Chemistry Commons^™

Postmortem Vitreous Humor As An Alternative Matrix To Peripheral Blood For Benzodiazepine Detection, Sara Bussey

Honors Theses

Benzodiazepines are commonly prescribed secondary drugs of abuse that cause Central Nervous System depression through the neurotransmitter gamma aminobutyric acid. While not commonly fatal on their own, benzodiazepines have a minor risk for physical dependence and abuse. They also can have cumulative effects with other medications that can lead to overdose situations; thus, they are considered secondary drugs of abuse. While peripheral blood is considered the standard for xenobiotic detection in postmortem forensic toxicology, it is important to consider the validity of alternative matrices that could be analyzed in the event that blood was not available due to circumstances like …

The Development Of High Throughput Assays For Identification And Evaluation Of Small Molecule Modulators Of The Pri-Microrna-18a—Hnrnp A1 Interaction, Emile N. Van Meter

Dissertations

Therapeutics targeting RNA is a rapidly growing field. While only 1.5% of the human genome encodes genes for protein, over 70% o=f the human genome contains the genes for noncoding RNAs that regulate protein expression and function. Expanding the paradigm of small molecule drug discovery from traditional protein targets to include RNA would broaden the therapeutic landscape and provide new methods to modulate previously undruggable targets. miRNAs (miRs) have been found to be aberrantly expressed in many disease states, including neurodegenerative diseases and cancers making them promising therapeutic targets. The production of functional, mature miRs requires multiple proteins in a …

Mechanistic And Evolutionary Insights Into A Group Of Nicotine And Hydroxynicotine Degrading Flavoenzymes, Zhiyao Zhang

Dissertations

Flavoprotein amine oxidases (FAOs) are key enzymes in various kinds of metabolic pathways, mediating redox reactions via flavin cofactors. While most FAOs function as oxidases that readily reduce oxygen to hydrogen peroxide, a few outliers of the FAO family act as dehydrogenases that suppress the reaction with oxygen. The molecular basis for this divergence in function remains poorly understood.

The work presented in this study investigates the fundamental mechanisms of how flavincontaining enzymes activate or suppress their reaction with different electron acceptors to achieve high turnover rates. The overall body of work is divided into three different sections that (1) …

Probing Shielding Tensor Components Of Amino Acids Using Nuclear Magnetic Resonance, Shiva Agarwal

Dissertations

Chirality is fundamental to terrestrial life. While most amino acids exist as nonsuperimposable mirror images, amino acids in terrestrial life are homochiral, with the L-enantiomer being ubiquitous. The detection of an excess of L-amino acids in carbonaceous meteorites suggests that extraterrestrial processes may have contributed to this enantiomeric excess (ee). One proposed mechanism, the magnetochiral model, provides a potential explanation for this phenomenon in stellar environments characterized by strong magnetic and electric fields and the presence of relativistic leptons. According to this model, subtle differences in the electronic environments of chiral amino acids under such conditions …

Preservation And Integrity Of Laboratory Solutions: Understanding The Impact Of Storage Practices On Chemical Stability And Experimental Accuracy, Azza Al Jahdhami

Honors Theses

Chemical storage methods represent a key matter ignored within labs, educational sites, workplaces, and even households. Many people, including various students and instructors within the chemistry field, are unaware of the proper methods for storing and disposing of common chemicals. This study aims to understand the effects of storage practices on chemical stability and experimental accuracy, dealing with the following questions: What kind of effects result from improper chemical disposal? How can improper storage affect the overall chemical effectiveness? Why is sink disposal of many solutions discouraged, and why is waste container disposal always necessary?

Through a literature review, this …

Utilizing Drainage Induced Pfas Enrichment In Cascade Generated Foam For Efficient Removal At Wastewater Treatment Plants, Ethan Samuel Coffin

Dissertations

Observed trends in municipal solid waste landfills reveal a distinct disparity between per- and polyfluorinated alkyl substances (PFAS) composition entering in waste, mostly as diPAP and FTOH, and leaching out as FTCA and PFCA. These patterns are elucidated by compiling PFAS compositions in paper, textiles, and carpet, with known precursor transformations that generate FTCA and PFCA in leachate. Landfill leachate is commonly discharged to wastewater treatment plants (WWTP), which are ineffective at degrading PFAS and only serve as key conduits and discharge points for PFAS to the environment. Foam fractionation has been identified as a promising technology for concentrating and …

