Physical Sciences and Mathematics Commons^™

Synthesis Of Bulky And Polar Galactonoamidines For The Inhibition Of The Human Α-Galactosidase, Ifedi Orizu

Graduate Theses and Dissertations

Glycosidases are amongst the most abundant enzymes in nature. This is due to their role in the degradation of carbohydrates which are the major source of carbon or earth. The absence or malfunction of glycosidases is implicated in numerous diseases such as cancers, diabetes, and lysosomal storage disorders, which make them important drug targets for study in medicinal chemistry. The seminal work by Pauling and Wolfenden showed that enzymes bind to their substrate at the transition state with very strong affinity. Wolfenden estimated the dissociation constant to be around 10-22M. This encouraged the design of glycosidase inhibitors which mimicked one …

Developing A Microdialysis Sampling-Based Biofilm/Macrophage Co-Culture Model, Alda Diaz Perez

Graduate Theses and Dissertations

The host immune system and bacterial cells are known to interact during the human lifetime. Bacteria secrete a wide variety of signaling molecules, known as quorum sensing (QSC) molecules, that modulate the host immune system. While immune-biofilm interactions involve this chemical signaling network, the mechanisms through which this occurs are not well understood. This work aimed to develop a new method that can be used not only in vitro settings but also in vivo. The microdialysis sampling technique has widely been used in in vitro and in vivo settings in humans, mice, and rats for the collection of neuropeptides, cytokines, …

Electrochemical Oxidation Of Individual Silver Nanoparticles: Exploring The Effect Of Particle Shape, Capping Ligand, Electrolyte, And Potential On The Signal, Jazlynn Sikes

Graduate Theses and Dissertations

Nanomaterials have revolutionized science and technology. Their unique properties can be exploited, and nanoparticles are being used as catalysts, antimicrobials, drug delivery vehicles, sensors, and more. However, the fundamental properties of nanomaterials and their interactions with their surrounding environments are still poorly understood. In this work, a single-particle approach was used to observe the effects of capping ligand, surrounding solution, and particle shape on the oxidative process to gain deeper understanding of silver nanoparticle properties. When allowed the opportunity, the particles will adsorb to the electrode surface then oxidize in rapid succession upon electrode activation, regardless of capping ligand as …

An Experimental Study Of Evaporites On Titan: Implications For Lake Composition And Future Missions, Ellen Czaplinski

Graduate Theses and Dissertations

Titan is the only other planetary body in the solar system with liquid on the surface. With a surface temperature and pressure of 89 – 94 K and 1.5 bar (N2), respectively, Titan’s lakes are comprised of liquid hydrocarbons, predominantly methane and ethane. Over time, Titan’s lakes may evaporate, leaving behind residual deposits (evaporites). The evaporation processes and composition of the evaporites is poorly understood. I address these outstanding questions by experimentally investigating the physical and spectral properties of evaporites at Titan surface conditions using an experimental chamber.

Chapter 1 addresses the formation of ethylene evaporites. Ethylene evaporites form more …

Predicting The Hydration Free Energy Of Small Alkanes And Alcohols From Custom, Electronic Structure-Based Force Fields, T. Ryan Rogers

Graduate Theses and Dissertations

Mathematical theories reveal the fundamental physics involved in experimentalphenomena. Computer models of such theories are routinely used to corroborate or explain experiments and predict properties of chemical systems. Therefore, an important effort in computational chemistry is the development of more accurate and efficient chemical models. Current-generation models are only beginning to approach experimental-quality predictions of hydration free energies (HFEs).Using computations of quantum mechanical (QM) forces and classical simulations based on these forces, I investigate models to predict several properties of solutes and solutions. This dissertation is a collection of projects exemplifying methods used to gain insight into chemical systems.

