Physical Sciences and Mathematics Commons^™

Copper-Indazolate Nanojars: Synthesis And Characterization, Nicholas Alexander Rudell

Masters Theses

The field of synthetic supramolecular chemistry has exploded since the first syntheses of crown ethers by Charles Pedersen in the 1960s, leading to further development in the area of macrocycles and incorporation into a vast array of metal-organic structures. Supramolecular chemistry came to the forefront of science with the 1987 Nobel Prize in Chemistry, awarded jointly to Donald J. Cram, Jean-Marie Lehn, and Charles Pedersen “for their development and use of molecules with structure-specific interactions of high selectivity.”

Nanojars are supramolecular metal-organic complexes with a high affinity for hydrophilic anions and can efficiently transfer such anions from water into organic …

Kinetic And Structural Characterization Of Pseudooxynicotine Amine Oxidase From Pseudomonas Putida S16, Vishakha Choudhary

Masters Theses

Our laboratory has previously shown that nicotine oxidoreductase (NicA2), a member of the flavin-containing amine oxidase family, uses a cytochrome c protein (CycN) as its electron acceptor rather than characteristically accepted molecular oxygen. Within the Pseudomonas putida S16 genome, the nicA2 gene forms an operon with cycN and pseudooxynicotine amine oxidase (pnao), another flavin containing amine oxidase enzyme. The first two steps in the nicotine catabolism pathway are catabolized by NicA2 and Pnao. Through redox chemistry, NicA2 converts nicotine to pseudooxynicotine and Pnao converts pseudooxynicotine to 3-succinoylsemialdehyde-pyridine. In this thesis, we characterize the kinetic and structural properties of …

Development Of High Throughput Assays For Identification And Evaluation Of Small Molecule Inhibitors Of Microrna-31 Expression, Jackline A. Onyango

Masters Theses

Dysregulated expression of miRNAs has been linked to numerous cancers. On the other hand, miRNAs are potential drug targets due to the ability of their precursor molecules to fold into ligand binding structures. Small-molecule modulators of miRNAs offers opportunity for the development of new therapeutic agents and tools to further probe the mechanisms of miRNA functions. To facilitate the identification of miRNA modulators, the appropriate screening systems are needed, which would be adaptable for high-throughput applications, and allow for quantitative measurements. In this text, we present a molecular beacon-based assay to identify molecules that inhibit miRNA-31 processing by Dicer and …

Assessing The Robustness And Versatility Of Nanojars For Anion Binding, Mia Lily Ann Jawor

Masters Theses

Supramolecular chemistry is a field in chemistry that focuses on intermolecular bonds in a “host-guest complex” or supramolecular assemblies. Nanojars are supramolecular assemblies of the formula [anion⊂{Cu(μ-OH)(μ-pz)}_n] (n = 27‒33) which incarcerate kosmotropic anions, such as carbonate (CO₃^2‒), sulfate (SO₄^2‒) and hydrogen phosphate (HPO₄^2‒). Nanojars consist of three [Cu(μ-OH)(μ-pz)]_x (x = 6‒14, except 11) rings that are assembled similarly to Matryoshka dolls, where the top and bottom rings act as guests for the central ring. The larger central ring is bound to the two smaller rings by multiple …

An Analysis Of Factors Influencing Chemistry Students’ Choice Of Major And Career, Jennifer Marie Ribble

Masters Theses

In recent years there has been a push to increase the number of STEM graduates in the United States in order for the nation to retain its position as a global leader in the sciences. If educators are to address recruitment and attrition issues in STEM fields it is important to understand student perspectives related to choosing both a major and a career in chemistry. The present study explores the decision-making process students utilize to choose chemistry as a major and as a career, their perception of what careers are available to someone with a degree in chemistry and what …

Computational Study Of The Nature Of Tetrel Bond, Yama Aman

Masters Theses

For more than a hundred years, the type of a chemical bond has been distinguished according to the relative electronegativities of chemical units at the ends of a bond. Whereas, the bond of unequally electronegative on both ends is called a polar covalent or even ionic bond or a non-polar covalent bond in case of both equal. Regardless the type of bonded elements, the whole idea for the bond was believed to be electron driven only. In the 20th century the development of the idea, that not just the electronic relation but specific elements are also able to characterize the …

