Physical Sciences and Mathematics Commons^™

Copper-Indazolate Nanojars: Synthesis And Characterization, Nicholas Alexander Rudell

Masters Theses

The field of synthetic supramolecular chemistry has exploded since the first syntheses of crown ethers by Charles Pedersen in the 1960s, leading to further development in the area of macrocycles and incorporation into a vast array of metal-organic structures. Supramolecular chemistry came to the forefront of science with the 1987 Nobel Prize in Chemistry, awarded jointly to Donald J. Cram, Jean-Marie Lehn, and Charles Pedersen “for their development and use of molecules with structure-specific interactions of high selectivity.”

Nanojars are supramolecular metal-organic complexes with a high affinity for hydrophilic anions and can efficiently transfer such anions from water into organic …

The Study Of Corrosion On Additive-Manufactured Metals., Braydan Daniels

Electronic Theses and Dissertations

The purpose of this study was to investigate and compare the corrosion mechanisms between wrought and additive-manufactured (3D-printed) copper and stainless steel. The experimental procedure consisted of measuring the open circuit potential, electrochemical impedance spectroscopy, linear sweep voltammetry, Tafel analysis, surface topology, and scanning electron microscopy for each metal within salt water, tap water, sulfuric acid, and synthetic body fluid (excluding copper in synthetic body fluid).

Overall, printed stainless steel was more corrosion-resistant than wrought stainless steel in tap water and synthetic body fluid based on OCP, LSV, and surface topology results. Additionally, printed copper was more corrosion-resistant than wrought …

Use Of Electrochemical Techniques And Statistical Analysis To Investigate The Pitting Probability Of Copper, Sina Matin

Electronic Thesis and Dissertation Repository

The development of a safe permanent disposal plan is essential for the long-term disposal of used fuel bundles. Nuclear Waste Management Organization (NWMO) has been investigating the deep geologic disposal of nuclear waste which offers the optimum passive safety system with a negligible probability of release of radionuclides into the environment.

The proposed used fuel containers (UFC) for the permanent disposal of high-level nuclear waste in Canada is comprised of a carbon steel vessel coated with a 3 mm corrosion-resistant copper layer deposited using a combination of electrodeposition and cold spray deposition. Although copper is often considered to be thermodynamically …

Characterization Of Deposited Copper Oxide Films On Copper Substrates, Millicent Castillo

Electronic Thesis and Dissertation Repository

The deposition of copper oxide films on copper substrates was investigated by the electrochemical, thermal, and hydrothermal oxidation of copper. The formed oxides were characterized using various surface analytical techniques to determine the film’s morphology, composition, and thickness. The results show that by growing oxides electrochemically, a duplex layer composing of CuO and Cu₂O film was formed on the copper surface, having characteristics of being porous and possessing needle-like structures. An oxide film composed of CuO and Cu₂O, which shows minimal porosity and possess mixtures of crystalline and non-crystalline structures, is formed on the copper surface …

Surface Modification Of Carbon-Based Electrodes For Electrochemical Conversion Processes: Oxygen Reduction Reaction And Bicarbonate Conversion, Udari Shyamika Kodithuwakku Arachchige

Theses and Dissertations--Chemistry

Oxygen reduction reaction (ORR) and conversion of bicarbonate into value-added chemicals are two significant electrochemical processes for energy storage and conversion. ORR is an important electrochemical reaction in fuel cells and metal-air batteries that provide power conversion and storage capacity, respectively, for portable electronics, and electric vehicles. However, the performance of catalysts (e.g., platinum-based) is critically limited by slow kinetics, inefficient four-electron pathway, and surface deactivation. This limited performance of platinum-based catalysts, the scarcity of platinum, and vulnerable supply chains for critical minerals require the development of alternative electrocatalysts now more than ever. Carbon-based materials possess several key properties that …

Copper-Catalyzed Dehydrogenative Decarboxylation Reactions Of Carboxylic Acids To Alkenes, Michael P. Stanton

Graduate Theses, Dissertations, and Problem Reports

Linear alpha olefins (LAOs) are important building blocks in the production of linear low-density polyethylene, a plastic used in products such as shrink wraps, plastic bags, tubing, plasticizers, among others. Commercial methods for generating LAOs utilize ethylene oligomerization, but this method is reliant on fossil fuels and leads to unselective product formation. Synthesis of LAOs from renewable resources, namely carboxylic acids, by decarbonylative dehydration strategies has been well studied, however, this method has inherent drawbacks rooted in the formation of internal olefin side-products through isomerization pathways. With the goal of avoiding internal isomerization, this thesis explores a dehydrogenative decarboxylation strategy …

