Chemistry Commons^™

Adsorption Of Polyisobutylene-Based Dispersants Onto Carbon Black, Travis Paul Holbrook

Dissertations

The formation of carbonaceous by-products (e.g. soot) during the operation of an internal combustion engine is unavoidable and the aggregation of this soot leads to deleterious effects including abrasive wear of the engine, increased oil viscosities, and sludge deposition. Dispersants, which are composed of a hydrophobic tail and a polar headgroup, are used as oil additives to aid in the suspension and stabilization of the soot particles. Polyisobutylene succinimide (PIBSI) is the most well-studied class of dispersants and is characterized by a linear architecture and polyamine headgroup that interacts with soot by acid-base and dipole-dipole interactions. As such, there remains …

The Antimicrobial Activity And Cellular Targets Of Plant Derived Aldehydes And Degradable Pro-Antimicrobial Networks In Pseudomonas Aeruginosa, Yetunde Adewunmi

Dissertations

Essential oils (EOs) are plant-derived products that have been long exploited for their antimicrobial activities in medicine, agriculture, and food preservation. EOs represent a promising alternative to conventional antibiotics due to the broad-range antimicrobial activity, low toxicity to human commensal bacteria, and the capacity to kill microorganisms without promoting resistance. Despite the progress in the understanding of the biological activity of EOs, many aspects of their mode of action remain inconclusive. The overarching aim of this work was to address these gaps by studying molecular interactions between antimicrobial plant aldehydes and the opportunistic human pathogen Pseudomonas aeruginosa. We initiated …

Alkalinity And Mineral Concentration Estimation In Commercial Drinking Water, Holly Mills

Honor’s College Freeman Research Journal

Several aspects of water and water quality were reviewed and investigated in this study; the effects of dehydration on human health, the role of alkalinity in drinking water, and the actual levels of alkalinity and other minerals in commercial drinking water. Hydration plays a critical role in human physical performance as well as in the prevention of chronic diseases. This experiment was conducted to determine if the level of acidity ( or alkalinity) of commercial alkaline water are truly above the normal ph levels, and to identify the salts in each type of water. Based on researches, a more alkaline …

Characterization Of The Dimerization Domains On The Mannose-6-Phosphate/Insulin-Like Growth Factor Ii Receptor, Tyler Degener

Theses/Capstones/Creative Projects

The mannose-6-phosphate/insulin-like growth factor II (M6P/IGF2) receptor is a transmembrane protein known to sequester growth factors from the extracellular matrix. This behavior suggests a mechanism of tumor suppression. Structurally, the receptor’s extracellular region is segmented into 15 homologous repeats, which are divided further into 5 triplet domains, labelled 1-3, 4-6, 7-9, 10-12, and 13-15. What is notable about the triplets is their propensity to form dimers with triplets on a second M6P/IGF2 receptor. In fact, previous studies indicate that this protein functions optimally when dimerized. Thus, the purpose of this experiment is to characterize these domain interactions. Using a urea …

Advances In Liquid Chromatography And Liquid Chromatography- Mass Spectrometry For The Chiral Analysis Of Amino Acids And Differentiation Of Isomeric Amino Acid Residues In Peptides/Proteins From Complex Matrices, Siqi Du

Chemistry & Biochemistry Dissertations - Archive

Amino acids are essential building blocks in all living organisms. Initially it was believed that only L-amino acids were relevant in higher organisms, and D-amino acids were laboratory artifacts. Today, various D-amino acids have been detected in different organisms, including humans, and some even play essential roles in biological processes. In addition, abnormal D-amino acid levels have been reported in patients with different diseases. The variations in D-amino acid levels might be of some diagnostic value. However, our knowledge of D-amino acids remains limited and most of the D-amino acids are not well investigated due to the lack of a …

Direct Functionalization Of Inert C-H And C=C Bonds Using Copper And Zinc Catalysts Supported By Fluorinated Ligands, And The Chemistry Of Fe(Co)5 And Its Analogs With Coinage Metal Ions, Tharun Teja Ponduru

