Chemistry Commons^™

Organic-Inorganic Hybrid Materials For Piezoelectric/Triboelectric Nanogenerator, Aminur Rashid Chowdhury

Theses and Dissertations

Nanogenerator has been a major focus among researchers of recent time due to its versatile use in everyday life. Though the discovery of the piezoelectricity and the triboelectricity dates back to 19th century, the use of these phenomena has not been in practical use till 2006. In this study we demonstrate the practical application of piezoelectric and triboelectric nanogenerator comprised of different copolymer and piezoelectric ceramic. The largely known piezoelectric polymer Polyvinylidene fluoride (PVDF) has also been utilized. The enhancement of piezoelectric properties of PVDF has been achieved by utilizing surface activation of accommodating ceramic. The Li doped ZnO has …

Computational Studies Of High-Oxidation State Main-Group Metal Hydrocarbon C-H Functionalization, Clinton R. King

Theses and Dissertations

High-oxidation state main-group metal complexes are potential alternatives to transition metals for electrophilic C-H functionalization reactions. However, there is little known about how selection of the p-block, main-group metal and ligand impact C-H activation and functionalization thermodynamics and reactivity. Chapter 2 reports density functional theory (DFT) calculations used to determine qualitative and quantitative features of C-H activation and metal-methyl functionalization energy landscapes for reaction between high-oxidation state d10s0 InIII, TlIII, SnIV, and PbIV carboxylate complexes with methane. While the main-group metal influences the C-H activation barrier height in a periodic manner, the carboxylate ligand has a much larger quantitative impact …

Modification Of Chemical Vapor-Deposited Carbon Electrodes With Electrocatalytic Metal Nanoparticles Through A Soft Nitriding Technique, Enoch Amoah

Electronic Theses and Dissertations

Metal nanoparticles have been widely used for many catalytic and electrocatalytic applications due to their larger surface area-to-volume ratios and higher densities of active sites compared to bulk materials. This has resulted in much interest in understanding the electrocatalytic behavior of metal nanoparticles with respect to their structure. However, most research on this topic has employed collections of nanoparticles. Due to difficulties in controlling and characterizing particle loading and interparticle distance in nanoparticle ensembles, single nanoparticles studies have recently become a topic of great interest. In this study, a soft nitriding technique was applied to chemical vapor-deposited carbon ultramicroelectrodes (UMEs) …

Synthesis Of Diazonium N-(Perfluoroalkyl) Benzenesulfonimide Polymers For Proton Exchange Membrane Fuel Cells (Pemfcs), Helal Alharbi

Electronic Theses and Dissertations

The objective of the research is to synthesize the diazonium N-(perfluoroalkyl) benzenesulfonimide (PFSI)zwitterionicpolymers as electrolytes in polymerelectrolyte membrane (PEM) fuel cells. The proposed diazoniumPFSI zwitterionic polymer (I) is expected to enhance the thermal and chemical stability, increase the proton conductivity of electrolytes, and improve the catalyst efficiency for PEM fuel cells. Synthesis of the perfluorobenzoyl peroxide initiator, homopolymerization of perfluoro (3-oxapent-4-ene) sulfonyl fluoride,coupling reaction with4-sulfamonylacetanilide, couplingreaction with 4-nitrobenzene sulfonyl amide, n-deacetylation reaction, and diazotization reactionhave been carried outsuccessfully in the lab. The intermediate chemicals are characterized by GC-MS, IR, NMR, and GPC spectroscopies.

Peroxide Sensing Using Nitrogen-Doped And Platinum Nanoparticle-Modified Screen-Printed Carbon Electrodes, Chidiebere Ogbu

Electronic Theses and Dissertations

Nitrogen-doped carbon materials have garnered much interest due to their abilities to behave as electrocatalysts for reactions important in energy production (oxygen reduction) and biosensing (hydrogen peroxide reduction). Here, we demonstrate fabrication methods and determine electrocatalytic properties of nitrogen-doped screen-printed carbon (N-SPCE) electrodes. Nitrogen doping of graphite was achieved through a simple soft-nitriding technique which was then used in lab-formulated screen-printing inks to prepare N-SPCEs. N-SPCEs displayed good electrocatalytic activity, reproducibility and long term stability towards the electrochemical reduction of hydrogen peroxide. N-SPCEs exhibited a wide linear range (20 µM to 5.3 mM), reasonable limit of detection of 2.5 µM, …

Immobilization Of Electrocatalytically Active Gold Nanoparticles On Nitrogen-Doped Carbon Fiber Electrodes, Daniel Mawudoku

