Chemistry Commons^™

Synthesis And Characterization Of Complex Molecular Assemblies On Surfaces, Nitesh Madaan

Theses and Dissertations

The research presented in this dissertation is focused on the construction of complex molecular structures on planar gold and silicon dioxide surfaces using a variety of surface modification techniques, along with thorough surface characterization at each modification step. The dissertation is structured into six separate chapters. In Chapter 1, an introduction to the importance and implications of molecular level surface modification, commonly employed surface modification methods, and available surface characterization techniques is presented. Chapter 2 shows applications of novel methodologies for the functionalization of gold surfaces using alkane dithiol self-assembled monolayers and thiol-ene click chemistry. The resulting functionalized gold substrates …

Part I: Synthesis And Biological Evaluations Of Potent Class L Selective Histone Deacetylase Inhibitors Part Ii: Aqueous Complexes For Efficient Sizebased Separation Of Americium From Curium Part Iii: Designing Strong Chiral Bronsted Acids And Their Application For Oxaxinanones Derivatization And The Aza-Henry Reaction, Joseph Steve Ulicki

Theses and Dissertations

PART I: SYNTHESIS AND BIOLOGICAL EVALUATIONS OF POTENT CLASS l SELECTIVE HISTONE DEACETYLASE INHIBITORS

Histone deacetylase inhibitors (HDACi) have found a wide variety of medicinal uses and are most noted for their specific apoptotic action towards cancer cells1. Several hydroxamates and tetrapeptides HDACi have since been moved on to phase 1 and 2 clinical trials, with FK228 & SAHA having already been approved for treatment of advanced cutaneous T-cell lymphoma (CTCL). FK228 & SAHA are pan-HDACi which d compounds describes the unselective inhibition for any of the 11 Zn2+-dependent HDAC isoforms. Research in the past five years, has shifted towards …

Identification And The Significance Of Selective Proteins In Bile And Plasma Of Normal And Health-Compromised Chickens, Balamurugan Packialakshmi

Graduate Theses and Dissertations

During the last 50 years, animal breeding programs in commercial poultry have made significant progress in the bodyweight gain of broilers but led to several metabolic and skeletal disorders. Lameness associated with proximal femur known as femoral head separation (FHS) or femoral head necrosis (FHN) is one of the major metabolic disorders in poultry industry. In order to select for healthy chickens, markers that can distinguish between healthy and affected birds are required. Biomarkers from blood represent an ideal and rich source of markers which can be obtained using minimally invasive methods. The biomarkers were explored in an experimental model …

Modification Of Pyrimidine And Purine Nucleotides By "Click" Chemistry: Design, Synthesis And Properties Study, Mohammad Mojibul Haque

Theses and Dissertations

This dissertation consists of three main parts, totaling five chapters, and focuses on developing novel nucleosides via "click" chemistry and studying their potential biological

properties. Chapter three describes the synthesis and properties of coumarin-modified fluorescent DNAs. Coumarin-modified 2'-deoxythymidine was synthesizedvia "click" chemistry and incorporated into oligodeoxynucleotides (ODNs) which induce photoreversible interstrand cross-link (ICL) upon 350/254 nm photoirradiation. The irradiation at 350 nminduces DNA cross-linking with ODNs containing coumarin. The cross-linked DNA products formed from coumarin are not fluorescent. Further investigation showed that coumarin moiety undergoes the (2π+2π) photocycloaddition with 2'-deoxythymidine (dT), 2'-deoxycytidine (dC), and to a much lower extent, 2'-deoxyadenine …

A Novel Method For Confirming The Presence Of Volatile Reduced Sulfide Compounds Via Inductively Coupled Plasma-Optical Emission Spectroscopy, Krystal Lynne Parker

Master's Theses

Millions of dollars in destruction in the past decade have resulted from the use of Chinese drywall in homes. There are also potential health hazards related to this corrosive material. As such, it is important to find a way to identify Chinese drywall. Drywall can be tested for certain markers, such as strontium, sulfur, and carbonates to identify it as corrosive Chinese drywall. The laboratory preparation and analysis should be efficient and cost effective. The methods previously used, such as an X-ray fluorescence gun have had issues with getting a proper reading due to the layers of other materials found …

Ranking Methods For Global Optimization Of Molecular Structures, John Norman Mcmeen Jr

Electronic Theses and Dissertations

This work presents heuristics for searching large sets of molecular structures for low-energy, stable systems. The goal is to find the globally optimal structures in less time or by consuming less computational resources. The strategies intermittently evaluate and rank structures during molecular dynamics optimizations, culling possible weaker solutions from evaluations earlier, leaving better solutions to receive more simulation time. Although some imprecision was introduced from not allowing all structures to fully optimize before ranking, the strategies identify metrics that can be used to make these searches more efficient when computational resources are limited.

