Chemistry Commons^™

Synthesis, Characterization And Cellular Uptake Of Magnesium Complexes Of Pyrones And Amino Acids, Derek Robert Case

Dissertations - ALL

This thesis focuses on the treatment of micronutrient deficiency, specifically hypomagnesemia, through the synthesis and solution- and solid-state characterization of "pharma grade", biorelevant magnesium complexes (nutraceuticals) utilizing short-chain peptides (di- and tri-), pyrones, and amino acids. There is further emphasis placed on determining the in vitro uptake of all produced complexes. This work aims to mitigate the shortcomings of current magnesium supplements and better illustrate an understanding of the factors impacting magnesium uptake. Specifically, 1) There is a paucity of information regarding the coordination of biorelevant ligands to magnesium, most of which was investigated between the 1950s and 1980s, and …

Signaling Studies Of Protein-Peptide Binding On Microelectrode Arrays, Kendra White

Arts & Sciences Graduate Student Theses and Dissertations

Electrochemical methods provide unique opportunities for non-traditional synthesis and analytical studies. Using electrochemistry, we are able to synthesize individually addressable molecular surfaces on microelectrode arrays and then utilize the surface to probe interactions between receptors and their biological targets. To date, cyclic voltammetry signals can be used to detect biological interactions between proteins and small molecules on the surface of an array, however those signals are often amplified by the presence of a large number of small molecules by any given electrode. This amplification makes it difficult to obtain binding data using the arrays that can be compared with existing …

Monitoring Bacteria Cultures Using Near Infrared (Nir) Binary Spectronephelometry (Bsn), Raman Spectra And Principal Component Analysis (Pca), Steven Ortiz

Dissertations - ALL

Current noninvasive methods cannot continuously and simultaneously monitor the concentrations of cells and media components that define the state of native bacterial cultures, because of changing turbidity. A new technique, binary spectronephelometry (BSN) has the same or better sensitivity and precision for population monitoring as optical density at 600nm (OD600), while simultaneously measuring metabolic processes. The BSN algorithm uses laser induced emission to probe mildly turbid media i.e., propagation of light occurs in the single scattering regime. A BSN "training set" associates a grid of elastic emission measurements, comprising Rayleigh and Mie scattering, and inelastic emission measurements, comprising fluorescence and …

Trichloroacetimidates As Outstanding Electrophiles For The Carbon-Nitrogen, Carbon-Oxygen And Carbon-Carbon Bonds Formation And Synthetic Studies Of Protein Phosphatase-5 (Pp5) Small Molecule Inhibitors, Nilamber Mate

Dissertations - ALL

Trichloroacetimidates have been previously used for glycosidic bond formation in carbohydrate chemistry and in Friedel-Craft reactions. Traditionally, trichloroacetimidates had be synthesized using an alcohol and strongly basic conditions, but in recent years milder preparation methods have been reported. Given the ease of preparation of these versatile reagents, their chemistry has been explored intensely in recent years. While few reported methods suggest they can react under promoter free conditions, activation by Lewis or Brønsted acid leads to a formation of a carbocation from benzylic trichloroacetimidates. Work described herein makes use of these convenient carbocation precursors for new reactions.Isatin is an ambidentate …

The Evaluation Of Radiometal Labeled Biomolecules For Imaging And Therapeutic Applications, Truc Huynh

Arts & Sciences Graduate Student Theses and Dissertations

Radiometals play a crucial role in nuclear medicine for the diagnosis and therapy of various diseases including cancer and neurological disorders. In fact, there is a broad range of radiometals that are currently in use for imaging and therapy such as 99mTc, 89Zr, 68Ga, 177Lu, and 64/67Cu. Radiometal use in nuclear medicine has been stimulated by advances in radionuclide production that allow for fast, reliable, and cost-efficient production and an extensive understanding of molecular targets and tumor biomarkers. In recent years, there has been a growing interest in theranostics - the combination of imaging and therapy related to the same …