Simulations …

Elucidating Collagen Degradation Synergy Between Col G And Col H From Hathewaya (Clostridium) Histolytica And Identifying Novel Structural Features In Hpt And Rec Domains From Vars Histidine Kinase In V. Alginolyticus, Perry Caviness

Graduate Theses and Dissertations

In this research the mechanisms by which Hathewaya (Clostridia) histolytica collagenases are secreted and work together to degrade collagens are investigated. While H. histolytica collagenases Col G and Col H have similar multi-domain structures the difference in number of and orientation of the domains hint that the two target different regions in collagen. Study small angle x-ray scattering (SAXS) was used to give a low-resolution envelope of full-length Col G and Col H and Col G/Col H non-catalytic domains bound to a collagen-like peptide (mini-collagen). SAXS derived envelopes along with structural information was used to tease out the mechanisms by …

Thiophene Derivative Monomers Co-Electropolymerized On Microelectrodes Within Arrays For Tailored Surface Chemistry And Electrochemical Properties, Benjamin J. Jones

Graduate Theses and Dissertations

Potentiodynamic co-electropolymerization of two thiophene derivatives, (2,3-dihydrothieno[3,4-b]dioxin-2-yl)methanol (1) and 4-((2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)-methoxy)-4-oxobutanoic acid (2), in aqueous solutions (0.02 M total monomer, 0.05 M sodium dodecyl sulfate (SDS) and 0.1 M LiClO4) on gold microband electrodes in an array was investigated. A modified Steglich esterification reaction between monomer 1 and succinic anhydride produced monomer 2 at 93.6% yield. Seven deposition solutions of the two monomers, defined by mol% of monomer 2 (0, 25, 34, 50, 66, 75, 100) generated seven sets of polymer films by cyclic voltammetry in a specially designed cell to conserve monomer. The onset potential for monomer oxidation and total …

An Experimental Investigation Of Liquid Hydrocarbons In A Simulated Titan Environment, Kendra Farnsworth

Graduate Theses and Dissertations

Saturn’s moon, Titan, has surface conditions (89–94 K, 1.5-bar atmosphere) that permit lakes of methane, ethane, and dissolved atmospheric nitrogen. The effects of atmospheric nitrogen on methane-ethane liquid properties is poorly understood, leading to uncertainty in Titan modeling. I address this question by experimentally investigating the physical properties of methane-ethane liquids under a 1.5-bar nitrogen atmosphere in a simulated Titan environmental chamber.

Chapter 1 addresses nitrogen dissolution kinetics in Titan’s liquid hydrocarbons. I found an exponential increase in nitrogen quantity and diffusion coefficients with increasing methane mol%. I find that Titan’s liquids are likely not saturated in nitrogen, with dissolution …

Understanding The Interfacial Reactions Initiating On Lithium Metal Surfaces In Next-Generation Battery Technologies, Joshua A. Lochala

Graduate Theses and Dissertations

Li-ion batteries have started to reach the theoretical maximum energy. Next-generation batteries represent the future of portable energy sources for vehicle electrification and grid energy storage. Li metal battery is one of the most promising next-generation battery technologies that could potentially double the cell-level energy of conventional Li-ion batteries. However, Li metal has multiple drawbacks that require addressing before realization. These drawbacks include dendrite formation leading to internal short and increasing internal resistance due to the breakdown of electrolyte, leading to rapid cell death. These problems stem from the interfacial reactions occurring during the plating and stripping of Li metal. …

Investigation Of The Structural, Electronic, And Thermoelectric Properties Of Mono- Chalcogenides, Aida Sheibani

Graduate Theses and Dissertations

The structural, electronic, and thermoelectric properties of GeTe are studied using density functional theory and Boltzmann transport equations. This material has a rhombohedral crystal structure in ambient temperature with a ferroelectric behavior due to lack of inversion symmetry. This study suggests that the presence of asymmetry in GeTe can lead to an improvement in the thermoelectric properties of this material. In addition, studies on introducing Group III, IV, and V dopants to GeSe show that while these impurities can improve the power factor and decrease the lattice thermal conductivity, they cannot enhance the figure of merit.

