Inorganic Chemistry Commons^™

Hypervalent Iodine Compounds With Carboxylate And Tetrazolate Ligands, Avichal Vaish

Chemistry Theses and Dissertations

In modern organic chemistry, hypervalent (HV) iodine(III) compounds are frequently used as oxidizing agents but application of λ³-iodanes in polymer and material chemistry is still underexplored. This dissertation describes the preparation of dynamic and self-healing materials by employing ligand exchange reactions involving HV iodine(III) compounds of the type ArIL₂ (Ar = Aryl, L = ligand, e.g., carboxylate or (pseudo)halide). These compounds can undergo ligand exchange reactions in presence of nucleophiles (Nu^-) to form ArINu₂. Diacetoxyiodo benzene was successfully employed as a crosslinker to prepare dynamic and self-healing gels derived from carboxylate-containing polymers. Furthermore, …

Greening Of Catalytic Processes Using First-Row Transition Metals For Atom Transfer Radical Addition And Transfer Hydrogenation, Gabrielle Pros

Electronic Theses and Dissertations

This work focused on “greening” catalytic processes, atom transfer radical addition (ATRA), which adds an alkyl halide across and alkene, and transfer hydrogenation/dehydrogenation, which reduces a carbonyl without needing direct H₂ gas. Part of “greening” of these processes is through using abundant first row metals, Cu and Ni for catalysis. One aim was to design new ligands which would be more active in these systems; the second was investigation of additives for catalyst regeneration to reduce the catalyst loading necessary for high yields.

The TPMA^* family was investigated in ATRA. Rate constants followed the expected trend, which increased …

Towards The Synthesis Of An Artificial Fluorescent Siderophore, Ashley Burns

Honors Theses

Siderophores are molecules capable of binding ferric ions with high affinity (Ka = 1052). This thesis outlines our attempts to synthesize an artificial siderophore, which incorporates a signaling group to help monitor the uptake of ferric ions. The artificial siderophore is a tripodal molecular receptor synthesized in a five-step procedure with a proposed final sixth step. Rhodamine 6G azide (95.0% yield) was formed from rhodamine 6G and the synthesis of 2-azidoethanamine was modified from the literature. The tripodal arm portion of the sensor was successfully synthesized by protecting the catechol of 2,3-dihydroxybenzaldehyde to form 3-formyl-1,2-phenylene dimethanesulfonate (98.8% yield). The reduction …

Oxygen Deficient Perovskites: Effect Of Structure On Electrical Conductivity, Magnetism And Electrocatalytic Activity., Ram Krishna Hona

Electronic Theses and Dissertations

The present thesis deals with the synthesis and study of the physico-chemical properties of perovskite based oxide materials. Several novel oxygen deficient perovskites (ODP) have been synthesized by conventional solid state synthesis method. The novel compounds are CaSrFe₂O_6-δ, CaSrFeCoO_6-δ, Ca₂Fe_1.5Ga_0.5O₅, CaSrFeGaO₅ and BaSrFe₂O₅. Their magnetic, charge transport and electrocatalytic properties have been studied. Structural effect on electrical conductivity, magnetic and electrocatalytic properties have been studied in some series of ODPs. CaSrFe₂O_6-δ, CaSrFeCoO_6-δ, Ca₂Fe …

Self-Assembly Of 2d And 3d Metallo-Supramolecules With Increasing Complexity, Bo Song

USF Tampa Graduate Theses and Dissertations

Synthetic organic chemistry played a crucial role in the construction of molecules through the formation and dissociation of covalent bonds. However, the laborious synthetic procedures as well as the low yield after multiple steps have restricted the pursuit of complicated giant molecules with high efficiency. Being complementary to organic synthesis, self-assembly provided an alternative route to achieving the giant architectures using weak non-covalent interactions in high efficiency, which is in analog to natural systems such as DNA, peptide, and protein. Among the various interactions, coordination has shown unique advantages in terms of directionality, reversibility and strength. Serving as a bottom-up …

Syntheses, Characterization, And Preliminary Evaluation Of Potential Ruthenium Anticancer Complexes Containing Schiff Base Ligands, Stephen Mensah

Theses and Dissertations

Platinum-based drugs have over the years been administered in the treatment of tumours.

