Chemistry Commons^™

A Quantitative Lc-Ms/Ms Method For Determination Of A Small Molecule Agonist Of Epha2 In Mouse Plasma And Brain Tissue, Bo Zhong, Yaxin Li, Nethrie Idippily, Aaron Petty, Bin Su Ph.D., Bingcheng Wang

Chemistry Faculty Publications

Compound 27 {1, 12‐bis[4‐(4‐amino‐6,7‐dimethoxyquinazolin‐2‐yl)piperazin‐1‐yl]dodecane‐1,12‐dione} is a novel small molecule agonist of EphA2 receptor tyrosine kinase. It showed much improved activity for the activation of EphA2 receptor compared with the parental compound doxazosin. To support further pharmacological and toxicological studies of the compound, a method using liquid chromatography and electrospray ionization tandem mass spectrometry (LC–MS/MS) has been developed for the quantification of this compound. Liquid–liquid extraction was used to extract the compound from mouse plasma and brain tissue homogenate. Reverse‐phase chromatography with gradient elution was performed to separate compound 27 from the endogenous molecules in the matrix, followed by …

The Effects Of Organic And Inorganic Nanoparticles On Bacterial Deactivation, Lauren Cooper

Mahurin Honors College Capstone Experience/Thesis Projects

Antibacterial resistance is one of the greatest problems in modern medicine, as healthcare professionals are experiencing more and more difficulty in providing effective care. As such, alternative methods of treatment are needed in order to overcome this issue. One recently proposed method of alternative treatment is photodynamic therapy. Photodynamic therapy is a light-based method of treatment that utilizes (1) a photosensitizing agent, (2) light, (3) produced oxygen species. When the photosensitizing agent is injected into an infected region of interest and then irradiated with a certain wavelength of light, the agent is photoactivated and begins to produce harmful forms of …

Nanoscale Control Of Metal Oxideand Carbonaceous Functional Materials, Benjamin W. Lamm

Theses and Dissertations

The controlled fabrication of nanometer scale devices is of fundamental concern for numerous technologies, from separations to electronics and catalysis. The complexity of device architectures calls for the development of synthetic methods that independently control each feature: pore dimensions, wall thickness, and any subsequent functional nanomaterial layers (e.g. photoactive electrocatalysts). Precision control over these orthogonal methods can be used to integrate 3D and 1D nanostructures.

This dissertation presents the development of techniques useful in fabricating highly controlled nanoscale devices. The growth of single-phase bismuth vanadate (BiVO4) by atomic layer deposition (ALD) is demonstrated for the first time, allowing for the …

Catalytic Upgrading Of Aromatic Oxygenates Related To Lignin, Nicholas A. Delucia

Theses and Dissertations

Lignin is one component of lignocellulosic biomass and is the only renewable, naturally-occurring source of aromatics in the world. However, lignin also provides a highly-oxygenated, complex, heterogeneous structure making the procurement of isolated aromatic molecules quite difficult. There has been extensive research in recent years to develop approaches to catalytically breakdown the lignin polymer into monomeric units. This works aims to develop a number of catalytic techniques for the upgrading of these monomeric units of lignin to produce means for producing chemical building blocks as well as suitable fuels from biomass sources.

A method for the silanolysis of alcohols has …

Kinetically Controlled Block Polymer Micelles: Cavitation Induced Exchange And Templates For Nanomaterials, Kayla Alice Lantz

Theses and Dissertations

Kinetically trapped micelles are emerging as a novel platform for a wide range of applications including drug delivery, nanoreactors, and templates for porous nanomaterials. Kinetic control affords decoupling of micelle size from subsequent applications. However, micelle homogenization and size tuning are inherently difficult due to the high barrier toward micelle chain exchange processes. These challenges can be resolved with the use of sonication, which enables switchable exchange where cavitation leads to chain exchange and cessation returns micelles to kinetic entrapment. Small-angle neutron scattering (SANS) measurements were used to quantify exchange during cavitation induced exchange (CIE). The extent of exchange was …

Analysis And Review Of The Effects Of Bacterial Competition On Efflux Pump Inhibition, Robert Leszcynski

Honors Theses

Multidrug resistant antibacterial strains are a dangerous problem for modern medical professionals. When cells of two different strains are grown together, they must compete with each other for nutrients. This competition can lead to the production of harmful compounds that are toxic to the competing strain. One such compound may be a compound that inhibits the efflux of antibiotics from the cell. When the cells compete with one another, one or both of the cells will produce compounds that are harmful to the competing strain.