Ensemble And Single Particle Studies Of Cation Exchange In Cuins2/Zns Qds And Their Application In Super-Resolution Imaging, Anh Tue Nguyen

Graduate Theses and Dissertations

Colloidal quantum dots (QDs) have great potential in many applications such as bioimaging, light emitting diodes, solar cells and lasers. However, a great number of studies have been focused on Cd based (II-VI) and Pb (IV-VI) based materials which are not suitable for mass production. Therefore, alternative types of QD containing less toxic materials have been introduced, including CuInS2 QDs. This I-III-VI semiconductor nanocrystals also attract lots of attention due to their large Stock shift, long fluorescence lifetime and high defect tolerance, making them attractive emitters for applications in bioimaging, photovoltaics and light emitting diodes.

In the first project, we …

Understanding Ice Mixtures Under Pluto Simulated Conditions And Their Implications For Geophysical Processes, Caitlin Joannah Ahrens

Graduate Theses and Dissertations

New Horizons at Pluto has given the planetary science community the first images of Pluto’s surface, including geologic wonders and compositional variability. Methane, nitrogen, and carbon monoxide make up the bulk of the volatile plutonian surface along with water ice. In this work, these three main volatiles are specifically investigated in the laboratory setting to understand the spectral properties and behavior of binary and ternary mixtures. The spectra are taken in the near-infrared wavelengths (1 – 2.5 µm) using Fourier transform infrared (FTIR) spectroscopy techniques utilizing the Pluto Simulation Chamber housed at the University of Arkansas, which can reach conditions …

Development Of Forward Osmosis Based Separations: A Novel Approach In Membrane Technology, Yu-Hsuan Chiao

Graduate Theses and Dissertations

Tackling the worldwide severe water shortage, the membrane technology is considered to be the most efficient approach and hence, used widely as a cost-effective sustainable solution. “Forward osmosis (FO)” has been the major attention in recent time. FO uses osmotic pressure as the driving force to draw the water passing the membrane and achieve the desired separation performance. In general, it is considered to be a process with tremendous potential to resolve the present-day water shortage with extremely low energy consumption. However, the challenges of membrane and draw solution regeneration associated with FO processes must be conquered prior to their …

Aglycon Modifications Of Ipomoeassin F: Synthetic Route Development And Analog Synthesis To Enable Further Sar Studies, Eric Barber

Graduate Theses and Dissertations

The ipomoeassin family of resin glycosides were discovered to have a high potency against numerous cancer cell line, with ipomoeassin F being the most potent among the family of natural products. Interestingly, one of the few differences between ipomoeassin F and the other compounds is the length of the fatty-acid derived aglycon. As the mechanism of action for this family of resin glycosides is unknown and didn’t have any significant COMPARE correlation with the recorded anticancer agents in the National Cancer Institute (NCI), further SAR studies are needed. Drawing on the differences between ipomoeassin F and the other ipomoeassins, it …

Probing Of Carbohydrate-Protein Interactions Using Galactonoamidine Inhibitors, Jessica B. Pickens

Graduate Theses and Dissertations

Glycoside hydrolases are ubiquitous and one of the most catalytically proficient enzymes known, and thus understanding their mechanisms are crucial. Most research has focused on the interaction of the glycon of substrates and their inhibitors within the active site of glycoside hydrolases. The inhibitors employed to probe these interactions generally had small aglycons (i.e. a hydrogen atom, amidines, small aliphatic groups, or benzyl groups). Here, the interactions of the aglycon with glycoside hydrolases are examined by probing the active sites with a library of 25 galactonoamidines. The studies described in this dissertation aim to increase the understanding of stabilization of …

Reactivity Of Photogenerated Amine Radical Cations, Qile Wang

Graduate Theses and Dissertations

Recently photoredox catalysis has emerged as a powerful tool in organic synthesis led by Professor McMillan, Stephenson, Yoon. Upon absorption of visible light, photocatalyst can be excited to its singlet state followed by intersystem crossing to form a long lived excited triplet state. While amine serves as electron donor, single electron transfer (SET) can happen between excited triplet photocatalyst and nitrogen atom on amine to give a reduced photocatalyst and amine radical cation.

