Chemistry Commons^™

Alkylation Of Benzene On Immobilized Phosphotungstic Acid, Kofi Kankam

Electronic Theses and Dissertations

Linear alkylbenzenes (LAB) are key intermediates in the synthesis of linear alkylbenzene sulfonate surfactants that are used in the manufacture of detergents. Production of LAB with traditional Lewis acids as catalysts, such as hydrofluoric acid, results in the formation of large amounts of toxic wastes and corrosion of industrial equipment. Phosphotungstic acid (PTA) has gained much attention in recent years as a solid catalyst for various alkylation reactions. This research work aims to develop a novel material based on PTA-containing silica gel, which can effectively catalyze LAB synthesis. Sol-gel synthesis of silica gel in the presence of PTA and tetraethyl …

Photoelectrical And Photoelectrochemical Characterization Of The Materials Used In Dye-Sensitized And Perovskite Solar Cells., Pom Lal Kharel

Electronic Theses and Dissertations

Solar energy is one of the most important alternative renewable energy sources to fulfill the increasing demand of energy in the world. Third-generation solar cells like dye-sensitized solar cells, perovskite solar cells, quantum dot solar cells, and organic solar cells are extensively studied to increase their photoconversion efficiency, and ultimately for their large-scale implementation. A dye-sensitized solar cell consists of a photoanode of a mesoporous film of titania sensitized with dye sandwiched with a counter electrode, which is usually a platinum-coated transparent conducting oxide, and a redox couple injected between the photoanode and counter electrode. Doping titania with rare-earth metal …

Design, Synthesis And Application Of Janus Gold Nanoprisms For Directed Self-Assembly., Md. Emtias Chowdhury

Electronic Theses and Dissertations

Colloidal Janus particles that possess more than one type of surface chemistry or functionalities have drawn significant interest due to their enormous potential in bottom-up synthetic strategies for complex superstructures. Moreover, the property of molecular recognition, tunability, and predictability of the DNA-mediated interactions enable a high degree of control over particle assembly to generate highly ordered nanostructures with emergent applications. In this dissertation, we present our works on the synthesis of Janus particles from anisotropic gold nanoprisms, and DNA- mediated assembly of nanoprisms and polymer beads in four major areas: 1) Facet selective asymmetric functionalization of gold nanoprisms for Janus …

The Utilization Of Metal-Ligand Cooperativity For Electrocatalytic Reduction And Catalytic Hydration., Steven Cronin

Electronic Theses and Dissertations

Small molecules are building blocks for developing larger materials. These small molecules could be extremely small, such as hydrogen, or larger such as a nitrile, but their impact on the global economy is massive. This dissertation describes a catalyst for three reactions involving small molecules; 1) the hydrogen evolution reaction, 2) the carbon dioxide reduction reaction, 3) nitrile hydration. The catalyst Zn(DMTH) (DMTH = diacetyl-2-(4-methyl-3-thiosemicarbazonate)-3-(2-pyridinehydrazonato)) use “metal-ligand cooperativity” between the Lewis acid Zn(II) metal ion and an uncoordinated Lewis base nitrogen in the ligand framework to activate substrates. The complex has been analyzed via NMR, UV/Vis, single crystal X-ray crystallography, …

Isolation, Structure Elucidation, And Synthesis Of Natural Products From Marine Cyanobacteria, Keren Solomon

Electronic Theses and Dissertations

This thesis describes the isolation, structure elucidation, and synthesis of natural products from marine cyanobacteria. A crude extract from a cyanobacterium collected in Curacao showed selective affinity for the dopamine D₅ receptor in a screen against a panel of CNS receptors. Due to the high similarity of the D₅ and D₁ receptor, to date there are no known ligands that differentiate them. Attempts to purify the compound responsible for this affinity led to the isolation of the known compound caylobolide A. A second extract from a cyanobacterium collected in Panama underwent bioassay-guided fractionation and yielded the novel …

(Pseudo)Phase Tuning In The Service Of Synthesis: Technologies For Sustainable Catalysis., Justin Douglas Smith

Electronic Theses and Dissertations

Strategies for manipulation of chemical phases were explored with emphasis on synthetic chemistry applications. Some strategies are fairly divergent from their origin, but all ultimately began from investigations of micellar media. Accordingly, Chapter 1 reviews the historical development of micellar catalytic processes. Chapters 2 and 3 detail development of synthetic methods in micellar solutions of designer surfactant PS-750-M. PS-750-M was designed to create benign micellar solutions which effectively mimic toxic organic solvents; it contains a proline-based linker between its hydrophobic and hydrophilic regions which imparts increased polarity to the micellar core. Chapter 2 details an interfacial nucleophilic substitution of perfluoroarenes …

