Organic Chemistry Commons^™

Photoacid-Catalyzed C–C And C–O Bond Formation And The Synthesis Of Triazole - Containing Bis(Indolyl)Methanes, Jason Saway

Seton Hall University Dissertations and Theses (ETDs)

From photosynthesis to transition metal-type photocatalysts, the conversion of light energy into chemical energy is a fundamental process in chemistry. While photochemistry is not new to the world of science, there has been a renewed interest in the field, specifically with the use of photocatalysts. There is a wide variety of compounds that function as photocatalysts, ranging from transitions metal complexes, organic dyes, and photoacids. Photoacids, which have typically been used for polymer synthesis and the pH modulation of biological systems and have recently gained popularity due to their catalytic potential. These compounds offer an efficient, cost-effective way to conduct …

Design And Synthesis Of Peripherally Selective Endocannabinoid Enzyme Inhibitors For Ocular Indications, Kezia Reji Thomas

Senior Honors Theses

Peripherally selective compounds have been found to stimulate endocannabinoid receptor activity, which has been observed to have positive physiological effects such as ocular wound healing and inflammation control. The activation of the cannabinoid 1 receptor via binding of the endogenous ligands, anandamide and 2-arachidonoylglycerol, has been indicated to elicit these effects. Both ligands are controlled by two hydrolase enzymes, fatty acid amide hydrolase (FAAH) and monoacylglycerol lipase (MAGL), which can be targeted for therapeutic inhibition. Sulfonamide derivatives of JZL195 containing carbamate functionalities in the southern region of the inhibitor compounds were produced using novel carbamate exchange reactions. Polar functionalities were …

Mechanisms Of Formation Of Novel Guanine-Guanine Cross-Links As Major End Products During One-Electron Oxidation Of Guanine Derivatives, Evan Dunn

Undergraduate Honors Theses

Guanine (G), as the most oxidizable base in DNA, is the major focus of studies of oxidation damage to DNA. The present thesis reports the first detailed characterization of G dimerization products potentially resulting from recombination of neutral G• radicals. Previous research has discovered a novel type of products of G• dimerization, D1 and D2, formed from one-electron oxidation of G derivatives. However, the mechanism of this dimerization remains elusive. While there appears to be a tautomeric equilibrium between two forms of G•, G(N₁-H)• or G(N₂-H)•, it remains unclear which intermediate participates in the formation of …

Synthesis Of A Phenyl Substituted Zinc Dipyrrin Complex For The Purpose Of Analyzing Aromatic Substitutions On The Characteristics Of Compounds Of This Class, Kole Owen

Undergraduate Honors Theses

The field of photochemistry is as innovative in development as it is broad in application. However, utilization of energy from the sun’s electromagnetic radiation remains secondary to the combustion of fossil fuels for the global energy consumption. This is neither a sustainable nor renewable system, and it has contributed to a major decline in the health of our global environment as the greenhouse gases emission has led to an incline in global temperatures and ocean acidity. To develop effective ways to utilize solar energy, experimental effort is being directed towards the understanding of photosensitizers, molecules which absorb solar radiation and …

Toward The Design, Synthesis, And Characterization Of Abiotic Coiled-Coil Peptides Via Solid-Phase Copper-Catalyzed Azide-Alkyne Cycloaddition (Sp-Cuaac) Click Reaction For The Preparation Of Controlled Self-Assembly Molecular Building Block, Liaquat Ali

Chemistry Theses

The production of cutting-edge materials, the development of novel medications, drug delivery systems, technological advancements, and biosynthesizing all depend on molecular building blocks. Proteins are required for the creation of intricate, well-organized structures, and coiled-coil protein domains are vital subunits for the oligomerization of protein complexes, gene expression, and the structural components of biological materials. The numerous interactions between a wide variety of amino acids make it difficult to assemble protein complexes with a particular shape. In the current study, we successfully designed and synthesized four different 32-residue peptides, each of which had two modified amino azide residues. These peptides …

Incorporation Of Thiophenes And Benzothiophenes Into Novel Pi-Extended Dibenzophosphole Systems, Joshua Kim, Conner Schell

Campus Research Day

Dibenzophospholes are molecules with extended pi conjugation. This project aims to incorporate thiophenes and benzothiophenes into dibenzophosphole systems by using 2-bromothiophene, 2-bromobenzothiophene, and 3-bromobenzothiophene as starting materials. An ethyne intermediate is created via the Sonagashira reaction, which is further reacted to form the novel dibenzophosphole system. The ultimate goal is to fuse the newly incorporated functional groups, creating an even greater degree of conjugation.

