Digital Commons Network^™

Cellulose Nanofiber-Reinforced Impact Modified Polypropylene: Assessing Material Properties From Fused Layer Modeling And Injection Molding Processing, Jordan Elliott Sanders

Electronic Theses and Dissertations

The purpose of this research was to investigate the use of cellulose nanofibers (CNF) compounded into an impact modified polypropylene (IMPP) matrix. A IMPP was used because it shrinks less than a PP homopolymer during FLM processing. An assessment of material properties from fused layer modeling (FLM), an additive manufacturing (AM) method, and injection molding (IM) was conducted. Results showed that material property measurements in neat PP were statistically similar between IM and FLM for density, strain at yield and flexural stiffness. Additionally, PP plus the coupling agent maleic anhydride (MA) showed statistically similar results in comparison of IM and …

Study Of 2,5-Diaminoimidazolone, A Mutagenic Product Of Oxidation Of Guanine In Dna, Hannah Catherine J. Pollard

Electronic Theses and Dissertations

2,5-diaminoimidazolone (Iz) is an important product of a 4-electron oxidation of guanine. The present research focuses on the mechanisms of formation of Iz via pathways initiated by guanine oxidation by one-electron oxidants (OEOs) generated by X-ray radiolysis in aqueous solutions. The kinetics of formation and yields of Iz in reactions of native highly polymerized DNA with different OEOs have been compared using an HPLC-based quantitative analysis of low-molecular products generated from the reaction of DNA-bound Iz with primary amines. Mechanisms of Iz formation in DNA have been investigated including oxygen and superoxide dependence as well as the hypothesis that 8-oxo-G, …

Water Chemistry Dynamics In Four Vernal Pools In Maine, Usa, Lydia H. Kifner

Electronic Theses and Dissertations

Vernal pools are small seasonal wetlands that are a common landscape feature that contribute to biodiversity in northeastern North American forests. However, even basic information about their biogeochemical functions, such as carbon cycling, is limited. Dissolved gas concentrations (CH₄, CO₂) and other water chemistry parameters were monitored weekly at the bottom and surface of four vernal pools in central and eastern Maine, USA, from April to August 2016. The vernal pools were supersaturated with respect to CH₄ and CO₂ at all sampling dates and locations. Concentrations of dissolved CH₄ and CO₂ ranged …

Chemoselective Reagents For Derivatization Of Trace--Level Volatile Carbonyl Compounds Using A Microreactor Approach., Mumiye A. Ogunwale

Electronic Theses and Dissertations

Detection and analysis of trace level volatile aldehydes and ketones has become a significant research frontier because of the applicability for environmental monitoring and assessment, noninvasive diseases diagnosis, and in food safety assessment for the US Food and Drug Administration. The number of derivatization reagents for detection of aldehydes and ketones has increased considerably over the last decade. However, the majority of these derivatization reagents are not efficient in derivatizing unsaturated carbonyl compounds due to the presence of electron withdrawing groups adjacent to the reactive functional moieties making them insufficiently nucleophilic. The analysis of trace-level carbonyl compounds challenges existing analytical …

Artificial Olfactory System For Multi-Component Analysis Of Gas Mixtures., Alexander Aleksandrovich Larin

Electronic Theses and Dissertations

Gas analysis is an important part of our world and gas sensing technology is becoming more essential for various aspects of our life. A novel approach for gas mixture analysis by using portable gas chromatography in combination with an array of highly integrated and selective metal oxide (MOX) sensors has been studied. We developed a system with small size (7 x 13 x 16 inches), low power consumption (~10 W) and absence of special carrier gases designed for portable field analysis (assuming apriori calibration). Low ppb and even sub-ppb level of detection for some VOCs was achieved during the analysis …

Evaluating Ligand Assisted Activation Of Small Molecules Through Proton Reduction And Alcohol Oxidation., Rahul Jain

Electronic Theses and Dissertations

Hydrogen is a potential alternate to the carbon fuels to meet the future demands for energy in an eco-friendly manner. Hydrogen produced by the electrolysis of water is stored in fuel cells which on demand can be converted into electrical energy upon the reaction with oxygen. In the quest for economically viable electrocatalysts for hydrogen evolution, the work in this dissertation describes evaluation of nickel based catalysts coordinated to redox active ligands, dialkyl/diarylphosphine benzenethiol and bis(thiosemicarbazone) for their ability to generate hydrogen with external acids as a proton source. A nickel complex with the benzenethiol ligand framework follows a traditional …

Creating Renewable Tunable Polymers From Hydroxymethylfurfural, Meredith C. Allen