Water Cluster Motifs In Structurally Similar N-(2-Aminoethyl)-1-Methylimidazole-2-Carboxamide Metal Complexes: Synthesis, Characterization, Thermal And Electrical Properties., Nina Saraei

Electronic Theses and Dissertations

Water is a remarkable molecule and in all of its forms exhibits an amazing collection of properties and functions. Besides its crucial role in life and many technological processes, water displays some unusual and anomalous properties at various interfaces and under different conditions. Although the role of hydrogen-bonding interactions and their fluctuations are well known to determine the properties of water, the main obstacle exists in the complexity of correctly describing the interactions between water molecules. The key to understanding the behavior of water is to collect precise structural data of various H-bonded water networks in diverse environments. In this …

Using Tandem Mass Spectrometry And Irmpd Spectroscopy To Determine The Intrinsic Reactions Of Uranyl-Containing Ions, Irena Tatosian

Electronic Theses and Dissertations

Developing a comprehensive understanding of the intrinsic reactivity of uranium-containing species remains an important goal, as it may influence future developments in areas ranging from new approaches to nuclear fuel processing to studies of the migration and fate of the element in the environment. At a more fundamental level, such studies contribute to the understanding of the role that 5-f electrons may play in chemical bonding, the so called “f-electron challenge”. Electrospray ionization (ESI) is an effective way to generate gas-phase complexes containing uranium and uranyl ions for subsequent studies of intrinsic structure and reactivity. Studies in the gas-phase are …

N-Terminal Imine Derivatization For Enhanced De Novo Peptide Sequencing: A Study Of The Fragmentation Pattern Generated From Cid Of Peptide-Imines, Khiry L. Patterson

Electronic Theses and Dissertations

In this work, the fragmentation pattern derived from model peptides derivatized to create N-terminal imines (Schiff bases) were evaluated. Collision-induced dissociation of the protonated peptide-imines ([M+H]⁺) generally produced complete series of the sequence informative a_n and b_n ions, now undoubtedly characteristic of the peptide ion species. A novel product ion was also observed, denoted the y^ǂ ion, determined by IRMPD spectroscopy and density functional theory to be generated from the elimination of the N-terminal amino acid residue despite the N-terminal modification. It was concluded the pathway involved a nucleophilic attack by an amide nitrogen and …

Photocatalytic Carbon Dioxide Reduction With Zinc(Ii) Dipyrrin Photosensitizers And Iron Catalyst, Senan Rasheed

Electronic Theses and Dissertations

Much of the energy used in the United States and around the globe is obtained from petroleum, natural gas, and coal. Photocatalytic CO₂ reduction can be used to transform CO₂ to useful fuels and making fossil fuels more renewable. Input of energy is required, and the sun can provide the required energy for this transformation. Photosensitizer, catalyst, and electron donor are required for photocatalytic CO₂ reduction.

Due to lack of earth-abundant sensitizers, zinc dipyrrin complexes were synthesized by previous group members and have been used as photosensitizers in this research. The ground and excited state electrochemical properties …

Mesoporous Adsorbents For Perfluorinated Compounds, Bertha Lotsi

Electronic Theses and Dissertations

Effective adsorbents for polyfluorinated compounds (PFCs) were successfully prepared. And they were tested in the adsorption of perfluorooctanoic and perfluorooctanesulfonic acids. Bridged silsesquioxanes containing secondary and tertiary amino groups were synthesized by sol-gel condensation of bis[3-(trimethoxysilyl)propyl]amine and bis[3-(methylamino)propyl]-trimethoxysilane in acidic media with surfactants. Obtained materials are mesoporous with a high BET surface area. They combine high structural stability with a high concentration of surface amino groups serving as adsorption sites. Batch adsorption tests demonstrated their extremely high adsorption capacity on PFCs: in some experiments, it reached up to 88% of the adsorbent weight. Adsorption of PFCs changed the surfaces of …

Immobilization Of Phosphotungstic Acid On Silica Surface For Catalytic Alkylation Of Aromatic Compounds, Anastasia Kuvayskaya

Electronic Theses and Dissertations

Superacidic mesoporous materials containing covalently embedded PTA were synthesized by sol-gel method. Tetraethyl orthosilicate (TEOS) and phosphotungstic acid (PTA) were used as precursors in the synthesis, ionic and nonionic surfactants were used as pore-forming agents, the reaction proceeded in acidic media. TEM images revealed mesoporous structure with embedded PTA clusters. FT-IR spectra of obtained materials contained characteristic bands of PTA at 957 cm-1. Synthesized catalysts had high BET surface area and high concentration of acidic sites. Alkylation of 1,3,5-trimethylbenzene by 1-decene demonstrated high catalytic activity. The catalyst obtained with Pluronic P123 as a template was the most effective and resulted …