Synthesis And Characterization Of Fluorescent Nanojars, Vageesha Warnajith Liyana Gunawardana

Masters Theses

Self-assembly is a powerful tool utilized by synthetic chemists to create large, intricate structures for a variety of applications such as drug delivery, adaptable materials and electronics. In contrast to stepwise synthesis, this process allows the formation of intricate molecular architectures starting from synthetically rudimentary building blocks. Nanojars are class of self-assembling, cyclic copper(II) pyrazolate coordination compounds that encapsulate oxoanions with negative two or three charge. The strong anion binding characteristics of nanojars have potential towards developing novel tools for detecting biologically and environmentally relevant anions such as carbonate, sulfate and phosphate.

This work addresses the design and synthesis of …

Organocatalyzed Synthesis Of Epoxides From Chalcones Utilizing Amino Acids, Sabrina N. Kegeler

Masters Theses

The epoxide functional group is important throughout the chemical and pharmaceutical industries, as well as in nature. In the chemical industry, epoxides are present in resins and fragrances. In the pharmaceutical industry, epoxide-containing compounds are used as intermediates in the manufacturing of drugs. In nature, many natural products contain epoxide groups and are used for medicinal purposes, and for models to create synthetic molecules.

One approach to epoxide synthesis involves the use of an alkene precursor, a base, and an oxidizing agent. This is where my investigations began. The first step was to optimize the epoxidation reaction, examining substrate scope, …

Apan Production Through Photooxidation Of Isoprene In The Presence Of NoX, Timothy Glidewell

Masters Theses

Peroxyacyl nitrates (PANs, RC(O)OONO₂) are of great importance in atmospheric chemistry. They act as transporters of reactive nitrogen, and radical delivery agents. There are no known natural emission sources of PANs; they are produced through reaction of volatile organic compounds (VOCs) and nitrogen oxides (NO_x) in the atmosphere.

VOCs can enter the atmosphere through biogenic and anthropogenic pathways. It has been estimated that isoprene makes up 70% of the biogenic VOCs (BVOCs) emitted annually. Isoprene has been shown to impact ozone levels in both rural and urban areas by sequestering and transporting NO_x in the form …

Characterization Of Γ-Butyrolactone Rings: A Computational And Toxicological Study, Donald C. Kidd

Masters Theses

Given the declining state of the natural environment, identifying green methodologies in synthetic chemistry is becoming paramount. An under explored area of green chemistry, is the use of catalytic systems in green solvents. One interesting concept in green chemistry is the use of N-Heterocyclic Carbenes (NHCs) as organocatalysts.

Thiamine or vitamin B1 was one of the first NHCs recognized. Thiamine is required for carbohydrate metabolism and helps the cell produce adenosine triphosphate (ATP). Over the last 20 years NHCs have been found to be efficient catalysts in carbon-carbon bond forming reactions.

But to date, little research has been done exploring …

Novel Spectroscopic Tools To Differentiate Drug-Dna Binding Interactions, Fadwa Dhafer Hamad

Masters Theses

DNA-drug interactions play a major role in therapeutics, diagnostics, forensics and imaging. Drugs bind to DNA in several ways based on the mode of interaction and they alter protein-DNA interactions or breaks/cleaves DNA that can lead to the cure of the disease. The major goal of the research carried out in this thesis is to develop novel optical spectroscopic tools that can differentiate Drug-DNA binding interactions mode whether its intercalation or minor-groove binding. To achieve this goal, we developed two-photon absorption (2PA) cross-section based technique to differentiate between Drug-DNA binding modes. The investigations were carried out on two drug molecules, …

Understanding College Students’ Exam Process In A General Chemistry Course, Angela Willson

Masters Theses

The main way most college chemistry courses assess what a student has learned is through a summative exam. After introductory science courses, such as general chemistry, many students cite poor teaching and disappointing grades in these courses as a reason for dropping out of STEM programs. There has been a lack of qualitative research on students’ experiences of the complete process of taking an exam from start to finish, or the exam process, which includes preparing for an exam, taking an exam, receiving feedback, and responding to feedback after the exam has been graded.

