Chemistry Commons^™

Effect Of Network Structure On Free Volume And Gas Transport Properties Of Thiol-Ene And Epoxy-Amine Networks, Ramesh Krishnan Ramakrishnan

Dissertations

Network parameters such as cross-link density or intermolecular interactions were used as effective parameters to control polymer chain packing or free volume and thereby control the mass transport properties of networks.

A series of polyethylene glycol (PEG) based thiol-ene elastomeric networks having a broad range of molecular weight between cross-links, M_c, (inverse of cross-link density) was prepared. The specific volume of the networks was studied as a function of temperature and pressure using high pressure dilatometry, and the obtained PVT data was fit using Simha-Somcynsky equation of state (S-S eos) analysis. Fractional free volume, quantified through S-S eos …

Structure-Property Relationships Of Solvent-Cast Organic Thin Films For Model Corrosion Control Coatings, Austin Maples

Dissertations

This dissertation aimed at answering several fundamental questions, specifically: 1) What is the effect of scribing parameters on visual corrosion assessments? 2) What role do molecular weight, residual solvent, and polymer composition have on morphological changes in organic thin films? 3) What alternatives to visual assessments could be implemented to better understand and detect corrosion before macroscopic failure? This research definitively proved that scribes can vary in type and dimensions, and yet are still comparable if the scribe dimensions before exposure are known. Furthermore, it demonstrated that solvents common to a variety of coating industries could become trapped within the …

Application Of Glycosyl Imidates And Nitrates In Carbohydrate Synthesis, Tinghua Wang

Dissertations

Carbohydrates are the most abundant molecules among the four essential classes of biomolecules that also include nucleic acids, lipids and proteins. Unlike proteins and nucleic acids, which follow template-driven synthetic pathways, there is no general route to the synthesis of carbohydrates. The stereoselectivity of the formation of O-glycosidic linkages and the regioselectivity of protection and deprotection of specific hydroxyl groups over others represent two of the major challenges in carbohydrate chemistry. This thesis is dedicated to the development of novel strategies for efficient synthesis of carbohydrate building blocks and stereocontrolled glycosylations for step-economy oligosaccharide synthesis. Novel glycosyl donors with difluoro-3H-indol-2-yl …

Synthetic And Theoretical Studies For Cyclization Reactions To Form C-C And C-N Bonds, Nicholas Jentsch

Dissertations

Natural product total synthesis provides an alternative method for obtaining medicinally relevant compounds in a more efficient process with higher yields than what nature can provide. Natural products pose significant synthetic challenges due to the unique heterocyclic skeletons with fused and spirocyclic ring systems. Therefore, it is paramount to develop efficient reaction methodologies targeting substructures such as cyclic ureas and spiro[4.5]decanes which are prominent among marine natural products and Lycopodium alkaloids, respectively. Presented here is a compilation of research seeking to develop synthetic methods for the construction of cyclic moieties such as those previously mentioned. The objectives that are addressed …

Investigation Of Vaporization Enthalpies And Vapor Pressures Of Organic Compounds By Correlation Gas Chromatography, Carissa Nelson

Dissertations

Thermodynamic properties of organic compounds are useful to scientists and manufacturers in many areas of research and technology. This work focuses on measuring and reporting these properties on materials of commercial, environmental and scientific interest. Vaporization enthalpies and vapor pressures of several organic compounds have been studied using correlation gas chromatography (CGC) and are reported here as well as in recent publications. The CGC method allows for the indirect measurement of these properties in instances where these materials are available only in mixtures or in very small amounts.

The qualities of these measurements for any chosen target are directly related …

Thermosetting Polymers Via Azide Alkyne Cycloaddition, Richard H. Cooke Iii

Dissertations

This dissertation exploits properties inherent to azide-alkyne cycloaddition and applies practical solutions to difficult problems. Chapter II addresses structure-property relationships in glassy azido-alkyne matrices by varying the identity of the central linkage within tetrapropargyl bis-aniline-type crosslinkers, and by the addition or omission of Cu(I) catalyst. This systematic study showed that an ether or methylene linkage yielded lower melting tetrapropargyl crosslinkers that were soluble in, and produced homogeneous, networks when cured with, a standard azido resin, di(3-azido-2-hydroxypropyl) ether of bisphenol-A; in contrast, a sulfone linkage yielded a relatively insoluble crosslinker and poorly dispersed, heterogeneous networks when reacted with the same …

Nanojars: Versatile Platform For Pyrazole Synthesis And Chemistry, And Selective Extraction Of Anions, Basil Mohammed Ahmed

Dissertations

This work is centered around nanojars, a family of nano-sized anion-incarcerating agents. It addresses various aspects of nanojar chemistry, such as synthesis strategies (including green methodologies) for pyrazole ligands needed for the preparation of nanojars, characterization and study of the mechanism of assembly of nanojars, and selective extraction of anions from water using nanojars.

