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Articles 1 - 30 of 78
Full-Text Articles in Physical Sciences and Mathematics
Molecular Devices For Measuring Weak Solvophobic Interactions And The Development Of Pedagogical Tools For Organic Chemistry Students, Alexander N. Manzewitsch
Molecular Devices For Measuring Weak Solvophobic Interactions And The Development Of Pedagogical Tools For Organic Chemistry Students, Alexander N. Manzewitsch
Theses and Dissertations
The main topics of this dissertation are: 1) the development and discussion of a new molecular balance for measuring alkyl-alkyl interactions in a wide array of organic solvents, 2) the development of linear solvation energy relationships between solvent interaction parameters and solvent accessible surface area (SASA) in CH-arene interactions, and 3) the development of online resources for helping undergraduate students perform organic chemistry mechanisms problems well.
The solvophobic effect, that is the forced association between two solutes due to intermolecular attraction of the solvent molecules, is ubiquitous in organic chemistry and responsible for many significant phenomena thereof. However, there is …
Ferrocenium Salt Aided Substitution Reactions And Synthesis Of Glycosylated Curcumin Derivatives, Deva Saroja Talasila
Ferrocenium Salt Aided Substitution Reactions And Synthesis Of Glycosylated Curcumin Derivatives, Deva Saroja Talasila
Dissertations
Organic synthesis has been significantly advanced with the employment of transition metal complexes. The discovery of transition metal catalysts provided the synthetic community with powerful tools for accelerating reactions and making them more selective and efficient. Many chemical reactions do not happen without a catalyst.
Iron-based catalysts have several advantages for the chemical industry because it is a non-toxic and ecologically friendly metal. Our group previously found that ferrocenium cations with a 3+ oxidation state of iron-catalyzed propargylic substitution reactions at low temperatures. The sandwich structure of ferrocenes allows substituents to be introduced on the cyclopentadienyl rings, which allows for …
Theory Of Aqueous Solvation: Uninterrupted, Cyclic Hydrogen-Bonding Essential For Accurate Keto-Enol Energies And Grotthuss Tautomerism Of Acetone, Mark Recznik
Electronic Theses and Dissertations
Keto-enol tautomerization (KET) is a fundamental process impacting a range of molecular phenomena in organic and biochemistry. However, the accurate computation of solution-phase KET energies remains a challenge, even for prototypical acetone.
In Part I, keto-enol tautomers of acetone were incorporated into solvent clusters that interact via uninterrupted, cyclic hydrogen-bonding (UCHB) networks. An empirical model was created to predict accurate KET energies, Etaut, of simple carbonyl compounds. Based on the availability of experimental data and structural simplicity, acetone was selected as a prototype. A discrete-continuum strategy was employed – accounting simultaneously for local noncovalent interactions and bulk-phase effects …
Lipophilic Probes For Cellular Ethylene Detection, Morgan R. Brown
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 …
Design, Synthesis, And Catalytic Application Of Crystalline Porous Nanomaterials, Zainab Abdullah Almansaf
Design, Synthesis, And Catalytic Application Of Crystalline Porous Nanomaterials, Zainab Abdullah Almansaf
Graduate Theses and Dissertations
Chapter 1: COFs (covalent organic frameworks) are a new type of microporous crystalline polymer connected by organic units via strong covalent bonds. Due to their well-defined crystalline structures and excellent chemical and thermal stabilities, COF materials are considered promising candidates in applications such as gas adsorption, catalysis, and energy storage.Chapter 2: A new covalent organic framework (COF) based on imine bonds was assembled from 2-(4-formylphenyl)-5-formylpyridine and 1,3,6,8-tetrakis(4-aminophenyl)pyrene, which showed an interesting dual-pore structure with high crystallinity. Postmetallation of the COF with Pt occurred selectively at the N donor (imine and pyridyl) in the larger pores. The metalated COF served as …
Developing Covalent-Organic Frameworks For Protecting Against Radiation, Megan J. Francis
Developing Covalent-Organic Frameworks For Protecting Against Radiation, Megan J. Francis
