Simple Arenes As Aryne Synthetic Equivalents Via Sulfonium Salt Intermediates, Riley A. Roberts

Student Research Symposium

Arynes are ephemeral molecules that are yet to be fully exploited in synthetic strategy because they are often challenging to access. These reactive intermediates participate in a myriad of reactions that conventional chemistry is incapable of, making them extremely useful for the synthesis of important molecules like pharmaceuticals and agrochemicals. While classical approaches for synthesizing arynes employ cheap starting material, extremely harsh reagents are necessary to generate the aryne. In contrast, methods that do not require harsh reaction conditions do require starting material that is exceedingly difficult to synthesize. To access arynes quickly and efficiently, the work described herein aims …

Synthesis And Characterization Of Ternary Pt Nanoally Catalysts For Fuel Cells, Ylith Peck

Undergraduate Honors Theses

A hydrogen fuel cell is an electrochemical device that converts oxygen and hydrogen into electrical energy while producing water as the only by-product, which has attracted growing interest, especially in the automotive industry. This technology is efficient and has zero pollution to the environment, in contrast to the direct use of fossil fuels in combustion engines which produce pollution and greenhouse gas emissions. One of the key components for hydrogen fuel cells is the catalyst that operates at the cathode, which currently use platinum. Due to the scarce amount of platinum in the world, the manufacturing cost for fuel cells …

Part I: Synthesis Of Quinolones For Inhibition Of The Β-Barrel Assembly Machine In Gram Negative Bacteria; Part Ii: Synthesis Of Azo Dye Sensors For Detection Of Metal Ions In Aqueous Environments, Katryna Williams

Theses and Dissertations

Part I: Antibiotic resistance in Gram-negative bacteria is a growing cause of concern worldwide. Thousands of people die from antibiotic resistant bacteria every year. The β-Barrel Assembly Machine (BAM) in Gram-negative bacteria plays a role in antibiotic resistance as its porin, BamA, can regulate which molecules enter the cell, meaning it can prevent antibiotics from entering the bacterial cell. BamA exists in an open and closed form and is only selective in its closed form. BamA opens and closes through the H-bonding of two intramolecular β-strands. It is theorized that the creation of a β-sheet mimetic, based on work done …

Design, Synthesis, And Analysis Of Paired Coiled-Coil Peptidic Molecular Building Blocks Used For Linearly Controlled Self-Assembly Of Α-Helical Coiled-Coil Heterodimer Peptide Pairs, Jason Distefano

Chemistry Theses

Molecular building blocks are fundamental to biological synthesis and processes and have been utilized in advanced materials, drugs and drug delivery systems, and biotechnology. Proteins have been used as molecular building blocks for the construction of complex, well-ordered structures. Coiled-coil protein domains are essential subunits used for the oligomerization of protein complexes, gene expression, and structural elements of biological materials. The synthesis and assembly of proteins utilizing coiled-coil motifs are of great scientific interest due to their potential applications in disease treatment, biomechanical motors, nanoscale delivery systems, etc. However, assembling protein complexes with specific morphology is still challenging because …

Synthesis And Characterization Of Enantioenriched Deuterated And Fluorinated Small Molecules, Mitchell D. Mills

Master's Theses (2009 -)

The development of novel deuterated and fluorinated bioisosteres has significantly impacted the pharmaceutical and agricultural industry and created a growing demand for new synthetic methodology. Both deuterated and fluorinated small molecules exist at the forefront of drug discovery due to their unique ability to attenuate the pharmacokinetic properties of new and currently existing drugs. Selective, high-throughput methods for deuteration and fluorination are scarce in the literature, especially methods that introduce D or F atoms asymmetrically. Benzylic CH bonds are oftentimes key sites for enzymatic manipulation in metabolic processes, alteration of CH bonds to CD or CF bonds at the benzylic …

Antibacterial Activity, Structure-Activity Relationships, And Scale-Up Reaction Of 1,3,4-Oxadiazoles, Olivia Marie Smith