Alkylthiocarbamate Metal Complexes With Antiproliferation Activity., Kritika Bajaj

Electronic Theses and Dissertations

Bis(thiosemicarbazones) (BTSCs) and their metal complexes have been extensively studied for various applications including catalysis for hydrogen evolution reactions, treatment of neurodegenerative diseases, hypoxia imaging, and a wide range of pharmacological purposes including antitumor, antiviral, antibacterial, and antifungal agents. The paramount property that makes BTSC metal complexes interesting for their use in these applications is the reduction potential of the coordinated metal, which can be selectively tuned by varying the substituents present on the ligand framework. Although the BTSCs have shown a great deal of success as potential cancer therapeutic agents, they lack selectivity towards cancer cells. For this matter, …

Characterization Of Bimetallic Silver-Copper Nanoinks With Hydroxyethyl-Cellulose Additives, Daniel Brunick

Undergraduate Honors Theses

Coinage metal nanoparticles remain an intriguing subject for research due to their industrial versatility. Primary applications of coinage metal nanoparticles include printed electronics, solar panels, and sensors. Inks formulated with the nanoparticles are conductive and thus useful for fabricating sensors. Silver-copper nanoalloy inks are viable for the fabrication of flexible sensing devices for the detection of volatile organic compounds. One of the challenges is the ability to synthesize composition-controllable alloy nanoparticles at room temperature through wet chemical methods and achieve controllable sintering at room temperature. This work addresses the challenges by investigating the room-temperature synthesis of silver-copper alloy nanoparticles and …

The Effects Copper Has On Casting Glass, K. Malika Haver

Honors Projects

The aim of this honors project was to discern the difference between how various types of copper reacted with glass. The two disciplines that were connected were chemistry and glassblowing. The basic components learned in chemistry were applied to glass with an end goal of a project installation that visualized the discoveries with copper. The glassblowing technique used was lost wax casting, and the two types of copper used were copper foil and fine copper metal powder. The copper was found to turn the glass into various blues with the intensity and darkness of the blues being dependent on the …

Synthetic Methods For Improved Scope And Efficiency Of Copper-Catalyzed Regioselective Alkene Boracarboxylation, Steven William Knowlden

Graduate Theses, Dissertations, and Problem Reports

The synthesis of carboxylic acids is important to the chemistry community, owing to the broad applicability of these compounds as fine chemicals and pharmaceuticals. Method development over the last decade has focused on the preparation of carboxylic acids through transition metal catalysis utilizing CO₂ as a C1 synthon. Copper-catalyzed heteroelement(bora and sila)-carboxylation protocols provide functional group rich carboxylic acid products, yet remain underdeveloped and thus underutilized. Consequently, catalytic reductive difunctionalization methodologies in which CO₂ and B(pin) (pin = pinacolate: 2,3-dimethyl-2,3-butanediolate) are installed across the double bond of a vinyl arene were recently developed. These boracarboxylation protocols provided novel, …

Effects Of Gamma-Radiation On The Evolution Of Copper Corrosion Dynamics In Deep Geological Repository Solution Environments, Lindsay J. Grandy

Electronic Thesis and Dissertation Repository

The Canadian plan for permanent disposal of used nuclear fuel involves a used fuel container (UFC), a carbon steel vessel with a copper coating to provide the corrosion protection. The corrosion conditions for the copper layer of the UFC are expected to involve small, stagnant water volumes, pH values between 6 and 9, and a continuous flux of γ-radiation emitted from the radionuclides trapped in the fuel matrix. While γ-radiation does not affect the copper metal directly, humid air and water will radiolytically decompose into redox-active and acidic species which will be produced at constant concentrations and can alter the …

Copper Corrosion Dynamics Under Deep Geologic Repository Conditions, Masoumeh Naghizadeh

Electronic Thesis and Dissertation Repository

Canada’s plan for the permanent disposal of spent nuclear fuel involves a multiple-barrier system contained within a deep geologic repository (DGR). The key engineered barrier is the used fuel container (UFC), which is a copper-coated carbon steel vessel. The environments to which the copper coating will be exposed in the DGR are very different from those commonly encountered in copper corrosion studies. The copper (Cu) will be in contact with thin stagnant layers of water, and the corrosion system will be exposed to a continuous flux of γ-radiation. In the presence of γ-radiation, water and humid air decompose to redox-active …