My goal in this exploratory study …

Environmental Applications Of Chromatography-Mass Spectrometry, Wisam Abdulabbas Flayyih Al Isawi

Masters Theses

Gas chromatography-mass spectrometry (GC-MS) and liquid chromatographymass spectrometry (LC-MS) are powerful analytical techniques that combine the separation power in a stationary phase with the detection power of mass spectrometry. GCMS and LC-MS have gained dominant positions in identifying and quantifying different analyte species due to their high selectivity, high sensitivity, and high reproducibility.

My research utilizes the analytical power of LC-MS and GC-MS to address two environmental issues: 1) Identification of biodegradation products of the ionic liquid 1- butyl-3-methylimidazolium chloride (BMIMCl) by an activated sludge microbial community using LC-MS and 2) identification and quantification of polycyclic aromatic hydrocarbons (PAHs) in …

Application Of Electrospray Ionization Mass Spectrometry For Ionic Liquids And Their Biodegradation Products, Sepideh Rahbarirad

Masters Theses

Ionic liquids (ILs) are organic salts with unique physico-chemical properties and are used as green alternatives to volatile organic solvents. ESI-MS is a sensitive technique to detect these stable, permanent ions. My research focused on (1) Identification of biodegradation products of ionic liquids and (2) Multiplexed tandem MS by modulation of ionization efficiency.

Studies, have demonstrated that ILs are toxic to the environment, which makes their biodegradability an important consideration. In this work, metabolites generated during the biodegradation of 1-butyl-3-methylimidazolium chloride (BMIM), a degradation resistant and commonly used ionic liquid, are identified using high performance liquid chromatography-mass spectrometry (LC-MS).

Multiplexed …

Synthesis Of New Platinum-Based Anti-Cancer Drugs, Saud O. Albaroodi Yasser

Masters Theses

Cancer is considered the second leading cause of death after heart attack. Different treatments have been applied to kill cancer cells such as chemotherapy, which is the use of chemicals or drugs in order to treat cancer cells. Platinum-based anti cancer drugs are the backbone of chemotherapy, they play a crucial role in treating various malignant tumor. However, the disadvantages of these drugs are very painful on patients, such as nephrotoxicity and ototoxicity. In the last four decades, thousands of platinum-based anticancer drugs have been synthesized for hope in find a new drug with higher efficacy and less side effects.In …

Electron Transfer In Pnicogen Bond, Liangyu Guan

Masters Theses

Abstract is available for download as a separate file.

Chemistry Graduate Teaching Assistants: A Comparison Of The Classroom Discourse Within Expository And Problem-Based Learning Laboratories, Kelley M. Current

Masters Theses

Graduate Teaching Assistants (GTAs) commonly function as instructors within undergraduate chemistry laboratories. This study sought to explore and describe GTA classroom discourse within two distinct instructional modes, using discourse analysis as the theoretical framework. Theclassroom discourse within a series of verification style labs was comparedto the classroom discourse produced within a set of Problem-Based Learning (PBL) labs. The results suggest three primary findings: (1) the apparent relationship between the instructional mode and form of GTA classroom discourse, (2) the patterns in classroom discourse observed within a given instructional mode repeat, irrespective of content, and (3) the classroom discourse observed within …

Using Soil Organic Matter As An Iron Chelate To Enhance The Efficiency Of Modified Fenton Oxidition Of Diesel Fuel In Arctic Soils, Mary K. Sherwood

Masters Theses

Laboratory experiments were conducted to investigate the use of modified fenton chemistry on the treatment of three soils from the Canadian arctic, all with abundant soil organic matter, iron and manganese oxides, and diesel fuel contamination. The purpose of these studies was to (I) to assess modified fenton chemistry as a treatment option for petroleum-contaminated arctic soils, and (2) to evaluate the impact of soil organic matter on the modified fenton treatment of soils. Modified fenton treatment was compared for reactions in which ethylenediaminetetraacetate was added as a chelate vs. reactions in which the native soil organic matter was the …

Study Of The Insulin Mimetic Sodium Orthovanadate In Glucosamine Induced Insulin Resistnace In Primary Rat Hepatocytes, Kalan Mcpherson

Masters Theses

Insulin resistance and type II diabetes is a disease state characterized by a lack of sensitivity of insulin to provoke a proper response in insulin sensitive tissues. Currently, we utilize glucosamine to increase flux through the Hexosamine Biosynthetic Pathway (HBP) to induce an insulin resistance like state in primary rat hepatocytes. We tested the effectiveness of the insulin mimetic sodium orthovanadate to determine if it could elicit an insulin-like response under these conditions. Mixed results were obtained on the effectiveness of vanadate as an insulin mimetic in this insulin resistant model.