Tracking Disparate Colony Morphological Trends With Thermus Scotoductus, Matthew P. Leverick

Honors Theses

When plating most mesophilic bacteria, the colony shape, size, and color tends to be uniform when a single strain is present. When plating defined cell densities of T. scotoductus, however, the colonies were not of uniform size and shape while it grew on the surface. In this project, we sought to observe trends in colony morphology (shape and size) changes using the thermophile Thermus scotoductus on nutrient rich agar plates at 60°C. A general planktonic growth curve was also created to help characterize the activity of this bacterium. This project was our first attempt to characterize if this unusual phenomenon …

Boron Dipyrromethenes: Synthesis And Computational Analysis, Eduardo Rivé Lockwood

Honors Theses

Recently, there has been a growing interest in the boron dipyrromethene (BODIPY, 4,4′- difluoro-4-bora-3a,4a-diaza-s-indacene) compounds. BODIPY compounds have fascinating properties that allow for the absorption and emission of light in the near infrared region of the electromagnetic spectrum. These molecules are highly modifiable making them ideal chemicals for the use of photoelectric energy conversion such as for commercial use in dye sensitized solar cells (DSSCs). It has been previously shown that different meso compounds have only a slight effect on the absorptive capabilities of these BODIPY compounds. We believe that the BODIPY compounds’ lack of planarity is one of the …

Identifying Natural Inhibitors Of Bacterial Efflux Pumps, Marrisa Therriault

Honors Theses

Antibiotic resistance is a constantly progressing epidemic. Many strains of bacteria have developed a resistance to antibiotics, resulting in prolonged sickness and death. Resistance can be to a specific drug (single drug resistance) or to multiple drugs (multi-drug resistance). This resistance can be caused by a tripartite protein pump called an efflux pump that extends through the inner and outer membranes of the bacterium to pump antibiotics from the inside of the cell to the extracellular environment. In E. coli the efflux pump is called AcrAB-TolC. In the efforts to combat this problem, this experiment focuses on the inactivation of …

Structural And Functional Studies On 4-Hydroxy- Tetrahydrodipicolinate Reductase: Potential Drug Target In Bacteria, Swanandi Pote

Theses and Dissertations

Antimicrobial resistance has become an alarming public health concern since early 2000’s. Infections caused by multidrug resistant bacteria not only increase the mortality rate but also increase the economic burden globally. One approach to alleviate this issue is to find novel drug targets. In this regard, the bacterial lysine biosynthesis pathway provides several targets that may be used for design of antimicrobial compounds. Bacteria use lysine or meso-diaminopimelate to crosslink the peptidoglycan monomers in the bacterial cell wall. As such, we hypothesize that blocking this pathway will induce defects in the bacterial cell wall that are similar to those …

Synthesis And Characterization Of Tripodal Tris(Nitroxide) Aluminum, Gallium, And Indium Complexes, Audra J. Woodside , '19

Senior Theses, Projects, and Awards

One important challenge in green chemistry is the development of safe and sustainable catalytic systems for molecular transformations that do not rely on precious metals. In this vein, I explore how one can expand the utility of aluminum complexes. Aluminum is a prime choice for such catalytic development as it is relatively inexpensive (less than $2/kg), readily available, and non-toxic. Although there are ample examples of aluminum complexes acting as Lewis-acid catalysts, the lack of readily accessible multielectron redox states leaves aluminum complexes inept in redox-based transformations. In order for aluminum complexes to be used in redox reactions, I prepared …

Human Serum Albumin Nanoparticles For The Treatment Of Hepatocellular Carcinoma, Mina Hibino

Senior Honors Theses

Hepatocellular carcinoma (HCC) is an aggressive and destructive cancer of the liver. Currently available treatment plans are locoregional therapies aimed to decrease tumor burden, resection that surgically removes the tumor, or systemic therapies for advanced stage to extend survival. However, decompensation post-locoregional treatment and recurrence rates for HCC remain high despite the different treatment modalities. There is a great need for alternative and more effective treatment methods that will further dampen tumor burden while decreasing the risk of intra- and extrahepatic spread. The goal of this project was to develop a non-invasive therapeutic treatment to target HCC cells using human …

Development Of Nanomaterial Supports For The Study Of Affinity-Based Analytes Using Ultra-Thin Layer Chromatography, Allegra Pekarek

Department of Chemistry: Dissertations, Theses, and Student Research

Ultra-thin layer chromatography (UTLC) is a growing field in analytical separations. UTLC is a branch of planar and liquid chromatography that is related to thin layer chromatography. The main advantage of UTLC compared to other techniques is it uses much less material, allowing for faster and more sensitive separations to take place. The UTLC devices fabricated in this project used either silicon oxide or silicon nanopillars deposited on a glass slide using glancing angle deposition (GLAD). Even a thin layer of these nanopillars deposited on a glass slide provide a large surface area for the analyte to be separated. GLAD …