Senior Theses
This research focuses on the development of lightweight, thermostable dual-function materials for secondary radiation protection and sensing by the integration of hydrogen-rich aliphatic chains inside the porous matrix of covalent-organic frameworks (COFs). The main aims of this project are the synthesis of organic linkers for forming a robust porous COF, synthesizing the porous COF through a condensation reaction, the development of hydrogen-rich aliphatic chains, and integration of aliphatic chains into COFs through click chemistry. This manuscript outlines the methodology and development of a novel self-assembled crystalline, porous material engineered to combine the functions of a shield and sensitive dosimeter. The …
End Group Modification Of Linear Dendritic Block Copolymers (Ldbcs), Chinwe Udemgba
End Group Modification Of Linear Dendritic Block Copolymers (Ldbcs), Chinwe Udemgba
Honors Theses
Linear dendritic block copolymers are amphiphilic molecules that consist of a dendritic hydrophilic portion and a linear hydrophobic portion. Its unique ability to self-assemble into spherical nanoaggregates while having the potential to uptake and transport both hydrophilic and hydrophobic drugs makes these polymers an item of interest in regard to the drug delivery field. The synthesis of polyamidoamine-polylactide linear dendritic block copolymers was designed to address the common issues in drug delivery systems, including problems in permeability, solubility, stability, specificity, and retention. Though this linear dendritic block copolymer has previously been synthesized in our lab with cationic amine surface functionalities, …
Synthesis Of A Dd-Π-Aa Organic Dye For Dye-Sensitized Solar Cells, Hope Lovell
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 …
Photoassisted Synthesis Of Complex Polyheterocycles Via Rational Design Of Tailored Photoprecursors, Tina Alanna Holt
Photoassisted Synthesis Of Complex Polyheterocycles Via Rational Design Of Tailored Photoprecursors, Tina Alanna Holt
Electronic Theses and Dissertations
Natural products remain the most common source for drug leads, although diversity-oriented synthesis of unnatural complex molecules is gaining momentum. Our lab has been developing experimentally simple and straightforward approaches to complex molecular architectures via photochemical reactions involving a minimal number of experimental steps. In order to achieve this, photoprecursors were assembled via high yielding reactions. Next, we deployed photoinduced cycloadditions to create complex 3-dimentional structures. Lastly, with this obtained primary photoproduct, post-photochemical transformations were used to further grow its scaffold complexity.
One method to increase scaffold complexity is the [4+2] intramolecular cycloadditions of azaxylylenes, which are developed through standard …
The Application Of Machine Learning In Analyzing Organic Compounds From Nmr Spectral Data, Nicole Maia Powell
The Application Of Machine Learning In Analyzing Organic Compounds From Nmr Spectral Data, Nicole Maia Powell
Senior Independent Study Theses
Nuclear magnetic resonance (NMR) is used in organic chemistry to identify unknown organic compounds. The data obtained from an NMR spectrometer are typically shown in the form of a spectrum, which is then analyzed by an analytical chemist. The action of analyzing a spectrum, especially one of a large and complex molecule, is a long and tedious process. In this project, Python is used to implement hierarchical clustering on NMR data obtained from an NMR spectrometer at the College of Wooster to explore its application in NMR analysis. MATLAB is used to build a decision tree from the same data, …
Total Synthesis Of Cytotoxic Mansouramycins From Amino Acids, Beatriz Gamez
Total Synthesis Of Cytotoxic Mansouramycins From Amino Acids, Beatriz Gamez
Theses and Dissertations
Natural products produced by plants, animals, and microorganisms are of significant importance in chemistry for being major sources of molecular scaffolds essential for new drug discovery. Mansouramycins are cytotoxic bioactive compounds containing isoquinoline skeletons with substituents on the quinone and pyridine rings that may be difficult to synthesize. Synthetic processes exist for compounds B and D, however, there exists an absence of simple synthetic approaches to all four alkaloids.
