Chemistry Commons^™

Biomaterials: From Scaffold Design To Implant Optimization, Jennifer Marie Armen

Electronic Theses and Dissertations

This work encompasses three individual projects concerning biomaterials and their modifications. Chemically-Induced Cross-Linking of Peptidic Fibrils for Scaffolding Polymeric Particles and Macrophages EAK16-II (EAK) is a self-assembling peptide (SAP) that forms β-sheets and βfibrils through ionic-complementary interactions at physiological ionic strengths. The soft materials can be injected in vivo, creating depots of drugs and cells for rendering pharmacological and biological actions. The scope of the applications of EAK is sought to extend to tissues through which the flow of extracellular fluid tends to be limited. In such anatomical locales the rate and extent of the fibrilization are limited insofar as …

C-H On The Oxo Ferryl Wheel: Comparison Of Pyridine And Imidazole-Substituted Ligands For C-H Activation And Functionalization, Elizabeth Milem

Electronic Theses and Dissertations

The selective and efficient transformation of hydrocarbon feedstocks is of high value for industry and research. While Shilov-type organometallic methods have facilitated this goal, systems designed after nature’s use of cheap and abundant iron-based enzymes are desired for wider-scale applications. This work establishes hydrocarbon oxidation efficiency of synthetic pyridine-based ligands (BPMEN, BPMPN) compared to commercially available TPA with in situ generated catalysts. Literature studies of traditionally synthesized BPMEN systems and initial in situ studies offered evidence for enhanced reactivity (TON) as compared to TPA. Expansion to a propyl backbone to produce BPMPN tested the increased chelate ring size’s impact on …

Age, Growth, Foraging, And Trophic Ecology Of Bigeye (Thunnus Obesus) And Yellowfin (Thunnus Albacares) Tuna In Continental Shelf And Slope Regions Of The Northeast U.S., Riley S. Austin

Electronic Theses and Dissertations

Traditional stock assessments require, in part, accurate knowledge of growth relationships to estimate a variety of aspects involved in population conservation management of exploited species. In addition, the local distribution and condition of top pelagic predators is driven by detection of abundant forage aggregations and along with traditional stock assessments, should be considered for effective management of marine populations. Empirical analyses of these data are severely lacking for bigeye (Thunnus obesus) and yellowfin (Thunnus albacares) tuna in the Atlantic Ocean, especially for the former. Given historical studies’ observations of these two top predators use as biological samplers due to their …

Fabrication Of Particulates For Detecting Trace Level Analytes In Water Using Optical Spectroscopy And For Developing Thermoelectric Materials, Mohammed Nayeem Ibnul

Electronic Theses and Dissertations

The underlying concepts developed in this thesis involve particulate fabrication of known size using a bottom-up synthesis or a top-down milling process. This bottom-up approach was used for detection of analytes in water. Conventional UV-Vis spectroscopic based detection methods require target analytes to be soluble or have enough vapor pressure for analysis in the gas phase. We achieved an order in magnitude improvement in the detection limit over the standard molybdenum blue method for phosphate and arsenate by conversion of target analytes present in solution to a solid for quantification by UV-Vis and IR spectroscopy. Furthermore, by recording a visible …

Development Of Methods For Surface Modification Of Semiconductor Photocatalysts And Biopolymers For Applications In Water Treatment And 3d Printing, Sabrina Sultana

Electronic Theses and Dissertations

Surface modifications of metal oxides and polymer substrates are widely adopted approaches to alter the properties of these materials for use with specific applications. In the first part of my thesis, I describe how we have modified the surface of magnetic particles (Fe3O4) with layers of SiO2 and TiO2 to generate photocatalysts that remove toxic chemicals from drinking water. Semiconductor photocatalysts, such as TiO2 have gained much interest over the last 20 years as promising materials for water treatment. However, a main drawback centers on the difficulty to remove the catalyst from the water which has made it very difficult …

Sustainable Nanocatalysis In Water For C–C And C–N Cross-Couplings., Tharique Ahammed Ansari Nalakath

Electronic Theses and Dissertations

The development and application of various micelle-enabled nanopalladium-catalyzed organic transformations are discussed in this dissertation. These methodologies primarily harness the “micellar effect” imparted by the custom-designed amphiphile PS-750-M. Modern spectroscopic and imaging techniques were employed to systematically study the metal-micelle interactions and answer the fundamental questions regarding the operational nature of micellar catalysis. Chapter 1 reviews the history and evolution of organic synthesis, providing a critical outlook regarding the alarming inefficiency of contemporary synthetic practices indicating an inevitable transition to more sustainable synthetic techniques. In this context, the development of micellar catalysis is discussed, emphasizing its basic principles, applications, and …