Chemistry & Biochemistry Dissertations - Archive

Transition-metal catalyzed direct functionalization of inert C-H and C=C bonds through nitrene- and oxo-transfer reactions are powerful and attractive synthetic strategies for constructing C-N and C-O bonds (e.g. found in amines, aziridines, alcohols, and carbonyl compounds) directly from hydrocarbon feedstocks, and have significant synthetic potential in chemical processes leading to natural products, pharmaceuticals and biologically active molecules. Chapters 2 and 3 of this work mainly focus on nitrene- and oxo-insertion chemistry catalyzed by transition metal complexes. We employed different types of fluorinated ligands to support copper and zinc metal centers. Therefore, complexes [HB(3,5-(CF3)2Pz)3]Cu(NCMe), [H2B(3,5-(CF3)2Pz)2]Cu(NCMe), [H2B(3,5-(CF3)2-4-(NO2)Pz)2]Cu(NCMe), [{(3,5-(CF3)2Pz)ZnEt}2(μ-THF)], [{(3-(CF3),5-(t-Bu)Pz)ZnEt}2(μ-THF)], [{(3,5-(i-Pr)2Pz)ZnEt}2(μ-THF)], [N{(CF3)C(C6F5)N}2]CuNCCH3, and …

Systematic Approach To On-Line Supercritical Fluid Extraction – Supercritical Fluid Chromatography – Tandem Mass Spectrometry Method Development, Alison Paige Wicker

Chemistry & Biochemistry Dissertations - Archive

Coupling supercritical fluid extraction (SFE) on-line with supercritical fluid chromatography (SFC) – tandem mass spectrometry (MS/MS) provides a platform for extraction, separation, and detection in a single analysis. Utilization of this technique simplifies sample preparation while limiting sample loss and/or contamination and significantly decreases total analysis time. SFE-SFC-MS/MS requires consideration of many extraction and chromatographic variables to not only provide the most efficient extraction, but to analytically transfer the extracted analytes to the column for separation. There is a fundamental lack of understanding of how the variables in SFE affect those in SFC. In the first study, on-line SFE-SFC-MS/MS was …

High Confidence Identification Of Cross-Linked Peptides By Mass Spectrometry Cleavable Cross-Linking Technologies, Jayanta Kishor Chakrabarty

Chemistry & Biochemistry Dissertations - Archive

Mass spectrometry (MS)-based chemical cross-linking technique is a potential tool for understanding the protein structure and protein-protein interactions. However, low abundances of cross-linked products and the data complexity are the major challenges in this field. New strategies are required to pinpoint cross-linked peptides with high confidence. Our lab designed and synthesized a novel cross-linker with two differential MS-cleavable bonds, namely DUCCT. DUCCT-cross-linked peptide generates different diagnostic fragment ions in Collision Induced Dissociation (CID) and Electron Transfer Dissociation (ETD) (tandem mass spectrometric technique) which helps in the unambiguous identification of cross-linked peptide. We demonstrate the efficiency of DUCCT technology with model …

Oxygen Deficient Perovskites: Effect Of Structure On Electrical Conductivity, Magnetism And Electrocatalytic Activity., Ram Krishna Hona

Electronic Theses and Dissertations

The present thesis deals with the synthesis and study of the physico-chemical properties of perovskite based oxide materials. Several novel oxygen deficient perovskites (ODP) have been synthesized by conventional solid state synthesis method. The novel compounds are CaSrFe₂O_6-δ, CaSrFeCoO_6-δ, Ca₂Fe_1.5Ga_0.5O₅, CaSrFeGaO₅ and BaSrFe₂O₅. Their magnetic, charge transport and electrocatalytic properties have been studied. Structural effect on electrical conductivity, magnetic and electrocatalytic properties have been studied in some series of ODPs. CaSrFe₂O_6-δ, CaSrFeCoO_6-δ, Ca₂Fe …

Laser Spectroscopic Investigations Of Organic Alkoxy And Peroxy Radicals., Md Asmaul Reza