This project aims to provide a general total synthetic pathway to Mansouramycins A—D from amino acids for possible use in cancer treatment via these isoquinolinequinones. Preliminary experimentation suggests there may be …
Aryne-Guided C-H Functionalization Of Benzenoid Rings Using Diaryliodonium Salts, Aleksandra Nilova
Aryne-Guided C-H Functionalization Of Benzenoid Rings Using Diaryliodonium Salts, Aleksandra Nilova
Dissertations and Theses
The benzenoid core is a frequent and irreplaceable component of biologically active molecules. Structure function relationship of these compounds has been broadly analyzed and presented in numerous literature reports. Herein, we augmented existing knowledge by a broad analysis of the benzenoid substitution patterns in small molecule active pharmaceutical ingredients approved by the FDA. Our findings reveal a strong correlation that the most represented substitution patterns are those achieved via SEAr. Despite the rapid development of methods to functionalize benzenoid rings, the lack of synthetic methodologies to access sterically and electronically unfavorable positions is highlighted. We sought to establish …
Isolation, Structure Elucidation, And Synthesis Of Natural Products From Marine Cyanobacteria, Keren Solomon
Isolation, Structure Elucidation, And Synthesis Of Natural Products From Marine Cyanobacteria, Keren Solomon
Electronic Theses and Dissertations
This thesis describes the isolation, structure elucidation, and synthesis of natural products from marine cyanobacteria. A crude extract from a cyanobacterium collected in Curacao showed selective affinity for the dopamine D5 receptor in a screen against a panel of CNS receptors. Due to the high similarity of the D5 and D1 receptor, to date there are no known ligands that differentiate them. Attempts to purify the compound responsible for this affinity led to the isolation of the known compound caylobolide A. A second extract from a cyanobacterium collected in Panama underwent bioassay-guided fractionation and yielded the novel …
Development Towards An Ethylene Sensing Artificial Metalloenzyme, Mitchell Lee Ellinwood
Development Towards An Ethylene Sensing Artificial Metalloenzyme, Mitchell Lee Ellinwood
Electronic Theses and Dissertations
Ethylene (ethene) is the essential ripening hormone for climacteric plants, and consequently its detection and quantification is of considerable interest to the horticulture industry. Its detection however is a non-trivial pursuit, traditionally requiring expensive and inaccessible instrumentation that fail to provide in vivo information about ethylene. A ruthenium based fluorescent probe for the selective detection of ethylene has recently been developed, and it was envisioned that this probe could be made biocompatible by encasing it within a protein scaffold making it an artificial metalloenzyme. To this end biotinylated N-heterocyclic carbenes (NHCs) were synthesized, which can be appended onto the ruthenium …
Studies On The Size And Non-Planarity Of Aromatic Stacking Moiety On Conformation Selectivity And Thermal Stabilization Of G-Quadruplexes, Mandeep Singh
University of the Pacific Theses and Dissertations
Targeting DNA has the advantage over proteins for cancer remediation because of the fewer copies of the ligands required for the desired therapeutic effect. Traditionally, covalent DNA binders like alkylating agents have been used to induce genetic instability through the formation of DNA lesions and strand breaks, leading to cellular apoptosis. The primary drawback of this treatment is the non-specific binding that affects both cancerous and non-cancerous cells. G-quadruplexes are the DNA secondary structures that are present in abundance near the promoter regions of the oncogenes and are involved in the regulation of their activities. A ligand-mediated stabilization of G-quadruplexes …
Thioenamide Synthesis Inspired By Peptide Macrocycles, Joshua Allen Lutz
Thioenamide Synthesis Inspired By Peptide Macrocycles, Joshua Allen Lutz
LSU Doctoral Dissertations
Despite advances in medicine, antibiotic resistance threatens to return once preventable diseases to the human population. The microbisporicins are 24-amino acid antibiotic peptides belonging to the lantibiotic class, which pathogens have been slow to develop resistance. The uncommon post-translational modification S-[(Z)-2-aminovinyl]-D-cysteine (AviCys) is likely crucial to their activity, and appears in a small number of other peptides with compelling biological activities. Total synthesis of an AviCys-containing peptide has eluded the chemical community.
