Physical Sciences and Mathematics Commons^™

Quantum Chemical Studies Of Noncovalent Interactions And Multicenter Bonds Utilizing Local Vibrational Modes, Vytor Oliveira

Chemistry Theses and Dissertations

Noncovalent interactions play an important role for the design of novel drugs, better catalysts, synthesis of complex supramolecular structures, and so on. To develop new materials, a well-founded knowledge of how to control the strength of these interactions is desirable. Despite the many investigations done so far, a quantitative assessment of the intrinsic strength of most types of noncovalent interactions is still missing. Recently and for the first time, the Konkoli-Cremer local modes analysis was successfully used to probe the intrinsic strength of hydrogen and pnicogen bonds. We extended these investigations to more than 300 halogen and chalcogen bonds. A …

Metal Oxyhalides And Halides For Use As Electrode Materials In Li-Ion Batteries, Jonathan Mark Powell

Doctoral Dissertations

Synthesis of select metal halides and oxyhalides are explored in the form of direct fluorination using a fluidized bed reactor system, direct chlorination using hydrogen chloride gas, and a degradation dehydration reaction as novel methods towards the synthesis of these select metal halides and oxyhalides. The flexibility of the direct fluorination technique is demonstrated by the ability to vary the degree of fluorination based on the reaction conditions of temperature, time, and fluorine concentration. Conversion electrodes in the form of metal halides and metal oxyhalides are investigated as both anode and cathode materials for lithium ion batteries. The resulting electrochemical …

Multi-Scale Assembly Methodologies Of Poly(3-Hexylthiophene) Derivative Systems For Enhanced Optoelectronic Anisotropy, David William Bilger

Master's Theses

Conjugated polymers represent a class of semi-conducting materials with numerous applications in optoelectronic devices, including organic light-emitting diodes, field-effect transistors, and photovoltaics. Because of the numerous advantages of macromolecular systems, including solution processing and mechanical flexibility, conjugated polymers have become a burgeoning field of research with the hopes of producing cost-effective solution-based electronics. Importantly, optoelectronic device performance is heavily influenced by conjugated polymer backbone orientation and overall thin film morphology. As such, the processing conditions of these systems are important to the construction of high- performance optoelectronics. Polythiophenes are model conjugated polymers that have been studied extensively in halogenated organic …

Cadmium Chloride Dimensionality Changes From Ortho-Substituted Anilines, Stephanie Cernicek

Dissertations

Inorganic-organic hybrid metal halide materials have been of great interest recently due to the useful properties offered by such a combination. The inorganic portions usually consisting of MX₆^2- subunits, (M = Pb, Sn, Cd, Cu; X = Cl, Br, I) most often form 2-D perovskite layers where the metals are bridged by corner sharing halides. The organic portion, usually consisting of primary amines or anilines provides a template for the inorganic framework and in some cases, dictates the dimensionality (2-D, 1-D, 0-D) of the network. These materials have various applications in host-guest chemistry catalysis, and gas storage, or …

Ion Separations: Achieving Selectivity Through Rational Design In Solvent Extraction And Crystallization Systems, Neil Justin Williams

Doctoral Dissertations

The selective separation of ions from aqueous solutions has been a difficult challenge to address in the separation sciences. The difficulties associated with selective separations of ions are due to a multitude of chemical and physical differences between them. Additionally, the term ions encompass both positively charged cations and their counter parts the negatively charge anions. The work covered in this dissertation discusses the difficulties encountered during the selective separation of both oxoanions and cations. Apart from the Introduction Chapter 1 and Conclusion Chapter 10, the selective separations oxoanions and cations will be discussed separately with the dissertation being …

Pro- And Antioxidant Activity Of Selenomethionine: Preventative Measures Against Metal-Mediated Dna Oxidation, Austin Mroz

Graduate Theses - Chemistry and Biochemistry

DNA damage by reactive oxygen species (ROS) has been linked to several diseases.