Co2 Capture Utilizing Novel Deep Eutectic Solvents: Modeling, Process Simulation, And Cost Analysis, Nazneen Aspi Kolah

Masters Theses

One of the most pressing global issues that humans face is climate change caused by anthropogenic greenhouse gas emissions, especially carbon dioxide (CO2). Conventional solvents utilized for CO₂ capture, such as amines, are widely used in industrial applications due to their high CO2 absorption capacity. However, deep eutectic solvents (DES) have attracted a lot of academic attention recently due to their biodegradability and low energy for regeneration.

This research serves as a foundational proof-of-concept for using DESs in industrial gas separation processes. Five DES are evaluated for CO2 removal from flue gases. Aspen Plus is utilized to simulate the performance …

Comparison Of Atmospheric Pressure Chemical Ionization And Electrospray Ionization Mass Spectrometry For The Direct Analysis Of Hops Bittering Compounds, Chhiring Sherpa

Masters Theses

Hops acids are essential components in the beer brewing process containing alpha acids (α-acids) and beta acids (β-acids) as the major hops bittering compounds. Quantifying these acids is vital for quality control and determining bitterness levels and hops variety profiles. Current industry standards, like High-Performance Liquid Chromatography with Ultraviolet detection (HPLC-UV) and Ultraviolet Spectroscopy (UV-Vis), though effective, are time-consuming and solvent-intensive, providing incomplete information.

This research introduces a novel method using mass spectrometry with atmospheric pressure chemical ionization (APCI-MS) to analyze hops bittering acids without chromatographic separations. This approach offers rapid analysis, high throughput, and eco-friendliness.

Comparison with direct electrospray …

Hydrophobic Deep Eutectic Solvents: Liquid-Liquid Extraction Of Organic Water Pollutants, Abigail Louise Maletta

Masters Theses

Pollution is a topic of significant research within the scientific community. The massive demand for industrial processes to deliver the technology and resources we rely on has opened numerous avenues for pollutants to enter the environment, affecting air, water, soil, and the food chain. Oftentimes, these pathways are intertwined, and the interplay between water and air currents spreads pollution globally, creating a cascade of environmental impacts. Water, a vital resource for all forms of life, is particularly susceptible to industrial pollution. Among the most prevalent water pollutants are heavy metals, such as lead and mercury, and organic compounds, often released …

Diagnosing Discharge Events Within A Novel Miniature Simplified Coaxial Ion Trap Mass Analyzer, David Virgil Sirbescu-Stanley

Masters Theses

Mass spectrometry is a technique that organizes material samples by mass to reveal their chemical composition by forming a spectrum. Since their invention, ion trap mass spectrometers have undergone significant enhancements. This work, funded by the National Science Foundation and in collaboration with Brigham Young University, the Simplified Coaxial Ion Trap (SCIT), attempts to simplify ion trap geometry and combine three ion traps into one device. Successful demonstration of the SCIT functionality could reduce costs, reduce manufacturing complexity, and shrink total instrument volume. At the same time, trapping capacity and analytical efficiency will be increased. However, as discussed within, challenges …

Synthesis And Characterization Of Heavy-Metal Oxoanion- And Phosphonate-Binding Nanojars, Pooja Singh

Dissertations

Nanojars are an emerging class of anion-binding and extraction agents. These supramolecular coordination complexes (2 nm wide) exhibit exceptional anion binding strength that points to their possible application in the recovery of toxic or valuable anions from water bodies. Nanojars of the formula (TBA)2[XO3/42−⸦{CuII(μ-OH)(μ-pyrazolate)}n] (TBA = tetrabutylammonium cation; XO3/42− = anion; X = Se, Te, Cr, Mo, W, HP, HAs, HV; n = 26 – 36) are synthesized from Cu2+, OH−, pyrazole and the TBA salts of various anions. Nanojars possess hydrophobic exteriors with an array of pyrazolate ligands and hydrophilic interiors with a …

Rapid Reaction Studies On The Chemistry Of Flavin Oxidation In Urocanate Reductase, Niusha Delavari