Electronic Theses and Dissertations

Understanding the mechanism of combustion reactions is key for advancing internal combustion engine design, improving the efficiency of ignition chemical reactions, and reducing pollutant formation. In order to model the extremely complicated chemical kinetics of combustion processes, it is critical to detect and identify transient reactive chemical intermediates, particularly free radicals. Hence, it needs to be fully understood the gas-phase chemistry of organic compounds in the lower atmosphere. Over the past fifty years, parallel advancement in observational, experimental, and theoretical techniques, tremendous strides have been made in our understanding of the role of organic compounds in the atmosphere. Combustion chemistry …

Effects Of The Dihydrouracil Lesion On Dna Using 1h/31p 1d And 2d Solution Nmr, Benjamin M. Boyd

Graduate Theses/Dissertations

The effects of the dihydrouracil lesion in DNA were studied using two dimensional NMR spectroscopy. The sequence used was based off of the Drew-Dickerson Dodecamer, with the cytosine in the three position replaced by a dihydrouracil. All of the nonexchangeable proton chemical shifts, with the exception of the H2, H5’, and H5’’, of the lesioned DNA were identified using NOESY spectra and then compared to the chemical shift values of the Drew Dickerson Dodecamer. The largest differences in chemical shifts were observed in the nucleotides neighboring the lesion, both within the strand and on the opposite strand. The imino exchangeable …

Cuinse₂ Nanotube Arrays For Efficient Solar Energy Conversion, Wipula Priya Liyanage, Manashi Nath

Chemistry Faculty Research & Creative Works

Highly uniform and vertically aligned p-type CuInSe₂ (CISe) nanotube arrays were fabricated through a unique protocol, incorporating confined electrodeposition on lithographically patterned nanoelectrodes. This protocol can be readily adapted to fabricate nanotube arrays of other photoabsorber and functional materials with precisely controllable design parameters. Ternary CISe nanotube arrays were electrodeposited congruently from a single electrolytic bath and the resulting nanotube arrays were studied through powder X-ray diffraction as well as elemental analysis which revealed compositional purity. Detailed photoelectrochemical (PEC) characterizations in a liquid junction cell were also carried out to investigate the photoconversion efficiency. It was observed that the …

Ribbon Α-Conotoxin Ktm Exhibits Potent Inhibition Of Nicotinic Acetylcholine Receptors, Leanna A. Marquart, Matthew W. Turner, Lisa R. Warner, Matthew D. King, James R. Groome, Owen M. Mcdougal

Chemistry and Biochemistry Faculty Publications and Presentations

KTM is a 16 amino acid peptide with the sequence WCCSYPGCYWSSSKWC. Here, we present the nuclear magnetic resonance (NMR) structure and bioactivity of this rationally designed α-conotoxin (α-CTx) that demonstrates potent inhibition of rat α3β2-nicotinic acetylcholine receptors (rα3β2-nAChRs). Two bioassays were used to test the efficacy of KTM. First, a qualitative PC12 cell-based assay confirmed that KTM acts as a nAChR antagonist. Second, bioactivity evaluation by two-electrode voltage clamp electrophysiology was used to measure the inhibition of rα3β2-nAChRs by KTM (IC₅₀ = 0.19 ± 0.02 nM), and inhibition of the same nAChR isoform by α-CTx MII (IC₅₀ = …

Qualitative Assay To Detect Dopamine Release By Ligand Action On Nicotinic Acetylcholine Receptors, Leanna A. Marquart, Matthew W. Turner, Owen M. Mcdougal

Chemistry and Biochemistry Faculty Publications and Presentations

A pheochromocytoma of the rat adrenal medulla derived (a.k.a. PC12) cell-based assay for dopamine measurement by luminescence detection was customized for the qualitative evaluation of agonists and antagonists of nicotinic acetylcholine receptors (nAChRs). The assay mechanism begins with ligand binding to transmembrane nAChRs, altering ion flow into the cell and inducing dopamine release from the cell. Following release, dopamine is oxidized by monoamine oxidase generating hydrogen peroxide that catalyzes a chemiluminescence reaction involving luminol and horseradish peroxidase, thus producing a detectable response. Results are presented for the action of nAChR agonists (acetylcholine, nicotine, and cytisine), and antagonists (α-conotoxins (α-CTxs) MII, …