Electronic Theses and Dissertations

The research here deals with the conversion of 5-hydroxymethylfurfural (HMF) into a tunable polymer. HMF is a known derivative that can be acquired from biomass via hydrolysis of cellulose followed by isomerization and finally selective dehydration. The process considered here is being developed to create tunable polymers from HMF and involves several different steps, three of which are covered here. The first step, an etherification, is the reaction of HMF with an alcohol. This step is significant because in this step the R-group from the alcohol is added to HMF and the branching portion formed is carried over to the …

Renewable Hydrogels From Norbornene-Functionalized Carboxymethyl Cellulose And A Short Dithiol Crosslinked Via A Thiol-Ene Reaction, Thomas Mcoscar

Electronic Theses and Dissertations

Cellulose-based hydrogels - three dimensional "solid" structures composed primarily of liquid water and held together by an interconnected polymer network - were created by first functionalizing carboxymethyl cellulose (CMC), a cellulose derivative, with carbic anhydride in a basic aqueous reaction with the intent of developing novel hydrogels from renewable materials. The product of this reaction, carbic CMC (cCMC), had a new norbornene group as a subsection of the carbic group. Norbornene is a reactive alkene structure that allows for further chemistry with cCMC, such as crosslinking. cCMC was crosslinked with 2,2'-(ethylenedioxy)diethathiol to create hydrogels using a water-soluble, UV-sensitive radical initiator …

A Novel Method For Synthesis Of Hydroxytyrosol, Emmanuel Onobun

Electronic Theses and Dissertations

Hydroxytyrosol, 3,4-dihydroxyphenolethanol, a naturally occurring polyphenol most common in olive tree (Olea europaea), is one of the most effective member of the polyphenols family, because of its remarkable antioxidant activity, its ability to inhibit oxidation of low density lipids (LDL), and its protection against DNA oxidative damage. Hydroxytyrosol, which is widely used in cosmetics and food supplements industries, can be purchased as an olive oil extract that contains low concentration of hydroxytyrosol besides other polyphenols. The price and low natural abundance of hydroxytyrosol make alternative synthetic sources very attractive. In this research, a novel method for the synthesis of pure …

Water-Soluble Pd And Pd-Alloy Nanoparticles As Catalysts In Biphasic Solvent., Shekhar Bhama

Electronic Theses and Dissertations

This dissertation shows the chemical synthesis of Pd and Pd-alloy nanoparticles (NPs) and their hydrogen and thermal stabilities for applications in the homogeneous and pseudo-homogeneous catalysis of organic reactions. Mainly, this dissertation describes 1) the chemical synthesis of Pd, PdPt, PdAu and Cu-Pd core-shell NPs coated with various organic ligands (thiols, amines and citrate), with different metal compositions in different synthetic environment, 2) the stability of solutions containing various NPs in the presence of hydrogen or varying temperatures, 3) the evaluation of the catalytic activity of Pd, PdPt, PdAu and CuPd NPs for hydrogenation/isomerization of allylic alcohols, and 4) the …

Transient Absorption Studies Of Cdse Nanocluster Passivated With Phenyldithiocarbamate Ligands., Yizhou Xie

Electronic Theses and Dissertations

Semiconductor nanocluster (SCNC) research is a rapidly growing field driven by the promising fact that properties of such materials can be tailored by modifying their size, shape, and structure. Combination of nanocluster and organic ligands provides even wider possibilities of design and development of effective and task-specific nanostructures. Understanding of and, eventually, control of energetics, interfacial interaction, and photoinduced processes in such highly heterogeneous structures is critical to invention of novel materials including those in photovoltaic devices. In the newly established Ultrafast Laser Facility (ULF), transient absorption pump-probe spectroscopy (TAPPS) has been employed to investigate the electron transfer (ET) and …

Controlled Electrochemical Synthesis Of Single One-Dimensional Metal Nanochains Across Microgap Electrodes., Amareshwari Konutham

Electronic Theses and Dissertations

This study mainly focuses on the fabrication of single one dimensional (1D) NP chains across the 5-micron gap of Au two electrode devices (TED). This has been achieved by electrochemical deposition of Ag onto the two electrodes, soaking the TED in 0.1 M Cetyltrimethyl ammonium bromide for 2-3 hours, and then close monitoring of the current as a function of time while a voltage across the two Ag coated Au electrodes in air. One dimensional Ag nanoparticle chain formation occurred by oxidation of Ag to Ag⁺ at the positive electrode followed by movement of Ag⁺ ions to the …

Ab Initio And Semi-Empirical Calculations Of Cyanoligated Rhodium Dimer Complexs, Yazeed Asiri

