Physical Sciences and Mathematics Commons^™

A Study On The Structure And Photodetachment Dynamics Of Copper Based Molecular Anions Using Photoelectron Spectroscopy, Nicholas Stephen Holtgrewe

Arts & Sciences Electronic Theses and Dissertations

This dissertation represents a study of the effects of electron molecule interactions in the detachment and dissociation dynamics of copper based molecular anions. Results are presented on the photodetachment of small copper oxide CuO_n⁻ (n = 1, 2) and copper fluoride CuF _n⁻ (n = 1, 2) molecular anions. Effects of different resonances are explored using the photoelectron angular distributions (PADs) and the relative intensity variations in vibrational channel cross sections. The specific resonances studied include dipole bound resonances, in which the electric dipole moment of the neutral molecule captures the outgoing electron, and electronic Feshbach resonances, …

Copper Mediated, Transmetallation Coupling Reactions Using High Intensity Ultrasound, Bryan J. Musolino

Doctoral Dissertations

This dissertation summarizes research efforts focused on the use of boron and copper acetate to form new carbon-carbon and carbon-heteroatom bonds. Two new methods were developed using high intensity ultrasound as the reaction energy source. The first focused on the homocoupling of various aryl compounds using a commercially available polymer support. The use of this polymer support allows the reaction to proceed in an aqueous solvent system with only minimal preparation. The product yields were better than values reported in the literature using traditional reaction conditions and reaction times were decreased from 24-72 hours to 6 hours. The second method …

Synthesis Of Platinum And Platinum-Copper Branched Nanoparticles For Electrooxidation Of Methanol, Eric Courtland Taylor

Graduate Theses and Dissertations

Platinum and Pt alloys are among the most important heterogeneous catalysts for many organic reactions and electrochemical reactions associated with the fuel cell technologies. How to reduce Pt usage while maintaining the performance of the catalysts becomes a subject for intensive research in materials chemistry. For heterogeneous catalysis, the catalytic reactivity and selectivity are strongly correlated with different crystallographic facets exposed on the surface. The facets with high-index planes whose Miller indices with at one is larger than unity are generally more active than those with low-index planes (e.g., {100}, {111}, and {110}). Tuning the morphology of the nanoparticles to …

Multiscale Modeling Of Enzyme-Catalyzed Methanol Production By Particulate Methane Monooxygenase, Katherine K. Bearden

Doctoral Dissertations

In this work, the conversion of methane to methanol by the particulate Methane Monooxygenase (pMMO) enzyme is investigated using a multi-scale modeling approach. This enzyme participates in carbon cycling and aids in the removal of harmful atmospheric methane, converting it to methanol. The interaction between pMMO and a neighboring enzyme that is present in the same organism is studied, and the unknown pMMO active site is elucidated and tested for methane oxidation towards the production of methanol.

Fundamental knowledge of pMMO's mechanism is not fully understood. Understanding how this enzyme works in nature will provide information towards designing efficient synthetic …

Metallization Of Dna And Dna Origami Using A Pd Seeding Method, Yanli Geng

Theses and Dissertations

In this dissertation, I developed a Pd seeding method in association with electroless plating, to successfully metallize both lambda DNA and DNA origami templates on different surfaces. On mica surfaces, this method offered a fast, simple process, and the ability to obtain a relatively high yield of metallized DNA nanostructures. When using lambda DNA as the templates, I studied the effect of Pd(II) activation time on the seed height and density, and an optimal activation time between 10 and 30 min was obtained. Based on the Pd seeds formed on DNA, as well as a Pd electroless plating solution, continuous …

Determination Of Copper Speciation, Bioavailability And Toxicity In Saltwater Environments, Tara N. Tait

Theses and Dissertations (Comprehensive)

The speciation of copper plays a strong role in determining bioavailability and toxicity upon copper exposure in marine environments. Specifically, natural organic matter (NOM) can complex with copper, influencing speciation and decreasing bioavailability. The aim of this research was to determine accurate copper speciation values using literature and new techniques and applying the techniques that reflect the most accurate speciation values to investigate the influence of NOM quantity and quality on copper speciation and toxicity. The results from this study will have implications on the development of a marine Biotic Ligand Model (BLM). Free copper was measured using a flow-through …

Ruco To Extend The Scalability Of Ultra-Thin Direct Plate Liners, Daniel Verne Greenslit

Legacy Theses & Dissertations (2009 - 2024)

