Physical Sciences and Mathematics Commons^™

Homo- And Heterometallic Bis(Pentafluorobenzoyl)Methanide Complexes Of Copper(Ii) And Cobalt(Ii), Janell Crowder

Legacy Theses & Dissertations (2009 - 2024)

β-Diketones are well known to form metal complexes with practically every known metal and metalloid. Metal complexes of fluorinated β-diketones generally exhibit increased volatility and thermal stability compared to the non-fluorinated analogues, and thus are used extensively in various chemical vapor deposition (CVD) processes for the deposition of metal, simple or mixed metal oxides, and fluorine-doped metal oxide thin films. Furthermore, the electron-withdrawing nature of the fluorinated ligand enhances the Lewis acidity of a coordinatively unsaturated metal center which facilitates additional coordination reactions. The physical and structural properties of fluorinated β-diketonate complexes are discussed in Chapter 1 …

Dendrimer Modified Silica Nanoparticles As Fluorescent Chemosensors For The Detection Of Copper And Cyanide Ions, Alicia Luhrs

Master's Theses

A series of silica nanoparticle-based fluorescent chemosensors were synthesized for the sensitive and selective detection of Cu²⁺ ions in aqueous solution and subsequent CN^- ion detection. Silica nanoparticles (SNP) were modified with branching polyamidoamine (PAMAM) dendrimers, which function as selective turn-off Cu²⁺ ion chelators and platforms for the attachment of rhodamine isothiocyanate (RITC) or fluorescein isothiocyanate (FITC) fluorescent dyes. In the presence of Cu²⁺ ions, the emission of the fluorescent dye is quenched by Forster resonance energy transfer (FRET) and is dependent upon dendrimer generation, pH, fluorescent dye, and surface charge. The quenching effectiveness was analyzed …

Doped Tio2 Nanowires For Applications In Dye Sensitized Solar Cells And Sacrifical Hydrogen Production, Qasem Alsharari

Electronic Thesis and Dissertation Repository

This thesis explores the synthesis of metal oxide 1-D nanowires using a sol-gel method in supercritical carbon dioxide (sc-CO₂), as an environmental friendly enabling solvent. Porous nanowires were synthesized and their performance was tested in dye sensitized solar cell and sacrifical hydrogen production. Titanium isopropoxide (TIP) was used as a precursor for titania synthesis while copper, bismuth and indium were examined as dopants, respectively. The sol-gel reactions were catalyzed by acetic acid in CO₂ at a temperature of 60 °C and pressure of 5000 psi. It was observed that acetic acid/monomer ratio > 4 produced nanowires while a …

Novel Approaches For Assessment Of Copper Toxicity: Fast Scan Cyclic Voltammetry And Optical Bioassays, Annette R. Tremonti

Wayne State University Dissertations

Anthropogenic activities negatively impact fresh water ecosystems through toxic contaminants that are released into the environment. Copper (Cu) is a water contaminant that is fundamentally persistent once introduced into the environment that has the potential for bioaccumulation. Although Cu toxicity has been studied for decades, there is still a continuing problem with new sources and pathways. New approaches are needed to understand distribution and transport of Cu and its potential for complex biological impacts beyond the simple assessment of lethality. Several novel approaches were used in this research project to advance our understanding of Cu toxicity, including fast scan cyclic …

Modulation Of The Physiological And Biochemical Effects Of Copper Nanoparticles In Kidney Beans (Phaseouls Vulgaris) Treated By Kinetin, Suzanne Annette Apodaca

Open Access Theses & Dissertations

It is imperative to not only understand the impact of engineered nanomaterials (ENMs) in edible plants, but also the interactions they have with various additives used in agriculture. In this study, kidney bean plants were grown in potting soil treated with nano copper (nCu), bulk copper (bCu), and copper chloride (CuCl2) at concentrations of 0, 50, and 100 mg/kg for 55 and 90 days. At 15 days of growth, 0, 10, and 100 μm of kinetin (KN) were applied to plants. Plant tissue samples were harvested at 55 days and seeds were reaped at 90 days. Physiological and biochemical parameters …

A Novel, Ultra-Fast Electrochemical Tool To Study Speciation Of Trace Metals In Aqueous Solution, Pavithra Pathirathna

Wayne State University Dissertations

Trace metals play important roles in biological and ecological systems. In biology, trace metals act as catalytic or structural cofactors and regulate biochemical processes. In the environment, natural and anthropogenic sources of trace metals mobilized into natural waters where they can create harmful and persistent pollution. Trace metal chemistry in physiological and environmental systems can fluctuate rapidly which makes it difficult to clearly define trace metals’ roles in these systems with traditional analytical methods. Furthermore, these systems are often chemically harsh and physically delicate (e.g. the brain), factors that add to the challenge of analysis in real systems. Fast scan …