Electronic Theses and Dissertations

Studies of single, isolated nanoparticles provide better understanding of the structure-function relationship of nanoparticles since they avoid complications like interparticle distance and nanoparticle loading that are typically associated with collections of nanoparticles distributed on electrode supports. However, interpretation of results obtained from single nanoparticle immobilization studies can be difficult to interpret since the underlying nanoelectrode platform can contribute to the measured current, or the immobilization technique can adversely affect electron transfer. Here, we immobilized ligand-free gold nanoparticles on relatively electrocatalytically inert nitrogen-doped carbon ultramicroelectrodes that were prepared via a soft nitriding method. Sizes of the particles were estimated by a …

Aerobic Photolysis Mecbl: Structure And Electronic Properties Of Cbl-O-O-Ch3 Intermediate., Aida Bazarganpour

Electronic Theses and Dissertations

The photolysis of methylcobalamin (coenzyme B₁₂) results in homolytic cleavage of the Co-C bond, forming cob(II)alamin and the Co(II)/CH₃ radical pair (RP) which further react with O₂ to form the intermediate (R-O-O-Cbl) that involves in the aerobic photolysis. It has been suggested that the key intermediate (R-O-O-Cbl) involves in aerobic photolysis is the insertion of O₂ between the Co-C bond. Clearly, the exposure of light is needed to induce the activation Co-C bond for generating the Co(II)/CH₃ radical pair (RP). The intermediate (R-O-O-Cbl) undergoes further decomposition to aldehyde as the final product of aerobic …

Quality Of Wheat Grains (Triticum Aestivum) Generationally Exposed To Cerium Oxide Nanoparticles (Nceo2), Oluwasegun Michael Abolade

Graduate Theses/Dissertations

The impacts of generational exposure to engineered nanomaterial on grain quality are poorly documented. This study was performed on wheat grains harvested from plants grown in soil amended with cerium oxide nanoparticles (nCeO₂) at the 2^nd and 3^rd generations. Third generation experiment was performed at low and high nitrogen (N) soil levels. The goal was to investigate changes in grain fatty acid and elemental contents due to parental exposure (C₁ vs T₁ in 2^nd generation, C₁C₂ vs T₁T₂ in 3^rd generation) or current generation …

Synthesis And Characterization Of Gd-Doped Inp/Zns Quantum Dots For Use In Multimodal Imaging Probes, Molly Erin Duszynski

Graduate Theses/Dissertations

Quantum dots (QDs), which are intensely fluorescent nanocrystals ranging 2-10 nanometers in diameter, have shown promise in fluorescence imaging. However, in vivo applications of QDs are limited due to the opaque surrounding of tissue and bones. In this study, InP/ZnS QDs were doped with a paramagnetic atom in an attempt to render them MRI-active. We have further bioconjugated these nanoprobes to develop highly specific MRI-active probes that can be used for detection of neurodegenerative diseases. These bioconjugated nanoprobes detect a mutated form of alpha-synuclein that forms oligomers that are a hallmark of Parkinson’s disease andother alpha-synucleinopathies. Here, we have optimized …

Simple Photochemical Reduction Of Carbon Dioxide To Formate, Ovuokenye Omadoko

Electronic Theses and Dissertations

There is a need to develop techniques for conversion of carbon dioxide to other useful products such as methanol, formaldehyde, formic acid, formate, methane, and hydrocarbons. Carbon dioxide can be converted into these products using different methods such as photochemical, electrochemical, thermochemical and hydrogenation by bacteria. Formate is of interest due to its wide industrial applications which include it’s use in direct liquid fuel cells, as an additive in pyrolysis vapors, a precursor for biological fuels, and it is a key intermediate in methanogenesis breaking down complex organic compounds. In this work, conversion of carbon dioxide to formate was accomplished …

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 …

Computational And Experimental Studies On Energy Storage Materials And Electrocatalysts, Jared B. Moss

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

With the growing global population comes the ever-increasing consumption of energy in powering cities, electric vehicles, and portable devices such as cell-phones. While the power grid is used to distribute energy to consumers, the energy sources needed to power the grid itself are unsustainable and inefficient. The primary energy sources powering the grid, being fossil fuels, natural gas, and nuclear, are unsustainable as the economically-accessible reserves are continually depleted in exchange for detrimental emissions and air-pollutants. Cleaner, renewable sources, such as solar, wind, and hydroelectric, are intermittent and unreliable during the peak hours of energy usage, that is dawn and …

Electronic Transmutation: An Aid For The Rational Design Of New Chemical Materials Using The Knowledge Of Bonding And Structure Of Neighboring Elements, Katie A. Lundell