Steps Toward The Total Synthesis Of The Chrysosporazine Family, Katie Kaczynski

Electronic Theses and Dissertations

Cancer is one of the leading causes of death worldwide, with 19.3 million new cancer cases and 10 million deaths in 2020 alone. In the United States, cancer was the second leading cause of death after heart disease. One of the reasons that cancer is so frequently terminal is that cancerous cells frequently develop multidrug resistance (MDR) to frontline chemotherapeutical treatments, resulting in cancers cannot be treated and are inevitably fatal. This makes the discovery of ways to combat MDR so important in the treatment of cancer. The chrysosporazines are a family of recently discovered (2019) natural products that have …

Soymeal Based Bio-Based Adhesive For Wood Application, Prashant Kote

Electronic Theses & Dissertations

Introducing bio-based materials as an alternative to petroleum-based products has been the greatest challenge for the industry which may reduce environmental problems. Currently, most of the wood adhesive is prepared using formaldehyde which is a non-renewable source as well as toxic. In this research, soybean meal was used as a renewable bio-based source for wood adhesive which has a potential to replace formaldehyde-based adhesives. In this study, soymeal was chemically modified, characterized, and evaluated for its adhesion performance, flow behavior, service life, and thermal stability.

In the first, soymeal was modified using acid (HCl), alkali (NaOH), and salt (CaCl_{2 …}

Transistion Metal Chalcogenides And Phosphides For Energy Storage And Conversion Through Water Splitting, Kelsey Thompson

Electronic Theses & Dissertations

In contemporary society, there are many different ways that energy is used in daily life. From applications that require a high energy density to long-term storage in a stable manner, the requirements for energy usage are diverse. Therefore, the greater the number of uses a designed material exhibits, the more practical it may be for wide-scale manufacture. Two areas of particular interest for energy applications are fuel cells (to generate energy) and supercapacitors (to store energy). To provide cheaper and more durable alternatives for energy storage, electrodes containing CoMoO₄, NiMoO₄, CoMoS₄, NiMoS₄, …

One-Step Synthesis Of Corn Oil-Based Polyol For Highly Flame-Retardant Rigid Polyurethane Foams, Tenzin Ingsel

Electronic Theses & Dissertations

Rigid polyurethane foams (RPUF), heavily utilized in construction, refrigeration, and the automotive industries, are a significant class of polyurethanes. They can substantially enhance energy efficiency by improving thermal insulation. However, the application of petrochemical sources in polyurethane has raised environmental concerns.

Such concerns call for the development and application of new bio-based polyurethanes to potentially reduce humanity's over-reliance on nonrenewable sources.

In this work, corn oil-based polyol was synthesized via popularized thiol-ene reaction. The obtained polyol was characterized by wet chemistry methods, spectroscopic evaluations, and chromatography. Non-halogenated flame retardants of cost-effective and environmentally friendly nature were incorporated into the polyurethane …

Statistical Analyses Of Hemp Cannabinoid Test Results, Rachel J. Stegmeier

Senior Honors Projects, 2020-current

Cannabis sativa L. is a flowering plant used for recreational and industrial purposes that produces a class of compounds called cannabinoids. Industrial hemp is a strain of Cannabis sativa L. that has been propagated to have a low Δ 9 tetrahydrocannabinol (Δ⁹THC) and a high cannabidiol (CBD) content. With recent advancements in legislation, farms are now growing hemp for fiber, CBD production and other hemp derived product purposes but crops risk being destroyed if THC content levels exceed the current maximum legal limit of 0.3%. For the present study hemp samples were dried, ground, extracted with various alcohols, …

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 …

Synthesis Of Conjugated Polymers From Xanthene And Alkenyl Flanked Diketopyrrolopyrrole Monomers For High-Performance Electronic Applications., Ranganath Wijesinghe Wahalathantrige Don