Oxidative Damage To Dna 2´-Deoxyribose By Carbonate Radicals: Reaction Mechanisms And Products, Terence J. Moore

Electronic Theses and Dissertations

The carbonate radical anion (CO₃^•-, CR) is an important reactive oxygen species produced in vivo by one-electron oxidation of CO₂ or bicarbonate, constituents of the major physiological buffer. It was demonstrated for the first time by using an HPLC-based analysis of low-molecular products of DNA damage that CRs react with DNA 2΄-deoxyribose by the hydrogen abstraction mechanism. CRs exhibit a ~ 800-fold preference for one-electron oxidation of guanine over hydrogen abstraction from DNA sugar, in sharp contrast with •OH. CRs also have, as compared to •OH, an increased preference for the H1΄ abstraction, which is the …

Oxidative Stability Of Conjugated Linoleic Acid Rich Soy Oil Obtained By Heterogeneous Ruthenium Catalysis, Saurabh Ravindra Lele

Graduate Theses and Dissertations

Conjugated linoleic acid (CLA) has multiple health benefits but it is difficult to obtain sufficient CLA in a healthy diet to obtain the clinical effects. A CLA rich-soy oil (CLARSO) with up to 20% CLA has been produced by heterogenous catalysis but no studies of its oxidative stability have been reported. CLARSO and soy oil primary and secondary oxidation products were measured at 50oC in the dark. The CLARSO was less stable than soy oil but adsorption bleaching improved its oxidative stability. However, induction times were dependent on the analytical method used. Fatty acid oxidation kinetics was determined by measuring …

Cellular Zinc Trafficking: The Zinc Proteome And Its Reactions With Cadmium, Mohammad Ali Namdarghanbari

Theses and Dissertations

Metals play a crucial role in living systems. Iron, zinc, copper, molybdenum, and manganese are involved in many essential biological activities. Among transition metals, zinc after iron is the most abundant transition metal in the human body and the most abundant in the brain. It exists in more than 3000 proteins, which comprise about 10% of the human proteome. Zn2+ dyshomeostasis is associated with chronic diseases such as metabolic syndrome, diabetes and related complications, bone loss, growth retardation in young children, and neurological and behavioral problems. Despite a good knowledge obtained for metabolism of some metal ions such as copper, …

Method Development For The Analysis Of Aluminum, Calcium, Magnesium And Iron In Sedimentary Rocks, Zainab Ali Alhawdar

Electronic Theses & Dissertations

The focus of this study involved the analysis of sedimentary rocks by using atomic absorption spectroscopy. There are three classifications of sedimentary rocks: organic, formed as a result of vital activity of organisms such as coal; non-organic (chemical), formed in the process of evaporation of concentrated mineral solution such as limestone, dolomite, gypsum, salt and chert; and clastic (fragmental), formed from pre-existing rocks as a result of their fragmentation followed by further hardening and cementing such as conglomerate, breccia, sandstone, siltstone and shale. There are various analytical methods for analyzing sedimentary rocks, all of which require dissolving and digestion of …

Synthesis And Characterization Of Ln[Hfac]X And Ln[Fod]X Complexes For Thermochromatographic Separations, Matthew L. Marsh

Chancellor’s Honors Program Projects

No abstract provided.

Selective Indicators For Optical Determination Of Disease Biomarkers, Lovemore Hakuna

Dissertations and Theses

The most abundant biological thiols, homocysteine (Hcy), cysteine (Cys) and glutathione (GSH) have been the subject of intense research due to their association with a wide range of diseases. They play a key role in maintaining the redox status of biological systems. Selective detection methods for these thiols are challenging due to their similar structures and properties. Current commercially available detection methods use separations, fragile and expensive enzymatic or immunogenic materials and complex instrumentation. This has led to a global effort towards developing simple and inexpensive optical probes and indicators selective for specific biological thiols.