Undergraduate Honors Thesis Projects

Oxadiazoles are compounds in the field of organic chemistry that have been gathering interest in the medicinal chemistry and microbiology communities for their biological properties, which range from anti-inflammatory agents, to chemotherapy drugs, to antibiotics. The synthesis of oxadiazoles can be difficult due to the expensive and complex nature of the techniques used as well as the volatile reagents and elevated temperatures that are often required in organic synthesis. The Grote lab has recently developed a new method for the synthesis of 1,3,4-oxadiazoles under mild conditions. The goals of this thesis were thus twofold: to develop a viable scale-up procedure …

A Microfluidic Approach For Synthesis And Kinetic Profiling Of Branched Gold Nanostructures, Qi Cai, Valentina Castagnola, Luca Boselli, Alirio Moura, Hender Lopez, Wei Zhang, João M. De Araújo, Kenneth A. Dawson

Articles

Automatized approaches for nanoparticle synthesis and characterization represent a great asset to their applicability in the biomedical field by improving reproducibility and standardization, which help to meet the selection criteria of regulatory authorities. The scaled-up production of nanoparticles with carefully defined characteristics, including intrinsic morphological features, and minimal intra-batch, batch-to-batch, and operator variability, is an urgent requirement to elevate nanotechnology towards more trustable biological and technological applications. In this work, microfluidic approaches were employed to achieve fast mixing and good reproducibility in synthesizing a variety of gold nanostructures. The microfluidic setup allowed exploiting spatial resolution to investigate the growth evolution …

Encapsulation Of Molecular Probes In Polymer Nanoparticles For Visual Detection Of Heavy Metals In Water, Kyla Dewittie

Summer Scholarship, Creative Arts and Research Projects (SCARP)

Heavy metal contamination is a problem worldwide, and it has dangerous effects on humans and the environment. Lead is one of the most common metal toxins due to its presence in a variety of household items including paint and pipes. Mercury is another common toxin that is dangerous due to its long half-life which causes it to buildup in not only water sources, but also inhabiting wildlife. The consumption of both metals is detrimental to human health, therefore proper detection methods are needed. Various detection methods exist but are not cost or time efficient. Molecular probes could be a solution …

Synthesis And Characterization Of A Series Of Conducting Polymers Based On Indole And Carbazole, Mehmet Ergi̇ner, Belkis Ustamehmetoğlu, Esma Sezer

Turkish Journal of Chemistry

A series of indole (In) and carbazole (Cz) derivative monomers have been synthesized, such as 4-[3-carbazolyl] indole (4In-3Cz), 5-[3-carbazolyl] indole (5In-3Cz), 6-[3-carbazolyl] indole (6In-3Cz), 7-[3-carbazolyl] indole (7In-3Cz). The comonomers synthesized by Stille coupling reaction were characterized by 1H-NMR and elemental analysis. Potentiodynamic method was used for electropolymerization of comonomers, Indole, Cz, and the mixture of In and Cz. Electrochemical activities of resulting P[4In-3Cz], P[5In-3Cz], P[6In-3Cz], P[7In-3Cz], polyindole (PIn), polycarbazole (PCz) and P[In-co-Cz] films were investigated comparatively by CV at different scan rates, electrochemical impedance spectroscopy (EIS) and spectroelectrochemical measurements. The ionization potentials, Ip, specific capacitance, Csp, and optical band gap, …

The Investigation Of Fluorescence And Metal Interaction Properties Of Racemic 7,8,9,10-Tetrahydro-3-Hydroxy-4-(1-Hydroxyethyl)Benzo[C]Chromen-6-One, Hayretti̇n Ozan Gülcan, Kharar Tawfeeq Shukur, Açelya Mavi̇deni̇z, Okan Si̇rkeci̇oğlu, Mustafa Gazi̇