Computational Quantum Study Of Intermediates Formed During The Partial Oxidation Of Melatonin, Oladun Oladiran

Electronic Theses and Dissertations

Melatonin is a neurohormone produced by the pineal gland in the brain. It functions as an antioxidant to scavenge free radicals. Free radicals are reactive species; they often oxidize the cells leading to oxidative stress which may lead to severe health complications. Reaction of melatonin with free radicals is known to be stepwise, as such the stability of the intermediates can be examined. Thus, the possibility of using melatonin as an in vivo spin trap can be determined. Spin traps allow characterization of unstable radical species using electron spin resonance spectroscopy. In this research, ab initio quantum chemistry techniques were …

Synthesis And Characterization Of Carbon Monoxide Producers Bipyridine Flavonolate Palladium(Ii) And Platinum(Ii) Complexes: Potential Anti-Cancer Agents, Sarah Whitfield

Electronic Theses and Dissertations

Novel designed metal ligand complexes as prodrugs are useful in the effort to find more effective and selective anti-cancer treatments. Carbon monoxide, CO, is known to induce mitochondrial collapse in cancer cells. Herein is described the synthesis of seven novel bipyridine flavonolate palladium(II) and platinum(II) complexes with the property of releasing carbon monoxide, and their characterization with FTIR, UV-Vis, fluorescence, NMR, and ESI mass spectra. Their ability to release carbon monoxide was investigated through oxygenation reaction under various conditions of temperature and light irradiation. The nitroxygenation reaction of the palladium complexes was also studied with nitrosyl hydride, HNO, generated in …

Functional Nanomaterials By Combining Aminooxy Chemistry And Iodine Activation At Momolayer Protected Clusters., Tirtha Raj Sibakoti

Electronic Theses and Dissertations

Aminooxy (-ONH₂) groups are most commonly known for their chemoselective reaction with carbonyl compounds (aldehydes/ketones) under mild reaction conditions. Aminooxy-based click chemistry is a versatile means of ligation as evidenced by broad application in material science, biology, biochemistry, analytical chemistry, and nanoscience. Our work exploits the facile reaction of aminooxy groups presented on the surface of gold (Au) or palladium (Pd) monolayer protected clusters (MPCs) with various aldehydes via oximation reactions, which form the robust oxime ether adducts. The functionalization of hexanethiolate-stabilized Au MPCs with a newly developed trifunctional amine-containing aminooxy alkanethiol ligand by thiol place-exchange affords aminooxylated …

Computational Modeling Of Photolysis And Catalysis Reactions In Vitamin B12-Dependent Enzymes., Abdullah Al Mamun

Electronic Theses and Dissertations

Vitamin B₁₂ is a complex organometallic molecule, the derivatives of which such as adenosylcobalamin (AdoCbl) and methylcobalamin (CH₃Cbl) act as a cofactor in numerous enzymatic reactions. These two biologically active cofactors contain a unique organometallic Co-C σ bond. Important feature of this Co-C bond is that it can be activated by both thermally and photolytically inside the enzymatic environment as well as in the solution. In the case of enzymatic reactions where AdoCbl molecule act as a cofactor, the cleavage of the Co-C bond constitutes the key catalytic step. The most intriguing features of this cleavage is …

Electrochemical Reduction Of Carbon Dioxide And Carbon Monoxide For The Production Of Green Fuels And Chemicals., Jacob M. Strain

Electronic Theses and Dissertations

It has become apparent that closing the carbon cycle on this planet in order to mitigate disastrous consequences of runaway global warming has become one of the most pressing issues of our civilization. One of the ways we need to accomplish this goal is by finding news methods to generate fuels that will be carbon neutral. Renewable fuels and green chemicals will be a major component of closing the carbon cycle and restoring our planet’s ecosystem into a sense of balance. A method that can help achieve this goal is the reduction of CO₂. If CO₂ can …

Controlling Transition Metal-Catalyzed Alkyne Annulations Utilizing Polarized Ynol Ethers, Brandon L. Coles-Taylor

Electronic Theses and Dissertations

Transition metal-catalyzed alkyne annulations have developed into incredibly powerful synthetic tools over there the past quarter century. These reactions provide rapid access to important organic scaffolds such as indole, quinoline, isoquinoline, indene, and isocoumarin scaffolds. Transition metal mediated alkyne annulations have proven invaluable in synthetic fields, such as natural product total synthesis, by offering efficient pathways to otherwise synthetically difficult to access substrates.