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Everything in the universe is made up of elements from the periodic table. Each element has its own role that it plays in the formation of things it makes up. For instance, pencil lead is graphite. A series of honeycomb-like structures made up of carbon stacked on top of one another. Carbon’s neighbor to the left, boron doesn’t like to form such stacked honeycomb-like structures. But, what if there was a way to make boron act like carbon so it did like to form such structures? That question is the basis of the electronic transmutation concept presented in this dissertation. …

Phosphonate-Directed Catalytic Asymmetric Hydroboration: Synthesis Of Functionalized Chiral Secondary And Tertiary Boronic Esters And Mechanistic Insights, Suman Chakrabarty

Department of Chemistry: Dissertations, Theses, and Student Research

Over the past 30 years, catalytic asymmetric hydroboration (CAHB) of alkenes has emerged as a leading methodology to access chiral primary and secondary boronic esters. However, it wasn’t until 2015 that directed-CAHB was for the first time shown to efficiently access chiral tertiary boronic esters. The latter are excellent precursors to synthetically challenging structural motifs such as chiral tertiary alcohols, carbinamines and all-carbon quaternary stereocenters via stereospecific C-B bond substitutions. This dissertation focuses on phosphonate-directed CAHB of diverse alkene substrates, including challenging stereodefined trisubstituted alkenes, to efficiently access multifunctional chiral secondary and tertiary boronic esters. Mechanistic insights obtained via deuterium …

Current-Use Pesticides In New Zealand Streams: Comparing Results From Grab Samples And Three Types Of Passive Samplers, Kimberly J. Hageman, Christopher H.F. Aebig, Kim Hoang Luong, Sarit L. Kaserzon, Charles S. Wong, Tim Reeks, Michelle Greenwood, Samuel Macaulay, Christoph D. Matthaei

Chemistry and Biochemistry Faculty Publications

New Zealand uses more than a ton of pesticides each year; many of these are mobile, relatively persistent, and can make their way into waterways. While considerable effort goes into monitoring nutrients in agricultural streams and programs exist to monitor pesticides in groundwater, very little is known about pesticide detection frequencies, concentrations, or their potential impacts in New Zealand streams. We used the ‘Polar Organic Chemical Integrative Sampler’ (POCIS) approach and grab water sampling to survey pesticide concentrations in 36 agricultural streams in Waikato, Canterbury, Otago and Southland during a period of stable stream flows in Austral summer 2017/18. We …

Highly Active Nanostructured Cos2/Cos Heterojunction Electrocatalysts For Aqueous Polysulfide/Iodide Redox Flow Batteries, Dui Ma, Bo Hu, Wenda Wu, Xi Liu, Jiantao Zai, Chen Shu, Tsegaye Tadesse Tsega, Liwei Chen, Xuefeng Qian, T. Leo Liu

Chemistry and Biochemistry Faculty Publications

Aqueous polysulfide/iodide redox flow batteries are attractive for scalable energy storage due to their high energy density and low cost. However, their energy efficiency and power density are usually limited by poor electrochemical kinetics of the redox reactions of polysulfide/iodide ions on graphite electrodes, which has become the main obstacle for their practical applications. Here, CoS₂/CoS heterojunction nanoparticles with uneven charge distribution, which are synthesized in situ on graphite felt by a one-step solvothermal process, can significantly boost electrocatalytic activities of I⁻/I₃⁻ and S²⁻/S_x²⁻redox reactions by improving absorptivity of …

Self-Assembly, Integration, Characterizations And Applications Of Plasmonic And Excitonic Nanomaterials, Bijesh Kafle

Chemistry and Chemical Biology ETDs

Plasmon on metal nanoparticles can efficiently confine, amplify light at the nanoscale. This property is beneficial for different applications such as harvesting energy of the broad solar spectrum, highly sensitive spectroscopy, photocatalysis, and many other optoelectronic applications. For plasmonic applications, it is necessary to understand the fundamental physical properties of the individual, coupled plasmonic nanomaterials, and their interaction with the surrounding environment, which is not fully understood yet. In this dissertation, the chemical and optical interaction in plasmonic interfaces has been investigated. Plasmon-enhanced photochemistry of p-aminothiophenol as a model molecule is investigated using highly sensitive surface-enhanced Raman spectroscopy (SERS). The …

Stereodynamical Control Of A Quantum Scattering Resonance In Cold Molecular Collisions, Pablo G. Jambrina, James F.E. Croft, Hua Guo, Mark Brouard, Balakrishnan Naduvalath, F. Javier Aoiz

Chemistry and Biochemistry Faculty Research

Cold collisions of light molecules are often dominated by a single partial wave resonance. For the rotational quenching of HD (v=1, j=2) by collisions with ground state para-H2, the process is dominated by a single L=2 partial wave resonance centered around 0.1 K. Here, we show that this resonance can be switched on or off simply by appropriate alignment of the HD rotational angular momentum relative to the initial velocity vector, thereby enabling complete control of the collision outcome.