Turkish Journal of Chemistry

The design or investigation of fluorescence probes continues to receive attention with respect to the diverse applications of spectrofluorometry. Depending on the highly sensitive character, fluorescence spectroscopy-based methodologies have been widely used in recent years in different sciences, including analytical, environmental, and medicinal chemistry areas. In our previous works, we have shown the iron (III) selective on-off sensor properties of benzo[c]chromen-6-one derivatives. In this study, we have extrapolated this research to 4-substituted analogues and investigated both fluorescent and metal interaction properties. Following the synthesis and structure identification studies, (±)-7,8,9,10-tetrahydro-3-hydroxy-4-(1-hydroxyethyl)benzo[c]chromen-6-one was found as a fluorescent molecule displaying fluorescence enhancement in the …

Design, Synthesis, And In Vitro Antitumor Activity Of 6-Aryloxyl Substituted Quinazolinederivatives, Meixia Fan, Lei Yao

Turkish Journal of Chemistry

Quinazoline derivatives are a class of important antitumor drugs known as small molecule inhibitors that include epidermal growth factor receptor (EGFR) inhibitors. Based on the structure of poziotinib, a series of 6-aryloxyl substituted quinazoline derivatives were designed and synthesized. The in vitro antitumor activities of the compounds were evaluated by the 3-(4,5-dimethyl-thiazol-2- yl)2,5-diphenyltetrazolium bromide (MTT) method using the human gastric cancer N87 (HER2), nonsmall-cell lung cancer H1975 (EGFRT790M/L858R), and A549 (EGFRWT) cell lines. The most promising compound 4m exhibited potent antitumoral activities with IC50 values of 6.3 nM and 7.5 nM for N87 and H1975 cell lines, respectively. Meanwhile, it …

Synthesis, Antioxidant Activity, Molecular Docking And Adme Studies Of Novel Pyrrolebenzimidazolederivatives, Fi̇kri̇ye Zengi̇n Karadayi, Rahman Başaran, Mehmet Murat Kişla, Bi̇nay Eke, Zeynep Alagöz

Turkish Journal of Chemistry

Several 5-(alkylsulfonyl)-1-substituted-2-(1H-pyrrol-2-yl)-1H-benzo[d]imidazole derivatives were synthesized and their antioxidant activities were investigated using lipid peroxidation (LPO) and 7-ethoxyresorufin O-deethylase (EROD) assays. Docking analysis with Human NAD[P]H-Quinone oxidoreductase 1 (NQO1) was also performed to gather thorough information about these compounds that have antioxidant activities. Moreover, their molecular descriptors and ADME properties were calculated using the SwissADME online program. As a result, most of our compounds possessed better affinity and created ample interactions with NQO1. The most potent compound 5j had LP inhibition value of 3.73 nmol/mg/min. Other compounds exhibited moderate activity on LP levels comparing to standard butylated hydroxy toluene (BHT). However, …

Leveraging The 1,3-Azadiene-Anhydride Reaction For The Synthesis Of Functionalized Piperidines Bearing Up To Five Contiguous Stereocenters, Jorge Garcia, Jane Eichwald, Jayme Zesiger, Timothy K. Beng

Student Published Works

A modular and scalable strategy, which remodels 3-methylglutaric anhydride to 2-oxopiperidines bearing at least three contiguous stereocenters is described. The approach relies on the chemoselective and stereocontrolled annulation of 1,3-azadienes with the anhydride component. The resulting acid-tethered allylic 2-oxopiperidines are then engaged in several selective fragment growth processes, including catalytic denitrative alkenylation, halolactonization, and Vilsmeier–Haack functionalization.