Analysis Of Drug–Protein Interactions During Diabetes By High-Performance Affinity Chromatography, Pingyang Tao

Department of Chemistry: Dissertations, Theses, and Student Research

High-performance affinity chromatography (HPAC) is a type of liquid chromatography in which solutes are separated based on their binding to a stationary phase that is a biologically-related agent. Sulfonylurea drugs have significant binding to proteins in blood, with most of this binding is believed to occur with human serum albumin (HSA). HSA is known to be modified as a result of the high serum levels of glucose that is present during diabetes, which may also alter the function of HSA as a binding agent for many drugs in circulation. Some modifications of HSA that can occur during diabetes involves early …

Synthesis And Structural Analysis Of Macrocyclic Arenes: Experimental And Computational Insights, Saber Mirzaei

Master's Theses (2009 -)

Synthesis, properties and applications of macrocyclic molecules have been one ofthe interesting branches of organic chemistry during the past century. Several classes ofmacrocyclic molecules, based on their repeating unit and connectivity pattern, have beendiscovered. Macrocyclic arenes, cyclo[n]veratrylenes, calix[n]arenes and pillar[n]arenes,were among the most interesting and studied molecules. The major difference betweenthese molecules is the methylene-bridged connectivity pattern. In the present thesis, Iattempted to synthesize these molecules using novel approach which has been developedin our group and performing some structural analysis using experimental andcomputational techniques.The first synthesized and investigated molecule is the …

Design And Synthesis Of Simplified Analogs Of The Natural Product Sordarin As Potential Antifungal Agents, Yibiao Wu

Dissertations (1934 -)

Invasive fungal infection is a life-threatening illness that causes high mortality, and is especially common among patients with compromised immune systems. However, currently there are only three major classes of clinically useful drugs capable of treating such infections. In addition, due to the fact that drug resistance has become a serious issue especially among patients who suffer from chronic infections, it is urgent to identify new drug candidates, particular those of new classes. The discovery of the natural product sordarin and its novel mechanism of action of inhibiting fungal protein synthesis via the fungal eukaryotic elongation factor 2 (eEF2) led …

Synthesis And Biological Applications Of Some Novel Urea And Thiourea-Quinoline Derivatives, Aysha Mohammed Alkaabi

Theses

Extensive literature survey reveals that 8-Hydroxyquinoline (8-HQ), urea, thiourea and piperazine exhibit wide biological activity profile such as anticancer, anti-Alzheimer, anti-viral, antibacterial and antifungal activity. Novel urea and thiourea-quinoline derivatives connected by piperazine moiety have been synthesized and purified using appropriate techniques (extraction, crystallization and column chromatography) followed by characterization using IR spectroscopy and NMR spectroscopy (both ¹H and ¹³C).

Biological activity, metal chelation properties and the photo-physical properties were studied for these novel compounds. Anti-bacterial study shows moderate activity for most of the compounds against P.aereginosa, S.aureus and Enterococcus at concentration 250 μM. Antifungal study showed …

Emergent Properties And Applications Of Self- Assembled Benzophenone-Containing Materials, Baillie A. Dehaven

Theses and Dissertations

Supramolecular assembly of benzophenone through urea hydrogen bonding interactions facilitates the formation of remarkably persistent triplet radical pairs upon UV-irradiation at room temperature, whereas no radicals are observed in solution. The generation of organic radicals is correlated to the microenvironment around the benzophenone carbonyl, the types of proximal hydrogens, and the rigid supramolecular network. High-Field EPR and variable temperature X-band EPR accompanied by simulations suggest a resonance stabilized radical pair through hydrogen abstraction. Previous work has shown that UV-irradiation of self-assembled benzophenone bis-urea host results in low quantities of radical pairs that can be used to enhance NMR signals …

Impact Of Glutathione Transporters On Subcellular Glutathione Pools And Cell Survival In Saccharomyces Cerevisiae, Crystal Conaway Mcgee

Theses and Dissertations

Thiol-disulfide redox homeostasis is integral for maintaining the redox status of proteins and other thiol-containing molecules within cells. Mitochondria are particularly vulnerable to disruptions in redox balance, due to production of reactive oxygen species (ROS) during oxidative metabolism. Among the many antioxidants and detoxifying enzymes existing in mitochondria, glutathione (GSH) has proven to be critical for the preservation of function and structural integrity of the organelle. Therefore, our studies are aimed at elucidating the factors that control mitochondrial GSH metabolism in the model eukaryote Saccharomyces cerevisiae (baker’s yeast). A critical component of understanding subcellular GSH homeostasis is identifying routes of …

Sustainable Polymers And Antimicrobial Biomaterials From Multicyclic Natural Products, Md Anisur Rahman

Theses and Dissertations

In this dissertation, the development of sustainable polymers and antimicrobial biomaterials from multicyclic natural products is illustrated. In Chapter 1, an overall background and recent development of sustainable polymers from natural product-based renewable biomass, antimicrobial biomaterials, and polymerization methods are introduced. Afterward, the primary research objectives of my doctoral research work are illustrated.

