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Leaving Ligand Effects On Reactivity And Solubility Of Monofunctional Platinum(Ii) Anticancer Complexes, Heidi Linn Hruska Millay 2019 Western Kentucky University

Leaving Ligand Effects On Reactivity And Solubility Of Monofunctional Platinum(Ii) Anticancer Complexes, Heidi Linn Hruska Millay

Masters Theses & Specialist Projects

Monofunctional platinum(II) complexes, such as phenanthriplatin and pyriplatin, have notably different characteristics from the bifunctional anticancer complexes, such as cisplatin and oxaliplatin, which have detrimental toxicities and resistance associated with them. The unique properties of the monofunctional complexes may be exploited to target cancer cells without producing the toxic side effects associated with the current FDA-approved platinum-based anticancer drugs. To advance the understanding of these monofunctional platinum(II) complexes, this study replaced the chloride leaving ligand with an acetate group, which should increase solubility and alter the rate of reactivity with key amino acid and nucleotide targets. Phenanthriplatin and ...


Interaction Of A Platinum Triamine Complex Having A Seven-Membered Chelate Ring With N-Acetyl-Lmethionine And Guanosine 5'-Monophosphate, Jae Ko 2019 Western Kentucky University

Interaction Of A Platinum Triamine Complex Having A Seven-Membered Chelate Ring With N-Acetyl-Lmethionine And Guanosine 5'-Monophosphate, Jae Ko

Masters Theses & Specialist Projects

In the 1960s, Rosenberg and his colleagues confirmed the anti-cancer activity of cisplatin. Although cisplatin was capable of killing testicular cancer cells there were also serious side effects. It was necessary to find alternate ways of overcoming side effects, and soon many researchers have discovered novel platinum compounds that show similar reactivity. Recently, replacing one chloride group to a heterocyclic amine group showed significant cytotoxicity with a different binding activity than cisplatin. Previously in our lab, [Pt(Me5dien)(NO3)]+ and [Pt(Et2dien)Cl]+ have been synthesized and reacted with NAcetyl- L-methionine (N-AcMet) and Guanosine 5’-monophosphate (5’-GMP) showed unusual ...


Synthesis And Characterization Of Multifunctional Transition Metal Oxide Nanoparticles Through A Modified Sol-Gel Method With Application In Energy Storage, Julien Lombardi 2019 The Graduate Center, City University of New York

Synthesis And Characterization Of Multifunctional Transition Metal Oxide Nanoparticles Through A Modified Sol-Gel Method With Application In Energy Storage, Julien Lombardi

Dissertations, Theses, and Capstone Projects

The Synthesis of transition metal oxide nanoparticles has been studied in great detail over the many years. The most studied transition metal oxide nanoparticles are perovskites of the ABO3 stoichiometry (A and B = transition metal) and more recently double perovskite crystal structures of the AA’BO6 or A2BB’O6 stoichiometry due to the many different properties arising from the many different combinations of elements possible. These materials have proven potentially useful in many fields, but due to properties such as ferroelectricity and ferromagnetism, the desire to integrate these materials into electronics is ever growing. Many ...


Synthesis And Characterization Of Heteronuclear Inorganic Complexes For The Photodegradation Of Persistant Organic Pollutants, Matthew A. Moyet 2019 University of Maine

Synthesis And Characterization Of Heteronuclear Inorganic Complexes For The Photodegradation Of Persistant Organic Pollutants, Matthew A. Moyet

Electronic Theses and Dissertations

The focus of this thesis is to investigate the structural modification and characterization potential of common photocatalysts that have various uses for environmental remediation purposes. Pollution involving organic chemicals is one of the most common scenarios found in communities throughout the country. Efforts to rid contaminated drinking water supplies of these chemicals include physical and chemical filters, which have limited ability and efficacy. This lack of efficient filtration services has led to an increased demand for more effective treatment methods. Chemical species that react in the presence of light are known as photocatalysts and have been used in previous studies ...


Using An Extended Broken Symmetry Approximation To Characterize Structure And Spectroscopic Properties Of 2fe-2s Clusters, Ashlyn M. Koval 2019 Duquesne University

Using An Extended Broken Symmetry Approximation To Characterize Structure And Spectroscopic Properties Of 2fe-2s Clusters, Ashlyn M. Koval

Electronic Theses and Dissertations

Iron-sulfur proteins perform a wide variety of biological functions that assist in mediating protein function via electron transfer reactions. The Rieske and mitoNEET iron-sulfur clusters have been shown to undergo proton coupled electron transfer facilitated by a histidine ligand. The protonation state of the histidine residue is key to understanding the mechanism of proton coupled electron transfer. This work reports a study of the 2Fe-2S ferredoxin, Rieske, and mitoNEET clusters using the extended broken symmetry approximation. Calculations were performed on the ferredoxin cluster to establish appropriate methodologies. Calculations were then performed for Rieske and mitoNEET clusters to suggest experiments capable ...