The primary challenge of AviCys synthesis is the construction of a thioenamide functional group. We demonstrate that acid-promoted reactions between an amide and …
Use Of Pope Engagement Index To Measure Cognitive Load Of Physical Modeling Activities In Organic Chemistry, Jenifer Calvert
Use Of Pope Engagement Index To Measure Cognitive Load Of Physical Modeling Activities In Organic Chemistry, Jenifer Calvert
Master of Science in Chemical Sciences Theses
Understanding how students learn and process information is critical to developing physical modeling activities that facilitate student learning by decreasing cognitive load in the working memory. Optimizing cognitive load during physical modeling activities in organic chemistry is the key to effective and efficient learning. Using EEG (electroencephalogram) and eye tracking technologies, researchers measured and recorded the cognitive processing of participants while they completed a chiral physical modeling activity. Analysis of the data using the Engagement Index developed by Pope et al provided information necessary to develop curriculum that does not undermine student learning due to excessive cognitive load.
Lewis Base Promoted Annulations Of Allenoates With 1,4-Naphthoquinones, Nicole Marie Shoup
Lewis Base Promoted Annulations Of Allenoates With 1,4-Naphthoquinones, Nicole Marie Shoup
Electronic Theses and Dissertations
Lewis base promoted cyclization of allenoates with electron deficient olefins open up the possibility to generate more complex organic structures. By generating more complex molecules, we are able to produce new compounds for biomedical and material applications. Both phosphine and amine Lewis bases offer interesting annulations with allenoates resulting in Lu or Morita–Baylis–Hillman type reactions. Once the Lewis base engages with the allenoate there can be several modes of nucleophilic reactivity that allows for the allenic ester to act as a two or three carbon synthon. The allenoate can then react with varying electron deficient olefins generating more complex molecules …
Synthesis And Conformational Studies Of Various Amides, Marcos Beltran-Sanchez
Synthesis And Conformational Studies Of Various Amides, Marcos Beltran-Sanchez
University of the Pacific Theses and Dissertations
In the past, aminocyclohexanol rings have been successfully utilized as pH-triggered molecular switches in various trans-2-aminocyclohexanol derivatives. By changing the groups on the amine nitrogen, these models provided a wide pH range in which a switch can occur. The pH-induced switch of conformation was monitored by 1H-NMR spectroscopy. The models were also incorporated into the bilayer membrane of liposome structures and tested for their ability to disrupt their membrane upon their conformational flip induced by a decrease in pH.
In this work, the amide bond has been studied as a molecular switch and various amide derivatives have been tested for …
Near-Infrared High Efficiency Organic Dye Sensitized Solar Cells (Dscs) And Biological Fluorescent Imaging Dyes, Yanbing Zhang
Near-Infrared High Efficiency Organic Dye Sensitized Solar Cells (Dscs) And Biological Fluorescent Imaging Dyes, Yanbing Zhang
Electronic Theses and Dissertations
With the energy consumption increase every year, the non-renewable energy sources such as fossil fuels, natural gas, and coal will not sustain forever. In this case, searching for a way to develop a renewable energy source is an emergency. For decades, dye-sensitized solar cells (DSCs) have received intensive attention due to their high power conversion efficiency and low material cost. This dissertation describes efforts to design and synthesize near-infrared organic dyes to apply to two systems: first, for use in the improvement of DSCs by the optimization of electron rich components such as ullazine and cross-conjugated -bridges to increase photon-to-electricity …
The Effect Of Oxidation, Thionation, And Dimerization On The Self-Assembly And Photophysical Properties Of Novel Discotic Materials, Katie M. Psutka
The Effect Of Oxidation, Thionation, And Dimerization On The Self-Assembly And Photophysical Properties Of Novel Discotic Materials, Katie M. Psutka
Theses and Dissertations (Comprehensive)