Applications Of Vanadium Phthalocyanine In Catalytic, Acid-Based Medium To Couple Sugar Molecules, Juan Ricardo Luna

Theses and Dissertations

The vanadium-substituted tetraazatetrabenzoporphyrin, vanadium phthalocyanine, was synthesized via reflux and characterized using FITR and XRD analysis. Subsequent to synthesis, the vanadium phthalocyanine was studied as a catalyst in redox reactions to convert fructose to different molecules, the products were predominately levulinic methyl ester and heptadionic acid. The ability to convert fructose to other compounds, such as alkyl levulinic derivative, is an important process to help eliminate reliance on traditional chemical feed stocks and promote alternative fuels. Levulinic acid has been commonly used as a starting material in the synthesis of biofuels and a precursor for pharmaceuticals, plasticizers, THF derivatives, γ-valerolatone. …

Recent Studies On The Synthesis Of Medicinal Molecules., Paige Monsen

Electronic Theses and Dissertations

Medicinal chemistry interfaces synthetic organic chemistry, natural product chemistry and chemical biology, with a goal of yielding therapeutic agents. Natural products or compounds derived from natural sources such as plants, animals, and microorganisms, are often biologically active and render that compound a likely drug lead. For thousands of years humankind has utilized natural products for medicinal purposes and consequently scientists take advantage of both these compounds’ core structural characteristics and their modes of actions on selected targets as inspiration to develop therapeutics. Because the total synthesis of such complex molecules can be cumbersome and expensive, semi-synthetic methods on isolated natural …

Synthesis, Self-Assembly, And Material Applications Of Unimolecular Polyviologens, Abigail Delawder

Arts & Sciences Electronic Theses and Dissertations

Intellectual Gaps: Synthesis of high molecular weight, unimolecular, and sequence-defined polyviologens; spatiotemporal control over mechanical properties of materials using visible and near-IR light; on-demand, post hoc manipulation of materials

Intellectual Merit: Robust method for synthesizing higher-order polyviologens of distinct molecular weight; control the change in the mechanical properties of polymer-based, crosslinked materials using a wide range of wavelengths of light; degradation of viologen-crosslinked hydrogels

To understand fundamentally how viologens behave within a polymer chain, we needed a better and more efficient way of synthesizing these long chains of polyviologens. As simple as this process looks on paper, the synthesis is …

Synthesis And Characterization Of Novel Organic Ligands With Their Complexes Of Platinum, Copper And Uranium, Mustafa Adnan Yasin Aldulaimi

Dissertations

Transition metal complexes of symmetrical and asymmetrical Schiff bases have played a significant role in the field of coordination, inorganic, and bioinorganic chemistry as models for biological, analytical, industrial, and pharmaceutical applications. Over recent years a great deal of interest has developed in new transition metal complexes of Schiff base ligand. The preparation of novel organic ligands is the most important step in the development of metal complexes that exhibit unique properties and novel reactivity. To highlight the presentation of this dissertation and to provide more detailed investigations, the dissertation was separated into six chapters according to the sequence of …

Novel “Acid Tuned” Deep Eutectic Solvents Based On Protonated L-Proline, Patrycja Janicka, Andrzej Przyjazny, Grzegorz Boczkaj

Natural Sciences Publications

The paper presents new types of deep eutectic solvents (DESs) based on L-proline protonated using three different acids (hydrochloric, sulfuric and phosphoric)and playing the role of a hydrogen bond acceptor(HBA). Glucose and xylitol were used as hydrogen bond donors (HBD). A series of deep eutectic solvents with various mole ratios were obtained for the systems L-proline: glucose and L-proline: xylitol. Density, melting point, pH and viscosity of the synthesized DESs were determined along with the effect of water content, mole fraction of the HBA in DES and temperature on properties of the DESs. A wide range of densities (1343–1606 kg/m3), …

Exploration Of Fluorinated Α,Β-Dehydroamino Acids And Their Structure, Austin Lesueur

Undergraduate Honors Theses

This thesis explores the synthesis of fluorinated α,β-dehydroamino acids, specifically a fluorinated dehydrovaline derivative. Previous work has been done on the equivalent dehydrovaline derivative without fluorine present and this work builds toward the fluorinated version with the goal of comparing the two structurally. The synthesis presented here pulls from previous synthetic strategies employed for dehydrovaline while also exploring the synthetic impact of the electronegative fluorine atoms.