The Reactivity Of Ditetrelenes Towards Organophosphorus Oxides, Maissa Belcina 2019 The University of Western Ontario

The Reactivity Of Ditetrelenes Towards Organophosphorus Oxides, Maissa Belcina

Electronic Thesis and Dissertation Repository

The reactivity of tetramesityldisilene 4 and tetramesityldigermene 5 towards organophosphorus oxides was explored in this thesis. The reaction of dialkyl and diarylphosphine oxides and phosphites with ditetrelenes 4 and 5 resulted in a 1,3-addition to form diorganodisilyl and digermyl phosphinites 27, 28, 31, 32 and disilyl phosphites 35 and 36. The 1,3-addition resulted in a mild two electron reduction of the P(V) centre of the phosphine oxide and phosphite to a P(III) centre in the products, without the use of heat or a catalyst. The reaction of organophosphorus oxides provides another example of a main group ...


Palladium(Ii) Complexes Of A Bridging Amine Bis(Phenolate) Ligand Featuring Κ² And Κ³ Coordination Modes, Brendan J. Graziano, Bradley M. Wile, Matthias Zeller 2019 Ohio Northern University

Palladium(Ii) Complexes Of A Bridging Amine Bis(Phenolate) Ligand Featuring Κ² And Κ³ Coordination Modes, Brendan J. Graziano, Bradley M. Wile, Matthias Zeller

Chemistry and Biochemistry Faculty Scholarship

Bidentate and tridentate coordination of a 2,4-di-tert-butyl-substituted bridging amine bis­(phenolate) ligand to a palladium(II) center are observed within the same crystal structure, namely di­chlorido­({6,6′-[(ethane-1,2-diylbis(methyl­aza­nedi­yl)]bis­(methyl­ene)}bis­(2,4-di-tert-butyl­phenol))palladium(II) chlorido­(2,4-di-tert-butyl-6-{[(2-{[(3,5-di-tert-butyl-2-hy­droxy­phen­yl)meth­yl](meth­yl)amino}­eth­yl)(meth­yl)amino]­meth­yl}phenolato)palladium(II) methanol 1.685-solvate 0.315-hydrate, [PdCl2(C34H56N2O2)][PdCl(C34H55N2O ...


Capabilities And Limitations Of The Spin Hamiltonian Formalism In Single Molecule Magnets, Philip Ferko 2019 University of Missouri-St. Louis

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 ...


Unconventional Anticancer Metallodrugs And Strategies To Improve Their Pharmacological Profile, Maria Contel 2019 CUNY Brooklyn College

Unconventional Anticancer Metallodrugs And Strategies To Improve Their Pharmacological Profile, Maria Contel

Publications and Research

No abstract provided.


Synthesis Of Magnetic Ion Doped Ii-Vi Benzenechalcogenolate Molecular Clusters, Fumitoshi Kato 2019 University of Massachusetts Amherst

Synthesis Of Magnetic Ion Doped Ii-Vi Benzenechalcogenolate Molecular Clusters, Fumitoshi Kato

Doctoral Dissertations

Diluted magnetic semiconductor quantum dots (DMS-QDs) is a class of material prepared by introducing a small percentage of magnetic impurities to impart new magneto-optical properties to the host nanocrystal (NC). Such materials are regarded as promising candidates for their potential application in spintronic devices. The overall functionality of the DMS‑QD is highly dependent on the dopant position within the host structure. A thorough understanding of the doping mechanism is, therefore, critical to gain better control over the dopant speciation in nanocrystal lattice and material properties. In this work, we utilized II‑VI molecular clusters that are analogous to bulk ...


Modulating Dopant-Defect Interactions In Transition Metal Doped Colloidal Strontium Titanate Nanocrystals, William Harrigan 2019 University of Massachusetts Amherst

Modulating Dopant-Defect Interactions In Transition Metal Doped Colloidal Strontium Titanate Nanocrystals, William Harrigan

Doctoral Dissertations

Perovskites such as strontium titanate, a wide band gap semiconductor have been widely studied due to the multitude of potential applications in photocatalysis, multiferroics, sensing, and microelectronics. Various novel optical, electrical and magnetic properties can be imparted through the introduction of different transition metal dopant ions. The introduction of these impurities has been shown to impart functionality for various applications. The use of Cr3+has been shown to introduce defect levels into the band structure of SrTiO3and increase visible light utilization for photocatalysis. Transition metal doped highly crystalline colloidal SrTiO3nanocrystals (NC) were synthesized using two ...