Theses and Dissertations

In traditional electronics, inorganic materials such as silicon and germanium are used as semiconductors due to their outstanding semiconducting properties. Unfortunately, inorganic materials are rigid due to their high crystalline nature, and processing these materials is complex and expensive. Furthermore, traditional semiconducting materials do not have favorable mechanical properties in applications such as wearable devices and large-area applications with complicated shapes. Conjugated conducting polymers (CCPs) are being explored as alternative materials to conventional semiconductors due to their mechanical properties and high conductivity. CCPs offer properties such as solution and low-temperature processability, flexibility, thermal and optical properties that traditional semiconductors could …

Phosphorus Enriched Modified-Douglas Fir Biochar As A Soil Amendment, Beatrice Arwenyo

Theses and Dissertations

Biochar application as a soil additive is gaining global acceptance. In this era of climate change, biochar use for improved soil productivity is not just a sustainable eco-friendly substitute to synthetic fertilizer, but a noble contributor to the fight against climate change. Although biochar has been accredited with some environmental and agricultural benefits, most studies concentrated on agricultural and biowaste products as feedstocks. This research was designed to explore P-enriched modified-Douglas fir biochar potential as a soil additive. Using corn as a test crop, greenhouse studies were performed on acidic sandy soil, comparing phosphorus enriched modified-Douglas fir biochar efficacy to …

Functionalized Biochar Electrodes For Asymmetric Capacitive Deionization, Hellen Stephanie

Theses and Dissertations

Electrosorption-based capacitive deionization (CDI) has become a viable process for brackish water desalination and defluoridation. In this study, activated Douglas fir biochar is used as a low-cost electrode material with adsorption capacity comparable to activated carbon obtained from biomass precursors. Adding functional groups to the activated biochar enhanced salt removal capacity, providing cation and anion selectivity. The functionalized electrodes were prepared by Nafion, titanium isopropoxide, and p-phenylenediamine treatment, respectively, which introduced sulfonate, titanium dioxide and amine functional groups to the electrode surface. These modification methods are versatile and can be easily performed without sophisticated laboratory environment. Modified biochar electrodes …

A Modular Synthesis Of Processable And Thermally Stable Semi-Fluorinated Aryl Ether Polymers Via Step-Growth Polymerization Of Fluoroalkenes, Ketki Eknath Shelar

Theses and Dissertations

Tailored fluoropolymers remain the leading choice for a wide variety of advanced high-performance applications, including electronic/optical and energy conversion, owing to their unique blend of complementary high-performance properties. Amorphous semi-fluorinated polymers exhibit improved solubility and melt processability when compared to traditional perfluoropolymers. A leading class of semi-fluorinated aryl ether polymers includes perfluorocyclobutyl (PFCB), perfluorocycloalkenyl (PFCA), and fluoroarylene vinylene ether (FAVE) polymers. Monomers containing aromatic trifluorovinyl ethers (TFVE) are used to synthesize PFCB polymers via radical-mediated [2+2] cyclodimerization. On the other hand, FAVE and PFCA polymers are polymerized via base-mediated nucleophilic addition/elimination of bisphenols with TFVE monomers and decafluorocyclohexene respectively. The …

Insights Into Molecular Recognition And Reactivity From Molecular Simulations Of Protein-Ligand Interactions Using Md And Qm/Mm, Jerrano L. Bowleg

Theses and Dissertations

In this thesis, we have employed two computational methods, molecular dynamics (MD) and hybrid quantum mechanics/molecular mechanics (QM/MM) MD simulations with umbrella sampling (US), to gain insights into the molecular mechanism governing the molecular recognition and reactivity in several protein-ligand complexes. Three systems involving protein-ligand interactions are examined in this dissertation utilizing well-established computational methodologies and mathematical modeling. The three proteins studied here are acetylcholinesterase (AChE), butyrylcholinesterase (BChE), and peptidyl-prolyl cis-trans isomerase NIMA-interacting 1 (PIN1). These enzymes are known to interact with a variety of ligands. AChE dysfunction caused by organophosphorus (OP) chemicals is a severe hazard since AChE is …

