Chemistry Commons^™

Development Of Biomaterials For Drug Delivery, Raquel De Castro

Graduate Theses and Dissertations

Drug delivery systems (DDS) have highly evolved in the last decades with the development of hydrogels and nanoparticles. However, high systemic uptake, side effects, low bioavailability, and encapsulation efficiency continue to be a major hurdle faced by such DDSs.

Nanoparticles and hydrogels can be specifically designed for targeted DDSs to mitigate some of the problems. This dissertation aimed to design two DDSs for ocular drug delivery and one for cancer treatment. The first project sought to develop chitosan nanoparticles (Cs-NP) using PEGDA as a copolymer to encapsulate gentamicin (GtS) for ocular drug delivery. Cs-NPs contain positive charges that can interact …

Photothermal Response Induced By Nanocage-Coated Artificial Extracellular Matrix Promotes Neural Stem Cell Differentiation, Seunghyun Jung, Nathaniel Harris, Isabelle I. Niyonshuti, Samir V. Jenkins, Abdallah M. Hayar, Fumiya Watanabe, Azemat Jamshidi-Parsian, Jingyi Chen, Michael J. Borrelli, Robert J. Griffin

Mechanical Engineering Faculty Publications and Presentations

Strategies to increase the proportion of neural stem cells that differentiate into neurons are vital for therapy of neurodegenerative disorders. In vitro, the extracellular matrix composition and topography have been found to be important factors in stem cell differentiation. We have developed a novel artificial extracellular matrix (aECM) formed by attaching gold nanocages (AuNCs) to glass coverslips. After culturing rat neural stem cells (rNSCs) on these gold nanocage-coated surfaces (AuNC-aECMs), we observed that 44.6% of rNSCs differentiated into neurons compared to only 27.9% for cells grown on laminin-coated glass coverslips. We applied laser irradiation to the AuNC-aECMs to introduce precise …

Biochemical Characterization Of Small Molecule Inhibitor Binding On A Ras Related Gtpase And Its Effector Interactions, Djamali Muhoza

Graduate Theses and Dissertations

The Ras superfamily of GTPases has 167 proteins that are involved in various cellular processes such as proliferation, transformation, migration, and inhibition of cell death. Mutations, abnormal expression, and function of these proteins are observed in many diseases, including several forms of cancer. Even though these GTPases were among the first discovered oncogenes, no successful Ras drug candidate has successfully passed clinical trials. Drugs targeting these proteins have failed mainly because of the complexity of their regulation, their high affinity to GTP, and their structure’s dynamic nature. Recently, novel promising targeting approaches have renewed interest in the Ras drug discovery …

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 …

Remote Performance Modulation Of Ultrafiltration Membranes By Magnetically And Thermally Responsive Polymer Chains, Arijit Sengupta, Anh Vu, Xianghong Qian, Sumith R. Wickramasinghe

Chemical Engineering Faculty Publications and Presentations

Ultrafiltration membranes, that respond to an external magnetic field and local temperature have been developed. Surface-initiated activator-generated electron transfer (AGET) atom transfer radical polymerization (ATRP) has been used to graft poly(N-isopropylacrylamide) (PNIPAm) from the surface of 300 kDa regenerated cellulose membranes. The polymerization initiator was selectively attached to the entire membrane surface, only the outer membrane surface or only the inner pore surface. A superparamagnetic nanoparticle was attached to the end of the polymer chain. The DI water flux as well as the flux and rejection of bovine serum albumin were investigated in the absence and presence of a 20 …

Blood Driven Biopower Cells: Acquiring Energy From Reverse Electrodialysis Using Sodium Concentrations From The Flow Of Human Blood, Efecan Pakkaner, Chase Smith, Christina Trexler, Jamie Hestekin, Christa Hestekin

Chemical Engineering Faculty Publications and Presentations

With the growth of the healthcare industry, small scale power sources are needed to support advancements in medical implants, artificial organs, and sensors throughout the body. However, it remains a challenge to find safe, reliable, and stable power sources for these devices. In this study, a miniaturized reverse electrodialysis (RED) biopower cell design using physiological salinity concentration differences between renal bloodstreams is explored for its potential to be used as a power supply for implantable medical devices. Two small scale RED devices produced consistent power for up to three to ten days, depending on the device design. A two-fold decrease …

Soil Quality Indices As Affected By Long-Term Burning, Irrigation, Tillage, And Fertility Management, Helen C.S. Amorim, Amanda Ashworth, Kristofor R. Brye, Brian J. Wienhold, Mary C. Savin, Phillip R. Owens, Sergio Silva