Synthesis And Characterization Of A Homogeneous Cobalt Catalyst For The Hydrogenation Of Acetone To Isopropanol, Joselyn G. Molina 2019 Seattle Pacific University

Synthesis And Characterization Of A Homogeneous Cobalt Catalyst For The Hydrogenation Of Acetone To Isopropanol, Joselyn G. Molina

Honors Projects

To lessen environmentalstrain and decrease dependency on noble metals for catalysis, first-row metals are continuously being explored as alternative catalysts for reactions of interest, particularly those that close the carbon cycle or promote fuel production. Recently, homogeneous cobalt catalysts have been shown to be viable options for effective hydrogenation of C-O double bonds, with cobalt-triphos being of particular interest. Here, we report the characterization of synthesized a cobalt-triphos complex by nuclear magnetic resonance spectroscopy and optical spectroscopy. Analysis of the electrochemistry of the cobalt-triphos complex suggests promising electrocatalytic capability for the hydrogenation of acetone to produce isopropanol.


Non-Traditional Metallation Of Metallothioneins With Xenobiotic Therapeutic Metals, Daisy L. Wong 2019 The University of Western Ontario

Non-Traditional Metallation Of Metallothioneins With Xenobiotic Therapeutic Metals, Daisy L. Wong

Electronic Thesis and Dissertation Repository

The rise of the Anthropocene has seen more global pollution than before in history. With the explosion of consumer electronics in the last half century, the rise of metal pollution from their extraction and disposal results in the unnatural introduction of heavy and rare metals into the ecosystem. Organisms have a metal defense protein, metallothionein, which has multiple roles in essential metal regulation and protection against minimal toxic metal exposure. However, these modern heavy metals prominent in electronics are not found biologically and their interactions in the body are generally unknown. Some of these metals are employed as therapeutic agents ...


Synthesis, Stabilization, And Modification Of Zinc Oxide Nanoparticles For Biological Applications, Allison Kimberly Freese 2019 Missouri State University

Synthesis, Stabilization, And Modification Of Zinc Oxide Nanoparticles For Biological Applications, Allison Kimberly Freese

MSU Graduate Theses

Nanoparticles have become very useful as delivery systems in biomedicine. The nanoparticles can be layered with different compounds to produce a vessel for transport of biological materials. Specifically, gold nanoparticles layered with a reducing agent, lysozyme, and polyelectrolytes can be synthesized to transport lysozyme into a cell. However, zinc oxide nanoparticles are cheaper, biocompatible nanoparticles that can be used for the same process. Here in, zinc oxide nanoparticle conjugates were synthesized, modified, and analyzed to be used as a biological material delivery system. The zinc oxide nanoparticles were synthesized using zinc chloride and sodium hydroxide. The particles were then layered ...


Towards Trigonal Prismatic Hexanuclear Copper Complexes For Catalytic Water Oxidation, David I. Kreiger 2019 Florida International University

Towards Trigonal Prismatic Hexanuclear Copper Complexes For Catalytic Water Oxidation, David I. Kreiger

FIU Electronic Theses and Dissertations

Our planet is running out of energy resources and traditional renewables are not easily transported nor will be sufficient to cover the void left by fossil fuels. Therefore, a new energy storage system needs to be adopted. The medium with highest energy density that is readily available is hydrogen from water. However, to access hydrogen, water needs to be oxidized and water oxidation catalysts (WOCs) will be required for widespread adoption. In pursuit of WOCs, several hexauclear copper complexes were synthesized and characterized, including the isolation and characterization of a mixed-valent Cu6 (formally, CuII5CuIII) complex ...


Oxidative C–C And C–Heteroatom Reactivity Of High-Valent Nickel Complexes, Sofia Marie Smith 2019 Washington University in St. Louis

Oxidative C–C And C–Heteroatom Reactivity Of High-Valent Nickel Complexes, Sofia Marie Smith

Arts & Sciences Electronic Theses and Dissertations

ABSTRACT OF THE DISSERTATION

Oxidative C–C and C–Heteroatom Reactivity of High-Valent Nickel Complexes

by

Sofia M. Smith

Doctor of Philosophy in Chemistry

Washington University in St. Louis, 2019

Professor Liviu M. Mirica, Chair

Professor Kevin D. Moeller, Co-Chair

Nickel catalysts are commonly used for cross-coupling reactions such as Negishi, Kumada and Suzuki couplings. While Ni(0), Ni(I), and Ni(II) intermediates are most relevant in these transformations, Ni(III) and Ni(IV) species have also been recently proposed to play a role in catalysis. The formation of C–C and C–heteroatom bonds plays a fundamental role ...