Electronic Theses and Dissertations

Molecular modeling, using both ab initio and semi-empirical methods has been undertaken for a series of dirhodium complexes in order to improve the understanding of the nature of the chemical bonding in this class of homogeneous catalysts. These complexes, with carboxylamidate and carboxylate ligands, are extremely functional metal catalysts used in the synthesis of pharmaceuticals and agrochemicals. The X-ray crystallography shows anomalies in the bond angles that have potential impact on understanding the catalysis. To resolve these issues, minimum energy structures of several examples (e.g. Rh₂(NHCOCH₃)₄, Rh₂(NHCOCH₃)₄NC, Rh …

Role Of Nanoparticles In Voltammetric Signal Enhancement Exhibited By Layer-By-Layer (Lbl) Gold Nanoparticle-Modified Screen-Printed Carbon Electrodes (Spces), Ben K. Ahiadu

Electronic Theses and Dissertations

Screen-printed electrodes (SPEs) have found wide use as sensing platforms due to their simple fabrication, customizability in terms of geometry and composition, and relatively low cost of production. Nanoparticles have been incorporated in or interfaced with SPEs in order to improve sensor response or provide electrocatalytic capabilities. Though nanomaterial-modified SPEs are becoming increasingly common sensing platforms, the benefits provided by nanomaterials are often determined through voltammetric studies with common redox probes, such as ferricyanide. However, recent reports have documented the ferri-/ferrocyanide redox couple to be an unreliable system for characterizing some carbon-based electrodes due to the dependence of its electrochemical …

Homogeneous Ligand-Centered Hydrogen Evolution And Hydrogen Oxidation : Exploiting Redox Non-Innocence To Drive Catalysis., Andrew Z. Haddad

Electronic Theses and Dissertations

Hydrogen is a promising carbon-free fuel / energy carrier and is an essential building block for many industrial and agricultural processes. Rising energy demands have ignited interest in the development of carbon-free and carbon neutral energy sources. In this context, hydrogen is an attractive candidate—being energy-dense, carbon-free—and easily accessible through a two-electron reduction of water. Accordingly, many electrochemical homogeneous catalyst systems have been studied, with a focus on understanding the mechanism of hydrogen evolution proceeding through metal-hydride intermediates. However, there has been a renaissance in hydrogen evolution reaction (HER) catalyst design, with many groups implicating ligand redox non-innocence as a …

Development Of Recyclable Gold Nanoparticles For Routine Benchtop Catalysis In Organic Transformations., Shengzong Liang

Electronic Theses and Dissertations

Homogeneous gold catalysis is a popular research area due to its high efficiency. Various gold catalysts have been utilized in organic synthesis and their reaction mechanisms are also well understood. However, most gold catalysis suffers from high catalyst loading or catalyst decay problems. In addition, homogeneous gold catalysts are not recyclable. These disadvantages have limited their application in large-scale synthesis and also caused a serious waste of this precious metal. A solution for these problems is to use a recyclable heterogeneous gold catalyst. So in this study, with the aim of making gold chemistry greener we successfully used heterogeneous gold …

Functionalized Silica Gel For Adsorption Of Cesium From Solution, Kenneth Marshall Seaton Iii

Electronic Theses and Dissertations

Mesoporous silica gel containing embedded phosphotungstic acid (PTA) was synthesized by sol-gel co-condensation of tetraethyl orthosilicate with PTA in acidic media. The obtained material had high Brunauer-Emmett-Teller Theory (BET) surface area and pore volume. A characteristic band of the Keggin structure of PTA was present in its FT-IR spectrum while its X-ray diffraction patterns were absent. This proved the embedding of PTA on a sub-molecular level and not as a second phase. Acidic sites were determined by neutralization with base in aprotic solvent, followed by titration of the remaining base with an acid. The material demonstrated high adsorption capacity of …

Mechanochemical Synthesis Of Fuels From Sustainable Sources Utilizing Solid Catalysts, Jacob Todd

Electronic Theses and Dissertations

Mechanochemistry requires less solvents which results in less waste generation. The question becomes can we apply mechanochemistry to current chemical reactions and reduce the generation of waste. This process can be simple or can be very extensive resulting in the generation of large amounts of waste and very little product. A significant advantage of mechanochemistry is the reduced need for solvents that would be common place for reactions. Mechanochemistry transfers energy to reagents via impacts from milling media. Energy can be transferred to the reagents no matter their state-of-matter. Much of the current studies in mechanochemistry today are done using …