Development, Evaluation, And Application Of Chromatographic Resolution Enhancement Strategies, Garrett Hellinghausen

Chemistry & Biochemistry Dissertations - Archive

With the emergence of advanced separation technologies, like high-efficiency stationary phases bonded with superficially porous particles, or sub-2 μm fully porous particles, faster and more effective methodologies are possible for liquid chromatographic analyses. Such advanced approaches can be easily applied to achiral separations but require more extensive optimization for chiral separations. Chiral molecules are subjected to extensive characterization of their enantiomeric pharmacological properties due to requirements of the Food and Drug Administration. Herein, fundamental chiral method development strategies are thoroughly discussed for hundreds of small molecules using conventional and newly synthesized chiral selectors bonded to high-efficiency supports. In these strategies …

Towards The Synthesis Of An Artificial Fluorescent Siderophore, Ashley Burns

Honors Theses

Siderophores are molecules capable of binding ferric ions with high affinity (Ka = 1052). This thesis outlines our attempts to synthesize an artificial siderophore, which incorporates a signaling group to help monitor the uptake of ferric ions. The artificial siderophore is a tripodal molecular receptor synthesized in a five-step procedure with a proposed final sixth step. Rhodamine 6G azide (95.0% yield) was formed from rhodamine 6G and the synthesis of 2-azidoethanamine was modified from the literature. The tripodal arm portion of the sensor was successfully synthesized by protecting the catechol of 2,3-dihydroxybenzaldehyde to form 3-formyl-1,2-phenylene dimethanesulfonate (98.8% yield). The reduction …

Understanding And Controlling Lithium Microstructure During Electroplating For Energy Applications, Yang Tian

Graduate Theses and Dissertations

Lithium-ion batteries are reaching the specific theoretical capacity limit, while lithium metal batteries are regarded as the ideal energy storage system for the next generation “beyond lithium-ion” battery systems. The lithium metal anode is considered as the “Holy grail” of anodes due to its relatively low electrochemical potential (-3.04 V vs SHE) and high theoretical capacity (3860 mAh g-1). However, the application of lithium metal anodes is hindered because of significant reaction between metallic lithium and electrolytes, as well as uneven electro-plating, which leads to dendrite formation, causing safety problems.

The kinetic parameters of Li ions such as diffusion coefficient …

Rotational Tuning Of Transmembrane Helix Properties Based On The Precise Placements Of Aromatic And Charged Residues, Matthew J. Mckay

Graduate Theses and Dissertations

Designed model transmembrane peptides and oriented 2H and 15N solid-state nuclear magnetic resonance (NMR) spectroscopy were used to analyze how simple sequence modifications can influence peptide structure, behavior and dynamics as well as for determining the pKa of glutamic acid at the membrane interface. The GW5,19ALP23 (acetyl-GGALW(LA)6LWLAGA-amide) peptide framework adopts a well-defined tilted orientation in lipid bilayers (DLPC, DMPC and DOPC) and undergoes low amounts of dynamic motion. The sequence was initially modified by moving the Trp residues outwards to positions 4 and 20. This new sequence GW4,20ALP23 (acetyl-GGAW(AL)7AWAGA-amide) displays high amounts of signal averaging of NMR observables caused by …

Probing Of Carbohydrate-Protein Interactions Using Galactonoamidine Inhibitors, Jessica B. Pickens

Graduate Theses and Dissertations

Glycoside hydrolases are ubiquitous and one of the most catalytically proficient enzymes known, and thus understanding their mechanisms are crucial. Most research has focused on the interaction of the glycon of substrates and their inhibitors within the active site of glycoside hydrolases. The inhibitors employed to probe these interactions generally had small aglycons (i.e. a hydrogen atom, amidines, small aliphatic groups, or benzyl groups). Here, the interactions of the aglycon with glycoside hydrolases are examined by probing the active sites with a library of 25 galactonoamidines. The studies described in this dissertation aim to increase the understanding of stabilization of …

Reactivity Of Photogenerated Amine Radical Cations, Qile Wang

Graduate Theses and Dissertations

Recently photoredox catalysis has emerged as a powerful tool in organic synthesis led by Professor McMillan, Stephenson, Yoon. Upon absorption of visible light, photocatalyst can be excited to its singlet state followed by intersystem crossing to form a long lived excited triplet state. While amine serves as electron donor, single electron transfer (SET) can happen between excited triplet photocatalyst and nitrogen atom on amine to give a reduced photocatalyst and amine radical cation.