Step-Growth Polymerization Of Perfluoro-Vinyl Ether, -Cycloalkenes, And -Acyclic Alkenes With Bisphenols Containing Variable Polycyclic Aromatic Cores, Karl Mpumbwa Mukeba

Theses and Dissertations

This dissertation reports the synthesis and characterization of semi-fluorinated polymers derived from the polymerization of bisphenols with fluoroalkenes. A series of diverse bisphenols were chosen from popular commercial bisphenols and new polycyclic aromatic hydrocarbon (PAH) derived bisphenols requiring synthesis. Step-growth condensation polymerization of bisphenols with three different fluoroalkene types was performed while probing polymerization conditions and the structure/properties relationship of the resulting fluoropolymers. The fluoroalkene monomers were chosen from bis(trifluorovinyloxy)biphenyl (TFVE), perfluorocyclohexene (PFCH), and perfluoro acyclic monomers, namely, perfluoro(4-methyl-2-pentene) and 1-perfluoroheptene to undergo this chemistry.

This work is divided into four parts based on the polymerization methodology.

The first …

Knocking Down Nox: Examining The Effects Of Transportation Electrification On Urban Ozone Production In The South Coast Air Basin, Jason Beal

Macalester Journal of Physics and Astronomy

With last year’s commitment to all in-state sales of new passenger cars and trucks being zero-emission by 2035 (California Executive Order N-79-20), California is leading the charge for transportation electrification in the United States. Despite being at the forefront of climate change management and mitigation, California has some of the worst air quality in the nation. While primarily motivated by a desire to reduce carbon dioxide emissions and reliance on fossil fuels, transportation electrification will also have a significant impact on local air quality. The goal of this study is to quantify and qualify this impact in the context of …

The Identification And Quantification Of Organophosphate Flame Retardants In Raw Materials Utilized In Polyurethane Production, Lindsay Tudor

Master of Science in Chemical Sciences Theses

Flame retardant additives are utilized in various polyurethane applications to comply with industry and flammability standards. Federal regulations and restrictive standards continue to tighten controls on certain impurities found in flame retardant blends. These restrictions include the limitation of organophosphates. Extensive research has been conducted to examine the effects of organophosphates in humans. To date, researchers have predominantly focused on the final product, mainly furniture and bedding products, rather than the raw materials utilized in production. Industrial chemists continue to grapple with the development of an effective method for detecting and quantifying organophosphate compounds in various flame retardant mixtures as …

Prediction And Confirmation Of A Switch-Like Region Within The N-Terminal Domain Of Hsirt1, Angelina T. Huynh, Thi-Tina N. Nguyen, Carina A. Villegas, Saira Montemorso, Benjamin Strauss, Richard A. Pearson, Jason G. Graham, Jonathan Oribello, Rohit Suresh, Brooke Lustig, Ningkun Wang

Faculty Research, Scholarly, and Creative Activity

Many proteins display conformational changes resulting from allosteric regulation. Often only a few residues are crucial in conveying these structural and functional allosteric changes. These regions that undergo a significant change in structure upon receiving an input signal, such as molecular recognition, are defined as switch- like regions. Identifying these key residues within switch-like regions can help elucidate the mechanism of allosteric regulation and provide guidance for synthetic regulation. In this study, we combine a novel computational workflow with biochemical methods to identify a switch-like region in the N-terminal domain of human SIRT1 (hSIRT1), a lysine deacetylase that plays important …

Analyzing The Interactions Of Thermoresponsive Coacervate-Forming Biodegradable Polyester Encapsulation On Model Protein Structure And Activity, Conner Casterline