Nanojars are neutral, supramolecular coordination complexes of the general formula [anion⊂ {Cu(μ-OH)(μ-pz)}_n], formed by the reaction of Cu²⁺, HO^‒ and pyrazolate ions (C₃H₂N₂‒, pz^‒) in the presence of oxoanions with large hydration energy …

Fluorescent Probes And Functionalized Nanoparticles For Bioimaging: Synthesis, Photophysical Properties And Applications, Xinglei Liu

Dissertations

The development of new organic molecular probes with excellent photophysical properties and high fluorescence quantum yields is of considerable interest to many research areas including one- and two-photon fluorescence microscopy, fluorescence-based sensing methodologies, and cancer therapy. Series of organic linear-/non-linear optical molecules including squaraine derivatives, and fluorene derivatives as well as other bioconjugates are designed and synthesized during the doctoral study for the aim of ion detection (Chapter 5), photo dynamic therapy, and deep-tissue imaging (Chapter 4). These optical probes are capable of absorbing light in the near infrared (NIR) window and thus have deeper penetration and cause less photodamage …

Kinetic Study Of Free Radical-Radical Reactions Of Combustion Importance At Elevated Pressures, Chao Yan

Dissertations

Combustion mechanisms consist of hundreds elementary reactions of free radicals and stable molecules. Radical-radical elementary reactions play important roles due to the high concentration in which free radicals are accumulated in combustion systems. Radical-radical reactions are typically multi-channel. Some of the channels might be of chain propagation or even chain branching nature, while other channels might be of chain termination nature. The relative importance of different channels is pressure dependent. Compared to radical-molecule reactions, radical-radical reactions are much less studied. This is due to the difficulties of well characterized quantitative production of radical species as well as due to the …

Functional Emulsions Via Thiol-Ene Chemistry, Douglas Amato

Dissertations

Polymer particles (micro to nano) with tunable functionality have emerged as a promising and viable technology platform for applications including coatings, cosmetics, nanomedicine, and imaging. Unfortunately, the lengthy polymerization time and lack of intrinsic functionality in the monomers used to fabricate particles is an industrial challenge. Thiol-ene chemistry cirmcumvents these limitations with very rapid polymerization kinetics, high reaction yields, with supressed side reactions and inherent functionality. This dissertation demonstrates the utility of thiol-ene/yne polymerization in miniemulsion and microfluidics to generate functional materials in a one-pot-method. The functionality is typically generated via off-stoichiometry thiol-ene (OSTE) resins which allow for either excess …

Photoelectrochemical Studies On Non-Noble Metal Based Catalysts Towards Tandem Solar Water Splitting, Arun Siddarth Sridhar

Dissertations

Photoelectrochemical (PEC) water splitting makes direct use of solar energy incident on semiconductor photoelectrodes, and it is a convenient, economic option to produce high purity hydrogen at low temperatures. The use of multiple light absorbers can increase overall solar energy utilization and provide a solution to the trade-off between overall band gap and band edge positioning of photoelectrodes specific to solar water oxidation and water reduction. The study of non-noble metal based catalysts for hydrogen evolution reaction (HER) and oxygen evolution reactions (OER) are essential for economic practical commercialization of photo-electrolyzers. This dissertation focuses on the use of a variety …

Polymer Nanocomposites Containing High Aspect Ratio Particulates: Innovation In Co-Extruded Multilayer Barrier Films, Kevin Meyers

Dissertations

Delaminated montmorillonite (MMT) clay/ maleic anhydride grafted LLDPE nanocomposite multilayer films with alternating layers of LDPE were produced through multilayer co-extrusion. The MMT concentration within the nanocomposite layers was increased through annealing the films in the melt due to a mismatch in interdiffusion rates of the polymer layers. Analysis of the nanocomposite layers upon annealing revealed that the platelets impinged upon one another resulting in significant improvement in oxygen barrier in the multilayer system, exceeding the results of bulk nanocomposites.