Masters Theses

Urocanate reductase (UrdA) is a bacterial flavin-dependent enzyme that reduces urocanate to imidazole propionate, enabling bacteria to use urocanate as an alternative respiratory electron acceptor. Elevated serum levels of imidazole propionate are associated with the development of type 2 diabetes and, since UrdA is only present in humans in gut bacteria, this enzyme has emerged as a significant factor linking the health of the gut microbiome and the metabolic disorder insulin resistance. Here we investigated the chemistry of flavin oxidation by urocanate in the isolated FAD domain of UrdA (UrdA’) using anaerobic stopped-flow experiments at 4 °C. This analysis unveiled …

Chemical And Genetic Composition Analysis Of Organic And Nonorganic Tortilla Chips, Aubrey White-Day

Honors Theses

The aim of this study was to explore the chemical and genetic differences between organic and nonorganic tortilla chips using GC-MS and PCR. Twenty chip brands were selected: 10 organic and 10 nonorganic. A survey on shopping preferences was created and distributed to compare results of public opinion to experimental data. It yielded 212 responses. All organic chip brands, and one out of ten nonorganic chip brands, tested negative for GMOs. This study concluded that there are minimal chemical differences based on Jaccard similarity indicies and stark genetic differences between organic and nonorganic tortilla chips. In comparing statistical analyses to …

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 …

Characterization Of Shinella 6-Hydroxy-(L)-Nicotine Oxidase (6hlno-Se), Kaitrin Funckes

Honors Theses

6-hydroxy-(L)-nicotine oxidase, isolated from the organism Shinella sp. HZN7 (6HLNO-SE), is an enzyme that during the catabolism of nicotine catalyzes the oxidation of (S)-6-hydroxynicotine to 6-hydroxypseudeooxynicotine. This enzyme is a member of the monoamine oxidase (MAO) structural family of flavoproteins, which contain a highly conserved FAD-binding domain. Within the binding domain is a conserved lysine residue that can be traced throughout evolutionary history in this family. 6HLNO isolated from Arthrobacter nicotinovorans serves as a model enzyme for the one isolated from Shinella as both catalyze the same reaction in this biochemical pathway and much has been studied about the Arthrobacter …

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 …

Analysis Of The Zebrafish Olfactory System Using Immunohistochemistry And Enhanced Techniques Of Desorption Electrospray Ionization Mass Spectrometry (Desi-Ms), Tara Lynn Maser

Dissertations

Desorption electrospray ionization (DESI-MS) is an ambient ionization technique where the sample is analyzed directly from a surface with very minimal sample preparation under ambient conditions and follows ESI-like ionization mechanisms. DESI-MS has proven powerful in analyzing or imaging lipids and other small molecules directly from biological samples and even allows for subsequent histological staining and analyses. However, DESI-MS is less widely used for protein analysis due to a lack of sensitivity and the complex diversity of proteins in biological samples.

A major goal of this research has been to obtain new neurobiological knowledge by combining histology and mass spectrometry …

Mechanisms And Applications Of Improved Protein Analysis By Desorption Electrospray Ionization Mass Spectrometry (Desi-Ms), Roshan Javanshad

Dissertations

Electrospray ionization mass spectrometry (ESI-MS) is a soft ionization technique that allows detection of macromolecules, such as intact proteins, by the formation of multiply charged ions from solutions. Desorption electrospray ionization mass spectrometry (DESI-MS) is an ambient ionization technique that directly samples analyte from a surface during ESI-MS analysis. Although DESI-MS is highly accomplished at the analyses of metabolites, lipids, and other small molecules, it is far more limited when it comes to protein analysis. While most of the field in ambient ionization MS has moved towards primarily applications, our approach has been to explore the use of DESI-MS and …

Lxr Acts As A Differentiator In The Regulation Of Fas And G6pdh Gene Expression Under Insulin Resistant Conditions, Jaafar Hachem

Dissertations

Diabetes is a chronic disease that effects 10 percent of the world’s population and causes more than 1.5 million deaths a year and billions of dollars in associated health care cost. It can lead to very serious complications such as renal failure, liver cirrhosis, heart attack, and vision loss. The most common type of diabetes is type 2 diabetes. Type 2 diabetes arises when blood glucose levels remain chronically high due to insulin resistance. The reason for this elevation is due to the failure of insulin to allow tissues to uptake glucose causing problems in subsequent metabolic pathways. Over the …