Master of Science in Chemical Sciences Theses

Protein therapeutics hold high efficacy in treatment for various diseases including cancer and diabetes. However, the treatment cost is generally higher than other therapeutics mainly due to in vivo protein degradation. This drawback creates demand for more efficient delivery methods to preserve the function and integrity of protein therapeutics. Thermoresponsive coacervate-forming biodegradable polyesters (TR-PEs) are a thermoresponsive molecular packaging system used in protein therapeutic research. The term coacervate refers to a phase-separated solution in which a dense polymer phase separates from the aqueous phase to form nanodroplets within solution, capturing bioactive molecules. Limited research demonstrates if TR-PEs can encapsulate and …

Inorganic Cesium Lead Mixed Halide Based Perovskite Solar Materials Modified With Functional Silver Iodide, Vincent Obiozo Eze, Lucas Braga Carani, Haimanti Majumder, M. Jasim Uddin, Okenwa Okoli

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Inorganic CsPbIBr2 perovskites have recently attracted enormous attention as a viable alternative material for optoelectronic applications due to their higher efficiency, thermal stability, suitable bandgap, and proper optical absorption. However, the CsPbIBr2 perovskite films fabricated using a one-step deposition technique is usually comprised of small grain size with a large number of grain boundaries and compositional defects. In this work, silver iodide (AgI) will be incorporated as an additive into the CsPbIBr2 perovskite precursor solution to prepare the unique perovskite CsI(PbBr2)1-x(AgI)x. The AgI additive in the precursor solution works as a nucleation promoter which will help the perovskite to grow …

Towards Upcycling Biomass-Derived Crosslinked Polymers With Light, Ravichandranath Singathi, Ramya Raghunathan, Retheesh Krishnan, Saravana Kumar Rajendran, Sruthy Baburaj, Mukund P. Sibi, Dean C. Webster, Jayaraman Sivaguru

Chemistry Faculty Publications

Photodegradable, recyclable, and renewable, crosslinked polymers from bioresources show promise towards developing a sustainable strategy to address the issue of plastics degradability and recyclability. Photo processes are not widely exploited for upcycling polymers in spite of the potential to have spatial and temporal control of the degradation in addition to being a green process. In this report we highlight a methodology in which biomass-derived crosslinked polymers can be programmed to degrade at ≈300 nm with ≈60 % recovery of the monomer. The recovered monomer was recycled back to the crosslinked polymer.

Characterization Of Bimetallic Silver-Copper Nanoinks With Hydroxyethyl-Cellulose Additives, Daniel Brunick

Undergraduate Honors Theses

Coinage metal nanoparticles remain an intriguing subject for research due to their industrial versatility. Primary applications of coinage metal nanoparticles include printed electronics, solar panels, and sensors. Inks formulated with the nanoparticles are conductive and thus useful for fabricating sensors. Silver-copper nanoalloy inks are viable for the fabrication of flexible sensing devices for the detection of volatile organic compounds. One of the challenges is the ability to synthesize composition-controllable alloy nanoparticles at room temperature through wet chemical methods and achieve controllable sintering at room temperature. This work addresses the challenges by investigating the room-temperature synthesis of silver-copper alloy nanoparticles and …

Synthesis And Characterization Of Hydrazine Derivatives Of Coumarin For Bioorthogonal Chemistry Inside Cells, Akiva J. Grimaldi

Undergraduate Honors Theses

Protein carbonylation is one manifestation of oxidative stress, which is characteristic of many diseases. Our lab has developed several coumarin-hydrazine based fluorescent probes capable of detecting carbonylation in live cells via the formation of hydrazone conjugates. As an effort to expand and improve on these achievements, this work presents new data regarding the synthesis and characterization of three such probes. Two of the probes—julolidine coumarin hydrazide (JCH) and trifluoromethyl coumarin hydrazine (TFCH)—were previously synthesized by our lab. Here, JCH is studied in terms of its reaction speed and fluorescence enhancement in acylhydrazone formation with aldehydes under various conditions and catalytic …

Synthesis And Characterization Of Sustainable And Biobased Copolymers From Lignocellulosic, Guery Saenz