Analysis And Differentiation Of Uniform And Localized Corrosion Of Cu, Roshan J. Daljeet

Electronic Thesis and Dissertation Repository

The current plan for disposal of used nuclear fuel in Canada involves sealing the waste in steel containers coated with 3 mm of copper and burying them in a deep geologic repository (DGR). The purpose of the copper coating is to provide corrosion resistance. To achieve long term containment, it is necessary that the copper layer corrodes slowly and predictably via active dissolution rather than passivating due to film formation. Film formation could allow pitting corrosion to occur in early phase repository conditions when groundwater ions such as Cl– , SO4 2– and HCO3 – play a dominant role in …

Galvanic Corrosion Of Carbon Steel Coupled To Copper In Used Nuclear Fuel Containers, Lindsay J. Braithwaite

Electronic Thesis and Dissertation Repository

Deep geological containment of used nuclear fuel will rely on multiple engineered and natural barriers, two of which are the copper-coated used fuel containers and the compacted bentonite clay buffer boxes in which the containers will rest. This work focused on possible galvanic interactions between the copper coating and the steel substrate of the container, which may occur at a hypothetical through-coating defect. In the presence of various amounts of chloride, bentonite, and oxygen, corrosion of the copper/carbon steel couple was studied using electrochemical tests complemented by surface characterization and 3D X-ray imaging. We investigated the effects of copper-to-steel area …

The Electrochemical And Corrosion Study Of Copper For Nuclear Waste Containers Under Deep Geological Disposal Conditions, Mengnan Guo

Electronic Thesis and Dissertation Repository

The proposed method for the safe disposal of Swedish, Finnish, and Canadian high-level nuclear waste (HLNW) is to isolate it in iron or steel containers with an outer copper (Cu) shell or coating and bury it in a deep geological repository (DGR). Copper has been selected as the corrosion barrier due to its stability in the aqueous anoxic environments anticipated in DGR conditions. The container will initially be exposed to humid aerated conditions which will evolve to cool and anoxic as radiation fields in the fuel decay and heat production ceases. When the DGR is cool and anoxic, sulphide (SH …

Fabrication, Characterization And Applications Of Chemically Modified Planar Metallic Electrodes From Copper Clad Sheets, Rana T. K. Alsaidi

Theses

In this work, we developed a fabricating method for planar electrodes by milling and cutting copper-clad sheets. The main objectives of this thesis are to produce customized planar electrodes with different geometries with relatively higher reusability compared to the screen-printed electrodes available by commercial vendors. The fabricated electrodes from copper-clad sheets were electroplated with different metals using commercial electroplating baths to produce different metallic planar electrodes. Also, the fabrication of planar electrodes with cavities to be filled with modified carbon paste was done. The electroplated planar electrodes were characterized by the cyclic voltammetry technique. In addition to that, they were …

The Influence Of Radiolytically Produced Nitric Acid On The Corrosion Resistance Of Copper-Coated Used Nuclear Fuel Containers, Joseph P. Turnbull

Electronic Thesis and Dissertation Repository

In Canada, the proposed disposal method for high level nuclear waste involves sealing the waste in steel containers with a 3 mm outer copper coating and burying it in a deep geologic repository. However, the thickness of the container is significantly reduced making a reassessment of the influence of γ-radiation, emitted by the waste form, on container corrosion a potential licensing requirement. Under humid aerated conditions, the formation of nitric acid is expected, potentially resulting in the formation of droplets or wetted layers on the container surface. Currently available literature on the corrosion of copper in nitric acid does not …

Structure, Surface, And Interfacial Modifications Of Carbon And Supported-Metal Electrodes For Electrochemical Carbon Dioxide Conversion, Namal Wanninayake

Theses and Dissertations--Chemistry

Currently, the global emission of greenhouse CO₂ is over 36 billion tons per year. Consequently, the atmosphere's CO₂ concentrations have exceeded 400 ppm, which is the highest reported in the last three million years. The accumulation of CO₂ is the most critical origin for today's climate change; thus, closing the carbon cycle is vital to reverse the detrimental impacts of climate change. Under this goal, the electrochemical reduction of CO₂ into commodity fuels and chemicals via renewable energy is one of the most promising strategies to recycle CO₂. Despite significant progress made in electrocatalysis, …

Investigation Of Underpotential Deposition Of Copper At Heated Gold Loop Screen-Printed Electrodes In A Variety Of Water Samples, Eun-Ju Lee

Legacy Theses & Dissertations (2009 - 2024)