Cyclopropylamines or cyclobutylamines can be oxidized by excited photocatalyst to generate amine radical cations and due to the ring strain, subsequent C-C bond cleavages can lead to …

Rotational Tuning Of Transmembrane Helix Properties Based On The Precise Placements Of Aromatic And Charged Residues, Matthew J. Mckay

Graduate Theses and Dissertations

Designed model transmembrane peptides and oriented 2H and 15N solid-state nuclear magnetic resonance (NMR) spectroscopy were used to analyze how simple sequence modifications can influence peptide structure, behavior and dynamics as well as for determining the pKa of glutamic acid at the membrane interface. The GW5,19ALP23 (acetyl-GGALW(LA)6LWLAGA-amide) peptide framework adopts a well-defined tilted orientation in lipid bilayers (DLPC, DMPC and DOPC) and undergoes low amounts of dynamic motion. The sequence was initially modified by moving the Trp residues outwards to positions 4 and 20. This new sequence GW4,20ALP23 (acetyl-GGAW(AL)7AWAGA-amide) displays high amounts of signal averaging of NMR observables caused by …

Asymmetric Synthesis Of The C29-C34 Moiety Of Fragment A Of The Antascomicin B & Thermal Azole Based Claisen Rearrangements, Dharma Theja Nannapaneni

Graduate Theses and Dissertations

The dissertation describes asymmetric synthesis towards C29-C34 moiety of fragment A of the Antascomicin B and Thermal azole based Claisen rearrangements. In chapter 1, we describes asymmetric synthesis towards C29-C34 moiety of fragment A of the Antascomicin B. The non-immunosuppressant Rapamycin, Ascomycin, and Tacrolimus (FK506), strongly binds with FKBP12, the ligand FKBP12 complexes responsible for immunosuppressive activity. Antascomicin B structurally related to Rapamycin, Ascomycin, and Tacrolimus (FK506), binds strongly to FKBP12, yet does not shown immunosuppressive activity. The ligand FKBP12 binding complexes shown to have potent neuroprotective and neurogenerative properties in mouse models of Parkinson’s disease. The linear synthesis of …

Understanding And Controlling Lithium Microstructure During Electroplating For Energy Applications, Yang Tian

Graduate Theses and Dissertations

Lithium-ion batteries are reaching the specific theoretical capacity limit, while lithium metal batteries are regarded as the ideal energy storage system for the next generation “beyond lithium-ion” battery systems. The lithium metal anode is considered as the “Holy grail” of anodes due to its relatively low electrochemical potential (-3.04 V vs SHE) and high theoretical capacity (3860 mAh g-1). However, the application of lithium metal anodes is hindered because of significant reaction between metallic lithium and electrolytes, as well as uneven electro-plating, which leads to dendrite formation, causing safety problems.

The kinetic parameters of Li ions such as diffusion coefficient …

Modification And Optimization Of Conducting Polymer-Modified, Redox-Magnetohydrodynamics (R-Mhd) Pumping For Enhanced And Sustained Microfluidics Applications, Md Foysal Zahid Khan

Graduate Theses and Dissertations

In this work, a novel microfluidic pumping approach, redox-magnetohydrodynamics (R-MHD) has improved by materials and device optimization to use in lab-on-a-chip applications. In R-MHD, magnetic flux (B) and ionic current density (j) interacts to generate body force (FB) in between active electrodes, according to the equation FB = j×B. This unique fluid pumping approach is scalable, tunable, generates flat flow profile, and does not require any channels or valves. Pumping performance, such as speed scales with the ionic current density (j) and duration depends on the total charge (Q). The ionic current density (j) results from the conversion of electronic …

