Chemistry Commons^™

Conversion Of Cafo Manure Into A Slow-Release Fertilizer, Richard Allan Williams Iii

Honors Projects

Alginate polymer is known to form gel through the process of Ionotropic gelation. By use of extrusion and diffusion setting manure was encapsulated into gel beads. These beads were then tested to determine their potential for further testing as a manure treatment process. From the limited data in this preliminary study, it appears as though there is potential for further testing of alginate beads as a treatment process for manure. The treatment is potentially valuable because of the ease of filtration of the alginate beads, the low cost of transportation of the dehydrated beads, and because the limited data suggests …

Phosphonium/Phosphate Ionic Liquids As Lubricant Additives: The Synthesis And Testing Of Six Novel Ils, Matthew Scott Welmers

Graduate Theses - Chemistry and Biochemistry

In this study, ionic liquids (ILs) are defined as ionic materials with a melting temperature >100oC. ILs are characterized by their organic moieties which prevent crystallization, forcing the liquid phase. ILs are desirable as lubricant additives because of their ability to be fine-tuned by varying the identity of the cation/anion as well as the various organic functional moieties therein. Several novel phosphonium/phosphate ILs have been successfully synthesized via a simple, straightforward process. In this work a series of symmetric and asymmetric anionic phosphodiesters are developed and coordinated with two asymmetric alkyl phosphonium cations. These ILs are tested in SAE 10W30 …

Extracting (1,3/1,6)-Β-Glucans From Saccharomyces Cerevisiae: A Fungal Immunotherapeutic, James C. Elliott

Undergraduate Honors Theses

The goal of this research was the development of a method to extract pure (1,3/1,6)-β-glucans from Saccharomyces cerevisiae. These β-glucans are of pharmaceutical importance because an animal’s immune system can recognize glucan molecules, and these molecules can act as immunomodulators, essentially turning on the immune system. The problem in the past has been that previously published methods produce β-glucans with low side chain lengths and few branching occurrences. This issue was tackled by a multivariable approach that reduced extraction steps, initial sample size, and concentrations of reagents used. This method has been shown to produce greater yields of β-glucans while …

Identification Of Protein Palmitoylation Inhibitors From A Scaffold Ranking Library, Laura D. Hamel, Brian J. Lenhart, David A. Mitchell, Radleigh Santos, Marc A. Giulianotti, Robert J. Deschenes

Mathematics Faculty Articles

The addition of palmitoyl moieties to proteins regulates their membrane targeting, subcellular localization, and stability. Dysregulation of the enzymes which catalyzed the palmitoyl addition and/or the substrates of these enzymes have been linked to cancer, cardiovascular, and neurological disorders, implying these enzymes and substrates are valid targets for pharmaceutical intervention. However, current chemical modulators of zDHHC PAT enzymes lack specificity and affinity, underscoring the need for screening campaigns to identify new specific, high affinity modulators. This report describes a mixture based screening approach to identify inhibitors of Erf2 activity. Erf2 is the Saccharomyces cerevisiae PAT responsible for catalyzing the palmitoylation …

Surface And Interfacial Design And Control Of High Performing Thermoplastics: Polysulfones And Beyond, Katrina Marie Knauer

Dissertations

The study of a class of materials almost always begins with the development of an understanding of properties in the bulk state. However, it is the study of surface critical phenomena that has led to a number of new important insights into polymer behavior. A systematic understanding of physical properties in the immediate vicinity of surface and interfacial layers, which cannot be deduced by simple extrapolation of bulk properties, is of significant importance for advancements in polymer applications where the interface drives performance, such as in membranes, coatings, drug-delivery systems, medical devices, and composites.