Electronic Structure And Stability Of Ligated Superatoms And Bimetallic Clusters, William H. Blades

Theses and Dissertations

Quantum confinement in small metal clusters leads to a bunching of states into electronic shells reminiscent of shells in atoms. The addition of ligands can tune the valence electron count and electron distribution in metal clusters. A combined experimental and theoretical study of the reactivity of methanol with Al_nI_m⁻ clusters reveals that ligands can enhance the stability of clusters. In some cases the electronegative ligand may perturb the charge density of the metallic core generating active sites that can lead to the etching of the cluster. Also, an investigation is conducted to understand how the bonding …

Fabrication, Characterization, And Application Of Carbon Nanoparticles For The Detection Of Heavy Metal Ions In Aqueous Media, Aaron Michael Simpson

MSU Graduate Theses

This research set out to develop a method for producing Carbon nanoparticles (CNPs) from glycerol and use them to detect Cu2+, Hg2+, and Pb2+ ions in aqueous solution. Three synthesis methods were developed using the following mixtures: (1) glycerol and silica, (2) glycerol, silica, and H3PO4, and (3) glycerol with H3PO4. The structure of the particles was characterized using a variety of spectroscopic techniques. Size distributions were obtained from scanning electron microscopy images. The particles were spherical with average diameters of 66, 58, and 89 nm respectively and believed to consist of a carbon core with carboxylic acid and alcohol …

Coinage Metal Silylphosphido Complexes Stabilized By N-Heterocyclic Carbene Ligands, Bahareh Khalili Najafabadi

Electronic Thesis and Dissertation Repository

N-Heterocyclic carbenes (NHCs) are strong σ-donating ligands and thus, promising candidates for decorating and stabilizing metal-phosphide nanoclusters. While much research has been focused on the coordination of NHC ligands to different coinage metal centers in order to synthesize mononuclear organometallic complexes, their application in nanocluster chemistry has been relatively unexplored. The work described in this thesis involves employment of NHC ligands for stabilizing coinage metal t-butylthiolate and silylphosphido complexes. These complexes are promising molecular precursors for formation of larger NHC-stabilized nanoclusters.

In particular, the ligation of NHCs to [CuS^tBu] and [AgS^tBu] was developed as an …

Application Of Lipid Styryl Dye For Staining Intracytoplasmic Membranes In Gram-Negative Bacteria, Theodore J. Hammer

Williams Honors College, Honors Research Projects

Intracytoplasmic membranes are structures that form within cells which help facilitate a variety of different metabolic processes. This feature of intracellular membranes makes them particularly valuable for studying compartmentalization and cell dynamics in bacteria. In the past, transmission electron microscopy has been the primary method for imaging bacteria with intracytoplasmic membranes. Because transmission electron microscopy takes images of a cell in fixed slices, it’s impossible to follow a cell’s growth and development over time. Fluorescence microscopy is a particularly effective method of measurement that can combat these issues when evaluating live bacterial cells. Here, standard biochemical laboratory procedures were used …

Synthesis, Structural Variations And Trends In The Properties Of Unique Dinuclear And Polynuclear Complexes Of Bis(Pyrazolyl)Methane Ligands In Solid State And Solution, Andrea Eva Pascui

Theses and Dissertations

The semi-rigid ligands, p-[CH(pz)₂]₂C₆H₄, L_p, m-[CH(pz)₂]₂C₆H₂, L_m, and m-[CH(3,5-Me₂pz)₂]₂C₆H₄, L_m* (pz = pyrazolyl ring), link two bis(pyrazolyl)methane units into a single molecule by a rigid phenylene spacer and are used to study the structural variations and magnetic interactions in self-assembled first row, divalent transition metal complexes in polymeric, dinuclear and dinuclear metallacyclic settings. The formation of these architectures highly depend on the geometry of these ligands: anti, the …

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 …

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 …

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 …

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 …

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 …

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] …

Investigations Of Intramolecular Copper (I)-Arene Interactions Using A Ns2-Macrocyclic Ligand With Different Pendant Aryl Arms, Paul J. Lee