Highly selective chemical probes and …

Experimental Evidence For Colloid-Facilitated Transport Of Plutonium, Hilary Emerson

All Dissertations

Colloid-facilitated transport of the actinides has been observed previously in the field on the kilometer scale. The objective of this work is to investigate the mechanisms of colloid-facilitated transport with controlled settings and conditions. The experimental work in this dissertation investigates transport of a ternary complex with iron oxide colloids, organic ligands and actinides in the presence of quartz or a natural sandy soil as well as simplified systems building up to the ternary complexes. The first three papers investigate the following: (1) unsaturated transport of iron oxide colloids in a natural sandy soil lysimeter with and without natural organic …

Computational And Experimental Investigation Into Yield Behavior And Cure Rate Dependence Of Thermoset Polymers, Christopher Harold Childers

Dissertations

This dissertation is broken down into two primary sections: firstly, the development and improvement of molecular dynamics simulations of thermoset matrix polymers including their use in understanding molecular response to applied strain deformation and secondly, the discernment of a cure heating ramp rate dependence of the final molecular and macro-molecular properties of thermoset matrix polymer.

The molecular dynamics section will discuss the development of molecular dynamics simulations of thermoset epoxy/amine matrix polymers, and the implementation of this work to determine the underlying molecular level events that cause thermoset matrix polymer yield. It will report a novel method for the determination …

Spectroscopy And Gas-Phase Binding Of Modified Desferrioxamine B Indicator Displacement-Based Sensors, William Scott Jones

Dissertations

A coupling reaction has been used to successfully synthesize two novel probes utilizing coumarin derivatives as fluorophores. The structure, spectroscopy, and thermodynamics of these probes were characterized and studied. These probes, along with a classical probe using a N-methyl-anthranilate fluorophore, are used to take advantage of the ability of siderophores to coordinate Fe³⁺ ions which is coupled with the attractive phosphorescence properties of lanthanide ions. The use of lanthanide metals to create an indicator displacement assays is a novel application of these probes for the detection of Fe³⁺ ions. The use of Tb³⁺ ions as the indicator …

Continuous Polymer Reactor Design, David Sujay Kingsley

Dissertations

Twin screw extruders can be used as continuous polymer reactors to process polymers, which are conventionally made through batch reactors. Batch processes have certain undesirable qualities such as improper mixing and the inability to precisely control the reaction, which leads to variation between batches and potential exotherms. The work presented in this dissertation investigates the use of continuous polymer reactor designs to efficiently process renewable sourced thermoplastic polyurethanes (TPU), and prepreg epoxy matrix prepolymers.

The overall goal of this research is to highlight the modularity of twin screw extruders as continuous polymer reactors to synthesize the relevant polymers. Chapter I …

Investigation Of Glassy State Molecular Motions In Thermoset Polymers, Jianwei Tu

Dissertations

This dissertation presents the investigation of the glassy state molecular motions in isomeric thermoset epoxies by means of solid-state deuterium (²H) NMR spectroscopy technique. The network structure of crosslinked epoxies was altered through monomer isomerism; specifically, diglycidyl ether of bisphenol A (DGEBA) was cured with isomeric amine curatives, i.e., the meta-substituted diaminodiphenylsulfone (33DDS) and para-substituted diaminodiphenylsulfone (44DDS). The use of structural isomerism provided a path way for altering macroscopic material properties while maintaining identical chemical composition within the crosslinked networks.

The effects of structural isomerism on the glassy state molecular motions were studied using solid-state ²H …

Molecular Probes For The Detection Of Zn2+ And Fe3+ Ions, Erendra Manandhar

Dissertations

A number of molecular probes have been designed and synthesized for the detection of Zn²⁺ and Fe³⁺ ions. Two types of functional groups have been incorporated into the molecular scaffolds to utilize different fluorescent mechanisms. The first class of receptors contains a pyrene moiety. These molecular probes use the excimer mechanism for the detection of Zn²⁺ ion. The probes work well in an organic solvent with a detection limit of 20 nM (one ppb). Alternatives are made to make them water soluble, but this proved to be difficult. An interesting ion-induced self-assembly system will also be discussed. …

Utilization Of Aqueous Raft Prepared Copolymers To Improve Anticancer Drug Efficacy, Andrew Christopher Holley