Optical Gas Imaging Survey Of Oil And Gas Wells In The Uinta Basin, Utah, Seth Lyman, Trang Tran, Marc L. Mansfield

Browse all Datasets

This is a dataset of oil and gas well pads which were surveyed for hydrocarbon emissions with an optical gas imaging camera deployed from the ground at pad edges. The data are described thoroughly in a peer-reviewed paper: Lyman S., Tran, T., Mansfield, M. Ravikumar, A., 2019. Aerial and Ground-Based Optical Gas Imaging Survey of Uinta Basin Oil and Gas Wells.

These are example videos collected during a hydrocarbon emissions survey of oil and gas well pads in Utah.

ExampleGroundVideo.mp4 is a video created with an optical gas imaging camera of an emission plume from well pad equipment. The video …

Capabilities And Limitations Of The Spin Hamiltonian Formalism In Single Molecule Magnets, Philip Ferko

Dissertations

The rational design of molecular magnetic materials is an ongoing effort involving physics, materials science, and chemistry. A common approach to design of complexes and interpretation of magnetic data is the spin Hamiltonian formalism. In this approach, magnetic data is interpreted through constants extracted from the parameterization of data. In design, certain structural motifs are pursued, rationalized by the minimization or maximization of terms in the spin Hamiltonian. In this work, monometallic complexes were prepared to simplify magnetic behavior and allow the examination of specific factors that influence single molecule magnetism like coordination geometry, ligand identity, symmetry, and spin-orbit coupling. …

Small Angle X-Ray Scattering Study Of Conformational Changes In Steroid Responsive Activator (Sra) Rna Upon Binding With Suppressor Protein Sharp, Diane Diatta

Master of Science in Chemical Sciences Theses

ABSTRACT

Differentiation and proliferation are known to be influenced by steroid stimulation. The steroid receptor activator (SRA) RNA is a large RNA transcript indicated to be an epigenetic regulatory component in the steroid receptor coactivator-1 (SRC-1) acetyltransferase complex. It is needed for a response to steroid hormones by tumor cells. However, this activity is hindered by suppressive RNA binding proteins like the SMRT/HDAC1-associated repressor protein (SHARP), which binds the STR7 domain of SRA RNA through its four RNA recognition motifs (RRMs); it is not fully understood how SHARP executes this role as there are no SRA RNA-SHARP structures available for …

60th Annual Rocky Mountain Conference On Magnetic Resonance

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 60th annual meeting of the Rocky Mountain Conference on Magnetic Resonance, co-endorsed by the Colorado Section of the American Chemical Society and the Society for Applied Spectroscopy. Held in Denver, Colorado, July 21-25, 2019.

Improving Performance Of The Smd Solvation Model: Bondi Radii Improve Predicted Aqueous Solvation Free Energies Of Ions And PkA Values Of Thiols, Saber Mirzaei, Maxim Vadimovich Ivanov, Qadir K. Timerghazin

Chemistry Faculty Research and Publications

Calculation of the solvation free energy of ionic molecules is the principal source of errors in the quantum chemical evaluation of pK_a values using implicit polarizable continuum solvent models. One of the important parameters affecting the performance of these models is the choice of atomic radii. Here, we assess the performance of the solvation model based on density (SMD) implicit solvation model employing SMD default radii (SMD) and Bondi radii (SMD-B), a set of empirical atomic radii developed based on the crystallographic data. For a set of 112 ions (60 anions and 52 cations), the SMD-B model showed …

Calculation Of Molecular Vibrational Spectra On A Quantum Annealer, Alexander Teplukhin, Brian K. Kendrick, Dmitri Babikov

Chemistry Faculty Research and Publications

Until recently molecular energy calculations using quantum computing hardware have been limited to gate-based quantum computers. In this paper, a new methodology is presented to calculate the vibrational spectrum of a molecule on a quantum annealer. The key idea of the method is a mapping of the ground state variational problem onto an Ising or quadratic unconstrained binary optimization (QUBO) problem by expressing the expansion coefficients using spins or qubits. The algorithm is general and represents a new revolutionary approach for solving the real symmetric eigenvalue problem on a quantum annealer. The method is applied to two chemically important molecules: …

The Chemistry And Biology Of Cyclophostin, The Cyclipostins And Related Compounds, Christopher Spilling

Chemistry & Biochemistry Faculty Works

Cyclophostin, the cyclipostins and the salinipostins are structurally related cyclic enolphosphate natural products. This mini review describes their isolation, synthesis and biological activities. In addition, the synthesis and biological activities of monocyclic enolphosphate and mono and bicyclic enolphosphonate analogs are presented.