First, the surface and interfacial modification …

Microdialysis Studies Using Porcine Pancreatic Elastase To Guide Mathematical Modeling Of Microdialysis Sampling For In Vivo Measurements., Mason W. Young

Biomedical Engineering Undergraduate Honors Theses

Microdialysis sampling uses a semi-permeable membrane to allow solute collection by diffusion. When used in conjunction with other instruments, analytes in question can be quantified. Matrix Metalloproteinases (MMPs) are enzymes involved in numerous biological processes where they serve the role of degrading extracellular matrix. Microdialysis sampling, in coordination with further analysis methods, can be used in order to measure the activity of these enzymes in a region of the body instantaneously. The intention of this project is to determine ways of measuring in vitro activity of elastase from porcine pancreas using determined activity values and the collection of elastase products. …

Energy Transfer And Localization In Molecular Crystals, Mitchell A. Wood

Open Access Dissertations

With the aim of developing new technologies for the detection and defeat of energetic materials, this collection of work was focused on using simulations to characterize materials at extremes of temperature, pressure and radiation. Each branch of the work here is collected by which material response is potentially used as the detectable signal.

Where the chemical response is of interest, this work will explore the possibility of non-statistical chemical reactions in condensed-phase energetic materials via reactive molecular dynamics (MD) simulations. We characterize the response of three unique high energy density molecular crystals to different means of energy input: electric fields …

Rhenium(I) Complexes Of Tetraazatetrapyridopentacene (Tatpp): Synthesis, Characterization, Reactivity, Anticancer Potential And Luminescent Probe To Determine Cellular Localization, Pooja Ahuja

Chemistry & Biochemistry Dissertations - Archive

The ruthenium polypyridyl complexes [(phen)2Ru(tatpp)Ru(phen)2]4+ ([P]4+) and [(phen)2Ru(tatpp)]2+ ([MP]2+) are promising anti-tumor agents that arrest H358 NSCLC tumor growth in mouse tumor models and show cytotoxicity in the low micromolar range towards a number of platinum sensitive NSCLC lines (H358, H226, HOP62, H2087). Dose escalation toxicity studies in mice reveal that [MP]2+ and [P]4+ are tolerated without any short term side effects at levels up to 40 mg drug/kg mouse and >160 mg drug/kg mouse respectively with no obvious side effects, when administered as IP injection. Mechanistic studies reveal that much of the anti-tumor activity is primarily due to the …

Application Of Novel Heterosubstituted Vinylimidazoles: An Approach En Route To The Total Synthesis Of Axinellamine A, Abhisek Ray

Chemistry & Biochemistry Dissertations - Archive

Our group is primarily interested in the total synthesis of oroidin-based pyrrole-imidazole-containing marine sponge-derived alkaloids. These pyrrole-imidazole natural products are a growing class of alkaloids with exotic connectivity, unique topologies, and high nitrogen content. Presence of 2-aminoimidazole and pyrrolecarboxamide fragments in the structure represent their signature features. Due to their structural diversity and biological activity, many groups are interested in the total synthesis of these natural products. It has been proposed that many of the alkaloids in this family are produced in nature by dimerization of the simplest member, oroidin. In this dissertation we have explored a biosynthetic hypothesis disclosed …

Regulation Of The Reaction Between Cytochrome C And Cytochrome Oxidase, Jennifer Silva-Nash

Chemistry & Biochemistry Undergraduate Honors Theses

Irreversible brain damage is commonly seen in patients that have suffered strokes, cardiac arrest, or other brain ischemia events. The hypoxic conditions result in neuron death, and previous studies have shown that additional damage occurs when blood flow is restored. It is thought that the lack of energy production during post-ischemia events also causes severe brain damage, as the brain heavily depends on oxidative phosphorylation. Cytochrome c (Cyt c) plays a crucial role in this energy production by means of the electron transport chain (ETC), transferring electrons between complexes ΙΙΙ (cytochrome bc1) and ΙV (cytochrome c oxidase, CcO). Mitochondrial …

Staphylococcal Nuclease And Ubiquitin Local Folding Energies And Rates Using Peps-Hdx-Esi-Ms, Julie Rhee