Dissertations

The advent of controlled radical polymerization (CRP) techniques, along with advancements in facile conjugation chemistry, now allow synthetic tailoring of precise, polymeric architectures necessary for drug/gene delivery. Reversible addition- fragmentation chain transfer (RAFT) polymerization and its aqueous counterpart (aRAFT) afford quantitative control over key synthetic parameters including block length, microstructure, and placement of structo-pendent and structo-terminal functionality for conjugation of active agents and targeting moieties. The relevance of water-soluble and amphiphilic (co)polymers synthesized by RAFT for in vitro delivery of therapeutics in biological fluids is an especially attractive feature. In many cases, polymerization, binding, conjugation, …

Enzyme, Cosolvent, And Substrate Interactions In Ple Hydrolysis Reactions And Evaluation Of The Stability Of An Unnatural Glutathione Analogue, Maureen Elizabeth Smith

Dissertations

Prochiral diester malonates have been hydrolyzed in the presence of Pig Liver Esterase (PLE). Several of the diesters produced the respective half-ester in moderate to high enantioselectivity. A series of cosolvent assays were performed to evaluate the ability of the cosolvent to influence the enantioselective outcome of the hydrolysis reactions. Ethanol produced the largest changes in enantioselectivity of all solvents evaluated. The isoenzymes of PLE were also evaluated and provided very different enantioselective outcomes than that of crude PLE. A series of NMR titrations was performed to explore the interactions between the substrates and ethanol cosolvents.

Improvements to our previously …

Tuning Responsiveness Of Polypeptide Based Block Copolymers For Drug Delivery, Ashley J. Johnson

Dissertations

The goal of this dissertation was to tune the pH response and self-assembled morphologies of amphiphilic polypeptide block copolymers for use as drug delivery vehicles. Poly(L-lysine) and poly(L-glutamtic acid) are responsive, ionizable polypeptides that undergo secondary structure transitions, from α-helix to random coil, whereby the change in conformation of the peptide chain results in changes to the global morphology of a self-assembled system. The main focus of this work was to understand how changes in the polymer composition and the local environment can lead to control over the behavior of the overall system. First, the responsive behavior of poly(L-lysine) block …

Sign Me Up! Determining Motivation For High School Chemistry Students Enrolling In A Second Year Chemistry Course, Nilda N. Camarena

Theses and Dissertations - UTB/UTPA

A sample of 108 Pre-AP Chemistry students in Texas participated in a study to determine motivational factors for enrolling in AP Chemistry and University Chemistry. The factors measured were academic attitude, perceptions of chemistry, confidence level in chemistry, and expectations/experiences in the chemistry class. Students completed two questionnaires, one at the beginning of the year and one at the end. Four high school campuses from two school districts in Texas participated. Two campuses were traditional high schools and two were smaller magnet schools. The results from this study are able to confirm that there are definite correlations between academic attitudes, …

Simultaneous Determination Of Multiple Actinide Elements In A Variety Of Soils Utilizing A Standardized Sequential Extraction Protocol, Sherry Alina Faye

UNLV Theses, Dissertations, Professional Papers, and Capstones

To obtain a better understanding of the mobility of actinide element contaminants in the environment, the association of the contaminants with specific host phases of soils and sediments must be investigated. This investigation is most commonly conducted using sequential extraction techniques that employ the selective dissolution of soil phases with increasingly aggressive chemical treatment. Though several sequential extraction studies exist in literature, conclusions cannot be made by direct comparison of data due to the lack of uniformity in the protocols used. This work aims to continue development of a standard sequential extraction protocol and expanding its capabilities to include the …

Technetium Sulfide: Fundamental Chemistry For Waste Storage Form's Application, Maryline Ghislaine Ferrier

UNLV Theses, Dissertations, Professional Papers, and Capstones

Technetium is the lightest radioelement. The isotope ⁹⁹Tc has around a 6% yield from ²³⁵U with a half-life of 2.13 x 10⁵ years. The high mobility of TcO₄^-, the common chemical form of technetium in the environment makes ⁹⁹Tc an isotope of concern in nuclear waste management. Despite its important role in radiopharmaceuticals and in the nuclear fuel cycle, the fundamental chemistry of technetium is not as well developed as that of the neighboring transition metals; one of the most striking examples being its sulfide chemistry.