Cyclopropylamines or cyclobutylamines can be oxidized by excited photocatalyst to generate amine radical cations and due to the ring strain, subsequent C-C bond cleavages can lead to …

Aglycon Modifications Of Ipomoeassin F: Synthetic Route Development And Analog Synthesis To Enable Further Sar Studies, Eric Barber

Graduate Theses and Dissertations

The ipomoeassin family of resin glycosides were discovered to have a high potency against numerous cancer cell line, with ipomoeassin F being the most potent among the family of natural products. Interestingly, one of the few differences between ipomoeassin F and the other compounds is the length of the fatty-acid derived aglycon. As the mechanism of action for this family of resin glycosides is unknown and didn’t have any significant COMPARE correlation with the recorded anticancer agents in the National Cancer Institute (NCI), further SAR studies are needed. Drawing on the differences between ipomoeassin F and the other ipomoeassins, it …

Development Of Forward Osmosis Based Separations: A Novel Approach In Membrane Technology, Yu-Hsuan Chiao

Graduate Theses and Dissertations

Tackling the worldwide severe water shortage, the membrane technology is considered to be the most efficient approach and hence, used widely as a cost-effective sustainable solution. “Forward osmosis (FO)” has been the major attention in recent time. FO uses osmotic pressure as the driving force to draw the water passing the membrane and achieve the desired separation performance. In general, it is considered to be a process with tremendous potential to resolve the present-day water shortage with extremely low energy consumption. However, the challenges of membrane and draw solution regeneration associated with FO processes must be conquered prior to their …

An Electrochemical Instrument For The Analysis Of Heavy Metals In Water Via Anodic Stripping Coulometry For Applications In Remote Sensing., Kelsey Lynn Kaht

Electronic Theses and Dissertations

From the high levels of arsenic in groundwater in Bangladesh to the lead contamination of drinking water in Flint, Michigan, there are incidents across the globe that highlight the need for a reliable instrument capable of monitoring heavy metals remotely and continuously in a variety of geographical locations. Typical instrumentation for water analysis, such as ICP and AAS, must be housed in a central lab and relies on an operator traveling to the collection site, obtaining a sample, and transporting it back to the lab. This analysis provides a snapshot of the water quality that is limited to the specific …

Electrochemical Determination Of Surface Area-To-Volume Ratio For Metal Nanoparticle Analysis., Jay Narayan Sharma

Electronic Theses and Dissertations

This dissertation describes an electrochemical approach for measuring the surface area-to-volume ratio (SA/V) of electrode-attached metal nanoparticles (NPs), which was used to analyze their size, aggregation state, and porosity. This dissertation further describes the effect of the metal NP electrode assembly method on the SA/V, which is related to metal NP catalytic activity and stability. Cyclic voltammetry (CV) in acid electrolyte followed by anodic stripping voltammetry (ASV) in KBr electrolyte allows the electrochemical measurement of the SA/V of electrode-attached Au nanospheres (NSs). In CV, the forward scan produces a thin surface Au₂O₃ layer on the Au NSs. …

Laser Spectroscopy Investigations Of Jet-Cooled Metal-Containing Free Radicals., Anam Chandra Paul

Electronic Theses and Dissertations

Metal-containing free radicals are important intermediates in metal-surface reactions and the interactions between metals and organic molecules. Among metal-containing free radicals, monovalent derivatives of alkaline earth metals have been extensively investigated by using spectroscopic techniques in a gas phase, mainly in Broida ovens or under supersonic-jet-cooled conditions. In the present study, the results of performed spectroscopic investigations of both metal-containing monoalkoxides (CaOR) and metal oxides (MO) radicals have been reported. Laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of the electronic transition of the calcium CaOR radicals have been obtained under jet-cooled conditions. Complete active space self-consistent field (CASSCF) and …