Spectroscopic Measurements Of Meibum Compositional, Structural, And Functional Relationships To Elucidate The Role Of Meibum In Dry Eye., Anthony Chigozie Ewurum

Electronic Theses and Dissertations

The major aim of my dissertation was to investigate the etiology of dry eye disease which affects about 7 million people in the United States, causing symptoms that can lead to visual disturbance. Correlation between dry eye and an abnormal lipid layer of the tear film has been found. Tear film lipids originate mostly from the meibomian glands. Cholesteryl ester (CE) and Wax ester (WE) lipids make up most of the human meibum lipidome and the CE/WE ratio has been shown to decrease in patients with meibomian gland dysfunction. Model studies using synthetic CE and WE, although providing some insight, …

Surface-Functionalized Chemiresistive Films That Exploit H-Bonding, Cation-Pi, And Metal-Halide Interactions., Prasadanie Karunarathna Adhihetty

Electronic Theses and Dissertations

The development of gas sensors for detection of volatile organic compounds (VOCs) has been of interest in the sensing field for decades. To date, the use of metal nanoparticle-based chemiresistors for trace VOC detection, particularly gold nanoparticle-based sensors, is of great interest due to their high chemical stability, ease of synthesis, unique optical properties, large surface to volume ratio, and high level of conductivity. Much effort has been devoted towards gold monolayer protected clusters (Au MPCs) as chemiresistors to detect harmful VOCs. The present thesis documents the results of our efforts to exploit the advantages of functionalized Au MPCs chemiresistors …

Development And Novel Applications Of Halogenating Agents., Sagar Ravso Mudshinge

Electronic Theses and Dissertations

Organic halides are extensively utilized as synthetic intermediates in areas such as pharmaceuticals, agrochemicals, and material polymers. While many halogenating agents have been developed, they continue to have low efficiency or selectivity, are difficult to handle, and often have limited substrate scope. To address this issue, our laboratory has developed novel halogenating agents with improved stability and efficiency. In these studies, we demonstrated a novel application of halogenating reagent, HCl·DMPU, in the nitrile synthesis. We developed a novel method for C−SCF₃/SeCF₃ cross-coupling reactions using gold redox catalysis. We developed a novel trifluoromethylating agent in a cost-effective and …

Structural, Charge Transport, Gas Sensing, Magnetic, Pseudocapacitive, And Electrocatalytic Properties Of Perovskite Oxides., Surendra Bahadur Karki

Electronic Theses and Dissertations

Perovskites are functional materials with the general formula ABO₃ (A = alkali, alkaline earth or lanthanoid cations and B = transition metal or main group cations). These materials are marked by a variety of crystal structures and interesting properties such as colossal magnetoresistance, ferroelectricity, multiferroicity, superconductivity, pseudocapacitance, gas sensing, charge transport, and electrocatalytic properties. The formula of perovskite can be written as AA’BB’O₆, when there is ordering between two cations over A and B-sites. Such compounds are called double perovskite oxides. Some amount of oxygen could be lost from crystal structure without decomposition of the phase. Such …

Nanomaterials For Sustainability: Using Spectroscopy And Quantum Chemistry For Microkinetic Modeling Of Thermo- And Photo- Catalysts, Amir Rahmani Chokanlu

Electronic Theses and Dissertations

Heterogeneous catalysis, including thermal- and photocatalysis, is a key technology toward developing industrial processes for a sustainable future. Therefore, the study of surface reactions and catalyst properties includes most studies in this area. There has been extensive work put into developing experimental and computational tools to understand surface and interface phenomena, describe mechanistic chemical transformations, and simulate the behavior of surface reactions to develop better catalysts and more efficient processes.