In traditional semiconductor technology a sputtered copper seed layer is used to improve the adhesion, microstucture, and electromigration characteristics of electrochemically deposited (ECD) copper. The seed layer is deposited on top of a Ta/TaN stack. The Ta layer acts as an adhesion and nucleation layer for the copper seed and the TaN serves as a diffusion barrier for the Cu. As the line widths continue to shrink, scaling each of these layers becomes more difficult. It would be advantageous for the interconnect to be composed of as much copper as possible, transitioning from the traditional liner seed stack to a …

Quality Assurance Plan Project For Copper Determination Using Flame Atomic Absorption Spectroscopy, Bharath Raparthi

All Capstone Projects

This study developed a method for determination of Copper by flame atomic absorption spectrometry (FAAS) from the soil samples and mine tailings using Perkin Elmer AAnalyst 800 atomic absorption spectrometer. A detailed procedure has been developed with a detection limit of 0.12 mg/L. In the recent decades, pollution from heavy metals has been increased. Copper is one of the trace metals that has a significant impact and carries risk to the human health. Calibration curve was established with working range 0.1 ppm to 5 ppm with a correlation coefficient of 0.9994. Over 50 environmental samples from the historic Copper mining …

Geomorphological Approach To Toxic Trace Metal Distribution Across A Medial Bar Deposit In The Trout Brook Of The Park River Watershed, Hartford, Ct, Kelsey Semrod

Senior Theses and Projects

The Trout Brook, a major tributary of the Park River watershed, was sampled for heavy metals in sediment with a focus on Pb, Cu, Cd, and Zn. These metals are known to be contaminating the river due to a history of discharge from metal finishing industries. In a watershed-wide survey conducted in September 2011, high concentrations of metals were found in the Trout Brook, with some sites exceeding the probable effect concentration (PEC). The Trout Brook contains a Sanitary Sewer Overflow (SSO) and a vegetated medial bar that may be trapping sediment. Based on the results of the earlier studies, …

Biological Effects Of Copper On Prosopis Pubescens (Screw Bean Mesquite), Marian Nicte Zappala

Open Access Theses & Dissertations

Phytoremediation is an emerging technology for cleaning industrial and urban contamination (Peuke and Rennenberg, 2005). Many factors including germination rate, biomass changes, biochemical changes, and nutrient changes must be determined in order to utilize a plant for phytoremediation. Our results showed that Prosopis pubescens (Screw bean mesquite) is a hyperaccumulator of copper from copper sulfate and a feasible option to remediate fields with up to 200 ppm of copper sulfate.

Screw bean mesquite seeds are viable even after 30 years of storage. Both copper sulfate and copper nitrate decreased the germination rate of screw bean mesquite seeds. In soil grown …

The Influence Of Copper Substrate Orientation On Graphene Growth, Zachary Robert Robinson

Legacy Theses & Dissertations (2009 - 2024)

This dissertation is focused on determining the influence of the copper substrate on graphene grown by \ac{CVD}. Graphene, which can be grown in single atomic layers on copper substrates, has potential applications in future electronic devices. One of the key issues for the use of graphene grown by chemical vapor deposition for device applications is the influence of defects on the transport properties of the graphene. For instance, growth on metal foil substrates results in multi-domain graphene growth because the foil substrates themselves have a variety of different surface terminations. Therefore, they don't serve as a very good template for …

Characterizing Dissolved Organic Matter And Cu2+, Zn2+, Ni2+, And Pb2+ Binding In Salt Water And Implications For Toxicity, Rachael L. Diamond

Theses and Dissertations (Comprehensive)

The binding of metal to dissolved organic matter in aquatic environments is important in controlling the bioavailability and potential toxicity of metals such as Zn²⁺, Pb²⁺, Ni²⁺ and Cu²⁺. The purpose of this research is to: (i) quantify binding capacity to different sources of marine organic matter at environmentally relevant concentrations; (ii) test fluorescence quenching and voltammetric method for use in seawater conditions and; (iii) compare predicted speciation parameters with toxicological observations in the same samples.