This thesis aims to increase understanding of the relationship between molecular structure and liquid crystalline temperature range by exploring the effects of oxidation, thionation, and dimerization on the self-assembly and properties of novel discotic materials. First, two alkoxy-substituted dibenzanthracenequinones were prepared by oxidation of the corresponding dibenzanthracenes. The quinone induced a liquid crystalline phase in the hexaalkoxy dibenzanthracene derivative, but not in the tetralkoxy derivative. However, both of the resulting materials were un-reactive to any further synthetic modifications that could be used to improve their properties. In comparison, two heteroaromatic dithienoanthracenedicarboximides were successfully prepared, although the addition of the thiophene …
Investigating The Effects Of Pre-Laboratory Videos With Associated Questions On The Performance And Overall Laboratory Experience Of Organic Chemistry Students, Shareef Gamal Mohamed Kotb
Investigating The Effects Of Pre-Laboratory Videos With Associated Questions On The Performance And Overall Laboratory Experience Of Organic Chemistry Students, Shareef Gamal Mohamed Kotb
Health Sciences Student Work
Background: Teachers struggle communicating ideas to students (Moreno et al, 2001). One of the aspects of teaching that’s most concerning is when students experience cognitive overload: the total effort exerted by working memory to grasp new information (Mayer, et al, 2002). The educational community found that introducing multimedia in learning minimizes cognitive overload (Mayer, et al, 2002). Little research has related to undergraduate chemistry classes, specifically the relationship between organic chemistry pre-laboratory multimedia and student learning. Purpose: The purpose of this capstone is to investigate the subjective efficacy of integrating pre-laboratory videos for lab preparation in an undergraduate organic chemistry …
Photochemical Generation Of Carbenes And Ketenes From Phenanthrene-Based Precursors Part I: Dimethylalkylidene Part Ii: Diphenylketene, Tarini S. Hardikar, Tarini Hardikar
Photochemical Generation Of Carbenes And Ketenes From Phenanthrene-Based Precursors Part I: Dimethylalkylidene Part Ii: Diphenylketene, Tarini S. Hardikar, Tarini Hardikar
Honors Theses
Previous studies have shown that the photolysis of phenanthrene-based cyclopropyl precursors can generate carbenes. In this work, a novel phenanthrene precursor was synthesized and photolyzed to generate the dimethylalkylidene carbene, which was subsequently trapped by cyclohexene. The car- bene was not prone to an internal rearrangement as some other carbenes are, and instead favored the intermolecular addition reaction. The precursor also underwent a rearrangement via pericyclic processes. A theoretical analysis of the potential energy surface of the system is presented using coupled cluster and density functional methods. Preliminary analysis for the precursor via time-resolved laser flash photolysis (LFP) was performed. …
Study Of Vaporization Enthalpies And Vapor Pressures Of Potential Environmental Pollutants By Correlation-Gas Chromatography, Chase Patrick Gobble
Study Of Vaporization Enthalpies And Vapor Pressures Of Potential Environmental Pollutants By Correlation-Gas Chromatography, Chase Patrick Gobble
Dissertations
The focus of this dissertation is on the measurement and analysis of thermodynamic data, including vaporization, fusion, and sublimation enthalpies and vapor pressures of dialkyl phthalates, as well as aliphatic and aromatic primary and tertiary amines by correlation gas chromatography (CGC). These compounds are important industrial and pharmaceutical substances whose prolonged use and sometimes misuse with regards to their disposal has created an environmental concern. Thermodynamic properties, such as vaporization enthalpy and vapor pressure provide crucial information to numerous industries and fields of study that include the chemical and petrochemical industry, chemical engineering and environmental science. Dialkyl phthalates are essential …
Synthesis Of A Novel Cox-2 Inhibitor Analog For Pet Scan Imaging, Rebecca Neighbor
Synthesis Of A Novel Cox-2 Inhibitor Analog For Pet Scan Imaging, Rebecca Neighbor
Chancellor’s Honors Program Projects
No abstract provided.
Solvent Free Vanadium Mediated Organic Transformations, Garrett Oberst
Solvent Free Vanadium Mediated Organic Transformations, Garrett Oberst
Undergraduate Honors Thesis Collection
A mixture of vanadium(V) oxide and copper sulfate was used to catalyze oxidative transformations in a variety of organic compounds. Multiple functionalities were tested, including thiols, amines and alcohols. Various transformations were observed resulting in various oxidized products, including coupling reactions. Reactions were performed in a solvent-free environment due to the insoluble nature of vanadium(V) oxide in common organic solvents. Results were analyzed using HNMR and GCMS.
