Chemistry Commons^™

Comparing The Quantitation Of Opiates From Possible Drug Overdose Cases Using Results Of Blood Analysis And Liver Analysis, Lee Ann Garozzo

Forensic Science Theses

Currently the quantitation of opiates at the Erie County Medical Examiner’s Office Toxicology Laboratory is conducted through whole blood analysis. The objective of this thesis project was to determine if the analysis of opiates could be conducted through liver analysis, and if the analysis of opiates would provide a more accurate quantitation compared to the blood analysis. The quantitation of opiates was conducted from the livers of sixty-four possible overdose cases that were brought into the Erie County Medical Examiner’s Office between 2013 and 2015. Results showed that the opiate drugs could successfully be quantitated using the liver analysis. Generally …

Early Growth And Development Impairments In Patients With Ganglioside Gm3 Synthase Deficiency, H. Wang, A. Wang, Dan Wang, A. Bright, V. Sency, Aimin Zhou, B. Xin

Chemistry Faculty Publications

Ganglioside GM3 synthase is a key enzyme involved in the biosynthesis of gangliosides. GM3 synthase deficiency (GSD) causes a complete absence of GM3 and all downstream biosynthetic derivatives. The individuals affected by this disorder manifest severe irritability, intractable seizures and profound intellectual disability. However, we have found that most newborns seem symptom-free for a period of time after birth. In order to further understand the onset of the disease, we investigated the early growth and development of patients with this condition through this study. We compared 37 affected individuals with their normal siblings and revealed that all children with GSD …

Characterization Of Plethodontid Timp-Like Protein (Ptp) And Its Role In Tissue Remodeling During Pheromone Gland Development., Andrew Knight

College of Arts & Sciences Senior Theses

Plethodon shermani is a species of lungless salamander that has a complex courtship ritual during which the female straddles the male’s tail. The male then uses a submandibular mental gland to secrete nonvolatile proteinaceous pheromones to increase females’ receptivity to mating. Investigation of the pheromone extract indicated the presence of a protein, termed Plethodontid TIMP-like protein (PTP), with no pheromonelike activity that bears sequence similarity to a group of proteins known as Tissue Inhibitors of Matrix Metalloproteinases (TIMPs). PTP was functionally characterized by measuring its ability to inhibit a range of mouse and human Matrix Metalloproteinases (MMPs). The results of …

Development Of Sulfur And Selenium Halogen Bonded Synthons And Mechanosynthesis Of Halogen Bonded Cocrystals, Adam Michael Siegfried

All Dissertations

The halogen bond, XB, has been known since the nineteenth century. A XB involves the donation of electron density from a donor such as N, O, S, or Se to an electropositive region on another atom typically iodine or bromine. XB acceptors are Lewis bases and XB donors are Lewis acids keeping terminology hydrogen bonding. The highly directional characteristic of the halogen bond paired with phenyl embrace interactions provide very useful supramolecular synthons allowing for the engineering of cocrystals with specific directional bonding motifs.

Nitrogen electron acceptors such as quinoxaline, phenazine, 4,4’-bipyridine, and 4,4’-dimethyl-2,2’-bipyridine are cocrystallized with 1,4-diiodotetrafluorobenzene (1,4-F4DIB), 1,4-difluorotetraiodobenzine …

The Effects Of Hydrogen Bonding On The Reactivity Of Synthetic Ada Repair Protein Analogues, Josiah G. Elsberg

Boise State University Theses and Dissertations

The study of bioinorganic chemistry is an important field, as it can provide insight as to why Nature has chosen certain active sites and structures within different kinds of metalloproteins. Ada repair protein, a zinc-containing metalloprotein, is one such topic of interest. Although it is known that Ada RP is able to repair methyl-phosphotriester backbone damage by self-methylation of one of its cysteine groups, the mechanism is not fully understood. Two pathways have been proposed: a dissociative pathway where the Zn-S bond becomes a zinc/sulfur ion pair, and an associative pathway where a four ringed σ-metathesis occurs. Previous research has …

Energy Management Mechanisms Employed At The Human-Material Interface Of Traditional And Minimalist Shod Running, Nadine M. Lippa

Dissertations

From recreational to elite athletes, greater than 50% of runners sustain overuse injuries each year, prompting substantial research efforts to identify causes of—and solutions to—the high injury rate. Different shoe types and material property degradation have been related to injury. Two popular footwear types are traditional shoes with thick graded soles and minimalist running footwear with thinner foam and/or non-graded soles. Notwithstanding 45 years of significant modifications to shoe design features, gained knowledge in kinesiology, and advanced technologies in polymer science, runner injury rates have not decreased and EVA foam has remained the primary running shoe midsole material since the …