In chapter 2, designing block copolymer architectures toward tough bioplastics from renewable natural rosin was described. One of the most abundant natural biomasses is resin acids, however, most of the polymers derived from resin acids are brittle because of their bulky hydrophenanthrene pendant group. To overcome the …

Anion Pool Directed Electroorganic Synthesis, D.M.M. Madushanka Mevan Dissanayake

Theses and Dissertations

The “Anion pool” approach introduces a greener approach for derivatization of pharmaceutically important molecules by amalgamating both electrochemistry and organic synthesis. This is a base and metal free procedure carried out in organic solvents recommended for pharmaceutical preparations. The anion pool procedure generates reactive nitrogen nucleophiles in situ via electrochemical reduction of heteroaromatic substrates. The adoption of such a methodology prevents generation of waste from bases used for deprotonation. Hydrogen is the main by-product of generation of anion pool, which, if produced at a large enough scale could be used as a renewable fuel. These attributes comply with the principles …

Development Of Nickel Catalyzed Cross-Coupling Methodologies, Ryan J. Key

Theses and Dissertations

In this work, we have addressed some of the issues surrounding catalytic crosscoupling reactions by using a nickel terpyridine catalyst, [Ni(tpy)(py)(CH3CN)2](PF6)2 in the Buchwald-Hartwig amination reaction and a functionalized variant, [(2,2':6',2''- terpyridine-4'-benzoic acid)Ni(II)]Cl2 on SiO2, in Suzuki coupling. These processes are unique in the approaches taken to achieve reactivity. In the Buchwald-Hartwig amination reaction, we used photoredox dual catalytic methods to achieve a sustainable approach to generate secondary and tertiary amines. This report is unique in many ways; most importantly, this method uses N-centered radicals to generate new C-N bonds. This report is also the first report to show generation …

Structural Studies Of Dna Repeats Implicated In Cancer, Deondre Jordan , '19

Senior Theses, Projects, and Awards

DNA replication is an essential process for the survival of all organisms. Errors can occur during the process that leads to replication stress, which can promote genomic instability, a hallmark of cancer. The Brown lab conducted a genome wide study to identify sites and sequences linked to replication stress. Tandem DNA repeats comprised the sequences identified in this study. One particular DNA repeat (CAGAGG)ₙ stood out due to being highly associated with replication stress. Repeats such as (CAGAGG)ₙ are believed to fold into fold into intramolecular structures that physically block DNA polymerase during replication. Understanding the structures of these problematic …

Phytochemical Investigation Of Magnolia Grandiflora Green Seed Cones: Analytical And Phytoceutical Studies, Bo Garza, Alondra Echeverria, Felipe Gonzalez, Orlando Castillo, Thomas Eubanks, Debasish Bandyopadhyay

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Phytochemicals are inevitable part of human civilization. It is impossible to say exactly when menfolk started to take plant portions to cure various diseases. Phytochemical investigation of diethyl ether and ethanol extracts of Magnolia grandiflora green seed cones has been carried out. Extraction, isolation, and identification of the phytochemicals were carried out. Structures were determined by various analytical methods including extensive nuclear magnetic resonance, gas chromatography‐ mass spectroscopy, and X‐ray crystallographic analyses. Structures of the three compounds viz. 5,5′‐diallyl‐[1,1′‐biphenyl]‐2,2′‐diol (I), 3′,5‐diallyl‐[1,1′‐biphenyl]‐2,4′‐ diol (II), and (3S,3aS,8S,9aS,10aR,10bS,E)‐8‐hydroxy‐3,6,9a‐trimethyl‐3a,4,5,8,9,9a, 10a,10b‐octahydrooxireno[2′,3′:9,10]cyclodeca[1,2‐b]furan‐2(3H)‐one (III) were confirmed by X‐ray crystallographic analysis. GS‐MS studies of the isolated oil, eluted …

Cooperative Lewis Pairs Based On High-Valent Early Transition Metal Halides And Synthesis Of Their Nitride Complexes, Md. Mamdudur Rahman

Theses and Dissertations

Herein, we report the activation of relatively strong C–H and C–O bonds under mild conditions by a cooperative interaction of TaCl5 and PPh3. An unprecedented activation of nitrile adducts of high-valent transition metals with the formation of novel zwitterionic imido complexes was observed. The scope of the reaction includes a range of substituted unactivated nitriles including the C–H bond activation of both aliphatic and aromatic nitriles.