Model analysis demonstrated that increasing the nanoplatelet aspect ratio or initial concentration in the filled layers would lead to even …

Cationic Ruthenium Complexes In Catalysis: The Activation Of Propargylic Alcohols Through Electronically Tuned Complexes, Matthew James Stark

Dissertations

With increasing complexity of metal complexes, it is of worthwhile interest to pursue systematic examinations of ligand modifications to study their impact on the reactivity of a catalyst. To that end, this study aimed to understand the effect electron-withdrawing ligands conveyed to catalytic activity in the etherification of propargylic alcohols and related reactions. A number of half-sandwich ruthenium complexes bearing ligands with varying electron–withdrawing properties were synthesized and structurally characterized. Their electronic and structural properties were investigated utilizing X-ray crystallography, revealing that the series of complexes did not vary significantly in structure. The complexes were studied electronically with cyclic voltammetry, …

Development Of Rules Of Attraction For Intercalated Guest Molecules Inside Of A Hydrogen Bonded Framework, Matthew Fischer

Dissertations

Supramolecular chemistry has synthesized large and small molecules which host guest molecules for several decades. What started as a way to mimic of enzymes in nature, has exploded into a sea of materials such as porous coordination polymers, low-density metal-organic frameworks, inclusion compounds, and hydrogen bonded frameworks. We previously designed a layered framework consisting of a metal complex with coordinate covalent ligands. These ligands have peripheral carboxylic acid groups which hydrogen bond to organic pillars containing terminal amines. The layered structure is separated by these pillars, which are closed-packed, creating 1-dimensional channels able to co-crystallize molecules. There is interest in …

Steric Effects On The Formation Of Manganese Oxide Clusters And 2-Dimensional Ammonium Formate Architectures, Carl Oberle

Dissertations

It has been demonstrated by the Beatty group that altering the identity of the ortho-substituent of a dianiline counterion affects the assembly and dimensionality of a cadmium-chloride layer from 2-D to 0-D. This work seeks to extend this finding to metal oxide and organic hydrogen-bonded materials. By systematically increasing the ortho­-substituent’s size on the benzoate building block of reported manganese oxide clusters, of formula Mn_xO_y(O₂C-R)_zL_w (where R = Alkyl, L = neutral monodentate ligand), we aim to impact the self-assembly of these materials relative to their parent …

Chemical Synthesis Of Staphylococcal Oligosaccharides, Satsawat Visansirikul

Dissertations

The Gram positive, cluster forming bacteria Staphylococcus aureus belongs to the family of opportunistic pathogens that may cause blood stream infections when the integrity of skin is broken and the immune system can no longer fight the infection. S. aureus has become one of the most frequent causes of infections in newborns, surgical patients, trauma and burn patients, patients receiving an implant, and dialysis patients with high mortality rates. As a matter of fact, S. aureus has become one of the largest public health and economic impacts amongst all bacterial infectious diseases worldwide. This situation is further complicated by the …

Elucidation Of The Toxicity Of Anthropogenic Nanoparticles In Environments Containing Heavy Metals, Chartanay Bonner

Dissertations

The design, synthesis, and applications of anthropogenic nanoparticles continue to rise as technologies utilizing the unique chemical and physical properties of materials with nanoscale dimensions emerge. Engineered silver nanoparticles (Ag NPs) possess antimicrobial properties toward several strains of antibiotic-resistant bacteria. The manufacturing and use of Ag NPs have led to their increased presence in the environment as pollutants. The interaction of Ag NPs with other pollutants influence their surface properties, aggregation state, stability and consequently, their toxic response toward microbial pathogens. In the present study, we examined the interaction of heavy metal ions (Cd²⁺, Hg²⁺, and …

Functionalized Nanoporous Carbon Scaffolds For Hydrogen Storage Applications, Christopher Carr

Dissertations

Recent efforts have demonstrated confinement in porous scaffolds at the nanoscale can alter the hydrogen sorption properties of metal hydrides, though not to an extent feasible for use in onboard hydrogen storage applications, proposing the need for a method allowing further modifications. The work presented here explores how the functionalization of nanoporous carbon scaffold surfaces with heteroatoms can modify the hydrogen sorption properties of confined metal hydrides in relation to non-functionalized scaffolds (FS). Investigations of nanoconfined LiBH₄and NaAlH₄indicate functionalizing the carbon scaffold surface with nitrogen can shift the activation energy of hydrogen desorption in excess of …

Surface Modification For The Improvement Of Metal/Organic Semiconductor Interfaces, Jonathan Paul Hopwood