Synthesis And Characterization Of Novel Organic Ligands With Their Complexes Of Platinum, Copper And Uranium, Mustafa Adnan Yasin Aldulaimi

Dissertations

Transition metal complexes of symmetrical and asymmetrical Schiff bases have played a significant role in the field of coordination, inorganic, and bioinorganic chemistry as models for biological, analytical, industrial, and pharmaceutical applications. Over recent years a great deal of interest has developed in new transition metal complexes of Schiff base ligand. The preparation of novel organic ligands is the most important step in the development of metal complexes that exhibit unique properties and novel reactivity. To highlight the presentation of this dissertation and to provide more detailed investigations, the dissertation was separated into six chapters according to the sequence 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 …

Optimization Of Cation Exchange Chromatography Purification Of A Small Peptide: An Industrial And Practical Approach, Jamin Willoughby

Honors Theses

Ion exchange chromatography (IEX) is a common chemical separation technique that is used to separate ionizable target molecules from a liquid mixture mobile phase by adsorption of the molecule to a stationary phase. In chromatography, the stationary phase is a porous solid that the target molecule and mobile phase flows through, and is commonly referred to as the resin. Resins are commonly packed into hollow cylindrical columns. The mobile phase is the liquid solvent which flows through the column containing the stationary phase. The target molecule will have an affinity for the resin and adsorb to it, while impurities in …

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 …

Embedded Gold Nanoparticles For Metal Enhanced Photoluminescence, Hasna Alali

Dissertations

Noble metal nanoparticles (MNPs) have attracted great attention in electronics, solar cells and catalysis. Their unique optical properties and biocompatibility makes them useful in biological applications like imaging, drug delivery, therapy and diagnostic. At the surface of MNPs the collective oscillation of free electrons resonates with a particular wavelength of incident light, generating the Localized Surface Plasmons Resonance (LSPR). LSPR results in absorption and scattering of incident light. Scattering results in reflecting photons and absorption leads to enhanced photoluminescence and quenching of fluorophores, if the fluorophore is in the vicinity of MNPs.

Most of the studies in this regard have …

Biological Evaluation Of Fda-Approved Drugs As Mirna-31 Inhibitors Using Real Time Qrt-Pcr And A Luciferase Assay, Nicholas Sienkiewicz

Honors Theses

MicroRNAs (miRNAs) are a group of post-transcriptional, negative regulators of gene expression, consisting of ~19-24 nucleotides. Since their discovery in 1993, miRNAs have been found to be involved in a diverse amount of cellular and disease pathways, including certain types of cancer. Overexpression of certain oncogenic miRNAs, including miRNA-31, have been shown to play a role in cancer cell development. Recent findings have suggested that miRNAs play a significant role in every stage of colorectal cancer (CRC) initiation, progression, and development, as well as induce resistance to chemotherapy drugs like 5-FU. In particular, research has shown that increased levels of …

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 …

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 …

What A Career In Teaching Could Look Like For Me: My Journey Of Self-Reflection And Self-Discovery, Jashaun D. Bottoms

STEM Instructional Graduate Teaching Assistant Posters

I started the STEM Instructional Program the summer before my first teaching experience as a graduate student at WMU, and I saw it as a great training opportunity for the upcoming school year. As a General Chemistry II lab instructor, I would encounter students from various majors and backgrounds, with different learning styles and attitudes toward chemistry and math.

In order to effectively engage these students in a pre-lab lecture and to prepare them to complete the experiments, I needed to learn how to keep their attention, clearly explain and relay information in an interesting way, check their understanding, and …

Using Novel Spectroscopy Tool To Study Organized Self-Assemblies, Mohammad Rafe M Bin Hatshan

Dissertations

Organized self-assemblies are the cornerstones for countless biological processes and are integral parts of lipids, proteins, carbohydrates, nucleic acids, and cell membranes. Several man-made organized assemblies also play a vital role in interdisciplinary sciences that include micelles, reverse micelles, polymers, polyelectrolytes etc. Weak chemical interactions such as hydrogen bonding, p-p stacking, hydrophilic-hydrophobic and electrostatics often result in interesting organized self-assemblies. Understanding organized self-assemblies provides a huge opportunity to mimic naturally occurring biological macromolecules, design materials and develop strategies for specific applications. Several techniques are routinely used to understand the organized self-assemblies, and optical techniques play an important role in most …