Facile Synthesis Of Metal Oxides, Sulphides, And Phosphides For Enhanced Energy Applications, Alfred Nkhama

Electronic Theses & Dissertations

An access to reliable, sustainable, eco-friendly and cost-effective energy supply is being challenged by the global increase in population and the rapid technological advancement. Sophisticated systems, machinery and various devices being innovated, require the steady energy supply for their operations and applicability. To have reliable energy, numerous researches are being conducted through various approaches across the world. In this research work, the facile approach in investigating and tuning the materials properties was employed to improve energy properties of metal oxides. Nanostructured NiFe-oxide and CoFe-oxide were synthesized using a facile coprecipitation method. It was revealed that; nanostructured materials have favorable structures …

Applications Of Sodium Azide In The Synthesis Of Tetrazines And Hydrolysis Reactions, My Le

Honors Theses

The inverse electron demand Diels−Alder cycloadditions of heterocyclic azadienes have provided a robust methodology for synthesizing highly substituted and functionalized heterocycles. It is widely used in organic synthesis and the pharmaceutical industry in the divergent construction of screening libraries and bioorthogonal conjugation. Each heterocyclic azadiene was found to possess a unique reactivity toward different classes of dienophiles, display predictable modes of cycloaddition, and exhibit substantial substituent electronic effects impacting their intrinsic reactivity and cycloaddition regioselectivity. Synthesis of 1,2,4,5-tetrazine has been reported in the literature since the late 19th century, showing scientists' tremendous interest in its application.

Herein we attempt to …

Synthesis Of A Dd-Π-Aa Organic Dye For Dye-Sensitized Solar Cells, Hope Lovell

Honors Theses

This project investigates the synthesis of a DD-π-AA (dual donor/dual acceptor) organic dye as a potential sensitizer for dye-sensitized solar cells (DSCs). The design of this dye was based off previous research that found dual donor/dual acceptor dyes exhibited promising results when used in a DSC. The donor groups, acceptor groups, and π-bridge were chosen for their stability, ability to absorb in the near-infrared (NIR) region, and intramolecular charge transfer (ICT) abilities.

While many components of the dye were synthesized, the final stages of the synthetic scheme were not completed due to the loss of time from COVID-19. Had the …

Synthesis Of Bulky And Polar Galactonoamidines For The Inhibition Of The Human Α-Galactosidase, Ifedi Orizu

Graduate Theses and Dissertations

Glycosidases are amongst the most abundant enzymes in nature. This is due to their role in the degradation of carbohydrates which are the major source of carbon or earth. The absence or malfunction of glycosidases is implicated in numerous diseases such as cancers, diabetes, and lysosomal storage disorders, which make them important drug targets for study in medicinal chemistry. The seminal work by Pauling and Wolfenden showed that enzymes bind to their substrate at the transition state with very strong affinity. Wolfenden estimated the dissociation constant to be around 10-22M. This encouraged the design of glycosidase inhibitors which mimicked one …

The Synthesis Of Photoswitchable Triptan Derivatives, Chelsea Sainsbury

Honors College

Serotonin has various functions throughout the body and directly effects many neurological diseases/disorders, like depression, that are linked to the dysregulation of serotonin. Triptans are indole containing drugs that bind to a subset of serotonin receptors (5-HT1Band 5-HT1D) and are used to treat migraines. In this project, the synthesis of anindole intermediate is attempted. Ideally, an azobenzene would have been added to the 5th position (replacing the primary amine). Azobenzenes are compounds composed of 2 benzene rings connected by a nitrogen-nitrogen double bond that can switch between cis and trans conformations by absorbing different wavelengths of light. The transformation of …

Nitro Group Reduction For Use In Organic, Cathodic Materials, Brock G. Goeden

Honors Thesis

The industrial demand for higher capacity, light-weight battery materials has skyrocketed in recent years due to heavy investments in portable electronics, electronic vehicles, and renewable energy sources. However, rechargeable battery technology has seen little improvement since the invention of the Lithium-Ion battery in the 1980s. The low energy density of the traditionally utilized LiCoO2 cathodic material (specific capacity: 272 mAh g-1), has limited its potential to meet these increasing demands. To solve this problem, our research group is investigating new types of lightweight, organic, polymeric materials with conductive backbones as a possible replacement for the cathodic materials in Lithium-Ion batteries. …