Information regarding the solubility of copper and copper compounds is important for risk assessment and can be …

Prevention Of Iron- And Copper-Mediated Oxidative Dna Damage By Neurotransmmitters And Related Compounds: Evidence For Metal Binding As An Antioxidant Mechanism, Carla Garcia

All Theses

An array of health concerns have been attributed to oxidative DNA damage from the hydroxyl radical (*OH), and the presence of the most biologically available metals iron and copper perpetuate the production of this radical through the Fenton and Fenton-like reactions, respectively. The concentrations at which flavonol and polyphenol antioxidants prevent 50% of DNA damage (IC50) were measured using gel electrophoresis assays upon Fe(II)/H2O2- and Cu(I)/H2O2-mediated DNA damage (Chapter 2). Results show that catechol- and gallol-containing antioxidants differ greatly in preventing DNA damage by Cu(I)/H2O2, compared to Fe(II)/H2O2, behavior that was explained using electron paramagnetic resonance spectroscopy. Semiquinone and other …

The Impact Of Sulfide Mineral Weathering On The Isotopic Signatures Of Fe And Cu In Metal-Rich Streams, Ana Lourdes Gutierrez

Open Access Theses & Dissertations

The oxidative weathering of sulfide minerals, like pyrite, at the Earth's surface controls the formation of acid mine drainage sites as well as the Fe isotope composition of these areas and the main processes taken place. In this study, water and rock samples were collected from acidic drainages (most from abandoned mining sites) from the St. Juan Mountains in Colorado. The water samples were measured in-situ for dissolved oxygen, dissolved Fe(II), pH, and conductivity. Filtered acidified, unfiltered acidified, and Fe-oxide samples were analyzed for their metal concentrations. Ion-exchange chromatography was applied to both water and digested oxide fractions in order …

Supramolecular Organization Of Nanoparticles, Brenda M. Porta Linnell

Open Access Theses & Dissertations

The study of supramolecular structures with nano-architectures has become an active area of research in recent years. They have the potential to generate functional materials with applications in medicine and emerging technologies. In this dissertation, the supramolecular organization of gold nanoparticles (AuNP) and other nano-scale structures such as discrete styrene-based polymers was investigated. The synthesis and characterization of metal-mediated AuNPs systems using pendant ligands on the AuNP such as 11-diethylenetriamine-undecane-1-thiol, 11-Mercapto-undecanoic acid [2-(2-amino-ethylamino)-ethyl]-amide, Bis(11-oxo-nicotinic acid, undecine)disulfide, and 11-mercaptoundecanoic acid, and using Cu(II) to mediate the formation of supramolecular AuNP systems with sizes of 200 nm ¡V 3 fÃ?m, are …

Guanidines, Amidines And Carbamides As Novel Sigma Receptor Ligands For Post-Stroke Therapeutics, Michelle Yolanda Cortes-Salva

USF Tampa Graduate Theses and Dissertations

Stroke is the 3^rd leading cause of death in the United States. For this reason, it has become our goal to find a drug that is capable of reestablishing intracellular and extracellular Ca⁺² flux upon direct binding to the sigma receptor, which can be delivered easily and efficiently. Our active research focuses the development of guanidine analogues that can serve as therapeutic drugs which target sigma 1 and sigma 2 receptors having a direct effect on Ca⁺² levels on the cell. The use of symmetrical guanidine analogues such as N,N'-di-o-tolyl guanidine (o-DTG) as therapeutic drugs for ischemic …

Structural And Electronic Properties Of Noble Metals On Metal Oxide Surfaces, Fei Wang

LSU Doctoral Dissertations

Noble metals on metal oxide surfaces play crucial roles in many catalysis applications. Due to extreme complexity of the interfaces and catalytic reaction processes, basic science studies of model systems are needed to guide the construction and optimization of new industrial catalysts. We have employed ultra-high vacuum techniques to investigate the morphology, electronic structure, and surface reactivations of clean metal-oxide/metal nanocluster interfaces in ideal conditions. The systems we chose are Ag/TiO2, a popular photocatalyst, and Cu/ZnO, recently a hot candidate for liquid fuel production. The main characterization techniques that we have employed include Scanning Tunneling Microscopy (STM), Photoemission Spectroscopy (PES), …

Pvd Cu Trench-Fill By Viscous Flow At High Temperatures, Zhiyuan Wu

Legacy Theses & Dissertations (2009 - 2024)

The scaling of integrated circuits has led to new challenges in Cu interconnect fabrication. It is getting difficult to fill narrow trenches, e.g. 20 nm wide, by Cu electroplating. In this work, a high temperature PVD Cu viscous flow trench fill process was explored to overcome the difficulties of filling narrow and high aspect ratio trenches.