Dissertations

Organic electronics have become much of the forefront of scientific research due to their advantages over tradition electronics as well as their applications in consumer devices, medical devices, and harnessing renewable sources of energy. Despite their appeal, two major obstacles are responsible for poor performance and limited applications. These problems occur at the interface between the two main components of the devices, the organic semiconductor and the metal electrodes. The first, high electrical resistance, is a result of the misalignment between the metal’s free electrons and the organic semiconductor’s conduction band. We seek to capitalize on this misalignment using light-responsive …

Biophysical Studies Of Guanine Nucleotide-Binding Alpha Subunits, Brian Leverson

Dissertations

Guanine nucleotide-binding (G?) proteins have been intensely studied over the years due to their role as signal transduction proteins. Proper function depends on three flexible switch regions that are involved in the relatively slow hydrolysis of GTP, allowing for the proteins to act as a molecular on/off switch. The structure of a protein is essential to its biological function. Occurrences of mutations in the genes GNAS and GNAI1 to highly conserved arginine residue in the switch II region have been detected in several types of cancers.

Utilizing the combinations of temperature denaturation, kinetics assays, and molecular dynamics, we plan to …

Application Of Synthetic Organic And Medicinal Chemistry Toward Medical Advances In Cancer, Antibiotics, And Drug Delivery, Marlon Lutz

Dissertations

Cancer and bacterial infections are a great concern in our society and have affected populations worldwide. The objective of this research was to discover new therapies for treating bacterial infections and cancer, and for promoting drug delivery.

DapE is an essential component in succinylase biosynthetic pathway, which is critical to production of lysine and m-DAP which both are essential in protein synthesis and bacterial peptidoglycan cell wall construction. Synthetic approaches were developed to prepare a new substrate for the N-succinyl-L,L-diaminopimelic acid desuccinylase (DapE) enzyme enabling the discovery of new antibiotics that inhibit DapE.

MMPs are over expressed in cancer, in …

Structural And Chemical Consequences Of High Oxygen Coverages On Rh(111), Rachael Gabrielle Farber

Dissertations

Partial oxidations of small molecules over metal surfaces are central to many heterogeneously catalyzed reactions. However, the identity of the actual surface species that promote or hinder these reactions has remained elusive for a variety of reasons. Recently, the understanding of the role of surface oxides in catalytic activity has changed. Instead of being thought of as poisons, they are now believed to be effective promoters of selective catalysis.

Rhodium (Rh) effectively promotes oxidation reactions and is a benchmark system for models of heterogeneously catalyzed chemistry. For this reason, Rh(111) was chosen as the model system for this dissertation work. …

The Enzymatic Activity And Inhibition Of Dape Encoded N-Succinyl-L,L-Diaminopimelic Acid Dessucinylase, Tahirah Heath

Dissertations

The bacterial enzyme DapE is a hydrolase in the late stage of the mDAP/lysine biosynthetic pathway that catalyzes the hydrolysis of N-succinyl-L,L-diaminopimelic acid (L,L-SDAP) to succinic acid and L,L-diaminopimelate (DAP). The product DAP is ultimately converted to m-DAP and then to lysine which is used in the construction of proteins, whereas for humans, lysine is an essential amino acid obtained through diet. DapE has been shown to be conserved across many strains of bacteria. The m-DAP produced through the succinylase pathway is used by both gram negative and gram-positive bacteria in the construction of the essential peptidoglycan cell wall. Because …

Principles Of Surface Chemistry Central To The Reactivity Of Organic Semiconductor Materials, Gregory J. Deye

Dissertations

Organic thin-films are rapidly becoming implemented as semiconducting materials in electronic devices and as a result, surface reactivity plays an increasingly important role in the improvement of semiconducting properties. My dissertation addresses how organic thin-films react with gaseous molecules. Previous reports of chemical reactions on organic surfaces claim, “phase rebuilding reaction mechanisms,” whereby reactions only proceed if chemisorbed adsorbate molecules are able to traverse through voids in the molecular lattice. The over-assumptions of this model and lack of correlation to reaction temperature make understanding of organic substrate reactivity incomplete. In contrast, I argue applied heat causes deformation of the molecular …

Air-Processed Polymer Photovoltaics: Advanced Morphological Characterization And Synthesis Of New Materials For Increased Light Absorption, Levi Moore

Dissertations

Organic photovoltaics (OPVs) have undergone intense development in recent years due to their potential to produce inexpensive, flexible, lightweight, and portable solar cells utilizing organic photoactive materials. Polymer-based OPVs have recently surpassed the 10 % in laboratory-scale devices, but require strict processing conditions in inert environments. Materials and processing methods that are workable in air are therefore desired. In addition to the light-absorbing and charge transport properties of the active layer materials, the morphology, crystallinity and orientation of the components of the phase-separated blend are paramount in determining OPV device performance This dissertation explores the processing of the model polymer …