Phenolate Derivatives Of Octanuclear Iron-Oxo-Pyrazolato Complexes; Enantiomeric Resolution Of T-Symmetry Species, Konstantinos Lazarou 2019 Florida International University

Phenolate Derivatives Of Octanuclear Iron-Oxo-Pyrazolato Complexes; Enantiomeric Resolution Of T-Symmetry Species, Konstantinos Lazarou

FIU Electronic Theses and Dissertations

Octanuclear ferric complexes involving achiral phenolates of the general formula [Fe8(μ-O)4(μ-pz)12(R-C6H4O)4], (R = 4-NO2, 4-CN, 4-F, 4-Cl, 4-I, 4-CH3O, and 3-NO3), where synthesized and characterized by single crystal X-ray crystallography, elemental analysis, 1H-NMR, UV-Vis, IR, 57Fe Mössbauer spectroscopy and electrochemical methods (cyclic and differential pulse voltammetry). Results indicate that the nature of the phenolate substituents allows the fine tuning of the spectroscopic data of the compounds.

Subsequently, this project focused on the resolution of the racemic octanuclear iron-oxo-pyrazolato complex [FeIII8 ...


Development Of Bismuth Oxyhalide Photocatalysts For Environmental And Industrial Applications, Robert Arthur 2019 University of Maine

Development Of Bismuth Oxyhalide Photocatalysts For Environmental And Industrial Applications, Robert Arthur

Electronic Theses and Dissertations

Heterogeneous semiconductor photocatalysis, of interest for water splitting and environmental remediation applications, uses light to drive reactions. Metal oxide and sulfide semiconductors have been previously studied but have limitations that include large band gap energies and high rates of recombination. Bismuth oxyhalides (BiOX) are an emerging class of photocatalysts with tunable band gaps and low rates of recombination due to their unique crystal structures. Studies of BiOX photocatalytic activity have largely focused on removal of azo dyes from aqueous solutions, with little attention paid to degradation byproducts. Furthermore, these catalysts have not been explored as a means to conduct organic ...


Optical Memory Behavior, Metallophilic Luminescence, And Chemical Sensing Ability Of Inorganic And Organometallic Complexes: Development Of Optoelectronic Materials, Aaron D. Nicholas 2019 University of Maine

Optical Memory Behavior, Metallophilic Luminescence, And Chemical Sensing Ability Of Inorganic And Organometallic Complexes: Development Of Optoelectronic Materials, Aaron D. Nicholas

Electronic Theses and Dissertations

This dissertation is divided into three sections: (1) optical memory, (2) metallophilic-based luminescence, and (3) chemical sensors. (1) Optical memory behavior of d10metal Cu(I) thiocyanate salts are investigated to explore their potential use in the development of digital data storage devices. From this study we have discovered a new class of CuSCN(3-BrPy)2optical memory material which undergo a reduction in emission intensity upon laser irradiation. This loss of emission intensity can be reversed simply by heating the sample to room temperature. The mechanism by which this emission loss occurs has been studied, revealing a migrating ...


Synthesis, Characterization And Crystal Growth Of I2-Ii-Iv-Vi4 And I4-Ii-Iv2-Vi7 Diamond-Like Semiconductors With Potential In Ir-Nlo Applications, Jennifer Glenn 2019 Duquesne University

Synthesis, Characterization And Crystal Growth Of I2-Ii-Iv-Vi4 And I4-Ii-Iv2-Vi7 Diamond-Like Semiconductors With Potential In Ir-Nlo Applications, Jennifer Glenn

Electronic Theses and Dissertations

In this dissertation, several new and existing diamond-like semiconductors (DLSs) were synthesized and investigated for their potential in infrared nonlinear optical (IR-NLO) applications. In Chapter 2 growth of large single crystals of Li2MnGeS4 was carried out using iodine vapor transport and a newly created graphite-tube containment system. This crystallization method produced sizable single crystals on the scale of 2x1x1 mm3, that were used to determine the material’s magnetic properties. Magnetization data indicate that the compound is antiferromagnetic with a Néel temperature of 10 K and an effective magnetic moment of 5.6 /f.u.. The ...


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