Antioxidants are one method of combating the effects of ROS; selenium-containing antioxidants have shown promise in alleviating in vitro DNA damage. This study aims toelucidate the effects of selenomethionine (SeMet) on DNA damage mediated by Cu(II),Fe(II), or Cr(III) metal ions. HPLC analysis was used to probe the oxidative effects of SeMet by quantifying the oxidative damage marker, 8-hydroxy-2’-deoxyguanosine. Prior literature indicates that the antioxidant activity of SeMet is potentially concentration dependent; however, HPLC results in this study indicate a metal-ion dependency. In order to better understand the …

An Electrochemical Characterization Of A Vanadium-Based Deoxydehydration Catalyst, Joel Eric Baker

Graduate Theses and Dissertations

Alternative methods for the conversion of polyols into olefins, be it for carbon storage or hydrocarbon fuel production, have become prevalent in today’s chemical industry. One process in particular, deoxydehydration (DODH) has been proven effective in taking sustainable biomass derivatives and converting them through the utilization of various homogenous metal catalysts. While this process may show productive yields and material conversion, it is hindered by the need of a sacrificial reductant. This makes a novel process economically unviable and relatively unused outside of scientific research. That fact begs the question: Can the process be improved? It is proposed here that …

Persistence In Stem: Development Of A Persistence Model Integrating Self-Efficacy, Outcome Expectations And Performance In Chemistry Gateway Courses, Shalini Srinivasan

Theses and Dissertations

STEM persistence has been an important issue, especially in the context of underrepresented groups based on race and gender. Researchers in the last decade or so have been examining the powerful impact that affective and cognitive factors can exert individually on performance and persistence. It is only reasonable to hypothesize that combining affective and cognitive measures would offer a more thorough understanding of factors that impact students’ performance and STEM persistence. Evaluating these outcomes in the context of gateway courses is particularly essential due to the non-negligible percentage of students who drop out of these courses or decide to change …

Synthesis Of 4-Iodo-3-(2-Iodoaryl) And 4-Bromo-3-(2-Bromoaryl) Sydnones And Their Reactions With Sodium Sulfite, Sodium Borohydride, And Iodine Monochloride, Kyle Jacob Liddy

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One goal of the Turnbull research group has been the synthesis of dihalogenated arylsydnones; i.e. sydnones with halogen substitution on the sydnone ring itself, as well as at the position on the aryl ring ortho to the sydnone. Further, it has been of interest to explore the reactivity of these compounds, once obtained. The present study examined the synthesis of 4-iodo-3-(2-iodoaryl)-, or “diiodo”, and 4-bromo-3-(2-bromoaryl)-, or “dibromo”, sydnones and the reactions of these compounds with Na2SO3 (sodium sulfite) and NaBH4 (sodium borohydride) to create a better understanding of the reactivity of diiodo and dibromo arylsydnones in general. Additionally, the reactivity …

Tying The Knot: Applications Of Topology To Chemistry, Tarini S. Hardikar

Honors Theses

Chirality (or handedness) is the property that a structure is “different” from its mirror image. Topology can be used to provide a rigorous framework for the notion of chirality. This project examines various types of chirality and discusses tools to detect chirality in graphs and knots. Notable theorems that are discussed in this work include ones that identify chirality using properties of link polynomials (HOMFLY polynomials), rigid vertex graphs, and knot linking numbers. Various other issues of chirality are explored, and some specially unique structures are discussed. This paper is borne out of reading Dr. Erica Flapan’s book, When Topology …

Using Nucleotide Analogs As Biochemical Probes To Evaluate The Mechanisms Involved In Translesion Replication By A High Fidelity Dna Polymerase, Anvesh Dasari

ETD Archive

Translesion DNA synthesis (TLS) allows DNA polymerases to incorporate nucleotides opposite and beyond damaged DNA. This activity is an important risk factor for the initiation and progression of genetic diseases including cancer. My study evaluates the ability of a high-fidelity DNA polymerase to perform TLS with 8-oxo-guanine, a pro-mutagenic DNA lesion formed by reactive oxygen species. Using modified purine and non-natural indole analogs as biochemical probes, I have evaluated the influence of desolvation, hydrogen bonding interactions, and shape complementarity towards nucleotide binding and incorporation opposite the miscoding lesion 8-oxo-guanine by the high fidelity gp43exo- DNA polymerase. In Chapter II, I …

Liposome-Coated Magnesium Phosphate Nanoparticle For Delivery Of Cytochrome C Into Lung Cancer Cells A549, Weizhou Yue

University of the Pacific Theses and Dissertations

Proteins are large biomolecules that have great therapeutic potential in treating many human diseases. However, chemical/enzymatic degradation, denaturation, and poor penetration into cells are some of the challenges for clinical use of intracellular proteins.

