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 …

High-Pressure Studies On The Transition From Red Phosphorus To Black Phosphorus, Heng Xiang

Electronic Thesis and Dissertation Repository

Black phosphorus (BP) is a promising material in many research fields. However, the transition process from amorphous red phosphorus (ARP) is elusive and hence hinders large scale synthesis and applications. This work describes the application of the high-pressure method to study the transition process from ARP to BP.

In this thesis, the following three objectives were achieved: (1) to understand the mechanism of the transition, (2) to facilitate the synthesis of BP by taking the advantage of less pure ARP, (3) to propose new methods of synthesizing BP-based materials, such as the moderately oxidized BP and the black phosphorus/ amorphous …

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 …

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 …

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 …

Investigations Of The High Pressure Effects On Structural Properties And Co2 Adsorption Performance Of Mofs Using Vibrational Spectroscopy, Shan Jiang

Electronic Thesis and Dissertation Repository

The pre- and post-combustion carbon dioxide capture has drawn much attention in the past few decades owing to the increasing concentration of CO₂ in the atmosphere. Among all the potential solid adsorbents for CO₂ capture, metal-organic frameworks (MOFs) are a promising class of materials due to their large surface areas, high tunability and their high selectivity for gas adsorption applications. It has been widely demonstrated that the application of high external pressure in gigapascal level can substantially tune the structure, pore size and opening of porous material. Consequently, the structural, as well as gas adsorption properties of these …

Providing Molecular Insight For Understanding Anion Exchange Membrane Conductivity, Michael Kwasny

Doctoral Dissertations

Anion exchange membranes (AEMs) are notorious for having both low alkaline stability and poor ion conductivity in fuel cell operation conditions, with solutions to these two challenges often being developed independent of each other. The chemical instability of an AEM is viewed through degradation of the polymer backbone and the cationic species and improving a material’s stability is approached by altering the polymer backbone, the cation, or both. On the other hand, poor ion conductivity is typically addressed by modifying bulk membrane properties such as increasing the ion exchange capacity (IEC), changing the morphology, or increasing the water uptake. These …

Progress Toward Durable Icephobic Materials, Matthew J. Coady

Electronic Thesis and Dissertation Repository

Ice accumulation is a major engineering challenge in many fields including aerospace, power generation, transportation, and infrastructure. A variety of solutions are being researched to address this challenge. Perhaps the most promising method of combating ice accumulation is by applying coatings with low values of interfacial ice adhesion strength, τ_ice. Icephobic materials are those with ice adhesion below 100 kPa, and it has been shown that passive delamination can occur on surfaces with τ_ice below 20 kPa. While various low adhesion surfaces have been prepared, durability concerns pervade applications where surfaces experience repeated icing or freeze-thaw cycles, …

Zinc–Phosphorus Clusters For Solution Synthesis Of Zinc Phosphide Nanoparticles, Kyungseop Lee

Electronic Thesis and Dissertation Repository

Synthesis of zinc phosphide (Zn₃P₂) nanoparticles is an emerging topic of investigation as Zn₃P₂ is a candidate material for the next generation solar cells. Despite the early discovery of its favorable electronic properties that are well-suited for photovoltaic applications, a major focus of synthetic strategy was with vapor/chemical deposition methods. Solution methods with greater control over size, crystal structure and composition at a lower production cost, has been underdeveloped in comparison. In this context, this thesis describes the synthesis, characterization and reactivity of zinc phosphido clusters: [Zn₂(μ-PPh₂)₂(PPh …

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. …

Methodologies For Metal Functionalization Of Phosphorus Based Photopolymer Networks, Vanessa Béland

Electronic Thesis and Dissertation Repository

Photopolymer networks with phosphonium cation, alkyl phosphine and olefin functionality were designed, synthesized and functionalized with metals by metathesis, coordination and hydrometallation reactions, respectively. The materials were strategically designed so that the metal functionalization step could be monitored and quantified. In some cases, this involved characterization by IR, NMR, or X-ray spectroscopic techniques, or by comparison to molecular analogues. It was found that by using a bi-functional photopolymer network, the material could be bi-metallized by orthogonal mechanisms. All metallized polymer networks were tested for their suitability as precursors to metal-containing ceramics. The polymers were pyrolyzed, and on analysis it was …

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 …

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

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

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 …

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, …