (THIQ) nonsaccharide allosteric antithrombin activators was designed, synthesized, and biochemically evaluated to establish their structure–activity relationship (SAR). An N–arylacyl THIQ analog having carboxylate at position–3, …

Ferritin Diversity: Mechanistic Studies, Disease Implications, And Materials Chemistry, Robert Joseph Hilton

Theses and Dissertations

The study of ferritin includes a rich history of discoveries and scientific progress. Initially, the composition of ferritin was determined. Soon, it was shown that ferritin is a spherical, hollow protein. Eventually, over several decades of research, the structure and some function of this interesting protein was elucidated. However, the ferritin field was not completely satisfied. Today, for example, researchers are interested in refining the details of ferritin function, in discovering the role of ferritin in a variety of diseases, and in using ferritin for materials chemistry applications. The work presented in this dissertation highlights the progress that we have …

What Happens To Student Engagement And Understanding Of Chemistry When Cross-Curricular Activities And Assignments Are Used In An Honors Chemistry Class?, Heather L. Keller

Theses and Dissertations

The focus of this action research study was to determine if cross-curricular learning strategies could be used in a chemistry class to increase both student engagement and understanding of chemistry content. Two strategies were implemented in an honors chemistry course of sophomores and juniors. Participants were chosen on a voluntary basis, those students who chose not to participate still needed to complete the activities, however, their grades and responses were not included in the data. Participating students were required to complete a consent form and obtain parental permission. Students completed a creative writing activity and a kinesthetic activity in which …

Increasing Student Achievement With Cooperative Learning, Curriculum Changes, And Portfolio Assessment, Lois S. Allen

Theses and Dissertations

The purpose of this project was to determine if student achievement could be approved by curriculum changes within a cooperative learning framework and the use of portfolio assessment. Students in two classes were involved in the study. Both classes received the same instruction, worksheet and quizzes. In addition, one class worked individually to complete the worksheets to prepare for weekly quizzes. The other class used the cooperative learning technique - Student Teams Achievement Divisions. The cooperative learning students worked in groups of four to complete the worksheets to prepare for the weekly quizzes. The goal was to have everyone in …

Introduction To The Fundamentals Of Chemistry, Rose C. Knowles

Theses and Dissertations

This thesis designs a curriculum to fulfill the charter of the Community college in providing an opportunity for an individual student whether traditional or non-traditional to prepare to become more proficient in chemical understanding and be able to apply the concepts and knowledge taught to a career or advanced study. The curriculum should benefit those individuals who either lack or have a poor background in chemistry and strengthen their reasoning ability. This paper presents a comprehensive comparison of textbooks currently being published for introductory chemistry. Texts reviewed were readily found on library shelves and supplied through major distributors; chemical journals …

Groundwater Of The Spiritwood Lake Area, Stutsman County, North Dakota, Frank J. Schulte

Theses and Dissertations

The Spiritwood Lake study area is in a generally undulating to rolling glacial plain 17 miles north and east of Jamestown, North Dakota. Spiritwood Lake is about 50 feet below the surface of the bedrock plain in a former melt-water channel. In the study area, glacial drift unconformably overlies the Pierre Shale, the youngest pre-Pleistocene sediment. The boundary between the two units is marked by a zone of shattered Pierre Shale. The top of this shattered zone forms a plain of moderate relief which probably was the preglacial surface of the study area.

Two large valleys can be distinguished in …

Collector-Depressant Equilibria For The Flotation System Potassium Ethyl Xanthate-Potassium Cyanide-Molybdenite, Connell Bolton Roberts

Theses and Dissertations

This dissertation involves a study of the collector-depressant equilibria of the flotation system potassium ethyl xanthate-potassium cyanide-molybdenite, based upon mineral-air bubble contact measurements made by a modified captive bubble technique. The Cook theory of single site free acid adsorption is used to interpret the data. The standard free energies of adsorption of ethyl xanthic acid and hydrocyanic acid on molybdenite are calculated.