Functionalizing Β-Cyano Oligo(P-Phenylene Vinylene) Chromophores For Use In Mechanochromic Materials, Alexander J. Wink

Honors Theses

Mechanochromic materials are materials that change color upon mechanical deformation. This concept can be applied in areas of quality control, since the knowledge of damaged parts will easily be detected due to a color change in the material that has undergone deformation. Typically these types of materials are enabled by employing functional small molecules. Often, these are conjugated organic molecules or chromophores, which fluoresce different colors determined by the stimulus (or lack thereof) acting upon the material. In this work, we explore a new avenue to elicit color changes in polymeric materials based on the process of restriction of intramolecular …

The Effect Of Acrylic Acid On Ring Formation In Polyacrylonitrile, Elisha Cade Willis

Honors Theses

The addition of comonomers into carbon fiber precursor, polyacrylonitrile (PAN), has shown to have effects on the extent of stabilization and thermal behavior.1 Acrylic Acid (AA) was added at varying initial apparent weight percent and added via semibatch reaction to copolymerize with acrylonitrile to form carbon fiber precursor. Accompanying batch reactions were synthesized for comparison. Degradation was found to be greater in the semibatch reactions although overall was comparable to the batch reactions. Differential scanning calorimetry (DSC) confirmed the addition of higher concentrations of AA into the reaction resulted in a less intense exotherm upon cyclization, along with a greater …

Investigation Of How Hydrogen Bonding Affects The Enantiomeric Excess Of Pig Liver Esterase Promoted Hydrolysis Of Pro-Chiral Substrates, Jacob E. Pruett

Honors Theses

Pig Liver Esterase is a cost effective enzyme for ester hydrolysis. In our group, it is vital for creating chiral molecules for the synthesis of unnatural amino acids of potential biological importance. It has been previously found that the enantiomeric excess (%ee) of the PLE hydrolysis reaction increases drastically with the addition of co-solvents that are able to both accept and donate hydrogen bonds. This research endeavors to see if substrates of enhanced hydrogen bonding ability also increase the stereoselectivity of PLE hydrolyses. Diester malonate was covalently linked with a furan ring in both the third and second position from …

Synthesis And Application Of (R)-3-Methylpyrrolidine-3-Carboylic Acid, Shelby D. Dickerson

Honors Theses

L-Proline is an amino acid widely used in pharmaceutical and biotechnological research due to its catalytic activity and biological relevance. L-Proline has been recognized and utilized as an organocatalyst, which allows cleaner, more sustainable reactions. However, one issue with L-proline is its low solubility in organic systems, limiting its reactivity and efficiency, especially when considering industrial research. Two reactions that utilize L-Proline are the Michael and Aldol but require 100 mol% of L-Proline and 30 mol% of L-Proline, respectively. This research will focus on the synthesis of an analogue of L-Proline utilizing inexpensive, commercially available reagents. A variety of organic …

Automated Data Acquisition Of Deet Time-Dependent Concentration Profiles, Ryan D. Coleman

Honors Theses

Spatial insect repellents must maintain a sufficient concentration in the vapor phase to successfully deter pests. However, little is known regarding correlation of concentration to efficacy nor does there exist a standard testing protocol to measure efficacy in air. Among existing spatial repellents, DEET is the most common active ingredient. This research focuses on application of sensor-based technologies to monitor the concentration levels of DEET under static conditions.

Metal oxide semiconductor sensors feature conductivity variance in response to absorption and desorption of volatile organic compounds. Advantages of these sensors include cost, versatility, and sensitivity. Metal oxide semiconductor sensors were chosen …

Synthesis Of Acceptors For Use In Donor-Acceptor Copolymers And Characterization Of These Polymers, William D. Walker

Honors Theses

In this thesis, a selenium-derivatized acceptor was synthesized to examine the heavy atom effects of selenium on the position of the frontier molecular orbitals (HOMO/LUMO band gap) as opposed to sulfur in a donor-acceptor copolymer for use in light harvesting and detection applications. Over the course of this research, standard operating protocols for ultraviolet-visible (UV-Vis-NIR) and Fourier transform infrared (FT-IR) spectroscopies, as well as cyclic voltammetry (CV) characterization techniques were established. Once synthesized, the polymers were characterized through use of the established characterization protocols. The selenium-derivatized polymer exhibited a bathochromic shift compared to the sulfur analogue, with a solid-state absorption …