Barrier Properties Of Polymer Nanocomposites With Graphene Oxide And Its Derivatives: Mechanism And Applications In Anticorrosive Coatings, Yidan Guan

Dissertations

Metallic devices made from steel or aluminum are subjected to deterioration by environmental contaminants over time. As one of the corrosion control methods, organic coatings show many advantages due to their low cost, versatility, decoration aesthetics and effective protections. Corrosion protection theories and failure modes of organic coatings are still not fully understood due to complicated interactions in the coating-metal-environment system, however, it is widely agreed that the barrier nature of polymeric materials towards aggressive species, such as oxygen, water, electrolyte, plays a key role. Improved barrier property of polymer nanocomposites (PNCs) with two-dimensional (2D) carbon filler, graphene and graphene …

Electrophilic Cleavage And Functionalization Of Polyisobutylenes Bearing Unsaturations In The Backbone And Synthesis Of Polymers For This Process, Christopher Campbell

Dissertations

In the first project, we demonstrated a new reaction, which is a subset of the Friedel‑Crafts alkylation reaction, in which the alkylating carbocation undergoes a cleavage reaction prior to reaction with the aromatic substrate. This reaction was discovered by the observation that when a PIB containing a large amount of coupled fraction was subjected to a mixture of protic and Lewis acids (HCl/TiCl₄) in the presence of an alkoxybenzene compound, the coupled fraction was quantitatively converted to its constituent monofunctional chains, which became functionalized by the alkoxybenzene.

In the second project, a commercial polymer, poly(isobutylene-co-isoprene) (butyl …

Interactions Between Amyloid-Beta And Microglial Cells, Lisa Gouwens

Dissertations

Alzheimer’s disease (AD), the most common cause of dementia, is a neurodegenerative condition characterized by loss of memory and intellectual abilities. Intracellular plaques of aggregated amyloid-beta (Ab) protein are a well-known pathology associated with AD. Although symptoms usually appear late in life, the accumulation of Ab begins decades earlier and causes activation of microglia, the brain’s immune cells. The ensuing inflammation contributes significantly to neurodegeneration. Determination of the particular form of Ab that causes the most damage in the brain is one of the major questions in the AD field. My research focused on the interactions of microglia with monomers, …

Thermochemistry Of Fluorinated Aldehydes And Corresponding Radicals;Thermochemistry And Kinetics Of Diethyl Ether And Ethyl Oxirane Relative To Reactions Under Atmospheric And Combustion Conditions, Douglas Lee Purnell Jr.

Dissertations

Fundamental thermochemical properties including enthalpies (ΔH°f 298), entropies (S°(T)), heat capacities (Cp(T)), and bond dissociation energies (BDEs) for several common and complex hydrocarbon fuel species are determined using computational chemical methods. ΔH°f 298 values are calculated using isodesmic reactions with the CBS-APNO, CBS-4M, CBS-QB3, G2, G3, G4, Weizmann-1 (W1U) and M06-2X, ωB97X, B3-LYP with basis set 6-31G+ (d,p) and 6-31G++(d,p) calculation methods. Structures, moments of inertia, vibrational frequencies, and internal rotor potentials are calculated for contributions to entropies and heat capacities. Kinetic rate parameters are calculated for hydrogen abstraction and …

Electrogenerated Chemiluminescent Studies Of 9,10-Diphenylanthracene, Rubrene, Tris(2,2'-Bipyridine)Ruthenium(Ii) Species, And Their Derivatives For Sensitive Detection Of Biomolecules, Pradip Bastola

Dissertations

This dissertation explored and investigated the coreactant electrogenerated chemiluminescent (ECL) properties of unmixed and mixed systems of highly efficient ECL emitters, such as 9,10-diphenylanthracene (DPA), rubrene (RUB), and tris(2,2′-bipyridine)ruthenium(II) [(Ru(bpy)₃²⁺)] species as well as their water-soluble derivatives, which can serve as ECL labels for sensitive bioanalysis of single or multiple analytes. The screening of most favorable common ECL coreactants, their concentration effects along with the effect of working electrode materials on ECL behavior, and energy transfer related interactions between ECL emitters were systematically investigated. In addition, a strategy for improvement of ECL signals with the use of …