This thesis describes experimental and theoretical investigations to explain the reaction mechanism of ethanol conversion to value-added products over an MgO/SiO2 catalyst, a kinetic model describing the surface changes during …

Functionalized 𝜹-Hexalactones (Fdhls): Bio-Derivable Monomers To Synthesize Renewable Polyester Thermoplastics, Atik Faysal

Electronic Theses and Dissertations

Most thermoplastics are made from limited fossil-fuel sources and these plastics have very deleterious impacts on the environment. Finding a renewable source to synthesize new thermoplastic polymers with tunable properties like biodegradability, heat resistance, and moisture resistance are ongoing research interests. Lignocellulosic biomass is a promising renewable feedstock for biobased monomers and polymers production. In this work, functionalized 𝛿-hexalactone (FDHL) monomers are hypothesized to be synthesizable from lignocellulosic sourced hydroxymethyl furfural (HMF) and lignin-derived pendant groups, generating a variety of aliphatic polyesters and potentially overcome current polymer challenges. Achieving a higher glass transition temperature (T_g) is one of …

Charged-Particle Interactions To Generate Novel Coatings And Materials, Pradnya D. Rao

Electronic Theses and Dissertations

A typical paper coating formulation contains anionically charged pigments and latex to provide a high-quality surface for printing. However, during application and drying, the latex can migrate to the surface or deep into the paper, resulting in weak coating layers or the need to use a high latex content to obtain the same strength properties. In this thesis, we have explored the introduction of cationically charged particles into the suspension as a way to reduce the amount of binder in the coatings, improve coating strength and reduce binder migration. With these aims in mind, we have generated cationic precipitated calcium …

Dynamic Interactions In Semiconducting Polymers; New Materials For Soft Electronics With Biomimetic Properties, Michael Udunyi Ocheje

Electronic Theses and Dissertations

The development of materials that can stretch while remaining conductive has generated significant research interest. The push for the development of these materials is due to their potential for cheaper, more durable electronics with the new functions (stretchability and healability) and form factors required for the next generation of wearable and skin-inspired electronics. Polymeric semiconductors have emerged as prime candidates for the development of these materials, due to their π-delocalized network which makes them conductive, their synthetic versatility, and their intrinsic mechanical properties. Furthermore, their ability to be solution processed provides an avenue for printing, roll-to-roll, and large area solution …

Diketopyrrolopyrrole Derivatives For Single Material Solar Cells, Adam M. Cassar

Electronic Theses and Dissertations

Although diketopyrrolopyrroles (DPPs) have been extensively studied as organic pigments and dyes and as building blocks for molecular and polymeric organic electronic materials, their propensity for self-organization has been given surprisingly little attention. Self-organization provides control over the morphology and supramolecular structure of materials and, consequently, the performance of a material. The dependence of performance on supramolecular structure is particularly delicate in bulk heterojunction organic solar cells and the emerging low-cost single material organic solar cells (SMOSC). Most donor-acceptor dyads and triads presently developed for SMOSCs consist of dyes as electron donors and fullerene derivatives as electron acceptors, but their …

Lipophilic Probes For Cellular Ethylene Detection, Morgan R. Brown

Electronic Theses and Dissertations

The structure of ethylene is simple, yet its biological effects are significant. When considering its role in biology it is almost exclusively regarded as a plant hormone. Research on ethylene from plants was progressed by several advancements in analytical instrumentation, from its discovery to elucidation of its signaling pathway. There is currently limited understanding of ethylene’s role in mammals, but evidence suggests that it may be a biomarker for oxidative stress! Additional tools and technology are crucial to study this surprising and important signaling role in mammals. Our group has developed molecular ethylene probes as a strategy to detect ethylene …

Esipt-Enabled Alkyne Migration Provides Rapid Access To Benzoxazinones, Andrés G. Muñoz

Electronic Theses and Dissertations

Benozoxazinones have long been of interest to agrochemical scientists and medicinal chemists because of their widespread biological activity. These scaffolds are also of interest to synthetic chemists, who recognize the utility of benzoxazinones for accessing functionalized heterocycles. The use of efavirenz, a benzoxazinone-based reverse transcriptase inhibitor used in the treatment of HIV-1, has brought increased attention to this privileged pharmacophore. While there exist numerous strategies for synthesizing benzoxazinones, methods that do not require the use of acutely toxic and environmentally hazardous reagents are lacking. Consequently, there is a need to develop new methods for constructing this valuable scaffold. Herein, we …

Dynamics And Turnover Of Lipid And Protein Domains In Cells And Supported Bilayers, Alan Weisgerber

Electronic Theses and Dissertations

Protein and lipid clustering is an important mechanism for cell processes such as exo- and endo-cytosis and creating functional signaling complexes. It has been seen that both lipids and proteins are involved with the formation of cluster domains on cell membranes, yet little is known about the interplay between the two. In this work I began with visualizing lipid sorting to artificially induced curvature in supported lipid bilayers, with lipid tails affecting the sorting differently to curvature. These results demonstrate that lipids sort to curvature on curved, supported lipid bilayers. The sorting depends on the number of lipids in the …