Synthesis Of Microgel Polymers As Catalysts, Hannah N. Miller

Chemistry & Biochemistry Undergraduate Honors Theses

New developments in organic synthesis show promise in achieving the best catalytic properties for the hydrolysis of glycosidic bonds through microgel polymers and transition metal complexes. A monomer mix of ethylene glycol dimethacrylate, butyl acrylate, and styrene form miniemulsion polymers after sonication and exposure to UV light. Gravimetrical analysis is used to determine the most suitable polymerization conditions by performing experiments at varying pH values, temperatures, monomer amounts, initiator amounts, and lamp heights. The final data show that the best polymerization conditions are a pH of 10.50 at 0°C with a high monomer ratio, 20% initiator amount, and a lamp …

Structural Variations Involving S-Block Metal Pyrazolates, Joshua Woods

Renée Crown University Honors Thesis Projects - All

Alkali and alkaline earth metal organometallics have been sought after for a variety of applications such as in electronic devices produced by novel metal organic chemical vapor deposition precursors, catalysts and as synthetic reagents. Despite significant advances in synthetic techniques, the chemistry of the highly reactive s-block metals is still relatively unexplored. It is difficult to predict properties, structure and binding modes of these compounds due to a number of factors including enhanced reactivity and tendency to aggregation due to the large metal diameter. On the other hand, many of the s-block metals are earth abundant and environmentally friendly, …

Exogenous Polyunsaturated Fatty Acid (Pufa) Scavenging Affects Phospholipid Profiles And Virulence Phenotypes In Vibrio Cholerae And Vibrio Parahaemolyticus, Anna Moravec

Honors Theses

AIM: This research had two primary objectives. First, this study sought to determine whether or not exposing Vibrio cholerae and Vibrio parahaemolyticus to polyunsaturated fatty acids (PUFAs) would lead to changes in their respective phospholipid profiles. Secondly, if membrane remodeling occurred, this study sought to determine the impact of membrane modifications on bacterial fitness by evaluating their effect on membrane permeability, biofilm formation, and response to stresses. METHODS: The Bligh and Dyer method was used to extract bacterial lipids, which were subsequently analyzed via thin-layer chromatography (TLC). The effect of fatty acids on bacterial fitness was assessed using stress, biofilm, …

Effects Of Cigarette Butts On Coastal Waters: An Elemental Analysis Of Seawater From St. Simon’S Island, Katherine Adorati

Honors Theses

Cigarette litter can have detrimental effects on the environment, specifically when taking into account that over 4.5 trillion cigarette butts are littered every year. Within seawater, trace elements present in cigarettes may leach into the ocean, having damaging effects on the marine ecosystem. The goal of this research was to investigate if elemental contaminants leached from cigarette litter are significant in samples of seawater collected near St. Simon’s Island at both high and low tides, surrounding a beach party during the Florida/Georgia football game which occurred on November 1, 2014. Samples were collected in the months prior to and during …

Direct Band Gap Gallium Antimonide Phosphide (Gasbxp1-X) For Solar Fuels., Harry Benjamin Russell

Electronic Theses and Dissertations

Photoelectrochemical water splitting has been identified as a promising route for achieving sustainable energy future. However, semiconductor materials with the appropriate optical, electrical and electrochemical properties have yet to be discovered. In search of an appropriate semiconductor to fill this gap, GaSbP, a semiconductor never tested for PEC performance is proposed here and investigated. Density functional theory (DFT+U) techniques were utilized to predict band gap and band edge energetics for GaSbP alloys with low amount of antimony. The overall objective of this dissertation is to understand the suitability of GaSb_xP_1-x alloys for photoelectrochemical water splitting application. Specifically, …

A Chemical Sensor For Cyanide, Rachel E. Lambert

Honors Theses

The cyanide ion and its gaseous form, hydrogen cyanide, are extremely toxic. Cyanide impairs cellular respiration by inhibiting cytochrome c oxidase, an enzyme in the electron transport chain, leading to cell death.

In a previous study, we synthesized an optical sensor that detects cyanide selectively. The aim of this project is to increase the sensitivity of this sensor. This can be achieved by utilizing the unique spectroscopic properties of lanthanide ions.