Foundational works performed by chemist such as Larock, Ackermann, Satoh, and Miura have been established through relying upon the usage of symmetrical alkynes. When unsymmetrical alkynes are used in annulation processes mixtures of regioisomers are often isolated. …

Iron In Urban Air Pollution, Joseph R. Salazar

Electronic Theses and Dissertations

The processes by which iron is solubilized are largely unknown. There are three hypotheses on how iron is soluble: 1) iron is thought to undergo an acid based solubilization process, 2) iron undergoes an oxidation/reduction process and reduces iron(III) to the more soluble iron(II), and 3) iron is bound to organic molecules, which solubilizes it. The 3 hypotheses on iron water-solubilized are explored by presenting two individual studies.

The first study investigates iron directly from car exhaust. Exhaust particles were collected from 32 vehicles. Iron solubility in these samples ranged from 0%-82% with the average iron solubility being 30%. X-ray …

Instrument And Application Development In Saturation Recovery And Rapid Scan Electron Paramagnetic Resonance, Joseph E. Mcpeak

Electronic Theses and Dissertations

Enhanced signal sensitivity by the use of Rapid Scan (RS) electron paramagnetic resonance (EPR), a technique that allows for much faster magnetic field scans than traditional field-swept techniques, has facilitated improved data acquisition for many types of samples. For example, irradiated fingernails for radiation dosimetry have been studied using RS-EPR, which resulted in substantial decreases in detection limits. Samarium-mediated reduction mechanisms in organic synthesis have been investigated by RS-EPR providing evidence for a radical intermediate. Spectra of organic radicals exhibiting both narrow lines and closely spaced hyperfine interactions have been recorded via RS-EPR. Well-resolved spectra can be recorded at a …

Development Towards An Ethylene Sensing Artificial Metalloenzyme, Mitchell Lee Ellinwood

Electronic Theses and Dissertations

Ethylene (ethene) is the essential ripening hormone for climacteric plants, and consequently its detection and quantification is of considerable interest to the horticulture industry. Its detection however is a non-trivial pursuit, traditionally requiring expensive and inaccessible instrumentation that fail to provide in vivo information about ethylene. A ruthenium based fluorescent probe for the selective detection of ethylene has recently been developed, and it was envisioned that this probe could be made biocompatible by encasing it within a protein scaffold making it an artificial metalloenzyme. To this end biotinylated N-heterocyclic carbenes (NHCs) were synthesized, which can be appended onto the ruthenium …

Volcanic Impact On Stratospheric Chlorine Chemistry And Perchlorate Formation: Evidence From Ice Cores, Joshua Andrew Kennedy

Electronic Theses and Dissertations

Perchlorate, suspected to be chemically formed in both the troposphere and stratosphere, has been recently measured in Arctic snow and ice cores. These comprise both discontinuous snow and ice cores from the Canadian Arctic and a continuous record of perchlorate was compiled from an analysis of Greenland ice cores. While the background perchlorate concentration typically is very low, a few spikes in concentration coinciding with deposition of volcanic sulfate were observed in the Greenland record, suggesting that perchlorate levels in the atmosphere may be impacted by volcanic eruptions. As of yet, no work has been done to investigate the connection …

Technology-Based Culturally Relevant Chemistry Education (Crce), Mercy Adoma Fosu

Electronic Theses and Dissertations

The relevance of chemistry concepts and principles remains a challenge for most students enrolled in college chemistry courses. Part of this problem is the disconnect with what students experience in their every-day lives, and how the material, specifically chemistry content is presented via textbooks, lectures, and laboratory teaching. Moreover, the teaching of general chemistry has traditionally focused on traditional, instructor-centric expository delivery of course materials, that treats students as empty vessels devoid of prior knowledge. Students prior knowledge and experiences are crucial in shaping their understanding of scientific concepts and principles. Even students with relatively low expectations for success in …

Screening Of Catalysts For The Subcritical Water Depolymerization Of Lignin, Balawanthrao Jadhav

Electronic Theses and Dissertations

The current world population is completely rely on the non-renewable resources such as coal, fossils, and natural gas to get the energy, fuel and value-added chemicals. The increasing the demand of utilizing non renewable resources leads to severe problems such as global warming, climate changes, and environmental pollution. The renewable resources such as wind, solar energy, and biomass is an alternative sources to overcome these problems and to save the environment. Biomass made up with the cellulose, hemicellulose, and Lignin. Lignin is a copolymer of phenolic monomers and inexpensive naturally occurring complex material to produce the value-added chemicals and various …