To study the underpotential deposition (UPD) of copper, three different types of water samples (TraceSelect® Ultra-pure water, Indian pond water at University at Albany and tap water) are used at a heated gold loop screen-printed electrode (GLE), which is a new type of heated working electrode for voltammetry measurements that is able to directly detect the copper content in the water samples. The anodic stripping analysis of copper is performed with these gold loop electrodes at room temperature of 25 °C and electrode temperature of 80 °C at two different deposition potentials, -0.20 V and +0.10 V. Furthermore, the concentration …

Galvanic Corrosion Of Copper-Coated Carbon Steel For Used Nuclear Fuel Containers, Thalia E. Standish

Electronic Thesis and Dissertation Repository

Carbon steel vessels coated with ∼3 mm of Cu have been proposed for the permanent disposal of used nuclear fuel in a deep geological repository (DGR) in Canada. In the event of an undetected defect in the Cu coating that exposes the steel substrate, galvanically accelerated corrosion of steel is, in principle, possible. To investigate this scenario, the progression of steel corrosion at the base of novel simulated through-coating defects was monitored electrochemically and imaged non-destructively using X-ray micro-computed tomography (micro-CT) as a function of time, O₂ availability (including anoxic conditions), and coating method (cold spray deposition (with and …

Chemical Speciation In Silver Bow And Blacktail Creeks: Implications For Bioavailability And Restoration, Johnathan Feldman

Graduate Theses & Non-Theses

Silver Bow and Blacktail Creeks, contaminated with toxic elements from mining, present a need for remediation and restoration. Trace elements are present in elevated concentrations, particularly copper. Determining element speciation will allow informed consideration of effective restoration strategies, by providing a foundation for assessing bioavailability and toxicity. The three goals are: determine how speciation varies between seasons and sites in four impacted sites from the greater Butte Area One, an impacted downstream site known as Santa, and a control site on Upper Blacktail Creek known as Blacktail; how these variations influence bioavailability and toxicity; and what causes these variations. Total …

Development Of Copper-Catalyzed Suzuki-Miyaura Coupling Using Alkylboron Reagents And Nickel-Catalyzed Alkene Dicarbofunctionalization Reactions, Prakash Basnet

Chemistry and Chemical Biology ETDs

This thesis is divided into two parts. The first part deals with the development of copper-catalyzed Suzuki-Miyaura coupling of alkylboron reagents for the first time. In the second part, we will discuss the development of novel nickel-catalyzed alkene dicarbofunctionalization reactions.

Part I. Cross-coupling reactions are versatile tools to form new carbon-carbon bonds and are widely used in the synthesis of various drug molecules, natural products and materials. However, these reactions are typically catalyzed by palladium, an expensive and rare metal which makes the reaction unsustainable in long-terms. Additionally, palladium-catalyzed cross-coupling reactions with alkylorganometallic reagents suffer from side reactions due to …

Coinage Metal Chalcogenide Clusters With N-Heterocyclic Carbene Ancillary Ligands, Alex Polgar

Electronic Thesis and Dissertation Repository

This thesis describes the synthesis and characterization of homo- and heterometallic group 11 – group 16 clusters with N-heterocyclic carbene (NHC) ligands. The clusters were prepared from reactive group 11 trimethylsilylchalcogenolate reagents (NHC-M-ESiMe3; M = Cu, Au; E = S, Se, Te) by silane deprotection reactions with phosphine- or phosphite-solubilized group 11 acetates (R3P-M-OAc; M = Cu, Ag, Au). Clusters were characterized by combustion analysis and spectroscopic methods in solution and the solid state. The clusters were phosphorescent at low temperatures with emission energies that depend on the metal/chalcogen composition, ancillary NHC ligand, cluster geometry and nuclearity, and local environment. …

Copper-Catalyzed Direct And Tandem Couplings, And Mechanistic Studies, Surendra Thapa

Chemistry and Chemical Biology ETDs

Cross-coupling reactions are exceptionally powerful tools to construct carbon-carbon (C-C) bonds. These reactions are widely used to synthesize natural products, polymers, agrochemical, organic materials and pharmaceutical compounds. However, these reactions are typically catalyzed by Palladium. Although these reactions are widely utilized and well developed, the use of noble metals like Pd raises a question about its long-term sustainability. We believe copper can be one of the best alternatives to palladium as it is more abundant, less expensive and less toxic. In addition, Pd-catalyzed transformations usually suffer from β-hydride elimination to afford undesired olefin and rearranged products, when it comes …