Unfortunately, platinum resistance and the severe side effects associated with the treatments has necessitated the research for new anti-cancer drugs. Ruthenium(II) and Ruthenium(III) complexes have shown promise as useful alternative anticancer agents. The lead candidates include the Ru(II) complex RAPTA-C, a ruthenium(II)-arene complex [Ru(η6-p-cymene)Cl2(1,3,5-triaza-7-phosphaadamantane)] and the Ru(III) complex NAMI-A [imidazoleH][trans-Ru(imidazole) (dimethyl sulfoxide)Cl4]. Both compounds have shown potent cytotoxic activity in several primary human tumor models. Unfortunately, NAMI-A could not advance in clinical evaluations due to limited efficacy in vivo, while the clinical evaluation of RAPTA-C is unknown. …

It's Elementary: A Review Of Forensic Analysis Techniques Of Inorganic Components Of Explosives, Sadie Schultz

Chemistry & Biochemistry Student Projects

No abstract provided.

Antioxidants And Beta-Carotene: A General Overview, A Research History, And Modern Scholarship, James Joseph Dickman Iv

Chemistry & Biochemistry Student Projects

This paper seeks to provide a cursory overview of oxidative stress and the accompanying biomolecules which are used to combat it. From there, the paper will provide a somewhat comprehensive list of major historical discoveries regarding antioxidant molecules, in particular beta-carotene. After this, an overview of more modern scholarship on the issue of these molecule’s antioxidant properties specific (from the 1970s onward) will be discussed up to modern times. The paper will conclude with an in depth look at the modern scholarship on beta-carotene that was performed here at Taylor University.

Bone Regeneration Via Inorganic/Organic Compatibility In A Newly Synthesized Hydrogel: Nhap-Bmp-2, Hannah Ewing

Chemistry & Biochemistry Student Projects

In this paper, nHAp-BMP-2 hydrogel is carefully synthesized in order to optimize the organic and inorganic compatibility which induces osteogenesis—the formation of new bone. This new method is a novel development within the medical field, giving more hope to those suffering from traumatic bone injuries. A drawback with using hydrogels is the difficulty of controlling peptide release in the affected areas. Too quick of a release alarms the human inflammatory response resulting in more substantial injury and an even prolonged recovery time. On the other hand, if the peptides that promote bioactivity are released too slowly, the bone will not …

Quantum Chemical Methods: Its History And Future, Erica Mitchell

Chemistry & Biochemistry Student Projects

No abstract provided.

Significance And Implications Of Vitamin B-12 Reaction Shema- Eth Zurich Variant: Mechanisms And Insights, David Joshua Ferguson

Chemistry & Biochemistry Student Projects

This is an undergraduate chemistry thesis document. This involves a discussion of the mechanisms and overall reactions involved in the total synthesis of vitamin B-12.

The History And Development Of Identification: Rediscovery And Application Of Egyptian Blue, Bailee Allen

Chemistry & Biochemistry Student Projects

The use of fingerprints as a form of identification in criminal cases has become a common method of conviction within the criminal justice system. However, with the recent rise in the number of people wrongly convicted, the typical sources of evidence have come into question about their reliability. Multiple common drawbacks found when using fingerprints dusting to obtain prints from crime scenes has led to researchers looking for more efficient ways to collect them that maintain high sensitivity and contrast. These are the two aspects that create the largest problem, especially on highly reflective and highly patterned surfaces. The discovery …

The Chemistry Of Jellybeans, Andrew Carter

Chemistry & Biochemistry Student Projects

Jellybeans are an amazing work of chemistry. In my paper, I outline the history and science behind this little candy. My paper describes taste receptors, molecular structure, and the analytical chemistry that help to make flavor science an interesting field of work.

Metallodrugs And Their Various Impacts On Disorders And Diseases, Paige Wagner

Chemistry & Biochemistry Student Projects

No abstract provided.