Gc×Gc-Ms And Parallel 2dlc-Ms Based Untargeted Metabolomics., Md Aminul Islam Prodhan

Electronic Theses and Dissertations

Untargeted metabolomics aims to analyze as many metabolites as possible in a biological system. Due to the vast complexity of the metabolome, bioanalytical platforms have been developed for untargeted metabolomics. While comprehensive two-dimensional gas chromatography mass spectrometry (GC×GC-MS) has been used in different scientific fields, its use in untargeted metabolomics is limited due to several challenges, such as complicated data analysis and limited accuracy of metabolite identification. Two-dimensional liquid chromatography mass spectrometry (2DLC-MS) has also been employed in untargeted metabolomics, but with limited metabolite coverage. This dissertation describes the efforts in developing new data analysis algorithms to improve the accuracy …

Study Of Amorphous Boron Carbide And Hydrogenated Boron Carbide Materials Using Molecular Dynamics And Hybrid Reverse Monte Carlo, Rajan Khadka

Graduate Theses/Dissertations

We present a computational study of amorphous boron carbide (a-B_xC) models using Molecular Dynamics (MD) studied with Stillinger-Weber (SW) and ReaxFF potential. The atomic structure factor (S(Q)), radial distribution function (RDF) and bond lengths comparison with other experimental and ab initio models shows that a random arrangement of icosahedra (B₁₂, B₁₁C) interconnected by chains (CCC, CBC) are present in a-B_xC. Afterward, Hybrid Reverse Monte Carlo (HRMC) technique is used to recreate a-B_xC structures. The existing SW potential parameters of Boron are optimized for the α-rhombohedral (Icosahedral B_{12 …}

Ultrafast Relaxation Dynamics In Graphene Oxide-Dye And Perovskites Nanocomposites, Abubkr A. Arzaq Abuhagr

Dissertations

Novel materials such as graphene oxide (GO), reduced graphene oxide (RGO), and Perovskites nanocomposites nanosheets have shown interesting electrical and optical properties. These materials have shown prominence in research regarding optical sensing applications. The interaction of different fluorescent molecules like dye molecules with GO, and RGO have been studied recently to develop novel optical sensors, photo-catalysts, and light-harvesting agents. In this study, we have monitored the excited state interactions of dyes covalently attached to GO and RGO nanosheets. Three amine derivatives of anthracene, pyrene, and coumarin were covalently bound to different systems via amide bonds and diazotization. Characterization of different …

Smart Sensors With Dual Modes Of Signal Transduction For Monitoring Molecules Pertinent To Health And The Environment, Jared T. Wabeke

Dissertations

The dissertation focuses on the design and synthesis of smart materials for the detection of molecules pertinent to environmental protection and healthcare. The use of computational simulations is pivotal toward advancing molecular design for targeted applications. Research was conducted to investigate the use of simulations to develop novel sensors with dual modes of signal transduction. The molecular properties were determined using computational modelling, and then used to elucidate the binding mechanism of the corresponding sensor complexes. Several molecules were produced that respond to important organic analytes, such as glucose and fenthion, an organophosphorus pesticide. Glucose is an exceedingly important biological …

Laser Spectroscopy Investigations On Molecular And Free Radicals Dynamics., Hamzeh Telfah

Electronic Theses and Dissertations

Studying molecular dynamics and chemical kinetics is important to understand the chemical behavior of renewable energy sources. Laser spectroscopy techniques are powerful tools for the identification and diagnosis of such processes. In this dissertation, using our laser spectroscopy techniques, biofuels and solar energy were targeted as renewable energy sources study. We have studied the ultrafast exciton dynamics for a series of methylammonium lead bromide (CH3NH3PbBr3) nanostructures, nanocrystals (NCs, 0D), nanowires (NWs, 1D), and nanoplatelets (NPs, 2D) as a promising solar energy materials.1-2 Aided by analysis of UV−visible absorption and photoluminescence spectra, features in the transient absorption (TA) spectra are assigned …