Development And Validation Of Advanced Analytical Methods For Pesticides, Per- And Polyfluoroalkyl Substances, And Opioids In Soil And Drinking Water, Christopher Skaggs

Electronic Theses and Dissertations

Environmental pollution from contaminants is a serious concern in a world where more and more pesticides and pharmaceuticals are being used, sometimes improperly and in excess. Since pesticides are used on practically every crop on Earth, it’s no surprise that these compounds are detected in soil, water, and processed agricultural commodities meant for human consumption. Additionally, because of the ubiquity of pharmaceuticals, specifically opioids, and their inherent addictive properties, these compounds are being over-consumed. Because current waste-water treatments can be insufficient to remove them from water sources, this consumption has led to the detection of these compounds in drinking water. …

Solvolytic Lignocellulosic Biomass Liquefaction, Mustafa Alluhaibi

Electronic Theses and Dissertations

Increasing energy demand, petroleum prices, global warming, and depleting fossil fuel resources are the main challenges faced by the human beings. Many scientists are searching for sustainable and alternative sources of fossil fuels as solutions to these challenges. Lignocellulosic biomass is one of the renewable and eco-friendly abundant sources that has been considered by both academia and industry sectors as a renewable source for bio-oil and chemicals. Direct liquefaction of biomass in the sub-/super-critical solvent has considered a practical method to convert lignocellulosic material into liquid fuel. However, undesirable properties such as poor stability, low energy value, and high acidity …

Characterization Of Naturally Derived Polymer By Oxidative, Thermal, And Spectrometric Methods, Ranen Roy

Electronic Theses and Dissertations

Extensive use of fossil fuel for different purposes has resulted in significant depletion of it at an alarming rate. Therefore, a potential and sustainable alternative source are badly needed at this moment. Nowadays, lignocellulose biomass is appealing to much interest by the researchers because of its potential nature as a renewable carbon source. It is the most abundant renewable source which is composed of cellulose, hemicellulose, and lignin. Among them, lignin is considered the 2nd most abundantly natural polymer after cellulose which comprises 10-30 % of biomass depending on the source and the environment. Lignin is a three-dimensional cross-linked organic …

Antidiabetic Activity Of Cissus Rotundifolia Plant Growing In Saudi Arabia, Saad Ali Alshehri

Electronic Theses and Dissertations

Diabetes mellitus (DM) is a metabolic disease characterized by high levels of blood glucose resulting from defects in insulin production or action. A world-wide increase in the diabetes rate is projected to reach pandemic levels over the next 10-20 years. Current data shows that high numbers of the population in Saudi Arabia suffer from diabetes and prediabetes. Non-traditional treatments of diabetes from medicinal plants has shown potential antidiabetic activity. A considerable percentage of the population still prefer or use medicinal plants as a treatment or supplement to traditional medicine. Cissus rotundifolia (family Vitaceae) is a known plant in southwestern Saudi …

Implementing And Assessing The Use Of A New Strategy For Training Chemistry Graduate Teaching Assistants, Amanda Hyett

Electronic Theses and Dissertations

Graduate teaching assistants (GTAs) largely contribute to undergraduate education but are often underprepared for their role as educators. Most graduate students attend graduate school to perform research and are then asked to teach for the first time without sufficient pedagogy training. To assist in increasing the GTAs pedagogical knowledge, a scenario-based activity series was developed and implemented for first- and second-year GTAs. Developing scenario-based scenarios from actual laboratory events provided GTAs with the opportunity to practice prior to engaging in the laboratory classroom. The Teaching Assistant Intervention Activities (TAIAs) included topics such as interpersonal skills and behaviors, group process, working …

Scavenger Hunt: The Search For Sulfur Mustard-Neutralizing Compound In 2-Chloroethyl Ethyl Sulfide (Cees) Treated Human Keratinocyte (Hacat) Epithelial Cells, Tanner Diemer

Electronic Theses and Dissertations

Sulfur mustard is a highly toxic and dangerous vesicant that has been utilized as a chemical warfare agent (CWA) since World War I. Despite its extensive history, an effective antidote to sulfur mustard exposure still does not exist. With detectable levels of unreacted sulfur mustard lasting days after initial contact, a window of opportunity exists to administer a “scavenger” to affected individual immediately and in the days following exposure in hopes of reducing harm by neutralizing unreacted sulfur mustard. For this strategy to be effectively implemented, it is essential to identify a candidate compound with excellent affinity towards sulfur mustard …