Chemistry & Biochemistry Undergraduate Honors Theses

In this study, Protein Equilibrium Population Snapshot Hydrogen-Deuterium Exchange Electrospray Ionization Mass Spectrometry (PEPS-HDX-ESI-MS) was applied to study the local regions of model proteins, staphylococcal nuclease and ubiquitin. The hydrogen deuterium exchange (HDX) has become a key technique for studying the structural and dynamic aspects of proteins in solution. This technique creates a rapid exchange between all of the exchangeable hydrogen ions with deuterium when the protein is exposed to a solvent. The PEPS method is an equilibrium-based method used to determine the populations of the closed native and open denatured states of a protein. By combining the applications of …

Influence Of Cholesterol On Single Arginine-Containing Transmembrane Helical Peptides, Jordana K. Thibado

Chemistry & Biochemistry Undergraduate Honors Theses

An essential component of animal cells, cholesterol exerts significant influence on the physical properties of the cell membrane and in turn, its constituents. One such category of constituents, the membrane proteins, are responsible for diverse and essential biological functions and often contain polar amino acids. Although sparse within the hydrophobic interior of lipid-bilayer membranes, polar amino acid residues are highly conserved and may play pivotal roles in determining specific structural and functional properties of key proteins. To gain greater understanding of the lipid membrane environment, and more broadly, cellular function, a model peptide framework termed “GWALP23” (acetyl-GGALWLALALAL¹²AL^{14 …}

The Evaluation And Implementation Of Magnetic Fields For Large Strain Uniaxial And Biaxial Cyclic Testing Of Magnetorheological Elastomers., Dave Gorman, Niall Murphy, Ray Ekins, Stephen Jerrams

Articles

Magnetorheological Elastomers (MREs) are “smart” materials whose physical properties are altered by the application of magnetic fields. In previous studies the properties of MREs have been evaluated under a variety of conditions, however little attention has been paid to the recording and reporting of the magnetic fields used in these tests [1]. Currently there is no standard accepted method for specifying the magnetic field applied during MRE testing. This study presents a detailed map of a magnetic field applied during MRE tests as well as providing the first comparative results for uniaxial and biaxial testing under high strain fatigue test …

Increased Hydride Transfer Rates Within T09a Mutant Of F420:H2 Nadp+ Oxidoreductase, Md Hasmat Ullah

Chemistry & Biochemistry Theses - Archive

F420:H2 NADP+ oxidoreductase (Fno) is an F420 dependent enzyme found in methanogens and sulfate reducing archaea. Fno catalyzes the reversible reduction of NADP+ to NADPH through the transfer of a hydride involving F420 cofactor. The focus of our work is to study the hydride transfer mechanism of Fno from Archaeoglobus fulgidus using site directed mutagenesis, steady-state and pre steady-state kinetic methods. Threonine 09 (T09) is a conserved residue within Fno. The hydroxyl (–OH) group of T09 interacts with the phosphate and ribose of neighboring NADPH. Therefore, T09 was converted into an alanine (T09A) to study its functionality within Fno and …

E56h + E59h Mutation Affects Binding Of The Recombinant Haemphilus Influenza Carbonic Anhydrase To A Ni-Nta Column, Eric D. Lebel, Kathleen Cornely

Chemistry & Biochemistry Student Scholarship

The Haemophilus influenzae carbonic anhy- drase (HICA) is important in converting carbon dioxide to bicarbonate in bacteria. Endogenous cellular proteins, like Escherichia coli carbonic anhydrase (ECCA), have been observed to bind to a Ni-NTA column, which can be used as a means of protein purification. The possibility ex- ists that proteins that do not normally bind to Ni-NTA, like HICA, can be engineered using site directed mutagenesis to introduce histidine resi- dues that would give the protein the capability to bind, allowing for a one-step purification method. Site-directed mutagenesis was used to introduce the double mutation of E56H + E59H …

Improving Photocatalytic Activity By Appending A Quinone To Ruthenium Polypyridyl Complex, Amy N. James