The lanthanide metal (europium or terbium) was added to a coumarin-glycine chemodosimeter in a DMSO solvent system. The sensor was titrated with several monodentate analytes including, nitrate, octylamine, 1-pentanethiol, …

Using Intrinsic Properties Of Polyaniline To Sense Expression Of The Microrna Let-7, Jared N. Gloria

Honors Theses

MicroRNAs are approximately 22-nucleotide long RNA molecules that function through decay and translational repression of messenger RNA. The microRNA let-7 is found to play a role in maintaining the fate of differentiated cells in humans. Thus, expression level of this microRNA is a reliable biomarker of tumor cell phenotype. However, there are significant limitations in the current profiling techniques of microRNA. The current methods like northern blotting, microarrays, RT-PCR, or using locked nucleic acid (LNA) for in-situ hybridization are either laborious, semi-quantitative, or expensive. In this research we try to address this issue by developing a fast, specific, and inexpensive …

Development Of Arginyl-Trna Synthetase From Pseudomonas Aeruginosa As A Platform To Screen For Inhibitors Of Protein Synthesis, Daniel Cantu

Theses and Dissertations

Pseudomonas aeruginosa is a Gram- negative bacteria that is the leading cause of mortality in immunocompromised patients. Arginyl-tRNA synthetase (ArgRS) is an enzyme that catalyzes the covalent attachment of arginine to the cognate tRNAArg during protein synthesis. Scintillation proximity assays (SPA) were adapted to the aminoacylation assay and used to screen, one natural compound library (800) and one synthetic compound library (890) to identify inhibitors of the activity of ArgRS. Five compounds were identified which inhibited greater than 50% of enzymatic activity, two of these compounds (BT04F10 and BT11F03) exhibited promising MICs against Gram+ bacteria and moderate activity against Gram- …

Molecular Mechanism For The Biosynthesis And Regulation Of Secondary Metabolites In Lysobacter, Simon Tesfamichael Tombosa

Department of Chemistry: Dissertations, Theses, and Student Research

This thesis presents regulatory and biosynthetic mechanisms by which microorganisms produce secondary metabolites that can potentially be developed into drugs beneficial to humans. The first section shows the role of small signaling molecules in regulating the production of one of the novel antifungal metabolites, heat stable antifungal factor (HSAF), from Lysobacter enzymogenes.

In the second part of the thesis I report our attempts to isolate and characterize the biosynthesis of WBP, a new secondary metabolite from Lysobacter antibioticus OH13. I have included the in-silico analysis of the gene cluster for WBP and the predicted biosynthetic pathway based on analysis …

Studies In Asymmetric Catalysis: Supramolecular Catalysis And Borane-Assisted Hydrogenation, Kazuya Toyama

Department of Chemistry: Dissertations, Theses, and Student Research

Metal-catalyzed catalytic asymmetric reactions have gained enormous attentions and the utilities of such reactions have facilitated natural products syntheses to afford highly bioactive molecules. While these reactions have provided reliable methodologies to transform basic reactants into product(s) with highly enantio- and regioselective manners, the incompatibility with a many functional groups and the associated need to employ protecting groups increases the number of synthetic steps required. Herein, a solution to such an issue has been proposed in catalytic asymmetric hydroboration of styrene derivatives where supramolecular catalysts developed by Takacs et al. were used to achieve highly regio- and stereoselective reaction on …

Curing Of Polymer Thermosets Via Click Reactions, Mark Richard Brei

Dissertations

In the first project, an azide functional resin and tetra propargyl aromatic diamines were fabricated for use as a composite matrix. These systems take already established epoxy/amine matrices and functionalize them with click moieties. This allows lower temperatures to be used in the production of a thermoset part. These new systems yield many better mechanical properties than their epoxy/amine derivatives, but their T_gs are low in comparison.

The second project investigates the characterization of a linear system based off of the above azide functional resin and a difunctional alkyne. Through selectively choosing catalyst the linear system can show …

Synthesis And Characterization Of "Click Inspired" Thiol-Ene-Fullerene Nanocomposites, Amber Danielle Windham

Dissertations

This work explores the covalent incorporation of C₆₀ and Sc₃N@C₈₀ fullerenes into thiol-ene networks by a facile, one-pot photochemical reaction with multifunctional thiol and alkene monomers. Synthesis of disulfide bonds within the tri-functional thiol monomer served to photochemically initiate the reaction when cleaved. This was followed by thermal curing of the pre-polymer for preparation of fullerene-containing thiol-ene films. Films were characterized by standard techniques including infrared spectroscopy, gel percent, and thermogravimetric analysis. The role of C₆₀ and Sc₃N@C₈₀ as suitable alkenes for free-radical reaction with multifunctional thiols was investigated by preparing a …

Addressing The Issues Of Drug Delivery Via Advanced Macromolecular Design, Brooks Allen Abel

Dissertations

The work described in this dissertation focuses on the development of synthetic approaches toward novel polymer architectures that specifically address the issues of in vivo drug delivery. Successful implementation of the synthetic methodologies described herein required fundamental investigations into the underlying chemistries in ways that now provide greater insights into the nature of the these chemical reactions.