Equipment Qualification Of Ion Mobility Spectrometry And Method Development And Validation For Pharmaceutical Equipment Cleaning Validation, Amy Lee Heiser

Masters Theses

Ion mobility spectrometry (IMS) instrumentation has been identified as a suitable technology for the detection and reporting of drug product and detergent residues from pharmaceutical manufacturing equipment. Ion mobility is not a new technology, but is entering the field of cleaning validation because of tightened requirements from the US Food and Drug Administration (FDA).

The purpose of this thesis is to outline a practical implementation of the analytical technique, Ion Mobility Spectrometry in a cleaning validation program. Ion Mobility Spectrometry (IMS) is fast and specific for the analysis of small organic molecules and has been gaining popularity in the pharmaceutical …

Direct Analysis Of Hops By Leaf Spray And Paper Spray Mass Spectrometry, Kari Blain

Masters Theses

The objective of this research is to develop a new and innovative method of hops analysis, which is much faster than standard testing methods, as well as reduce the amount of consumables and solvent used. A detailed discussion on the development of an ambient ionization mass spectrometry method called paper spray (PS-MS) and leaf spray (LS-MS) mass spectrometry will be presented. This research investigates the use of PS-MS and LS-MS techniques to determine the α- and β- acids present in hops. PS-MS and LS-MS provide a fast way to analyze hops samples by delivering data as rapidly as a UV-Vis …

Synthesis Of 1,1-Dialkyhydrazines And Their Hydroxyl Radical Degradation In Aqueous Environments, Benjamin F. Strong

Masters Theses

Determination of hydroxyl radical rate constants are essential to ensure adequate degradation of contaminants in wastewater. Hydrazines are an important class of organic contaminants and are the focus of this research. Ten 1,1-dialkylhydrazines are synthesized by the zinc reduction of the corresponding N-nitrosamines. Their hydroxyl radical rate constants are determined using the linear accelerator at the Notre Dame Radiation Laboratory at pH 4, 7, and 10.

Their rate constants are found to depend on the protonation state of the molecule. At pH 4 the molecules are fully protonated and hydrogen atom abstraction is favored from the alkyl chains. At …

Characterization Of P62, Hah1 And Their Interaction With The Wilson Disease Protein, Paul Sifuna Oshule

Masters Theses

Wilson disease is an autosomal recessive disorder resulting in the accumulation of copper in the body primarily in the liver and brain. In order to understand the pathogenesis of Wilson disease, our laboratory is studying several different proteins. Wilson disease protein (ATP7B) is a P-type ATPase which acts to remove excess copper from the cells. The p62 subunit of the dynactin complex is a protein whose function is still unknown but it has been proposed to have a copperdependent interaction with ATP7B. HAH1 is a human metallochaperone that binds copper as it comes into the cells from CTR1, a permease. …

Origin Of Size-Dependent Energy Transfer From Photoexcited Cdse Quantum Dots And Fluorescent Dyes To Gold Nanoparticles, Mariana Kondon

Masters Theses

The photoluminescence quenching of CdSe quantum dots (QD) and fluorescent dyes by hexanethiolate Mono layer Protected Clusters (MPCs) with core diameters of 1.1- 4 .9 nm is described.

The CdSe QD investigated had the following core diameters of 2.0, 2.6, 3.4 and 6.9 nm. The florescent dyes used were: Coumarin 440 (CM440), Fluorescein 548 (F548), Rhodamine 6G (R6G), Pyromethene 597 (PM597) and Lyssamine Dye (LD700). Experimental evidence suggests that the photoluminescence quenching of both CdSe QD and the fluorescent dyes occurs through energy transfer and that the AuMPCs are efficient quenchers in both cases. The larger MPCs are more efficient …

Optical And Electrochemical Molecular And Nanoscale Sensors For The Selective Detection Of Organophosphorus Based Pesticides, Chandrima De