Chemistry & Biochemistry Undergraduate Honors Theses

By converting natural light energy into chemical energy, chemists are studying ways to take advantage of clean energy. The rising precedence of “green chemistry” has led to academic interest in the activity of photocatalysts and harnessing visible light in an efficient, accessible, and safe manner. Photochemistry is an upcoming and fascinating field of study that has made significant progress, but also has great potential for future work. By utilizing light as a natural energy source, many reaction processes in chemistry can be viewed with a new perspective. Ru(bpy)₃²⁺ is one of the most widely used photocatalysts. An efficient …

Role For Reactive Oxygen Species In Methamphetamine Modulation Of Dopamine Release In The Striatum, David Matthew Hedges

Theses and Dissertations

Methamphetamine (METH) is a highly addictive substance that is highly prevalent in today’s society, with over 1 in 20 adults over 26 having taken it at least once. While it is known that METH, a common psychostimulant, acts on both the mesolimbic dopamine (DA) and nigrostriatal DA systems by affecting proteins involved in DA reuptake and vesicular packaging, the specific mechanism of what is known as METH neurotoxicity remains obscure, but has been shown to involve oxidative stress. Studies have shown that reactive oxygen species act on the same proteins that METH affects. Oxidative species have also been known to …

Crystal Structures Of (Z)-5-[2-(Benzo[B]Thiophen-2-Yl)-1-(3,5-Dimethoxyphenyl)Ethenyl]-1H-Tetrazole And (Z)-5-[2-(Benzo[B]Thiophen-3-Yl)-1-(3,4,5-Trimethoxyphenyl)Ethenyl]-1H-Tetrazole, Narsimha Reddy Penthala, Jaishankar K. B. Yadlapalli, Sean Parkin, Peter A. Crooks

Chemistry Faculty Publications

(Z)-5-[2-(Benzo[b]thio­phen-2-yl)-1-(3,5-di­meth­oxy­phen­yl)ethen­yl]-1H-tetrazole methanol monosolvate, C₁₉H₁₆N₄O₂S·CH₃OH, (I), was prepared by the reaction of (Z)-3-(benzo[b]thio­phen-2-yl)-2-(3,5-di­meth­oxy­phen­yl)acrylo­nitrile with tri­butyl­tin azide via a [3 + 2]cyclo­addition azide condensation reaction. The structurally related compound (Z)-5-[2-(benzo[b]thio­phen-3-yl)-1-(3,4,5-tri­meth­oxy­phen­yl)ethen­yl]-1H-tetra­zole, C₂₀H₁₈N₄O₃S, (II), was prepared by the reaction of (Z)-3-(benzo[b]thio­phen-3-yl)-2-(3,4,5-tri­meth­oxy­phen­yl)acrylo­nitrile with tri­butyl­tin azide. Crystals of (I) have two mol­ecules in the asymmetric unit (Z′ = 2), whereas crystals of (II) have Z′ …

An Analysis Of Environmentally-Persistent Free Radical Formation On Surrogate Soil Systems Containing Iron(Iii) And Copper(Ii) And The Potential Remediation Effects Of Laccases, Andrew Paul Mullet

Honors Capstones

No abstract provided.

Modeling The Formation Of Tetrahydropyranyl Radicals Via Hydrogen Abstraction, Robert Booth

Theses, Dissertations and Culminating Projects

A computational analysis was performed on the reaction between tetrahydropyran (THP) and atomic bromine in order to gain a better understanding of the energetics of the addition-elimination mechanism as compared to similar chemical reactions. Prior to the reaction energetics study, a separate analysis was performed on substituted tetrahydropyran derivatives in order to optimize the computational methods being used, to understand the extent of the anomeric effect in tetrahydropyran, and to understand solvent contributions to the energies of the tetrahydropyran derivatives. Trial calculations were performed using Hartree-Fock (HF) theory, Density Functional theory (DFT), and second-order Moller-Plesset perturbation (MP2) theory, and it …

The Effects Of Heavy Metals And Microbes On Extracellular Enzyme Activity At Liberty State Park, Eleanor Urenna Ojinnaka