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 pyriplatin compounds …

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 reactivity. Unlike most previously studied platinum …

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 …

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 …

Organic-Inorganic Hybrid Composites: Superhydrophobic Polymer Coatings With Photoreactive Perfluorinated Phthalocyanines, Abdul Azeez

Seton Hall University Dissertations and Theses (ETDs)

ABSTRACT

We report partly fluorinated and silicon-based polymers that incorporate inorganic/organic materials capable of generating reactive oxygen species (ROS) using only visible light and air. Polyvinylidene fluoride (PVDF), which incorporated a known perfluorinated phthalocyanine photosensitizer, F₆₄PcZn, supported on silicon and titanium oxides was further modified via chemical surface roughening to exhibit enhanced hydrophobicity when used as a coating. Water contact angles as high as ~159° have been observed, vs. ~ 92° for the unmodified polymer. The polymer matrix, however, does not resist the ROS it produces as evidenced by spectroscopic and SEM data. A polysiloxane matrix was similarly …

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(C₃₄H₅₅N₂O₂)]·1.685CH₃OH·0.315H₂O. Both complexes exhibit a square-planar geometry, with unbound phenol moieties participating in inter­molecular hydrogen bonding with co-crystallized water and methanol. The presence of both κ² and κ³ coordination modes arising from the same solution suggest a dynamic process …

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. …

Development Of Ni-Catalyzed Alkene Dicarbofunctionalization Reactions, Shekhar Kc

Chemistry and Chemical Biology ETDs

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

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

Publications and Research

No abstract provided.

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.

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

Graduate Theses/Dissertations

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 …

An In-Situ Study Of The Aqueous Speciation Of Uranium (Vi) Under Hydrothermal Conditions, Diwash Dhakal

Graduate Theses/Dissertations

Rigorous study of the speciation distribution of uranyl-chloride bearing solutions under hydrothermal conditions is important to understand the transport mechanism of uranium underground, which is of uttermost interest to parties studying the geological uranium deposits and those studying the possibilities of geological repositories for spent nuclear waste. I report an in-situ Raman spectroscopic study of the speciation distribution of aqueous uranyl-chloride complexes upto 500°C conducted using a HDAC as the high PT spectroscopic cell. The samples studied contained the species UO₂²⁺, UO₂Cl⁺, UO₂Cl₂⁰ and UO₂Cl₃^{- …}

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 specific heat …

Lanthanum-Based Perovskites As An Effective Electrocatalyst For Water Splitting And Energy Storage Applications, Xavier Martinez

Electronic Theses & Dissertations

Recent changes in global weather patterns have accented the need a shift from fossil fuels to a cleaner energy option. As part of an overall plan, hydrogen production for fuel cells offer substantial power without carbon emissions. Overall water splitting, with the aid of a low cost electrocatalyst could prove to be an abundant green fuel source. Utilizing readily available transition metals, three perovskite nanostructures were studied as a multifunctional material for hydrogen production as well as an energy storage material. LaCoO₃ (LCO), LaFeO₃ (LFO)_, and LaMnO₃ (LMO) were synthesized and characterized by X-ray diffraction (XRD) …

Deposition Of Platinum Particles On Surface-Modified Carbon Ultramicroelectrodes, Caitlin Millsaps

Undergraduate Honors Theses

Nanoparticles are used as electrocatalysts due to their large surface area-to-volume ratios. Most studies of nanoparticle electrocatalysis are performed on collections of particles on a support, which represent ensemble average behavior influenced by spatial distribution of the nanoparticles. Therefore, recent emphasis has been placed on analyzing electrocatalytic behavior of single particles. The focus here is to develop carbon ultramicro- and nanoelectrode platforms for studying the electrocatalytic properties of single metal nanoparticles. Ultramicroelectrodes were prepared using chemical vapor deposition of carbon in pulled quartz capillaries. Electrode diameters were determined by cyclic voltammetry. Electrodes were modified using a soft nitriding technique to …

Gas Chromatography Analysis Of Co2 Reduction Photocatalysis With Zinc Dipyrrin Complexes, Alex Day

Undergraduate Honors Theses

Bis(1,3,7,9-tetramethyl-5-mesityldipyrrinato)zinc(II) (ZnDPY) was synthesized in the lab by the McCusker group and a procedure was created to analyze its ability as a photosensitizer, a molecule that provides the energy for the reaction to occur by capturing light energy and turning it into a form that can be used by the photocatalyst. While more work is needed, preliminary steps have been made to create a process that can analyze the amount of carbon monoxide produced by a photocatalytic CO₂ reduction reaction with ZnDPY as the photosensitizer. Progress has been made via the setup of a reaction apparatus, targeted gas chromatography …