Honors Theses

Two macrocyclic ligands with a pendant phenyl group -N-[2-(l-phenyl)ethyl]-1-aza-4,8di thiacyclodecane (L1) and N-[2-0-phenyl)propyl]-1-aza-4,8-dithiacyclodecane, (L2) has been synthesized and characterized. The copper(I)-triphenylphosphine complex [LICu(PPhJ)]OTf , (2) was synthesized from L1 1/2(C6H6)[CuOTf]2, and PPh3. The complexes [LICu]OTf 1 and [L2Cu]OTf 3 were also synthesized and characterized using DC and IH NMR, UV-vis and lR spectroscopy, and ESI-MS. In CD2Cl2, 1 was found to have a fluxional behavior with the barrier ΔG to the process estimated at 9-11 kcal/mol. Variable temp. NMR spectroscopy of 1 gave compelling evidence that the phenylappended group is bound in an intramolecullar η2-fashion with the copper center. At …

Copper Complexation And Speciation In The Western South And Equatorial Atlantic Ocean, John A. Consolvo

Chemistry & Biochemistry Theses & Dissertations

Presented here are the first data on copper complexation and speciation in the South Atlantic Ocean. Samples were collected at six vertical profile stations and along the surface (1m) transect during the 1996 IOC Baseline Contaminant Survey. Copper complexation measurements were made for the surface transect (1m) samples and three of the six vertical profile stations (1m - ~500m) using differential pulse anodic stripping voltammetry (DPASV) with a thin mercury film, rotating glassy carbon disk electrode (TMFRGCDE).

A strong organic copper complexing ligand (L₁; log K' _cuL1/cu2+ > 11. 8 ± 0 .4) was detected in 57% of all …

Characterization And Implementation Of A Continuos Flow Trace Metal Preconcentration System For Inductively Couples Plasma Atomic Emission Spectrometry, Robert N. Sibley

Senior Scholar Papers

A continuous flow pre-concentration system for analysis of trace metals in natural waters was characterized and used to determine the copper(II) and lead(II) concentrations in seawater from Penobscot Bay, Maine. Pre-concentrated samples were analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES). System characterization involved elucidation of the thermodynamic complexation constants, KCu(II) and KPb(II), for Cu(II) and Pb(II) with the pre-concentration column chromatographic material. This was done in aqueous media of known pH and ionic strength. The column contained 8-hydroxyquinoline immobilized on Toyopearl HW-75 fractogel chromatographic resin. The buffer system used for metal binding experiments was an equimolar mixture of …

Photochemical Energy Storage (Photosensitized Isomerization Of Norbornadiene To Quadricyclane By Copper(I) Complexes), Dennis J. Fife

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

This research has focused on the sensitized photoisomerization step of a solar energy storage system based on the interconversion of norbornadiene (NBD) and quadricyclane (Q). Sensitizers studied in the photoisomerization were arylphosphine complexes of copper(I) halides [(Ph₃P)₃CuX, (MePh₂P)₃CuX, (DIPHOS)CuCl; X = Cl, Br, I and DIPHOS = Ph₂P(CH₂)₂PPh₂]. The lowest electronic excited state of the complexes can be an effective triplet energy sensitizer as evidenced by a maximum quantum yield of 1.0 with (MePh₂P)₃CuX. The sensitization mechanism of the L …

An Fe (Iii) - Initiated Oxidase Reaction With Ferroxidase-Ii, Glenn Alexander Hegamyer

Master's Theses

A reaction involving iron as an intermediary electron carrier for the coupling of electron transfer from an endogenous substrate to ferroxidase-I has been proposed.

The enzymic nature of the reacti on has been established and studies with iron chelating agents have demonstrated the involvement of Fe(III). The kinetic parameters of ferroxidase-11 with Fe (lll) were found to be quite similar to those previously established for Fe(Il). The participation by the copper associated with ferroxi dase-11 was ascertained by use of the copper chelating agent, diethyl -di thio-carbamate .

A variety of substances normally found in blood were surveyed as possible …

The Chelation Of Cu(Ii) With 1, 3-Bis(Tris(Hydroxymethyl)Methylamino)-2-Propanol And 1, 3-Bis (2-Hydroxyethylamino)-2-Propanol, David Andrew Jackson Jr.

Master's Theses

The chelating agent 1, 3-bis(2-hydroxyethylamino)-2-propanol dihydro­chloride was prepared and preliminary examinations of the Cu(ll) and Fe(lll) complexes were carried out spectrophotometrically. This dihydrochloride as well as 1, 3 bis(tris(hydroxymethyl)methylamino)-2-propanol dihydrochloride. were converted from the chloride salts to their corresponding ammonium bases. The conversion was carried out by passing an aqueous solution of each chloride salt through an ion exchange column containing Amberlite XE-78 resin.

Solutions of these bases were standardized for use in potentiometric titration&. Each ammonium base was titrated with standard perchloric acid at 20°C, 30°C, and 40°C. The dissociation constants. were calculated using these data. Aqueous solutions of …