Theses, Dissertations and Culminating Projects

The overall goals of this research were to 1) understand the influence of microbes and heavy metals on extracellular enzyme activity in soil environments and 2) explore the possibility of using living organisms, such as microbes, to improve the enzyme activity of contaminated, poor-functioning soil—bioremediation. Microbes exude enzymes into the soil, which are vital in the cycling of nutrients in soil communities. Thus, measuring extracellular enzyme activity can be used to quantify the health of soil. In this experiment, phosphatase enzyme was measured as a proxy for enzyme activity. The study site is a closed-off section of Liberty State Park …

Expression, Purification, Enzymatic And Inhibition Profile Of Brugia Malayi Dihydrofolate Reductase, Romy Perez-Abraham

Theses, Dissertations and Culminating Projects

Dihydrofolate reductase (DHFR) is an essential enzyme that plays an important role in the production of cofactors that are required in deoxyribonucleic acid (DNA) synthesis. The literature suggests that DHFR is a potential drug target for the elimination of the parasitic worm, B. malayi. B. malayi is one of the causative parasites of lymphatic filariasis, a globally neglected tropical disease. In this study, we expressed and purified B. malayi DHFR. Expression was carried out in E. coli with a His6-tagged construct, and purification was achieved through affinity chromatography using a special strain of E. coli cells called “LOBSTR.” The resulting …

Proof Of Concept For The Forensic Analysis Of Blood Spots To Distinguish Time Since Deposition And Relative Age Of Blood Spot Originator, Roselyn Rodrigues

Chemistry

In the field of forensics, blood is considered a highly useful tool. DNA found in blood is currently viewed as the best source of identifying a suspect; however, DNA analysis is mainly used as a comparative method. DNA analysis can single out a suspect they are physically present in custody or if a match is made through a database of stored profiles, such as the Combined DNA Index System (CODIS).1-3 There are new methods of DNA analysis that can identify a person of African/Caribbean decent, hair and eye color, and even the age of a person.4-6 However, this DNA analysis …

Effect Of Concentration, Temperature, And Base Changes On Retrovirus Dimerization, Ashley Colvin

Chemistry

RNA-RNA junctions between hairpin loops are a common feature of RNA retroviruses, accounting for their high mechanical stability. Dimerization of Moloney Murine Leukemia Virus (MMLV) is dependent on H3 stem loop interactions, which are an example of such a junction. H3 in MMLV dimerizes via a two base pair hairpin loop enhanced by two adjacent stacking bases. All atom, explicit solvent molecular dynamics pulling simulations were performed to examine the stability of the junction. Salt concentrations and temperatures were varied and unstacking times of the flanking bases and breaking times of the kissing bonds were calculated. Survival curves revealed that …

Employing Synergetic Effect Of Doping And Thin Film Coating To Boost The Performance Of Lithium-Ion Battery Cathode Particles, Rajankumar L. Patel, Yingbing Jiang, Amitava Choudhury, Xinhua Liang

Chemistry Faculty Research & Creative Works

Atomic layer deposition (ALD) has evolved as an important technique to coat conformal protective thin films on cathode and anode particles of lithium ion batteries to enhance their electrochemical performance. Coating a conformal, conductive and optimal ultrathin film on cathode particles has significantly increased the capacity retention and cycle life as demonstrated in our previous work. In this work, we have unearthed the synergetic effect of electrochemically active iron oxide films coating and partial doping of iron on LiMn_1.5 Ni_0.5O₄ (LMNO) particles. The ionic Fe penetrates into the lattice structure of LMNO during the ALD process. …

Evaluating The Role That A Putative Fxiii Binding Site Plays In The Reactivity Of Three Glutamines Within The Coagulation Substrate Fibrinogen Aα (233-425)., Chad A. Stephens