Only two technetium binary sulfide compounds had …

Neutron Study Of Structure And Dynamics Of Rigid Polymers, Naresh Osti

All Dissertations

The structure and the dynamics in two different classes of rigid polymers; ionomers and rigid luminescent polymers, have been investigated predominantly by neutron techniques. Rigidity of the backbones of both polymers affects their properties. For ionomers, it affects transport pathways, therefore, their applications for energy and separation membranes. In luminescent polymers, it determines the conformations of the chains and their electro-optical response. One group of the polymers consists of rigid hydrophobic para-phenylene backbone decorated with pendant phenyl side chains functionalized with sulfonic acid (SPP). The other family of polymers consists of poly para-phenyleneethynylene (PPE) backbone that becomes conjugated upon conformational …

Aminooxy Reagents In Nanomedicine And Bioanalysis., Stephanie Mattingly

Electronic Theses and Dissertations

The development of nanomaterials as medical diagnostic and therapeutic agents is a rapidly expanding field. A brief search of the literature revealed that roughly half of all articles related to nanoparticle-based drug delivery were published after the onset of this thesis research, over the past 4 years. A few nano-based formulations have entered into clinical use, including liposomal drug formulations, protein-linked drugs, and nanoparticle-based MRI contrast agents. The chemistry that enables conjugation of a functional cargo, whether a drug, a targeting element, or a radionucleotide, to a nanocarrier is thus a critical component for development. Oximation is one of the …

Probing The Unfolding And The Stability Of The Last Four Metal Binding Domains Of Wilson Disease Protein Using Circular Dichroism And Novel Spectroscopic Techniques, Ibtesam Yaseen Alja’Afreh

Dissertations

Wilson disease protein is a copper-transporting P_1B type ATPase. It has large N-terminal copper binding domain which is composed of six homologous sub-domains. Each of these six domains is ~72 residues and connected to one another by linking regions of various lengths. They all possess similar ferrodoxin fold, and metal-binding motif, MXCXXC.

The need of having six metal binding domains and the manner in which they are communicating with each other is not well understood. To better understand how the last four metal binding domains function, I pursued a detailed biophysical characterization of these domains. Using molecular biology I …

Ultrafast Interfacial Electron Transfer Across Molecule-Tio2 Nanocomposites: Towards Solar Cells And Two Photon Absorption, Edwin Mghanga

Dissertations

Interfacial charge transfer (ICT) across the molecule-TiO2 nanoparticle interface has gained enormous research attention for applications in dye sensitized solar cells (DSSC), photo-catalysis, water splitting and nonlinear optics. DSSCs are promising clean alternative energy sources. However, current DSSCs suffer from lower efficiencies and higher cost. Better understanding of the ICT processes in DSSCs can help solve these problems. We have used two strategies to understand ICT in the context of DSSCs. Firstly, we used a computationally validated anchor group, acetylacetonate (acac) to bind molecules to the semiconductor surface and facilitate charge separation. Secondly, we used natural dye sensitizers, …

Chaperone-Mediated Folding And Assembly Of Β-Propeller Proteins Into Cellular Signaling Complexes, Rebecca L. Plimpton

Theses and Dissertations

G protein signaling depends on the ability of the individual subunits of the G protein heterotrimer to assemble into a functional complex. Formation of the G protein βγ (Gβγ) dimer is particularly challenging because it is an obligate dimer in which the individual subunits are unstable on their own. Recent studies have revealed an intricate chaperone system that brings the Gβ and Gγ subunits together. This system includes the cytosolic chaperonin containing TCP-1 (CCT) and a co-chaperone phosducin-like protein 1 (PhLP1). Two key intermediates in the Gβγ assembly process, the Gβ-CCT and the PhLP1-Gβ-CCT complexes, were isolated and their structures …

Triggered Release Of Small Molecules From Solid Supports Using Heat Or An Applied Magnetic Field., Ralph Jacob Knipp

Electronic Theses and Dissertations

The reaction of an aminooxy moiety (RONH2) with an aldehyde or ketone carbonyl, an oximation reaction, results in the formation of robust oxime ether linkages. Oximation is a form of click chemistry and is chemoselective, occurs in a variety of solvents including water, and produces high yields with little to no purification. We were inspired to exploit the advantages of oximation reactions by attaching aminooxy-functionalized molecules to solid supports, thus allowing us to employ aminooxy chemistry in ways that cannot be achieved using solution phase. Chapter 1 provides a review of aminooxy chemistry, its advantages over similar reactions and its …