Substrate Specificity Of The Lipn Hydrolase From Mycobacterium Ulcerans, Stephanie Raynor
Substrate Specificity Of The Lipn Hydrolase From Mycobacterium Ulcerans, Stephanie Raynor
Undergraduate Honors Thesis Collection
Mycobacterium ulcerans is the causative agent of Buruli ulcer, a tropical skin disease that affects thousands of individuals annually. Recent studies have revealed that lipolytic enzymes are involved in the pathogenicity processes of mycobacterium and could be potential targets for novel antibiotics. LipN is one proposed serine hydrolase in Mycobacterium ulcerans that contains the conserved α/β hydrolase protein fold and utilizes the conserved catalytic traid of serine, histidine, and aspartate/glutamate. The physiological substrate and biological role of LipN from M. ulcerans have not yet been determined. In this study, LipN was cloned into a pET28a plasmid and overexpressed in an …
A Continuous Process Towards The Synthesis Of Quinolones, Stevara N. Clinton
A Continuous Process Towards The Synthesis Of Quinolones, Stevara N. Clinton
Theses and Dissertations
Abstract
The development of quinolones is described from the first quinolone to the latest fluoroquinolones. Quinolones have generated considerable interest since their discovery because of their antibacterial capabilities. Analogs incorporating the 4-quinolone ring system comprise a largely expanding group of synthetic compounds. The development of antibacterial resistance has created the need for an efficient synthesis of quinolones that can be easily adapted toward the assembly of quinolone based antibacterial drugs.
There are several reported approaches to the 4-quinolone ring system. Many of these methods use expensive starting materials, require the removal of high boiling solvents, or use high temperature conditions …
I. Synthesis Of Ascarosides For Biological Evaluation And Ii. Development Of Visible Light-Promoted Selenofunctionalization And Grafting Of Aryl Iodides, Elizabeth Susan Conner Balapitiya
I. Synthesis Of Ascarosides For Biological Evaluation And Ii. Development Of Visible Light-Promoted Selenofunctionalization And Grafting Of Aryl Iodides, Elizabeth Susan Conner Balapitiya
LSU Doctoral Dissertations
This dissertation focuses on analog synthesis for biological evaluation and visible light promoted method development. Chapter 1 centers upon the synthesis of Caenorhabditis elegans dauer pheromone analogs. C. elegans is a nematode which, in times of environmental stress, enters a dauer stage. Two highly conserved pathways, which play important roles in some diseases in higher organisms, monitor dauer formation: TGF-β and IGF-1. Dauer formation is triggered by the nematode’s chemosensation of the dauer pheromone, consisting of a group of previously-isolated ascarosides. These compounds differ in chain length, saturation, terminal functionality of side chain, ω vs. ω-1 oxygenation and presence of …
Enzyme, Cosolvent, And Substrate Interactions In Ple Hydrolysis Reactions And Evaluation Of The Stability Of An Unnatural Glutathione Analogue, Maureen Elizabeth Smith
Enzyme, Cosolvent, And Substrate Interactions In Ple Hydrolysis Reactions And Evaluation Of The Stability Of An Unnatural Glutathione Analogue, Maureen Elizabeth Smith
Dissertations
Prochiral diester malonates have been hydrolyzed in the presence of Pig Liver Esterase (PLE). Several of the diesters produced the respective half-ester in moderate to high enantioselectivity. A series of cosolvent assays were performed to evaluate the ability of the cosolvent to influence the enantioselective outcome of the hydrolysis reactions. Ethanol produced the largest changes in enantioselectivity of all solvents evaluated. The isoenzymes of PLE were also evaluated and provided very different enantioselective outcomes than that of crude PLE. A series of NMR titrations was performed to explore the interactions between the substrates and ethanol cosolvents.
Improvements to our previously …