College of Arts & Sciences Senior Theses

Formation of a stable thrombus in vivo depends on the interaction between fibrinogen and the transglutaminase factor XIII (FXIII). Characteristics of blood plasma, such as concentration of Ca2+, are well known to regulate the activation and subsequent reactivity of FXIII. Despite this knowledge, the role fibrin(ogen) plays in modulating FXIII activation and reactivity is not entirely delineated. Currently, the coagulation substrate fibrinogen Aα is proposed to contain a binding site for the active factor XIII with fibrinogen Aα E396 serving a major role. A series of mass spectrometry and NMR spectroscopy studies was conducted to assess whether putative interactions between …

Mechanism And Use Of Paired Ion Electrospray Ionization (Piesi) In High-Performance Liquid Chromatography-Mass Spectrometry (Hplc-Ms) For Sensitive Analysis Of Anionic Compounds, Hongyue Guo

Chemistry & Biochemistry Dissertations - Archive

In recent years, the paired ion electrospray ionization (PIESI) technique has been emerged as a promising alternative to overcome the inherent low sensitivity of negative ESI-MS. The current research focused on the further understanding of the mechanism of the enhanced sensitivity in PIESI based on previous studies, as well as novel applications of PIESI in sensitive and selective analysis of challenging anionic compounds. Specifically, this dissertation describes research in two areas: 1) The mechanism of PIESI in sensitive detection of anions was further investigated using two rational designed surface-active ion-pairing reagents. As compared to their corresponding non-surface-active ion-pairing reagents, the …

Highly Fluorinated, Coinage Metal Complexes Of Tris(Pyrazolyl)Borates With Additional Electron Withdrawing Groups And Pyrazolate Π-Stackings With Arenes, Naleen Bandupriya Jayaratna

Chemistry & Biochemistry Dissertations - Archive

Tris(pyrazolyl)borates are very popular ligands in inorganic chemistry, bioinorganic chemistry, and organometallic chemistry due to their attractive properties. It is possible to extensively modify the steric and electronic properties of these ligands by changing the pyrazolyl substituent groups. Taking into account the importance and current interest of fluorinated tris(pyrazolyl)borates and weakly coordinating anions in general, three new tris(pyrazolyl)borates, [HB(4-Cl-3,5-(CF₃)₂Pz)₃]-, [HB(3,4,5-(CF₃)3Pz)₃] and [HB(4-(NO₂)-3,5-(CF3)₂Pz)₃]- have been developed (Pz = pyrazolyl). Silver alkene adducts of the ligands have been isolated to evaluate the electronic properties of the ligands and to study their catalytic properties. These adducts found to be the most electron deficient …

Investigation Of The Tandem Alkylation-Cyclization Of Endocyclic Enol Ethers For The Preparation Of Unusual Oxygen Heterocycles, Sarah Mehdi

Renée Crown University Honors Thesis Projects - All

The purpose of this research is to study the alkylation and subsequent cyclization reaction of endocyclic enol ethers such as 2H-dihydropyran. This sequence is expected to yield oxygen heterocycles whose structures represent unique scaffolds with promising functionality.

A series of trichloroacetimidates were selected for the direct alkylation of 2H-dihydropyran. Following the alkylation, the addition of acid was expected to induce an intramolecular cyclization reaction that would yield the desired oxygen heterocycles. This stepwise scheme would then be converted into a tandem process in which the reaction would be expected to proceed in a single pot.

Studies showed that the alkylation …

Ruthenium Hydride Catalyzed Silylvinylation Of Terminal And Internal Alkynes And Synthesis Of Poly(Trimethylenecarbonate) And Poly(Dimethylacrylamide) Block Copolymer, Alec Beaton Jr.

Renée Crown University Honors Thesis Projects - All

Various propargyl alcohols were synthesized via Grignard reactions. These alkynic alcohols are tethered with dimethyl and biphenyl silicon tethers. These terminal alkyne substrates are reacted with RuHCl(CO)(H₂IMes)(PPh₃) as a catalyst under high pressure (80 psi) ethylene atmosphere to afford the 5-exo-dig trans-silylvinylation product in poor yield. Internal alkyne substrates are found to be much more efficiently transformed into the silylvinylation product, favoring one cycloisomer product over the other.