Electrochemical And Corrosion Examination Of Copper Under Deep Geologic Conditions For The Application Of Nuclear Waste Containers, Taylor L. Martino

Electronic Thesis and Dissertation Repository

Copper is the selected material for the fabrication of nuclear fuel waste containers in Sweden, Finland and Canada due to its corrosion resistance in the anoxic aqueous environments, anticipated in deep geological repositories. A potential oxidant for copper is bisulphide produced either by the dissolution of minerals or by sulphate-reducing bacteria. The primary goals of this thesis were to determine the mechanism of corrosion of copper in bisulphide environments and to investigate the chemistry of the bentonite porewater that will ultimately be in contact with the copper container.

The mechanism of sulphide film growth and the details of copper corrosion …

Il-17 Drives Copper Uptake And Activation Of Growth Pathways In Colorectal Cancer Cells In A Steap4-Dependent Manner, Evan Martin

ETD Archive

Colorectal cancer is a disease characterized by abnormal, invasive cell growth beginning in the colon or rectum. The third most common type of cancer worldwide, approximately one million new cases of the disease are diagnosed across the globe annually, resulting in an estimated 700,000+ deaths. One major risk factor associated with development of colorectal cancer is the presence of chronic inflammation in the large intestine, also known as colitis. Inflammation is a complex immune response against harmful stimuli, characterized by symptoms including heat, redness, swelling and pain. One important molecular mediator of this process is interleukin 17 (IL-17), a pro-inflammatory …

Il-17 Drives Copper Uptake And Activation Of Growth Pathways In Colorectal Cancer Cells In A Steap4-Dependent Manner, Evan Martin

ETD Archive

Colorectal cancer is a disease characterized by abnormal, invasive cell growth beginning in the colon or rectum. The third most common type of cancer worldwide, approximately one million new cases of the disease are diagnosed across the globe annually, resulting in an estimated 700,000+ deaths. One major risk factor associated with development of colorectal cancer is the presence of chronic inflammation in the large intestine, also known as colitis. Inflammation is a complex immune response against harmful stimuli, characterized by symptoms including heat, redness, swelling and pain. One important molecular mediator of this process is interleukin 17 (IL-17), a pro-inflammatory …

Electrodeposited Epitaxial Cobalt Oxides And Copper Metal, Caleb M. Hull

Doctoral Dissertations

"Electrochemical deposition methods are presented for the deposition of Co(OH)₂ and Cu metal. Paper I shows the deposition of β-Co(OH)₂ on Ti through electrochemical reduction of [Co(en)₃]³⁺ to [Co(en)₃]²⁺ in 2M NaOH. The catalytic properties of the deposited Co(OH)₂ towards water oxidation is found comparable to Co₃O₄, with the surface of the Co(OH)₂ converting to CoOOH during the reaction. Paper II gives the conditions suitable for epitaxial growth of Co(OH)₂ on Au(100), Au(110), and Au(111) following the same reduction mechanism as described in Paper I. …

Variety-Dependent Physiologic And Biochemical Effects Of Copper Nano Particles On Rosie And Green Bok Choy (Brassica Rapa) Phenotypes, Chaoyi Deng

Open Access Theses & Dissertations

The effects of Cu-based nanoparticles (NPs) in bok choy (Brassica rapa subsp. chinensis) are unknown. In this study, Rosie and Green, two varieties of bok choy, with different anthocyanin content, were cultivated for 70 days in soil amended with copper oxide nanoparticles (nano CuO), bulk copper oxide (bulk CuO) and copper chloride (CuCl2) at 75, 150, 300 and 600 mg Cu/kg soil. Cu and essential elements in tissues, and relative chlorophyll content, were determined. In both varieties, nano CuO treatments caused significantly more Cu uptake in roots and shoots, compared with bulk CuO and ion CuCl2 (p ≤ 0.05). Additionally, …

Structure And Activity Of Metallo-Peptides, Christian C. Tang

USF Tampa Graduate Theses and Dissertations

Metal ions are ubiquitously found in all living systems and play vital roles in supporting life forms by performing an array of biological activities. Such biological activities include binding and transforming organic molecules, and also acting as active centers and cofactors for catalysis of various acid-base and redox reactions in biological system. The main focus in bioinorganic chemistry is to elucidate the structural and functional roles of metals in biological systems. Among all transition metal ions, Cu²⁺ and Fe³⁺ are especially versatile and important due to their abilities to go through redox efficiently.

This dissertation can be divided …