Directly Polymerizable Co Releasing Molecules, Jackson Snow

Electronic Theses and Dissertations

Despite the commonly held consensus that carbon monoxide (CO) is toxic, it has been shown to be an essential signaling molecule in the human neuronal system and has been noted to have anti-inflammatory properties, act as a vasodilator, have anti-proliferative impacts on tumors, and many other beneficial effects. The current limitation to using CO as a therapeutic molecule is delivering the proper dosages using CO releasing molecules (CORMs) without exhibiting toxicity. The first chapter of this thesis will review the biological significance of CO in biological systems, the limitations of existing CORMs, and the properties of diphenylcyclopropenone (DPCP) that make …

Investigating Spatiotemporal Kinetics, Dynamics, And Mechanism Of Exosome Release, Anarkali Mahmood

Electronic Theses and Dissertations

Exosomes are small lipid-based vesicles that can carry biomolecules from one cell to another. While exosomes are crucial to maintain homeostasis in healthy cells, they are exploited by unhealthy cells to aid disease progression. Exosomes likely facilitate disease progression via the transfer of disease-causing biomolecules from unhealthy to healthy cells. Exosomes are generated in Multivesicular endosomes (MVEs) and are then secreted into the extracellular space to travel to other cells. Despite being a crucial step, very little is known about exosomes release mechanism and dynamics. To further our understanding of exosomes, specifically their secretion, my work has focused on investigating …

Electron Spin Relaxation Of Nitroxide Spin Labels And Relaxation Processes, Thacien Ngendahimana

Electronic Theses and Dissertations

MTSL is the nitroxide spin label that is most commonly used in site-directed spin labeling. However, due to rotation of its gem-dimethyl groups that average anisotropic interactions, T_m becomes short above about 70 K and this makes DEER experiments difficult at these temperatures. Strategies for decreasing spin echo dephasing and electron spin lattice relaxation rates are important for design of nitroxide spin labels and molecular qubits.

In searching for labels with longer T_m, new nitroxide spin labels devoid of gemdimethyl groups or with more rigid structures were synthesized at the University of Nebraska and pulsed EPR measurements …

Measurements Of Atmospheric Radicals, Heather L. Runberg

Electronic Theses and Dissertations

Atmospheric particulate matter (PM) is a global health concern. PM_2.5 is formed primarily through combustion processes such as automobile use and industrial activity. Natural sources of PM_2.5 result from events like volcanos and wildfires. Upon inhalation, PM_2.5 is small enough to travel deep into the lungs where it can form reactive oxygen species (ROS), such as hydroxyl radical (OH), causing oxidative damage to pulmonary tissues. PM_2.5 has been linked to cardiopulmonary diseases such as asthma, chronic obstructive pulmonary disease (COPD), and high blood pressure.

PM_2.5 is small enough to remain aloft and travel many hundreds …

Inhibitors Of Alpha-Synuclein Aggregation, Jemil Ahmed

Electronic Theses and Dissertations

Alpha-Synuclein (αS) – a neuronal, disordered, presynaptic protein – aggregates into amyloid fibrils and accumulates in the substantia nigra pars compacta of Parkinson's Disease (PD) patients. The aggregation and accumulation of αS amyloid fibrils leads to death of dopaminergic neurons; a hallmark of PD. Although it’s not clear why αS aggregates, prior studies have found that intrastriatal injection of fibril alone is sufficient to cause PD pathology in mouse and non-human primates models. These observations implicate αS as a therapeutic target against PD.

Unfortunately, there are three caveats when attempting to target αS. First, αS is a neuronal protein expressed …

Characterization Of A Three-Way Catalyst For High Efficiency Spark Ignition Engines, Cavin Hesketh

Electronic Theses and Dissertations

The push for environmental protection and sustainability has led to strict emission regulations for automotive manufacturers as evident in EURO VII and 2026 EPA requirements set to take effect in the coming years. The modern gasoline spark ignition (SI) engine typically employs various in-cylinder emission reduction techniques along with an exhaust after-treatment system to comply with emission standards. The three-way catalyst (TWC) is wholly responsible for removing the engine-out emissions including hydrocarbons (HC), carbon monoxide (CO) and nitrogen oxides (NOx). The main objective of this thesis is to investigate the impact of extensive exhaust gas recirculation (EGR) on …

Studies Of Layered Elastomeric Substrates And Shellac Films For Stretchable And Printed Electronics, Calum Noade