Bacterial-Mediated Photocatalytic Organic Oxidation, Peter J. Pellegrinelli

Theses and Dissertations

Bacteria, though well-known and widespread in scientific application, have plenty more opportunity to grow in the field of organic synthesis. The primary objective of this project was to apply the use of bioluminescent bacteria in an organic photoredox reaction intending to use the bacteria as a renewable source of light. This sustainable method, as opposed to high wattage bulbs, paves a green pathway for organic photocatalytic reactions. Using bioluminescent E. coli, the focus was on performing organic oxidation reactions with a recyclable photocatalyst. When using bacteria in conjunction with chemicals like nitromethane, it was an obstacle to keep the E. …

Inhibiting Nitroso Related Methylation Of Guanine Using Dietary Supplements And Flavonoids, Elijah Gocotano, Hannah Klose

Liberty University Research Week

Undergraduate

Basic

Additivity Of Diene Substituent Gibbs Free Energy Contributions For Diels–Alder Reactions Between Me2c=Cme2 And Substituted Cyclopentadienes, Thomas M. Gilbert, Austin S. Flemming, Brendan C. Dutmer

Faculty Peer-Reviewed Publications

Systematic computational studies of pericyclic Diels–Alder reactions between (H3C)2C═C(CH3)2, 1, and all permutations of substituted cyclopentadienes c-C5R1R2R3R4R5aR5b (R = H, CH3, CF3, F) allowed isolation of substitutional effects on Gibbs free energy barrier heights and reaction Gibbs free energies. “Average Substitution Gibbs Free Energy Correction” ΔGASC#‡/ΔGASC# values for each substituent in each position appeared to be additive. Substituent effects on barriers showed interesting contrasts. Methyl substitution at positions 5a and 5b increased barriers significantly, while substitution at all other positions had essentially no impact. In contrast, fluoro substitution at positions 5a and 5b lowered barriers more than substitution at other …

Synthesis And Properties Of Bio-Based 3d Printable Resins, Cameron Woods, Seth Taylor, Jeremiah Coughlon, Turner Perdue, Sourav Chatterjee, Jason E. Bara

Scholars Week

A photopolymer resin is a monomer that, when introduced to light of a certain wavelength, starts to polymerize into a solid. This has become a growing part of the 3D printing industry. There have been many advancements in the field of 3D printing, however, a lot of these resins are not environmentally friendly and even harmful if not handled in the correct manner. Plant based resins are becoming more and more popular because of their biodegradability and for the possibility of using renewable resources. Glycerol is a plant-based compound that is produced in excess in industry. Glycerol obtained from bioethanol …

Physiochemical Properties Of Urethane-Containing Ionic Liquids And Ionenes From A Non-Isocyanate Synthetic Approach, George Timmermann

Scholars Week

Ionic polymers that are designed to contain ionic liquids (ILs) in their backbones have been shown to exhibit a high degree of variability through changing the type of ionic character and the location of the ionic region within the molecule. This large amount of variability in both the structure and characteristics of ILs allows researchers to design task-specific ionic polymers and ILs for a variety of applications including gas separation membranes and solid polymer electrolytes. The synthesis of a specific class of ILs and ionenes through the incorporation of urethane groups with imidazolium rings by reacting carbonyl diimidazole with various …

Synthesis And Characterization Of Some Disubstituted Cyclopentadienyl Rhenium Complexes As Potential Candidates In Semiconductive Materials, Chloe Vernon

Senior Honors Theses

Since 2000, when the Nobel Prize in Chemistry as awarded for conductive polymer research few studies have been performed concerning the conductive capabilities of discrete organometallic compounds. For this project, organometallic compounds were formed specifically with a transition metal included in the structure. Through oxidation and reduction reactions, the variation in the electrical conductivity could allow for an analysis of whether this unique structure would allow for tunability. The goal of this research was to begin with aromatic substituted fulvenes and perform various multistep synthesis processes, utilizing thallium salt intermediates, to produce several disubstituted cyclopentadienyl rhenium complexes. In this project, …

Rage Inhibitors In Neurodegenerative Diseases, V. Prakash Reddy, Puspa Aryal, Pallavi Soni

Chemistry Faculty Research & Creative Works

Nonenzymatic Reactions of Reducing Sugars with Primary Amino Groups of Amino Acids, Proteins, and Nucleic Acids, Followed by Oxidative Degradations Would Lead to the Formation of Advanced Glycation Endproducts (AGEs). the AGEs Exert Multifactorial Effects on Cell Damage Leading to the Onset of Neurological Disorders. the Interaction of AGEs with the Receptors for Advanced Glycation Endproducts (RAGE) Contribute to the Activation of Intracellular Signaling and the Expression of the Pro-Inflammatory Transcription Factors and Various Inflammatory Cytokines. This Inflammatory Signaling Cascade is Associated with Various Neurological Diseases, Including Alzheimer's Disease (AD), Secondary Effects of Traumatic Brain Injury (TBI), Amyotrophic Lateral Sclerosis …

Microscale Chemical Manipulation And Imaging Using Photoactive Molecules And Light, Uroob Haris

Chemistry Theses and Dissertations

Chemical manipulation with light has been an active and growing area of research with important implications in materials science, biotechnology, and environmental science. From early investigations of light sensitive materials for photography in the 19^th century, to printing billions of transistors on a semiconductor chip in present day, scientists have gained a deep understanding of photochemistry and the processes that allow us to harness light for everyday applications. In this work, we explore microscale fabrication and molecular imaging using light and photoactive molecules as foundational tools. We develop a visible-light mediated technique for high resolution microscale chemical lithography comprising …