Crop, Soil and Environmental Sciences Faculty Publications and Presentations

Understanding the impacts of long-term agricultural practices on soil quality (SQ) is key for sustaining agroecosystem productivity. This study investigated conventional and no-tillage (NT), residue burning and no burning, residue level (high and low), and irrigation (irrigated and dryland) effects on soil properties, SQ, and crop yields following 16 yr of a wheat (Triticum aestivum L.)–soybean [Glycine max (L.) Merr.] double-crop system via the Soil Management Assessment Framework (SMAF). A field experiment was conducted in the Lower Mississippi River Delta region on a silt-loam soil. Bulk density, soil organic C (SOC), total N (TN), pH, electrical conductivity (EC), …

Application Of Zwitterions In Forward Osmosis: A Short Review, Yu-Hsuan Chiao, Arijit Sengupta, Micah Belle Marie Yap Ang, Shu-Ting Chen, Teow Yeit Haan, Jorge Almodovar, Wei-Song Hung, S. Ranil Wickramasinghe

Chemical Engineering Faculty Publications and Presentations

Forward osmosis (FO) is an important desalination method to produce potable water. It was also used to treat different wastewater streams, including industrial as well as municipal wastewater. Though FO is environmentally benign, energy intensive, and highly efficient; it still suffers from four types of fouling namely: organic fouling, inorganic scaling, biofouling and colloidal fouling or a combination of these types of fouling. Membrane fouling may require simple shear force and physical cleaning for sufficient recovery of membrane performance. Severe fouling may need chemical cleaning, especially when a slimy biofilm or severe microbial colony is formed. Modification of FO membrane …

Development And Validation Of A Dft-Based Force Field For A Hydrated Homoalanine Polypeptide, Ying Yuan, Zhonghua Ma, Feng Wang

Chemistry & Biochemistry Faculty Publications and Presentations

A new force field has been created for simulating hydrated alanine polypeptides using the adaptive force matching (AFM) method. Only density functional theory calculations using the Perdew–Burke–Ernzerhof exchange–correlation functional and the D3 dispersion correction were used to fit the force field. The new force field, AFM2020, predicts NMR scalar coupling constants for hydrated homopolymeric alanine in better agreements with experimental data than several other models including those fitted directly to such data. For Ala₇, the new force field shows about 15% helical conformations, 20% conformation in the β basin, and 65% polyproline II. The predicted helical population of …

Effects Of Resin Chemistries On The Selective Removal Of Industrially Relevant Metal Ions Using Wafer-Enhanced Electrodeionization, Humeyra B. Ulusoy Erol, Christa N. Hestekin, Jamie A. Hestekin

Chemical Engineering Faculty Publications and Presentations

Wafer-enhanced electrodeionization (WE-EDI) is an electrically driven separations technology that occurs under the influence of an applied electric field and heavily depends on ion exchange resin chemistry. Unlike filtration processes, WE-EDI can be used to selectively remove ions even from high concentration systems. Because every excess ion transported increases the operating costs, the selective separation offered by WE-EDI can provide a more energy-efficient and cost-effective process, especially for highly concentrated salt solutions. This work reports the performance comparison of four commonly used cation exchange resins (Amberlite IR120 Na⁺, Amberlite IRP 69, Dowex MAC 3 H⁺, and …

Electrocatalytic Redox Neutral [3+2] Annulation Of N-Cyclopropylanilines And Alkenes, Qi Wang, Qile Wang, Yuexiang Zhang, Yasmine M. Mohamed, Carlos Pacheco, Nan Zheng, Richard N. Zare, Hao Chen

Chemistry & Biochemistry Faculty Publications and Presentations

Although synthetic organic electrochemistry (EC) has advanced significantly, net redox neutral electrosynthesis is quite rare. Two approaches have been employed to achieve this type of electrosynthesis. One relies on turnover of the product by the reactant in a chain mechanism. The other involves both oxidation on the anode and reduction on the cathode in which the radical cation or the radical anion of the product has to migrate between two electrodes. Herein, a home-built electrochemistry/mass spectrometry (EC/MS) platform was used to generate an N-cyclopropylaniline radical cation electrochemically and to monitor its reactivity toward alkenes by mass spectrometry (MS), which …

Strain Control Of Layer-Resolved Negative Capacitance In Superlattices, Raymond Walter, Sergey Prosandeev, Charles Paillard, L. Bellaiche

Physics Faculty Publications and Presentations

Negative capacitance in BaTiO₃/SrTiO₃ superlattices is investigated by Monte Carlo simulations in an atomistic effective Hamiltonian model, using fluctuation formulas for responses to the local macroscopic field that incorporates depolarizing fields. We show that epitaxial strain can tune the negative capacitance of the BaTiO₃ ferroelectric layer and the overall capacitance of the system. In addition, we predict and explain an original switching of the negative capacitance from the BaTiO₃ layer to the SrTiO₃ layer at low temperatures for intermediate strains.