Experimental And Computational Study On Magnetic Nanowires Of Layered Titanates, Caleb Layne Heath

Graduate Theses and Dissertations

The intricate nanostructures of layered titanates are unique among nanomaterials due to their easy and inexpensive syntheses. These nanomaterials have been proven valuable for use in industries as varied as energy, water treatment, and healthcare, and can be produced at industrial scales using already existent equipment. They have complex morphology, and surface structure well suited to chemical modification and doping. However, there is a longstanding debate on their lattice structure after the doping. There is a long-unmet need to understand, using both experimental and simulation methods, how dopants alter the clay-like layered crystal structure and associated physical and chemical properties. …

Assessing Biofiltration Without Ozonation For Removal Of Trihalomethane Precursors In Drinking Water At The Beaver Water District Drinking Water Treatment Plant, Sana Ajaz

Graduate Theses and Dissertations

Biofiltration without pre-ozonation has the capability to remove natural organic matter (NOM) fractions that serve as precursors of disinfection byproducts (DBPs), which include the four regulated trihalomethanes (THMs) and dichloroacetonitrile (DCAN). Rapid small-scale column tests (RSSCTs) and Pilot Plant filters operated at empty-bed contact times (EBCTs) of 4, 8, and 16 minutes were used to evaluate the performance of nutrient-amended (free ammonia and phosphorus) biofiltration for THM and DCAN precursor removal, as measured using formation potential (FP) tests. NOM surrogates – which include dissolved organic carbon (DOC), specific ultraviolet absorbance (SUVA254) and fluorescence-PARAFAC components – were measured weekly throughout the …

Synthesis Of Dicamba Glucosides For The Study Of Environmental Dicamba Drift Effects On Soybeans, Holly Wallace

Graduate Theses and Dissertations

The most popular herbicide used for weed control has been glyphosate for many years in the Midwestern United States. Plants have begun to develop a resistance to glyphosate due to over use of the herbicide. This herbicide resistance has pushed farmers to turn to alternative herbicides such as dicamba and 2,4-D. Recently agrochemical companies have developed genetically modified crops that are resistant to herbicides such as dicamba. These modified crops allow farmers to spray their fields with dicamba without fear of crop damage. Farmers of non-genetically modified crops, however, suffer damage and loss of yield from herbicide drift effects of …

Molecular Dynamics Investigation Of The Thermodynamics Of Nanoscale Droplets And Kinetics Of Weakly Correlated Systems, Kai Yang Leong

Graduate Theses and Dissertations

The surface tension of nanoscale droplets of water was studied with molecular dynamics simulations using the BLYPSP-4F water potential. The internal pressure of the droplet was measured using a correlation between the pressure and density, established through a series of bulk simulations performed at pressures from 1 to 1000 bar. Such a procedure allows for reliable determination of internal pressure without the need to calculate the local Virial. The surface tension, estimated with the Young-Laplace relation, shows a good agreement with the Tolman equation with a Tolman length of -0.48 Å. The interface of a liquid water droplet is shown …

Chemical Strategies For Drug Development Of Fucose-Truncated Ipomoeassin F Analogues, Melissa Hirsch

Graduate Theses and Dissertations

Natural product synthesis has many applications in the field of chemical biology, due to the protein binding affinity to the complex three-dimensional structure. However, synthetic and structure-activity relationship studies concerning certain drug targets are scarce. For example, members of the ipomoeassin family have exhibited anti-cancer properties, but cost-effective optimization of these compounds has not yet been extensively studied. Ipomoeassin F, a natural glycoresin isolated from the leaves of the Ipomoea squamosa plant in the Suriname rainforest, has shown high cytotoxicity, with IC50 values measured at the low nanomolar range. Two studies by Postema and Fuerstner have outlined synthesis pathways for …