Nucleation, Wetting And Agglomeration Of Copper And Copper-Alloy Thin Films On Metal Liner Surfaces, Stephanie Florence Labarbera

Legacy Theses & Dissertations (2009 - 2024)

One of the key challenges in fabricating narrower and higher aspect ratio interconnects using damascene technology has been achieving an ultra-thin (~2 nm) and continuous Cu seed coverage on trench sidewalls. The thin seed is prone to agglomeration because of poor Cu wetting on the Ta liner. Using in-situ conductance measurements, the effect of lowering the substrate temperature during Cu seed deposition has been studied on tantalum (Ta) and ruthenium (Ru) liner surfaces. On a Ta surface, it was found that lowering the deposition temperature to -65°C increases the nucleation rate of the Cu thin film, and reduces the minimum …

Phytoremediation Of Copper Contaminated Waste Water Using Lemna Minor, Mark Apelt

Theses and Dissertations

The use of natural remediation methods to remove contaminants from waste water is becoming more popular. Plants have been used for several decades, yet their use for municipal waste water contaminated by heavy metals is limited to a few studies which focus on the Mercury and Chromium (Bennicelli, et.al, 2004). This study specifically attempted to determine the viability for using Lemna minor to remediate municipally generated wastewater contaminated with copper. The study used 100 ml samples of wastewater, artificially spiked with 8 mg/L of copper sulfate and seeded with approximately 100 Lemna minor fronds. Each treatment was repeated 15 times …

Chromium, Copper, And Arsenic Concentration And Speciation In Soil Adjacent To Chromated Copper Arsenate (Cca) Treated Lumber Along A Topohydrosequence, Donald Roy Schwer Iii

University of Kentucky Master's Theses

Arsenic (As), Chromium (Cr), and Copper (Cu) are ubiquitous in soils as a result of anthropogenic and geogenic processes. The fate of As, Cr, and Cu in the environment is largely governed by their speciation, which is influenced by soil physiochemical properties. This study investigated the influence of soil physiochemical properties and landscape position on As, Cr, and Cu concentration and speciation in soils adjacent to Chromated Copper Arsenate (CCA) treated lumber fence posts. Concentration gradients showed elevated total As and Cu adjacent to the three fence posts, which decreased with increasing distance from the posts. In addition, As and …

Application Of Copper And Zinc Isotopes To Fingerprint Metal Sources And Identify Attenuation Mechanisms In The Abandoned Waldorf Mine Area, Clear Creek County, Colorado, Suzan Aranda Luna

Open Access Theses & Dissertations

Acid rock drainage (ARD) is caused by the oxidative weathering of sulfide minerals. Sulfur is oxidized by dissolved oxygen or Fe(III) and sulfate ions, metals, and protons are released into the environment. Hence, the pH of nearby water and soils often decreases in response to ARD while metal concentrations increase. Because a large part of the Rocky Mountains of Colorado are highly mineralized (i.e., the Colorado Mineral Belt), ARD is a serious problem in this region. Moreover, the many abandoned mining areas in the Rocky Mountains that include waste rock piles, tailings impoundments, and surface disturbances add to the problem …

Effect Of Various Heavy Metals On The Enzymatic Activity Of Bacterial Alkaline Phosphatase, Maithah Maktoom Salmeen Al Nuaimi

Theses

Soil is a natural resource that is utmost importance from an agricultural as well as environmental perspective. Good soil health not only helps improve the quality and yield of agriculture products, but is also important for recycling of significant amounts of organic biomass. However, pollution of soil by various pollutants, such as heavy metals, pesticides or petroleum hydrocarbons, can lead to serious environmental as well as biological effects. This pollution can directly harm animals and human beings, leach into drinking water source, damage plants and vegetation, as well as affect the endemic microorganisms and insects living in the soil.

Microorganisms …

Investigations Of Grade Control, Macarthur Mine, Yerington, Nevada: An Oxidized Porphyry Copper System, Joseph Daniel Louis Lori

Open Access Theses & Dissertations

Supergene enriched, low-grade oxidized porphyry copper deposits are of great economic value. Oxidized porphyry sections are economic targets because even low-grade prospects have the potential to produce low-cost copper in an environmentally friendly fashion due to easy leachability and high recovery rates of the oxide mineralization. The MacArthur Mine, in the historic Yerington mining district of Nevada, is the focus of this study. The MacArthur is a tilted oxidized porphyry deposit, partially mined by open pit methods, hosted in the Jurassic Bear Quartz Monzonite of the Yerington batholith. The objective of the study is to define controls of copper oxide …

Copper Isotope Fractionation During Surface Adsorption And Intracellular Incorporation By Bacteria, Jesica Urbina Navarrete