Spatially Directed Functionalization By Co-Electropolymerization Of Two 3,4-Ethylenedioxythiophene Derivatives On Microelectrodes Within An Array, Benjamin J. Jones, Carol Korzeniewski, Jefferson H. Franco, Shelley D. Minteer, Ingrid Fritsch

Chemistry & Biochemistry Faculty Publications and Presentations

Electrodeposited conductive copolymer films with predictable relative properties (quantities of functional groups for further modification and capacitance) are of interest in sensors, organic electronic materials and energy applications. Potentiodynamic copolymerization of films in aqueous solutions of two different 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), containing 0.02 M total monomer (0, 25, 34, 50, 66, 75, 100 mol% 2), 0.05 M sodium dodecyl sulfate, and 0.1 M LiClO4, on gold microelectrodes in an array was investigated. Decreasing monomer deposited (m) from 0 to 100 mol% 2 is attributed to a decreasing pH that inhibits electropolymerization. Molar ratios of …

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 …

Corn And Soybean Response To Wastewater-Recycled Phosphorus Fertilizers, Shane Ylagan

Crop, Soil and Environmental Sciences Undergraduate Honors Theses

The ability to recycle phosphorus (P) from wastewaters could provide a sustainable, continuous source of P that might also help protect surface water quality from P enrichment. The mineral struvite (MgNH4PO4·6H2O) is an understudied material that can be created from Pcontaining wastewater and has been shown to have agricultural fertilizer value. The objective of this study was to evaluate the effects of electrochemically precipitated struvite (ECST), chemically precipitated struvite (Crystal Green; CG), diammonium phosphate (DAP), monoammonium phosphate (MAP), rock phosphate (RP), and triple super phosphate (TSP) on corn (Zea mays) and soybean (Glycine max) response in a 79-day greenhouse pot …

Dna Aptamer‑Based Rolling Circle Amplification Product As A Novel Immunological Adjuvant, Adil Sabr Al-Ogaili, Rohana Liyanage, Jack O. Lay Jr., Tieshan Jiang, Christine N. Vuong, Shilpi Agrawal, Thallapuranam Krishnaswamy Suresh Kumar, Luc R. Berghman, Billy M. Hargis, Young Min Kwon

Chemistry & Biochemistry Faculty Publications and Presentations

Several agonists to CD40 have shown to induce acquired immune responses. Here, we developed and evaluated the rolling circle amplification (RCA) products that are based on anti-CD40 DNA aptamers as a novel vaccine adjuvant. First, we developed DNA aptamers with specific binding affinity to chicken CD40 extra domain (chCD40ED). Next, we prepared the RCA products that consist of these aptamers to increase the spanning space and overall binding affinity to chCD40ED. Using 8 DNA aptamer candidates, 4 aptamer-based RCA products (aptamer RCAs) were generated, each consisting of two distinct aptamers. We demonstrated that all 4 aptamer RCAs significantly induced the …

Topology And Control Of Self-Assembled Domain Patterns In Low-Dimensional Ferroelectrics, Y. Nahas, S. Prohorenko, Q. Zhang, V. Govinden, N. Valanoor, L. Bellaiche

Physics Faculty Publications and Presentations

Whilst often discussed as non-trivial phases of low-dimensional ferroelectrics, modulated polar phases such as the dipolar maze and the nano-bubble state have been appraised as essentially distinct. Here we emphasize their topological nature and show that these self-patterned polar states, but also additional mesophases such as the disconnected labyrinthine phase and the mixed bimeron-skyrmion phase, can be fathomed in their plurality through the unifying canvas of phase separation kinetics. Under compressive strain, varying the control parameter, i.e., the external electric field, conditions the nonequilibrium self-assembly of domains, and bridges nucleation and spinodal decomposition via the sequential onset of topological transitions. …

Inversion Modeling Of Japonica Rice Canopy Chlorophyll Content With Uav Hyperspectral Remote Sensing, Yingli Cao, Kailun Jiang, Jingxian Wu, Fenghua Yu, Wen Du, Tongyu Xu