Development Of Ni-Catalyzed Alkene Dicarbofunctionalization Reactions, Shekhar Kc

Chemistry and Chemical Biology ETDs

Alkenes serve as one of the most important feedstocks for organic synthesis, having two vicinal sites for bond formation. In alkenes, both vicinal sites can be functionalized with two reagents in a process commonly known as alkene difunctionalization, which results in the formation of two new bonds. A number of alkenes difunctionalization reactions, such as diamination, dioxygenation, carboamination and carbooxygenation, are known. However, difunctionalization of alkenes with two carbon-based entities, termed alkene dicarbofunctionalization, is relatively less common. Development of such a process could provide a powerful method to introduce two different carbon fragments across an alkene in a regioselective manner, …

Optimization Of Protein Entrapment In Affinity Microcolumns Using Hydrazide-Activated Silica And Glycogen As A Capping Agent, John Vargas-Badilla, Saumen Poddar, Shiden Azaria, Chenhua Zhang, David S. Hage

David Hage Publications

Several approaches were compared for the entrapment of proteins within hydrazide-activated silica for use in affinity microcolumns and high performance affinity chromatography. Human serum albumin (HSA) and concanavalin A (Con A) were used as model proteins for this work. Items considered in this study included the role played by the solution volume, amount of added protein, and use of slurry vs. on-column entrapment on the levels of solute retention and extent of protein immobilization that could be obtained by means of entrapment. The levels of retention and protein immobilization were evaluated by injecting warfarin or 4-methylumbellipheryl α-D-mannopyranoside as solutes with …

More Homogeneous Capillary Flow And Oxygenation In Deeper Cortical Layers Correlate With Increased Oxygen Extraction, Baoqiang Li, Tatiana V. Esipova, Ikbal Sencan, Kıvılcım Kılıç, Buyin Fu, Michele Desjardins, Mohammad Moeini, Sreekanth Kura, Mohammad A. Yaseen, Frederic Lesage, Leif Østergaard, Anna Devor, David A. Boas, Sergei A. Vinogradov, Sava Sakadžić

Chemistry: Faculty Publications and Other Works

Our understanding of how capillary blood flow and oxygen distribute across cortical layers to meet the local metabolic demand is incomplete. We addressed this question by using two-photon imaging of resting-state microvascular oxygen partial pressure (PO2) and flow in the whisker barrel cortex in awake mice. Our measurements in layers I-V show that the capillary red-blood-cell flux and oxygenation heterogeneity, and the intracapillary resistance to oxygen delivery, all decrease with depth, reaching a minimum around layer IV, while the depth-dependent oxygen extraction fraction is increased in layer IV, where oxygen demand is presumably the highest. Our findings suggest that more …

Acid-Mediated N-Iodosuccinimide-Based Thioglycoside Activation For The Automated Solution-Phase Synthesis Of Α-1,2-Linked-Rhamnopyranosides, Victoria R. Kohout, Alyssa L. Pirinelli, Nicola L.B. Pohl

Chemistry Publications

Carbohydrate structures are often complex. Unfortunately, synthesis of the range of sugar combinations precludes the use of a single coupling protocol or set of reagents. Adapting known, reliable bench-chemistry reactions to work via automation will help forward the goal of synthesizing a broad range of glycans. Herein, the preparation of di- and tri-saccharides of alpha 1→2 rhamnan fragments is demonstrated using thioglycoside donors with the development for a solution-phase-based automation platform of commonly used activation conditions using N-iodosuccinimide (NIS) with trimethylsilyl triflate. Byproducts of the glycosylation reaction are shown to be compatible with hydrazine-based deprotection conditions, lending broader functionality …

Use Of Pope Engagement Index To Measure Cognitive Load Of Physical Modeling Activities In Organic Chemistry, Jenifer Calvert

Master of Science in Chemical Sciences Theses

Understanding how students learn and process information is critical to developing physical modeling activities that facilitate student learning by decreasing cognitive load in the working memory. Optimizing cognitive load during physical modeling activities in organic chemistry is the key to effective and efficient learning. Using EEG (electroencephalogram) and eye tracking technologies, researchers measured and recorded the cognitive processing of participants while they completed a chiral physical modeling activity. Analysis of the data using the Engagement Index developed by Pope et al provided information necessary to develop curriculum that does not undermine student learning due to excessive cognitive load.