Open Access Theses & Dissertations

Copper isotopes may prove to be a useful tool for investigating bacteria-metal interactions recorded in natural waters, soils, and rocks. However, experimental data that constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study we utilized Cu isotopes (65Cu) as a tool to investigate Cu-bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacterial species as well as with bacterial consortia from several natural environments. Adsorption experiments were conducted with live or dead cells over the pH range 2.5 to 6. Surface adsorption of Cu …

Extreme Ultraviolet Polarimetry With Laser-Generated High-Order Harmonics: Characterization Of Uranium, Nicole Brimhall

Theses and Dissertations

We developed an extreme ultraviolet (EUV) polarimeter, which employs laser-generated high-order harmonics as the light source. This relatively high-flux, directional EUV source has available wavelengths between 10 nm and 47 nm with easily rotatable linear polarization. The polarimeter has allowed us to characterize the optical constants of materials that may be useful for EUV optics. The instrument has a versatile positioning system and a spectral resolution of about 180, and we have demonstrated that reflectance as low as 0.1% can be measured repeatably at EUV wavelengths. We investigate the high harmonic source used for polarimetry measurements by documenting the spatial …

Recovery Of Fathead Minnows (Pimephales Promelas) Following Episodic Copper Exposure: A Biochemical, Physiological, Individual, And Population Perspective, Holly Zahner

All Dissertations

The US EPA utilizes the Biotic Ligand Model (BLM) when developing site-specific water-quality criteria for copper. The BLM was calibrated using toxicity data from fixed duration continuous exposures (48 or 96h LC50). However, exposures of copper in natural aquatic systems typically vary in concentration, duration, and may occur multiple times over the life-span of an organism. Additionally, organisms will experience periods in copper free water, potentially allowing them to detoxify and recover homeostasis. Yet, the BLM framework does not consider brief exposures (<24h), multiple exposures, latent responses, or organism recovery, potentially resulting in an inaccurate assessment of exposure toxicity. A recently proposed physiologically-based addition to the BLM will extend the applicability of the framework to brief, multiple pulse copper exposures. Thus, the overall goal of this research was to characterize the recovery of larval Pimephales promelas following episodic copper exposure at a biochemical, physiological, individual, and population level.
The response of whole-body sodium, whole-body Na+/K+-ATPase, and whole-body carbonic anhydrase in larval P. promleas was quantified …

Beta-Diketone And -Ketoenamine-Based Organic Building Blocks For Porous Metal Organic-Materials, Yoseph Solomon Marcos

LSU Doctoral Dissertations

This dissertation focuses on synthesis of multifunctional â-diketone and â-ketoenamine ligands and their reaction with metal ions, mainly Cu2+. Several new bi-, tri-, and tetrafunctional organosilicon â-diketone building blocks with â-diketone groups at approx. 109° (tetrahedral) were successfully synthesized. New thiophene based bifunctional ligands where the â-diketones are at about 145° are also reported here. We also prepared a range of new aryl-â-ketoenamines from their analogous â-diketones in very high yield using a simple microwave-assisted procedure. Reactions of organosilicon tris(â-diketone)s LH3 with Cu2+ were explored quite intensively. These ligands form metal-organic-polyhedra (MOPs) that are soluble in organic solvents, and insoluble …

Responses Of Problematic Cyanobacteria To Exposures Of Copper Containing Algaecides, O'Niell Tedrow

All Theses

Cyanobacteria (blue-green algae) are associated with production of potent hepatotoxins (Microcystis; microcystin) and dense surface and benthic mats (Lyngbya), which impede critical water resource usages. Water resource managers are in need of effective and efficient treatment techniques for these problematic algae in field situations. Applications of algaecides are considered in situations where algal problems become acute or when critical water usages are threatened. However, laboratory data are needed that accurately predict responses of algae prior to field-scale algaecide applications. Site water and algae were used in laboratory algal toxicity experiments to predict responses of the target alga following an algaecide …

Multifunctional Ligands For Supramolecular Chemistry, James Kakoullis

LSU Master's Theses

Metal-organic frameworks (MOFs) are the primary focus of the Maverick research group, almost exclusively with the acac moeity. Before such MOFs can be attempted, multifunctional ligands of the appropriate geometry for the desired MOFs first must be synthesized. In this thesis, the synthesis and characterization of two new β-diketone ligands, specifically, Re(CO)₃Cl(PyacH)₂, 2.2, Pphac₃H₃, 1.23, and its oxide 3.6, are described. Also in this thesis, attempts to synthesize other new MOFs will be discussed. The MOF for which Re(CO)₃Cl(PyacH)₂, 2.2 was designed was Re(CO)₃ClCu(pyac)₂] …