The cooperative action of a Lewis acidic high-valent transition metal halide (TaCl5 or NbCl5) and a weakly nucleophilic base (NEt3 or PPh3) leads to the deprotonation of a coordinated nitrile and subsequent rearrangement to …

Metal-Organic Frameworks: Photophysics, Energy Transfer, And Electronic Structure, Ekaterina A. Dolgopolova

Theses and Dissertations

The current landscape of technological and industrial related fields is looking for novel materials with enhanced performances, which will not only improve various fields in science, but also can ensure increased environmental safety. Recently, metal-organic frameworks (MOFs) have been shown as a promising type of material for a wide range of applications including gas storage and separation, sensing, and heterogeneous catalysis. The main advantages of MOFs rely on their modular structures as well as their porosity. For instance, the modular nature of MOFs provides a control over chromophore arrangement, systematic tuning of ligand design and synthetic conditions allowing one to …

Nanoparticles With Tunable Fluorophobic Effect Towards Multimodal Coassembly With Block Copolymers, Zachary Michael Marsh

Theses and Dissertations

Nanomaterials are often fabricated using block polymers to direct the placement of nanoparticles via selective intermolecular interactions such as hydrogen bonding. Fluorophobic interactions have emerged as a promising handle to control nanoparticle placement independently from typical hydrophilic approaches. A series of nanoparticles with tunable fluorophobicity were prepared to elucidate the key parameters for harnessing fluorophobic interactions in this context. Mixed ligand fluorinated nanoparticles (ML-FNPs) where prepared to examine the competing roles of each ligand towards fluorophobicity and solubility. The ML-FNP intermolecular interactions were first studied using a custom-made Quartz Crystalline Microbalance (QCM) based technique. The ML-FNPs were then examined for …

Interfacial Ligand Dynamics And Chemistry On Highly Curved Nanoparticle Surfaces: A Plasmon-Enhanced Spectroscopic Study, Esteban Villarreal

Theses and Dissertations

The dynamic interactions between capping ligands and nanoparticle surfaces play a critical role in guiding shape-controlled nanocrystalline growth, imparting unique physical and chemical properties to the nanoparticles. It has been well established that nanoparticles within the size regime of sub 5 nm possess unique heterogeneous catalytic properties, while sub wavelength metallic nanoparticles exhibit tunable plasmonic activity, when these properties are integrated into a single nanoparticle, it presents a significant opportunity to monitor, in real time, the molecular transformations associated with interfacial interactions at the nanoparticle surface. Using plasmon-enhanced Raman scattering as an ultrasensitive spectroscopic tool combining molecular fingerprinting with time …

The Investigation Of Nickel-Based Catalysts For The Oxidative Dehydrogenation Of Ethane, Justin Lane Park

Theses and Dissertations

The Investigation of Nickel-Based Catalysts for the Oxidative Dehydrogenation of Ethane Justin Lane ParkDepartment of Chemistry & Biochemistry, BYU Doctor of Philosophy Chemistry The advancement of creating ethylene from ethane via oxidative dehydrogenation (ODH) rather than the traditional direct dehydrogenation is right on the cusp of commercialization. The oxidative pathway provides a novel route that reduces the operating temperature of this reaction by 400-500°C. A variety of metals including Mo, V, and Ni that have redox properties suitable for the partial oxidation of small chain alkanes have been investigated. Currently, a MoVNbTe oxide is the most promising catalyst but it …

Time-Resolved Photoluminescence Of 6-Thienyl-Lumazine Flourophore In Cellulose Acetate Nanofibers For Detection Of Mercury Ions, Noura A. Al Shamisi

Chemistry Theses

Time-resolved photoluminescence measurements were used to characterize the photophysical properties of 6-thienyllumazine (TLm) fluorophores in cellulose acetate nanofibers (NFs) in the presence and absence of mercuric acetate salts. In solution, excited-state proton transfer (ESPT) from TLm to water molecules was observed at pH from 2 to 12. The insertion of the thienyl group into lumazine (Lm) introduces cis and trans conformers while keeping the same tautomerization structures. Global and target analysis was employed to resolve the true emission spectra of all prototropic, tautomeric, and rotameric species for TLm in water. However, in the NFs solid film no ESPT from TLm …