Previously, our group has developed cationic lipid-coated magnesium phosphate nanoparticle (LP MgP NP-CAT) formulations to enhance the intracellular delivery of the negatively charged protein catalase. The goal of the current research is to develop a formulation to deliver cytochrome c (CytC), a positively charged protein into lung cancer cells A549. Specifically, this thesis research prepares and tests liposome-coated magnesium phosphate nanoparticle for delivery of cytochrome c …

Synthetic Methods For Ester Bond Formation And Conformational Analysis Of Ester-Containing Carbohydrates, Sven Hackbusch

University of the Pacific Theses and Dissertations

This dissertation encompasses work related to synthetic methods for the formation of ester linkages in organic compounds, as well as the investigation of the conformational influence of the ester functional group on the flexibility of inter-saccharide linkages, specifically, and the solution phase structure of ester-containing carbohydrate derivatives, in general.

Stereoselective reactions are an important part of the field of asymmetric synthesis and an understanding of their underlying mechanistic principles is essential for rational method development. Here, the exploration of a diastereoselective O-acylation reaction on a trans-2-substituted cyclohexanol scaffold is presented, along with possible reasons for the observed reversal of stereoselectivity …

Improvement And Development Of Analytical Forensic Methods: Arson Investigation And Drug Detection In Fingerprints And Hair, Sarah Anne Glenn

Electronic Theses and Dissertations

Forensic science is the cornerstone of criminal investigations. Due to the overexposure of forensic science in the media, the true nature of forensic science is often overlooked. Forensic science is a rigorous exacting science that applies methods developed in the wider scientific community to the analysis of evidence collected from crime scenes. As far back as the 6th century people were using forensics to solve crimes. Since then the science behind forensic science has increased exponentially with new methods being researched and developed. This research aims to address two of the larger subsections of forensic science, arson and drug detection. …

Further Development Of Raman Spectroscopy For Body Fluid Investigation : Forensic Identification, Limit Of Detection, And Donor Characterization, Claire K. Muro

Legacy Theses & Dissertations (2009 - 2024)

The challenges to forensic body fluid analysis have placed limitations on the type of information that investigators can acquire and how that information can be collected. In recent years, Raman spectroscopy has proven itself useful for characterizing body fluids. In 2008, a large-scale investigation was undertaken to explore the use of Raman spectroscopy as a means of identifying body fluids. This work resulted in multidimensional Raman spectroscopic signatures for the five main body fluids: semen, peripheral blood, saliva, vaginal fluid, and sweat. These studies were incredibly successful and created the foundation for years of continued research. Accordingly, the studies included …

Coordination Chemistry Of Carboranes And Furan Ligands On Transition Metal Cluster Complexes, Emmanuel Joseph Kiprotich

Theses and Dissertations

Chapter 1 presents the most relevant literature in the field of carborane chemistry. The focus is on icosahedral carboranes and the different methods of boron or carbon atoms substitution and functionalization. The direct addition of transition metal to boron atoms is covered in detail as well as strategies for cage opening of icosahedral carboranes.

Chapter 2 reports the preparation of some of the first polynuclear metal carbonyl cluster complexes where the closo-carborane cage: o-C₂B₁₀H₁₂ serves as a ligand on the face of one (Os₃(CO)₉(µ₃-4,5,9-C₂B₁₀H_{10 …}

The Synthesis Of 3,5-Difluorobenzophenone Derivatives And Their Corresponding Peek Copolymers, Rachael Stuck

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Poly(aryl ether ketone)s (PAEK) are high performance thermoplastics, which are chemically robust, semi-crystalline, and stable at high temperatures. Of the family of PAEKs, poly(ether ether ketone) (PEEK) is a well-known semi-crystalline thermoplastic widely used for electronics, energy, industrial, and medical applications due to its resistance to solvents, radiation, heat, and other environmental factors. The traditional PEEK is prepared from 4,4’-difluorobenzophenone (2) and disodium hydroquinone. However, a challenge is processability, since due to its highly crystalline nature, PEEK possesses very limited solubility. An approach to solve these issues is to pre-functionalize PEEK polymers synthesized by nucleophilic aromatic substitution from 3,5-difluorobenzophenone (1) …