Masters Theses

Organophosphorus based pesticides are highly toxic and represent serious environmental concerns. These compounds tend to easily enter ground water and cause drastic pollution. The toxicity levels of the organophosphorus pesticides however are based on their structures, and hence methods for their selective detection are in high demand. The creation of new materials for sensing and actuation requires careful manipulation of the responsive units required to control analyte selectivity. We have successfully designed and synthesized a molecular sensor based on the family of stilbenes that not only can detect organophosphorus pesticides, but also distinguish between them. Four different pesticides have been …

Blocked Localized Wavefunction Analysis Of Π And Σ Bonds In The Metal Carbonyl, Kazuhito Nakashima

Masters Theses

The bonding features in group 10 and 11 metal carbonyls Ni(CO), Pd(CO), Pt(CO), [Cu(CO)]+, [Ag(CO)]+, and [Au(CO)]+ have been studied with BLW method. The carbon monoxide is well known as both a π acceptor and a σ donor. The π back bonding and o bonding are synergistic in these metal carbonyl complexes, because the π donation from the metals polarizes the metals and creates a negative force field as an additional driving force on the σ donation from the carbon end of CO vice versa. The synergistic effect in the metal-carbonyl bonds can be described by decomposing the binding energy …

Real-Time Analysis And Investigation Of The Mechanism Of The Palladium On Carbon Catalyzed Isomerization Of Megestrolacetate, Charlene K. Wiglesworth

Masters Theses

Megestrol Acetate is a semi-synthetic steroid hormone of the progestin family and currently used as a drug therapy in many areas including treatments of cancers and AIDS. The final step to form the bulk drug is an isomerization using palladium on carbon with cyclohexene as an activator. This step is sensitive to catalyst quality and is hazardous to sample because of the reactivity of the catalyst. Physical and catalytic properties of the catalyst were evaluated, as were the effects of solid support and different washing strategies. Response of the reaction mixture to catalyst poisons was studied as a function of …

N-(Deoxyadenosine-8-Yl)-4-Aminobiphenyl Adduct Formation In Vitro On Tp53 Exon7 Genome: Quantitation By Lc-Esi-Ms/Ms, Paul René Knoll

Masters Theses

The p53 protein has been documented to be mutated in more than 50% of late stage bladder cancers and tobacco causes 50% of all bladder tumors. The 4- arninobiphenyl (ABP) carcinogen comprises 5 ng per cigarette in the smoke and is a known bladder carcinogen. The research goal in the present study was to compare the reactivity of rat liver S-9 fraction activated 4-arninobiphenyl with the 45-mer sense strand of the TP53 exon7 gene to the respective anti-sense strand. The specific and sensitive technique of LC-tandem mass spectrometry (LC-MS/MS) was used for quantitation. The authentic standard of N-(adenine-8yl-)-4-arninobiphenyl (A-ABP) …

Nanomaterial Composites For The Detection Of Nerve Gas Analogs, Yogesh Datar

Masters Theses

The basis of the research work described here is the use of nanocomposite materials built by bottom-up approach for the selective detection of nerve gas analogs. Nanocomposites materials constructed by using nanoparticle-monomer-receptor (NMR) concept have been utilized to detect nerve gas analogs DCP and DMMP. Synthetic approach used in the construction of nanosensors involved use of robust platforms such as silica nanoparticles and fluorescent quantum dots. Highly conjugated receptor molecules were synthesized by using stilbeneoid compounds. A complete opto-nanosensor was developed by anchoring highly conjugated receptor molecules onto the silica nanoparticles as well as onto the quantum dots. The opto-nanosensors …

Synthesis And Characterization Of Ruthenium Bipyridyl Complexes For Detecting Nerve Gas Agents And Explosives, Arambe Gedara Aruna Weerasinghe

Masters Theses

Five novel 2,2 '-bis bi pyridine Ru(II) complexes have been synthesized and characterized using ¹H NMR, ¹³C NMR, ¹H-¹H-COSY, elemental analysis, fast atom bombardment or electrospray mass spectra and electronic absorption spectroscopy. Binding of Ru (11) complexes with nerve gas analogos such as diethyl chlorophosphate (DCP), dimethyl methyl phosphonate (DMMP) and hydrolyzed product (HCl) has been investigated by electronic absorption, fluorescence, and lifetime studies. Compound 1 showed a quenching in ³MLCT emission after an initial increase in intensity upon the addition of DCP with a bathochromic shift of 25 nm. Compound 2 exhibit a …