Electrical Engineering Faculty Publications and Presentations

Chlorophyll content is an important indicator of the growth status of japonica rice. The objective of this paper is to develop an inversion model that can predict japonica rice chlorophyll content by using hyperspectral image of rice canopy collected with unmanned aerial vehicle (UAV). UAV-based hyperspectral remote sensing can provide timely and cost-effective monitoring of chlorophyll content over a large region. The study was based on hyperspectral data collected at the Shenyang Agricultural College Academician Japonica Rice Experimental Base in 2018 and 2019. In order to extract the salient information embedded in the high-dimensional hyperspectral data, we first perform dimension …

Testing Flowering Perennial Plants In A Bermudagrass (Cynodon Spp.) Lawn, Paige Elizabeth Boyle, Michelle Wisdom

Horticulture Faculty Publications and Presentations

Most pollinating insects require a season-long succession of floral resources to fulfill life-cycle requirements. Incorporating forbs into turfgrass sites may create a season-long sequence of flowers to support foraging pollinators. However, persistence of forbs in warm-season turfgrasses such as bermudagrass (Cynodon spp.) may be affected by the competitive nature of the turfgrass and routine management practices such as mowing. A 2-year study was conducted to evaluate seven forbs (Bellis perennis L., Lotus corniculatus L., Prunella vulgaris L., Trifolium fragiferum L. ‘Fresa’, Trifolium repens L. ‘Durana’ and ‘Resolute’, Trifolium subterraneum L.) for persistence and ability to produce floral resources …

Chemistry And Biochemistry Authored Faculty Publications: Snapshot Of The Ranking Of Journals In Which They Published Based On Data From Journal Citation Reports (Jcr), Lutishoor Salisbury, Yang Tian, Jeremy Smith

University Libraries Faculty Publications and Presentations

This report presents a snapshot of the research output of the Chemistry and Biochemistry Department at the University of Arkansas for the period 2015-2019. The contents of the report were generated using Web of Science Core Collection databases and the Journal Citation Report only. It highlights the journals in which the researchers published and the ranking of those journals.

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 …

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.

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. …

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 …

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 …

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 …

Effect Of Charged Lipids On The Ionization Behavior Of Glutamic Acid Containing Transmembrane Helices, Brooke Nunn

Chemistry & Biochemistry Undergraduate Honors Theses

Transmembrane proteins make up critical components of living cells. Protein function can be greatly impacted by the charged state of its respective components, the side chains of amino acid residues. Thus far, in the lipid membrane, little is known about the properties of residues such as glutamic acid. To explore these properties, I have included glutamic acid in a suitable model peptide-lipid system for fundamental biophysical experiments. Within the system, I have placed a glutamic acid residue instead of leucine in the L14 position of the helical hydrophobic peptide GWALP23 (acetyl-GGALWLALALALAL¹⁴ALALWLAGA-amide). Substitutions of glutamine and aspartic acid serve …

In Situ Plant Uptake Of Excess Nutrients And Consequential Alteration Of Rhizosphere Dynamics, Srusti Maddala

Crop, Soil and Environmental Sciences Undergraduate Honors Theses

The use of phytoremediation in ecological remediation projects has numerous benefits including soil stabilization and nutrient uptake. Recently, microdialysis, a diffusion-based sampling technique commonly used in biomedical research, has been recognized as a candidate for monitoring chemical changes in the rhizosphere. The real-time, in situ data it provides about nutrient diffusion may improve the management and success of restoration projects. Therefore, the objective of this study was to employ the technique of microdialysis in the novel application of quantifying the diffusive flux of inorganic nitrogen compounds in the rhizosphere of native plants of Arkansas. The microdialysis technique was first optimized …

Enhancement Of Phase Change Material Sorbitol By Nanoparticle Inclusion For Improving Thermal Energy Storage Capabilities, Joshua Kasitz

Mechanical Engineering Undergraduate Honors Theses

Thermal management of electronic devices has become an increasingly vital field of study with the rapid miniaturization of many key electrical components. With the significant improvement of semiconductor manufacturing and intensified focus on interconnects, electronic devices have decreased in size at an incredible rate. Decreasing spatial requirements is essential to improving device capabilities as the electronic system is able to incorporate more components. Currently, electronic systems are drastically limited by the capabilities of their cooling mechanisms. Smaller devices lead to large increases in the energy density of the system and require more powerful cooling systems to maintain proper component operating …

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 …