Conformationally-Controlled Late-Stage Modifications For Sar Studies Of The C-3-Glcp Moiety Of Ipomoeassin F, Lucas Whisenhunt

Graduate Theses and Dissertations

The resin glycoside, ipomoeassin F has been shown to be extremely potent against multiple cancer lines (IC50 = 4.2-36 nM). However, the mechanism of action of this potent and complex natural product is still not fully understood. The α,β-unsaturated esters of the glucosyl moiety have been shown to be vital for the overall cytotoxicity of ipomoeassin F. Nevertheless, the importance of the tigloyl ester of the glucosyl moiety is still largely unknown. This work aimed to study the pharmacophore importance of the tigloyl ester by creating, an efficient, scalable, and flexible synthesis route for various analogs. The 18-linear step synthesis …

Development Of Microdialysis Probes In Series Approach Toward Eliminating Microdialysis Sampling Calibration: Miniaturization Into A Pdms Microfluidic Device, Randy Espinal Cabrera

Graduate Theses and Dissertations

A new microdialysis sampling method and microfluidic device were developed in vitro. The method consisted of using up to four microdialysis sampling probes connected in series to evaluate the relative recovery (RR) of different model solutes methyl orange, fluorescein isothiocyanate (FITC)-dextran average mol. wt. 4,000 (FITC-4), FITC-10, FITC-20, and FITC-40. Different flow rates (0.8, 1.0, and 1.5 µL/min) were used to compare experimentally observed relative recoveries with theoretical estimations. With increasing the number of probes in series, the relative recovery increases and ~100% (99.7% ± 0.9%) relative recovery for methyl orange was obtained. For larger molecules such as fluorescein isothiocyanate …

Green Chemistry Oxidative Modification Of Peptoids Utilizing Bleach And Tempo, Jesse Leland Roberts

Graduate Theses and Dissertations

Biotherapeutic drugs, derived from biological molecules such as proteins and DNA, are becoming an integral and exceptionally critical aspect of modern medicine. Compared to common pharmaceutical drugs, biotherapeutics are much larger in size and have greater target specificity, allowing them to treat many chronic diseases ranging from cancer to rheumatoid arthritis. The major issue with protein based therapeutics is that they readily undergo proteolysis, or enzymatic degradation, when administered through subcutaneous injections. Traditionally, biotherapeutic modification procedures have centered on the use of PEG derivatives. This process, called PEGylation, is unfavorable due to the increases in molecular weights of the proteins …

The Functionalization Of N-Cyclobutylanilines Under Photoredox Catalysis, Jiang Wang

Graduate Theses and Dissertations

While transition metal catalyzed cross coupling reactions have become one of the most useful strategies in constructing carbon-carbon and carbon-heteroatom bond formations, major disadvantages such as high reaction temperature, expansive metal catalysts input and limited reaction substrates scope have significantly downshifted the applications of those two electron involved transformations. Comparably, the studies on the redox coupling reactions are less investigated. Derived from single electron transfer process, the redox coupling reactions can be used to construct otherwise challenging chemical bonds efficiently, such as Csp3-Csp3 bond. Recently, visible light mediated photoredox catalysis has merged as a highly prominent tool in the development …

Instrumental Aspects Of Oxygen Sensing: Quantitation And Recalibration Of A Biofouled Oxygen Sensor, Marlena Patrick

Graduate Theses and Dissertations

In vivo oxygen sensing is a critical area of research for medical applications, such as ischemic stroke, but this important topic is not fully understood or resolved. In addition, the best method for calibration of in vivo sensors is as yet undetermined. For all implantable devices, biofouling, the adsorption of biological material to the device surface, is another significant problem with no clear or well-defined solution. One method employed is to apply a protective polymer membrane to the sensor surface in order to minimize the adsorption of biological material. The work described here investigates two polymers applied to a gold …