Multiscale Modeling Of Carbon Nanotube Synthesis In A Catalytic Chemical Vapor Deposition Reactor, Jonathan Troville

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The bottom-up analysis of Carbon Nanotube synthesis is not well understood. Specifically, the question as to how carbon adsorbs to a substrate inclusive of a supported catalyst may lead to the energetically favorable structure of a hexagonal close- packed structure along the wall, or walls, of the tube. A first time simulation using COMSOL Multiphysics has been generated in order to capture the gas-phase mech- anism which leads to carbon production. It is thought that the carbon adsorbs and the walls are formed from the bottom up and the inside out for multi-wall CNTs. The studies involved accurately setting up …

Antimicrobial Activity Of Fractionated Borohydride-Capped And Electrochemical Colloidal Silver, Marjorie M. Markopoulos

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Silver nanoparticles (AgNPs) and ionic silver (Ag+) are known to be broad-spectrum antimicrobial agents. Recent studies show these agents may be an alternative to the most widely used drinking water disinfectant, chlorine. Chlorine is a toxic industrial chemical with a lethal concentration of 430 ppm after 30 minutes. Additionally, chlorine can react with naturally occurring materials to produce a number of disinfection byproducts such as chloroform and trihalomethanes. Some of these byproducts pose cancer risks in addition to other negative impacts to human health. These would be eliminated with the use of Ag+ or AgNPs. The main goal of this …

The Synthesis And Characterization Of Double And Triple Tethered Indeno[2.1-C]Fluorendiones, Daniel K. Greene

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A series of terephthalate esters was synthesized via a Diels-Alder reaction between 2,5-dicarboethoxy-3,4-diphenylcyclopentadienone and various alkynes in order to study reaction conditions necessary to synthesize poly(indeno[2,1-c]fluorene-5,8-dione)s. Diethyl 2,3-diphenyl-5-butylterephthalate, 1,4-bis(3,4-diphenyl-2,5-di(ethoxycarbonyl) phenyl)butane and N,N,N-tris(3,4-diphenyl-2,5-di(ethoxycarbonyl)phenylmethyl)amine were synthesized and characterized by IR, 1H NMR, 13C NMR, 13C NMR DEPT135 spectroscopies as well as elemental composition. Hydrolysis conditions of the terephthalates using potassium hydroxide were also investigated. It was found that large stoichiometric equivalents of base coupled with reaction times over twenty-four hours afforded only partially hydrolyzed products. The synthesis of 6-butylindeno[2,1-c]fluoren-5,8-dione was successfully carried out by the sulfuric acid catalyzed, intramolecular, Friedel-Crafts cyclization of …

Hydrothermal Atomic Force Microscopy Investigation Of Barite Growth: The Role Of Spectator Ions In Elementary Step Edge Growth Kinetics And Hillock Morphology, Sarah A. Jindra

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To better understand the role of spectator ions in barite growth, the kinetics of step edge growth on barite (001) surfaces were studied under various salt solutions. Hydrothermal Atomic Force Microscopy (HAFM) was used to investigate the effect of background electrolytes (NaCl, NaBr and NaNO₃) as a function of saturation index and ionic strength (I) on barite growth sourced at dislocations at 108 ^oC. Results show that hillock morphology is affected by I, as well as type of anion, where the prevalence of steps aligned on the [010] direction is highest under Cl^{- …}

Synthesis Of Alkyl Substituted Phenylated Poly(Ether Ether Ketone Ketone)S, Matthew Cerone