Theses and Dissertations

Natural compounds have been the primary resource used to produce polymeric materials by humankind since the mid-1900s. Yet, progress in bio-based polymers from renewable feedstock has encountered some obstacles, mainly due to the low prices of petroleum-based monomers, compared to natural and sustainable materials. However, most commodity plastics are non-degradable materials, and solid plastic waste accumulation adversely affects the environment. As the world population is growing and demanding chemicals, energy, and plastics materials, polymer research is focusing on synthesizing bio-based and degradable polymers. Thus, biomass, a sustainable and inexpensive feedstock, is highly appropriate for designing alternative thermoplastics that are degradable …

Optimization Of Paper-Based Substrates For Surface Enhanced Raman Spectroscopic Biosensor Development, Kaylee M. Cappuccio

Undergraduate Honors Theses

Advancements in the field of analytical chemistry have greatly expanded the development of biosensors for the detection of a wide array of diseases. This study aims to optimize an affordable paper-based nanocomposite biosensor that utilizes surface-enhanced Raman spectroscopy (SERS). Specifically, it investigates the preparation parameters for a paper-based SERS substrate, including nanoparticle administration and drying procedures. A particular focus of this work is to assess how the wax-defined paper channels can effectively enhance SERS intensity. The results revealed that while the wax-printed wells can define the nanoparticle administration for SERS detection, wax backing may reduce the sensitivity of SERS by …

Multifunctional Carbon-Supported Cobalt-Nickel Compounds For Water Splitting And Energy Storage Applications, Wang Lin

Electronic Theses & Dissertations

In order to effectively reduce carbon emission and achieve the goal of mitigating climate change, hydrogen energy has high hopes as a representative of green energy. According to the most current and updated research, compounds of cobalt and nickel have been widely studied as alternatives instead noble metal materials as catalysts for the electrolysis of water. Based on some other research reports, a hydrothermal method to grow cobalt-nickel hydroxide on nickel foam that has been carbonized in advance was proposed. To compare the modification results of these materials by different activation methods, calcination, sulfidation, and phosphating were performed on the …

Orbital Analysis Of Bonding In Diarylhalonium Salts And Relevance To Periodic Trends In Structure And Reactivity, Shubhendu S. Karandikar, Avik Bhattacharjee, Bryan Metze, Nicole Javaly, Edward J. Valente, Theresa M. Mccormick, David R. Stuart

Chemistry Faculty Publications and Presentations

Diarylhalonium compounds provide new opportunities as reagents and catalysts in the field of organic synthesis. The three center, four electron (3c–4e) bond is a center piece of their reactivity, but structural variation among the diarylhaloniums, and in comparison with other λ3-iodanes, indicates that the model needs refinement for broader applicability. We use a combination of Density Functional Theory (DFT), Natural Bond Orbital (NBO) Theory, and X-ray structure data to correlate bonding and structure for a λ3-iodane and a series of diarylchloronium, bromonium, and iodonium salts, and their isoelectronic diarylchalcogen counterparts. This analysis reveals that the s-orbital on the central halogen …

Biophysical Insight Into The Sars-Cov2 Spike–Ace2 Interaction And Its Modulation By Hepcidin Through A Multifaceted Computational Approach, Hamid Hadi-Alijanvand, Luisa Di Paola, Guang Hu, David M. Leitner, Gennady M. Verkhivker, Peixin Sun, Humanath Poudel, Alessandro Giuliani

Mathematics, Physics, and Computer Science Faculty Articles and Research

At the center of the SARS-CoV2 infection, the spike protein and its interaction with the human receptor ACE2 play a central role in the molecular machinery of SARS-CoV2 infection of human cells. Vaccine therapies are a valuable barrier to the worst effects of the virus and to its diffusion, but the need of purposed drugs is emerging as a core target of the fight against COVID19. In this respect, the repurposing of drugs has already led to discovery of drugs thought to reduce the effects of the cytokine storm, but still a drug targeting the spike protein, in the infection …