Time-Resolved Phosphorescence Spectroscopy At Cryogenic Temperatures For The Environmental Analysis Of Polycyclic Aromatic Sulfur Heterocycles In Oil Contaminated Sites., Maha Al-Tameemi

Electronic Theses and Dissertations

The large volume of crude oil released into the Gulf of Mexico by the Deepwater Horizon (DWH) accident has raised considerable concerns over potential ecosystem impacts. The dispersion of harmful oil components into the ocean waters could pose long term risks to flora and fauna. Due to the complexity of oil contaminated sites, the unambiguous identification and quantitation of environmental pollutants often requires the sequence of high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS). A classic example is the analysis of the sixteen polycyclic aromatic hydrocarbons included in the priority pollutants list of the U.S. Environmental Protection Agency (EPA-PAHs). …

A Universal Electrochemical Biosensor For The Detection Of Nucleic Acids Based On A Four-Way Junction Structure, Dawn Mills

Electronic Theses and Dissertations

Electrochemical hybridization sensors have been explored extensively for analysis of specific nucleic acids. However, commercialization of the platform is hindered by the need for attachment of separate oligonucleotide probes complementary to a RNA or DNA target to an electrode's surface. This dissertation demonstrates that a single probe can be used to analyze several nucleic acid targets of different lengths with high selectivity, low cost and can be regenerated in 30 seconds by a simple water rinse. The universal electrochemical four-way junction (4J)-forming (UE4J) sensor consists of a universal DNA stem-loop (USL) probe attached to the electrode's surface and two adaptor …

Measuring And Modeling Nmr And Emission Spectra To Gain New Insight Into Challenging Organic Compounds, Jacob Powell

Electronic Theses and Dissertations

The advancement of theoretical methods in recent years has allowed the calculation of highly accurate spectroscopic parameters. Comparing these values to the corresponding experimental data can allow molecular structures to be elucidated. This dissertation details the use of experimental and theoretical data from nuclear magnetic resonance (NMR) and fluorescence spectroscopy to determine structure. Herein the NMR focus is on measuring & modeling chemical shift anisotropy and one-bond carbon-carbon J-coupling constants (1JCC). The fluorescence analysis models vibrationally resolved fluorescence spectra. Chemical shift anisotropy techniques were used to study two conflicting crystal structures of the n-alkyl fatty acid, lauric acid. These two …

Two-Component Covalent Inhibitors (Tcci) Of The Human Immunodeficiency Virus Reverse Transcriptase (Hiv-Rt), Carlos Ledezma

Electronic Theses and Dissertations

The traditional design of nucleoside reverse transcriptase inhibitors (NRTI's) involves the synthesis of chain-terminated nucleoside analogs. HIV-RT has relatively low fidelity which facilitates mutations that confer resistance towards NRTI's, also, drug promiscuity from NRTI's result in various side-effects that lead to poor patient adherence to treatment. We designed and tested two-component covalent inhibitors against HIV-RT. Our inhibitor design results in higher specificity due to its binary approach, which has previously been used in biosensing applications, where both components are necessary for therapeutic effect, and lower chances for mutagenesis because of its inhibitory action. The TCCI approach results in up to …

Monitoring Crystal Structure Refinements Using Solid-State Nmr Chemical Shift Tensors, Keyton Kalakewich

Electronic Theses and Dissertations

Inclusion of lattice-fields in density functional theory (DFT) methods has enabled the accurate calculation of solid-state nuclear magnetic resonance (SSNMR) chemical shift tensors. Calculated 13C and 15N tensors (i.e. 3 principle values per nucleus) can be used to monitor crystal structure refinements and to select the correct structure from a large population of computationally generated candidates. In this dissertation, chapter 2 describes a methodology to improve established crystal structures from three different diffraction techniques involving geometric refinement monitored using SSNMR tensor values. The calculated 13C tensors for three relatively simple organic compounds (i.e. acetaminophen, naphthalene, and adenosine) are shown to …

Nitrogen-Containing Materials For Mechanochemical Synthesis, Luminescence Analysis, And Heterogeneous Catalysis, David Nash

Electronic Theses and Dissertations

Various inorganic nitrogen-containing materials have been exploited for their different properties. Several nitride materials are commercially attractive due to their mechanical properties making them suitable for ceramic industries and wide bandgaps fitting for use as semiconductor and insulator materials, as well as optoelectronics. Nitride materials can exhibit versatility in applications such as the use of gallium nitride to make blue LEDs, nitrides of titanium and silicon being utilized as medical implants for their chemical inertness and hardness, and the heavy use of boron nitride as a solid lubricant in the cosmetic industry. Amines have been used as nitrogen-containing organic ligands …