In Section I, the synthesis of tunable pH- and CO₂-responsive sulfonamide-containing polymers using reversible addition-fragmentation chain transfer (RAFT) polymerization is described. Initially, poor polymerization control of methacryloyl sulfonamide (MSA) monomers was observed using traditional RAFT polymerization conditions. Ultimately, reducing the polymerization …

Preparation Of Novel Steroidal Conjugates As Potential Diagnostic And Therapeutic Agents With An Emphasis On Quinoid And Halogenated Moieties, Nuha Obaid Juma Alsoom

Theses

Steroids bonded to pharmaceutically active molecules are interesting candidates as therapeutic agents. In this work, a number of potentially bioactive residues, which include the quinoid moiety, have been synthesized as a simple steroid quinone hybrid, where the steroid component will be estradiol derived or the steroid cholesterol derived. For this purpose, two novel reactions have been explored namely, the modification of the APPEL reaction to connect residues by using PPh3/BrCCl3 for amidation and esterification of carboxylic acids. Another one is the hydrogenation reaction of alkenes by using NaBH4, AcOH, Pd/C and toluene or benzene in the presence of benzyl groups …

The Effect Of Pure Infrared Light On The Growth Of Rhodospirrilum Rubrum, Jordan Lee Wilkes

Undergraduate Honors Capstone Projects

Scientists who study aquatic ecosystems quickly notice a diversity of pathways that different microbes and organisms can use to metabolize nutrients found in common ponds or pools. Competition for vital resources, such as light and inorganic minerals, allow only certain organisms to grow in certain niches within these ecosystems. Rhodospirillum rubrum is a gram negative, photosynthetic bacteria that competes for light within aquatic ecosystems in order to survive. R. rubrum is believed to specifically absorb light for photosynthesis at wavelengths in the range of infrared light. It was found that R. rubrum indeed can grow in "dark", anaerobic environments by …

Immobilization Of Heteropolyacids In Silica Gel, Opeyemi Adetola

Electronic Theses and Dissertations

Silica gels containing incorporated heteropolyacids (HPAs) were synthesized in acidic media by co-condensation of tetraethoxysilane (TEOS) with phosphotungstic or phosphomolybdic acids using sol-gel technique. Effect of the synthesis conditions on their structure and morphology was studied. Yields of modified materials were some lower as compared to non-modified silica gels. All materials were mesoporous but contained micropores in their structures. Presence of bands of Keggin’s structures in FT-IR spectra along with absence of XRD patterns of crystalline HPAs confirmed their fine incorporation into silica network. Particle sizes of modified materials were 800-1100 nm excepting for W-containing sample obtained with trimethylstearylammonium chloride. …

Placental ‘€˜Omics’€™ Study To Understand The Pathogenesis Of Preeclampsia, Komal Kedia

Theses and Dissertations

Preeclampsia (PE) is a potentially fatal complication of pregnancy characterized by an increase in blood pressure (>140/90 mmHg) and proteinuria (>300 mg/24 hrs), often accompanied by edema. Symptoms of PE start after 20 weeks of gestation. If PE remains untreated, it can lead to eclampsia, grand-mal seizures responsible for most fatalities. PE is believed to affect 2-10% of pregnancies worldwide, and claims the lives of over 75,000 mothers and 500,000 newborns yearly. No therapeutic agents have been developed to prevent or cure PE. Part of the reason for this is the absence of a complete understanding of the …

Identification Of Synthetic Chemical Compound Inhibitors Of Pseudomonas Aeruginosa Protein Synthesis And The Development Of Lead Series, Stephanie O. Palmer

Theses and Dissertations

Pseudomonas aeruginosa is a ubiquitous Gram-negative bacteria and a primary cause of nosocomial infections. An aminoacylation/translation (A/T) assay was developed using P. aeruginosa components to perform poly(U) mRNA directed protein synthesis. Using scintillation proximity assay (SPA) technology a high-throughput screening (HTS) platform was developed. A synthetic chemical compound library (>900) was screened, 36 hit compounds were identified and molecular targets were determined. Compounds were analyzed for enzymatic inhibition (IC50) and inhibition of bacterial cultures (MIC). Time-kill studies determined bacterial growth to be bacteriostatic or bactericidal in the presence of inhibitor. Mechanism of action, effects on eukaryotic cytosolic and mitochondrial …