Electrospinning Fibers Via Complex Coacervation, Xiangxi Meng

Doctoral Dissertations

Electrospun fibers are high-surface-area materials widely used in applications ranging from batteries to wound dressings. Typically, an electrospinning precursor solution is prepared by dissolving a high-molecular-weight polymer in an organic solvent to form a sufficiently entangled solution. Our approach bypasses the requirement for entanglements and completely avoids toxic chemicals by focusing on using an aqueous complex coacervates solution. Coacervates are a dense, polymer-rich liquid phase resulting from the associative electrostatic complexation of oppositely charged macroions. We were the first to demonstrate that liquid complex coacervates could be successfully electrospun into polyelectrolyte complex (PEC) fibers. A canonical coacervate system was formed …

Comparisons Of Silver Nanoparticle Synthesis Methods By Microwave And Non-Microwave Using Hydrogen Gas As A Reducing Agent, Sofia Erech Hanapin

Honors Theses

Synthesis and characterization of silver nanoparticles are of current interest. This research project describes a simple and rapid synthesis of silver nanoparticles upon reduction of Silver (I) oxide (Ag2O) by molecular hydrogen (H2) at elevated temperature (70 – 100 °C) and a pressure of > 1 atmosphere by heating the aqueous mixture using a common kitchen microwave. This reaction generates naked silver colloids that contain no foreign stabilizers other than metal particles in aqueous media. Its application of an antibacterial effect was monitored by using biological cultures using the Kirby-Bauer Test.

An Investigation Of Cross-Links On Crystallization And Degradation In A Novel, Photocross-Linkable Poly (Lactic Acid) System, Nicholas Baksh

USF Tampa Graduate Theses and Dissertations

Polymeric molecular structure consists of repeating units bonded together. Mechanicalproperties can be altered without affecting chemical makeup by altering the number of these units. Small molecules can be introduced and/or polymers can be modified to form bonds between molecular chains. Cross-linking, as this is called, also introduces mechanical variation with minimal effects on chemical composition. Lastly, polymer chains reorient themselves in response to intermolecular forces. This temperature dependent response is known as crystallization. Although chemistry is unaltered, mechanical properties can depend highly on the percent of the sample that is crystallized.

Cross-linking is known to enhance the mechanical properties of …

Fabrication Of Metal-Silicon Nanostructures By Reactive Laser Ablation In Liquid, Eric J. Broadhead

Theses and Dissertations

Metal-silicon nanostructures are a growing area of research due to their applications in multiple fields such as biosensing and catalysis. In addition, silicon can provide strong support effects to metal nanoparticles while being more cost effective than traditionally used supports, like titania. Traditional wet-chemical methods are capable of synthesizing metal-silicon nanostructures with a variety of composition and nanoparticle shapes, but they often require high temperatures, toxic solvents, strong reducing agents, or need capping agents added to stabilize the nanoparticles. Laser processing is an emerging technique capable of synthesizing metal-silicon composite surfaces that offers a faster, simpler, and greener synthesis route …

Synthetic Pathways For Potential Platinum 1,10-Phenanthroline Compounds, Jacob Young

Mahurin Honors College Capstone Experience/Thesis Projects

There are extremely important uses for platinum when it comes to the treatment of cancers and dementias. One potential therapeutic combines platinum with a structure known as phenanthroline. This platinum phenanthroline structure is normally extremely water-insoluble, rendering it difficult to study and use in biological systems. The Williams’ Biochemistry Laboratory endeavored to find a simpler synthetic pathway for a water-soluble phenanthroline product. While unsuccessful in identifying a product as of yet, many synthetic pathways have been ruled out, and more hypothetical pathways are being formulated for testing.

Among the strategies analyzed are varying solvent, reagents, apparatus, methodology, and temperature in …