Electronic Theses and Dissertations

Wearable electronics are becoming increasingly common in daily life for a variety of uses. Wearable electronic devices that wish not to be bulky and cumbersome to the user must be stretchable and conformable to the human body. This is a challenge, however, as stretchable polymers are often not as conductive as metal conductors, and metal films applied to elastic substrates are themselves inelastic and will rupture at very low elongations, rendering devices unusable. By using subsurface modification of a multilayered elastomer and brittle layer system, it is possible to offer strain delocalization to a gold film in order to induce …

Elucidating Mechanisms For S-Nitrosoglutathione Reductase Activity And Control In Plants Using O-Aminobenzoyl-S-Nitrosoglutathione And A Novel Photo-Sensitive Probe, Leslie Ventimiglia

Electronic Theses and Dissertations

S-nitrosoglutathione reductase, (GSNOR) is widely accepted as the master regulator of stress through NO signaling and protein S-nitrosylation. GSNOR mediates stress response through the catalysis of its principal substrate S-nitrosoglutathione (GSNO). The instigation of various stressors in plants cause observable changes in plant phenotype, which are associated with changes in GSNOR activity. There are no current methods for measuring GSNOR activity directly in living plants. In this paper, a previously developed fluorogenic pseudo-substrate for human GSNOR, OAbz-GSNO, was applied to the Solanum lycopersicum plant model. OAbz-GSNO was identified as a promising novel pseudo- substrate to study changes …

The Design And Testing Of Fluorescence-Based Sensors For Phosphate And Phosphonate, Sara Hassanzadehroknabadi

Electronic Theses and Dissertations

Inorganic phosphate (Pi) is an essential compound for all living things, as it serves as a component of nucleic acids and ATP, which are required for plant growth and proliferation. However, when excess Pi enters the aquatic environment, it has severe detrimental effects through the induction of harmful algal blooms (HAB), which negatively impact aquatic life, the quality of drinking water as well as recreational activities. It is therefore critical to have fast, sensitive, and inexpensive sensors for Pi that quickly and quantitively measure its concentration in a field setting.

Phosphonates or organophosphorus compounds are phosphoric acids possessing alkyl or …

Structure And Mechanics Of Biomembrane Mimics In The Presence Of Vitamin E, Mitchell Dipasquale

Electronic Theses and Dissertations

Over the course of this dissertation, the fundamental behaviours and interactions between various analogs of vitamin E and biologically-relevant membranes will be explored. These analogs include the biologically active form, α-tocopherol; the most naturally abundant form γ-tocopherol; an oxidized product, α-tocopheryl quinone; and the synthetic stabile form, vitamin E acetate.

Beginning in Chapter 1, a foundation in membrane biophysics is established from a historical progression of the field. The importance of biomembranes is argued and a deep connection is established between structure and function. Key structural features of lipid assemblies, and role of lipid composition is defined, and with the …

A Comparison Of The Oxidative Addition Chemistry Of Tetrathiocins To P- And D- Block Elements, Lara Watanabe

Electronic Theses and Dissertations

This thesis describes the oxidative addition of 1,2,5,6-tetrathiocins to low valent transition metals and p-block elements. Chapter 1 provides a literature review of tetrathiocin reactivity and the related dithiete chemistry for both the p- and d-block elements. Chapter 2 describes the synthesis of a library of tetrathiocins used extensively through the rest of this thesis alongside the synthesis of a series of group 10 dithiolate complexes through the oxidative addition of tetrathiocins to M2dba3 (M = Pd or Pt) in the presence of the chelating phosphines dppe and dppf to generate complexes of general formula M(dt)(dppe) and M(dt)(dppf) [M = …

Evaluation Of Field-Level Screening, Sampling, Storage, And Laboratory Analysis Of Hydrogen Sulfide And Reduced Sulfur Species In Sagd Operations, Kaylee Colene Anagnostopoulos

Electronic Theses and Dissertations

Steam assisted gravity drainage (SAGD) operations extract viscous bitumen from the subsurface. During routine operations, fugitive gas can present as a surface casing vent flow (SCVF) or a gas migration (GM) in soils. Depending on regulatory thresholds, these fugitive gases can be classified as serious or non-serious. The presence of hydrogen sulfide (H2S) automatically classifies a well as serious by regulators. Thus, accurate detection and quantification is necessary to meet and exceed regulatory policies and provide the highest standards of environmental health and safety for the energy sector. This thesis investigates the impacts temperature and steam present …