Pc-01 Synthesis Of Zinc Glycoconjugated Phthalocyanines As A Potential Phototherapeutic, Jessica A. Silva-Conejo, Katrina Mccarter, Tessa Greene, Joshua V. Ruppel

SC Upstate Research Symposium

Photodynamic Therapy (PDT) uses photosensitizers that are activated by light to produce singlet oxygen that can cause cell damage and potential cell death. Phthalocyanines are promising photosensitizers due to their absorption at clinically relevant wavelengths, meaning that they absorb at a wavelength that can penetrate deeper into tissues.

One challenge with using Phthalocyanines is that they have very low solubility in biological media. One potential approach to increase solubility is through glycoconjugation. Glycoconjugation can also be used as a strategy to increase selectivity toward targeted tissues. Glycoconjugated phthalocyanines can be synthesized using a copper catalyzed azide-alkyne cycloaddition reaction, otherwise known …

Synthesis And Characterization Of New Azo Dyes Derived From Acyclovir And Sulfamethoxazole And Study Their Biological Activity, Abdul Rahman Y. Wahoud, Thanaa Shriteh, Ali Yousef, Mohammad Mazen Kondakji

Hadhramout University Journal of Natural & Applied Sciences

In this research, two new azo dyes, 9-(2-Hydroxy-ethoxymethyl)-2-(2-hydroxy5nitrophenylazo)-1,9-dihydro-purin-6-one and 4-(2-Hydroxy-napHthalen-1-ylazo)-N-(5-methyl-isoxazol-3-yl)-benzenesulfonamide, derived from Acyclovir and Sulfamethoxazole was synthesized. The first dye synthesis was started by diazation of acyclovir, then combined with 4-nitrophenol activated with potassium hydroxide 10%, yielding 80%, and its purity was verified by thin layer chromatography (TLC). The second dye synthesis was started by diazation of Sulfamethoxazole then combined with β-naphthol activated with potassium hydroxide 10%, yielding 87%, and its purity was verified by thin layer chromatography (TLC). The identity of the resulting pigments was determined based on spectroscopic methods such as infrared spectroscopy, proton nuclear magnetic resonance spectrum …

The Synthesis And Characterization Studies Of Modified Nucleobase In Pna And Dna, Gyeongsu Park

Electronic Thesis and Dissertation Repository

Nucleic acids have been extensively studied not only for their importance in biological systems as the medium of genetic information but also for their potential uses in therapeutic, diagnostic and other biological applications. As such, modified oligonucleotides and oligonucleotide analogues have drawn the attention of researchers from various disciplines. Modification of oligonucleotides can enhance their desired characteristics and engender unique properties, such as fluorescence, giving rise to a variety of applications. Peptide nucleic acid (PNA) is an oligonucleotide mimic with a pseudo-peptide backbone based on N-(2-aminoethyl)glycine that is renowned for high target binding affinity and resistance to enzyme degradation. …

Oligo [Poly(Ethylene Glycol) Fumarate] Gels With Photo-Sensitive Pendent Groups, Andrew Chung

Electronic Thesis and Dissertation Repository

Stimuli-responsive hydrogels are 3D polymeric structures that offer attractive qualities within the biomedical field due to their excellent biocompatibility and tunability to be employed in drug release, wound healing, and implants. Aliphatic polyesters are biodegradable polymers that naturally degrade by the process of simple ester hydrolysis. Oligo[poly(ethylene glycol) fumarate] (OPF) is a linear polyester containing repeating units of poly(ethylene glycol) and unsaturated fumarate. OPF naturally degrades through hydrolytic cleavage into poly(ethylene glycol) (PEG) and fumaric acid which is a naturally occurring compound found in the Kreb’s cycle. However, in some cases, it would be beneficial to activate or accelerate this …

Development Of An Lcms Method To Detect And Quantify Curcumin In A Novel Oral Formulation Of Turmeric, Brandon Renninger

Annual Research Symposium

No abstract provided.

Synthesis And Analysis Of Novel Troponoid-Based Chemical Probes, Alex Berkowitz

Dissertations, Theses, and Capstone Projects

Troponoids are a class of non-benzenoid aromatic species featuring a cycloheptatrienone ring and varying degrees of oxygenation. These scaffolds have proven ubiquitous amongst natural products, and have displayed promise as therapeutic agents against a variety of diseases. Herein, we will describe our efforts towards furthering troponoids as potential pharmaceuticals. In Chapter 1, we outline a kojic acid-derived oxidopyrylium cycloaddition/ring-opening method developed in our lab to generate ahydroxytropolones (aHTs). This route was successfully adapted to synthesize a small library of lipophilic aHTs that were proven to be effective against herpes simplex virus-1 (HSV-1) replication, while providing further insight into the mechanism …