Target Based Design And Synthesis Of Heterocycles In The Potential Treatment Of Cancer And Opportunistic Infection, Shruti Choudhary

Electronic Theses and Dissertations

Dose limiting toxicity and development of multidrug resistance by the tumors are the major limitations of current cancer chemotherapy. Microtubule targeting agents (MTAs) are a structurally diverse set of compounds that disrupt microtubule dynamics and exert their anticancer effect. Among the various classes of such agents, the colchicine site binding agents are particularly important as they circumvent the Pgp and β-III tubulin mediated clinical resistance. These resistance mechanisms, when manifested, are a major reason for the failure of clinically used agents such as taxanes and vinca alkaloids. A series of monocyclic pyrimidine analogs were designed and synthesized as colchicine site …

Lignin Transformation And Characterization Of Pyrolytic Products, Eric Amo Boakye

Electronic Theses and Dissertations

Lignocellulosic materials derived from plants have the ability to serve as feedstocks in place of depleting petroleum and coal for production of fuels and chemicals. Lignin forms about 30% of lignocellulosic material, and is the second most abundant non-fossil organic carbon source in the biosphere. However, it is often treated as waste or, in some instances, burned to supply energy. Developing an efficient and environmentally benign method to convert lignin to high value-added aromatic monomers (e.g., guaiacol, vanillin, acetovanillone, and eugenol) for synthesis of polymers is of interest. Mineral bases, such as NaOH and CsOH, or supported-metal catalysts (Pt, Ru, …

The Decline And Recovery Of Thermal Oxidative Stability Of Ultra-Low Sulfur Diesel Blends, Abigail Schoor Cohen

Electronic Theses and Dissertations

Dissertation supervised by Professor Bruce D. Beaver

The oxidative stability of ultra-low sulfur diesel (ULSD) has generally been expected to continuously decline over time. However, recent studies have suggested that it may fluctuate.^1-2 In this study, the oxidative stability of stored commercially purchased ULSD was monitored with a methanol extraction method.³ In this methodology, proposed by Hardy and Wechter, fuel blends are extracted with methanol before and after thermal stressing.⁴ The methanol-soluble layer contains the oxygenated and oxidizable components of the fuel (SMORS) and the change in this mass upon stressing thus represents the oxidative stability of …

Nitric Oxide Release From Poly(Lactic-Co-Glycolic Acid) Nanoparticles And Titanium Alloy, Nina A. Reger

Electronic Theses and Dissertations

Current methods for the treatment of bacterial infection involve the use of systemic antibiotics, which are high concentrations of antibiotics delivered over a long period time. Unfortunately, the use of systemic antibiotics can cause harmful side effects to the patient and increases the possibility for antibiotic resistance. The delivery of antibiotics or alternative antimicrobial compounds, such as nitric oxide, directly to the site of infection would decrease the amount of antibiotic necessary to treat a bacterial infection.

Poly (lactic-co-glycolic acid)/polyvinyl alcohol nanoparticles and a titanium- aluminum-vanadium metal oxide alloy implant were surface functionalized to deliver nitric oxide. Polymer nanoparticles can …

Rationalizing The Band Gap Tunability Of Semiconductors Via Electronic Structure Calculations, Matthew N. Srnec

Electronic Theses and Dissertations

The polymorphs of titanium dioxide and various diamond-like semiconductor materials are promising candidates in photovoltaic solar cell applications. Several of these polymorphs have been studied with experimental and computational methods, which often aim at tuning the electronic structure, particularly the band gap value of the crystalline solid. Prior studies report that the addition of a substituent into the structure of titanium dioxide decreases its band gap value, but the reasons for this are unknown. Possible explanations for the change in band gap involve the substituent atom's crystal radius, electronegativity, and ionization energy. Understanding the cause of these changes will provide …

Design, Synthesis And Biological Evaluation Of Novel Estradiol-Triazole Analogs Targeting Epidermal Growth Factor Receptors In Colorectal Cancer, Faez Alotaibi

Electronic Theses and Dissertations

Colorectal cancer is a life threatening and second cause of death from cancer in the United States. Several proteins (molecular targets) are highly expressed in Colorectal cancer (CRC). Among these molecular targets is Epidermal Growth Factor Receptors (EGFRs) which are overexpressed in cancer cells. Targeting and blocking the downstream signaling could lead to cease cell proliferation and division and hence control the spread of the disease. Molecular modeling is a powerful tool in drug discovery, which has been utilized to design many drug candidates that exhibit biological effect in many disease including cancer. Additionally, pharmacophores such as 1,2,3-triazole showed potency …