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A phenylated bis(fluorobenzoyl) monomer, 5-hexyl-2,3-diphenyl-1,4-bis(fluorobenzoyl)benzene, was synthesized via a four-step process. The first three compounds synthesized were diethyl 5-hexyl-2,3-diphenyl-1,4-benzenedicarboxylate, 5-hexyl-1,4-bis(hydroxymethyl)-2,3-diphenylbenzene and 5-hexyl-2,3-diphenyl-1,4-benzenedicarboxaldehyde. The final step involved the reaction of the Grignard formed from p-bromofluorobenzene with the dialdehyde to yield a diol intermediate which was oxidized to the bis(fluorobenzoyl) monomer by use of a Jones oxidation. The monomer was polymerized by nucleophilic aromatic substitution (NAS) with bisphenol-A, resorcinol, and hydroquinone in N-methyl-pyrrolidone (NMP) to yield novel, phenylated PEEKKs. The number-average molecular weights (Mn) for the polymers were found to be 35,700 g/mol, 34,800 g/mol and 28,000 g/mol, respectively and the weight-average …

Synthesis Of 4-Iodo-3-(2-Iodoaryl) And 4-Bromo-3-(2-Bromoaryl) Sydnones And Their Reactions With Sodium Sulfite, Sodium Borohydride, And Iodine Monochloride, Kyle Jacob Liddy

Browse all Theses and Dissertations

One goal of the Turnbull research group has been the synthesis of dihalogenated arylsydnones; i.e. sydnones with halogen substitution on the sydnone ring itself, as well as at the position on the aryl ring ortho to the sydnone. Further, it has been of interest to explore the reactivity of these compounds, once obtained. The present study examined the synthesis of 4-iodo-3-(2-iodoaryl)-, or "diiodo", and 4-bromo-3-(2-bromoaryl)-, or "dibromo", sydnones and the reactions of these compounds with Na2SO3 (sodium sulfite) and NaBH4 (sodium borohydride) to create a better understanding of the reactivity of diiodo and dibromo arylsydnones in general. Additionally, the reactivity …

Incorporation Of Indeno[2,1-C]Fluorenes Into Polymers Via Nucleophilic Aromatic Substitution, Nathaniel Brackett

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A difluoro indeno[2,1-c]fluorene monomer was synthesized by a four-step process. The first compound synthesized by a two-step process was 2,5- bis(ethoxycarbonyl)-3,4-di(4-fluorophenyl)cyclopentadienone. The next two compounds synthesized were diethyl 2,3-bis(fluorophenyl)-5-hexylterephthalate and 2,3- bis(fluorophenyl)-5-hexylterephthalic acid. The final step involved an intramolecular Friedel-Crafts acylation of the terephthalic acid derivative to form 3,10-difluoro-5,8- dioxo-5,8-dihydro-6-hexylindeno[2,1-c]fluorene. The difluoro monomer was reacted in a series of nucleophilic aromatic substitution (NAS) polymerization reactions with bisphenol-A in N-methyl-pyrrolidone (NMP) in an attempt to form novel poly(ether ether ketone ketone)s containing the indeno[2,1-c]fluorene structure. Analysis of the product by NMR and TLC showed the reaction was unsuccessful and the difluoro …

Hydrothermal Atomic Force Microscopy Investigation Of Barite Growth: The Role Of Spectator Ions In Elementary Step Edge Growth Kinetics And Hillock Morphology, Sarah A. Jindra

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To better understand the role of spectator ions in barite growth, the kinetics of step edge growth on barite (001) surfaces were studied under various salt solutions. Hydrothermal Atomic Force Microscopy (HAFM) was used to investigate the effect of background electrolytes (NaCl, NaBr and NaNO3) as a function of saturation index and ionic strength (I) on barite growth sourced at dislocations at 108 oC. Results show that hillock morphology is affected by I, as well as type of anion, where the prevalence of steps aligned on the [010] direction is highest under Cl- There is a modest increase in kinetic …

Investigating Potential Pollutant Sources Causing Lack Of Biodiversity In Lytle Creek And Indian Run, Amira Moayad Alsenbel

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Limited macroinvertebrate biodiversity in Lytle Creek that runs through downtown Wilmington, Ohio has been documented over decades with the lowest in Lytle Creek at Sugar Grove Cemetery. Lytle Creek, a tributary of the Little Miami River, is a conduit for storm water and wastewater from an airport, downtown storm water with input from local businesses, and a wastewater treatment plant. This study was conducted to see if heavy metal pollution in the sediment, water quality, and Escherichia coli (E. coli) could be contributing factors in reduced macroinvertebrate populations. Eight sites were chosen for sediment sampling to measure trace metals. Mercury …