Organic Chemistry Commons^™

Generative A.I.-Assisted Organic Chemistry Tutoring, Ji Kim

Open Educational Resources

By utilizing tools like ChatGPT, the project aims to provide detailed explanations, answer student questions, and assist with problem-solving, thereby creating a more interactive and personalized learning experience. This approach will help students grasp complex topics more effectively and improve their overall performance in chemistry.

Application Of A Novel Plasma-Based Advanced Oxidation Process For Efficient And Cost-Effective Destruction Of Refractory Organics In Tertiary Effluents And Contaminated Groundwater, Itay Even-Ezra, Anat Mizrahi, Daniel Gerrity, Shane A. Snyder, Andrew Salveson, Ori Lahav

Civil and Environmental Engineering and Construction Faculty Research

Corona discharge is emerging as a promising advanced oxidation process (AOP) for the treatment of a variety of organic contaminants, including compounds that are not effectively destroyed by more common AOPs. This paper presents laboratory and field results describing the destruction of regulated and Contaminant Candidate List (CCL) compounds in tertiary treated wastewater effluent and contaminated groundwater during the operation of a novel hydro-non-thermal-plasma (HNTP) AOP system. The system generates a plasma discharge above the target water matrix, which emits an “electron wind”, ultraviolet (UV) irradiation, O_3(g) and hydroxyl radicals (•OH) into a relatively thin water layer. The synergism …

Electron Rich Cobaltocenium Derivatives As Tunable Mechanophores For Mechanochemistry, Luis Daniel Ramos

Theses and Dissertations

In this dissertation, metallocene-containing polymers are investigated and probed for tunability in mechanochemistry. These metallocene moieties are experimentally and computationally characterized.

In chapter 1, relevant background and recent developments of metallocene-containing polymers are discussed. Additionally, the field of mechanochemistry is briefly introduced including applications and future directions within the field.

In chapter 2, design and synthesis of these metallocene-containing polyelectrolytes via ring opening metathesis polymerization (ROMP) are outlined. These polymers then undergo mechanophore activation via ultrasonication and relevant analysis and characterization of polymers both before and after ultrasonication are detailed. These polymers are comprised of differing electron donating substituents on …

Northern Fur Ssal Vibrissae Organochlorine Contaminant Concentrations, Dimitri Giarikos, Amy Hirons, Courtney White

SECLER Data

The eastern Pacific stock of northern fur seals (Callorhinus ursinus) on the Pribilof Islands has experienced population declines since 1980. The decline may be due to anthropogenic persistent organic pollutants (POPs) which bioaccumulate, are toxic, and persistent. This study conducted a comparison of 21 organochlorine (OC) and 39 polybrominated diphenyl ether (PBDE) analyte concentrations utilizing archived vibrissae (whiskers) from individual fur seals sampled in 1993 (n=30) and 2013 (n=41). The PBDEs had values five times greater than the legacy status OCs. There were no significant mean concentration differences between 1993 and 2013 for total organochlorines (ΣOCs), or total …

Northern Fur Seal Vibrissae Polybrominateddiphenylether Concentrations, Dimitri Giarikos, Amy Hirons, Courtney White

SECLER Data

The eastern Pacific stock of northern fur seals (Callorhinus ursinus) on the Pribilof Islands has experienced population declines since 1980. The decline may be due to anthropogenic persistent organic pollutants (POPs) which bioaccumulate, are toxic, and persistent. This study conducted a comparison of 21 organochlorine (OC) and 39 polybrominated diphenyl ether (PBDE) analyte concentrations utilizing archived vibrissae (whiskers) from individual fur seals sampled in 1993 (n=30) and 2013 (n=41). The PBDEs had values five times greater than the legacy status OCs. There were no significant mean concentration differences between 1993 and 2013 for total organochlorines (ΣOCs), or total …

Syntheses, Characterizations And Reactions Of Acene-2,3-Dicarbaldehydes, Glen Miller, Qian Liu

Faculty Publications

Here, we report improved syntheses, detailed characterizations and reactions of a series of acene-2,3- dicarbaldehydes including tetracene-2,3-dicarbaldehyde. DFT calculations corroborate and complement the experimental results. Tetracene-2,3-dicarbaldehyde and the benchmark organic semiconductor pentacene have isoelectronic p-systems and similar HOMO–LUMO gaps. Tetracene-2,3-dicarbaldehyde is soluble in a host of organic solvents (e.g., DMF, toluene, THF, chloroform, dichloromethane) and shows excellent photooxidative resistance in solution phases exposed to light and air. Further, it is readily sublimed from the solid-state without decomposition, and can be functionalized using different chemistries. We have demonstrated the utility of acene-2,3-dicarbaldehydes as reactants in the syntheses of novel diaryl-2,3-acenedimethanols and …

De Novo Synthetic Studies On Tetracyclic Triterpenoid Systems: Stereoselective Preparation, Biological Evaluation And Total Syntheses Of Euphol And Tirucallol, Joshua Nicholson

Dartmouth College Ph.D Dissertations

Tetracyclic triterpenoids have a rich history in biology, medicine, and chemistry. In terms of pharmaceutical relevance, compounds with this scaffold are one of the most successful classes with over 100 FDA approved examples. Despite this success, the vast majority of compounds within this class are prepared through semisynthesis. While this approach is undeniably successful, judged by the sheer number of medications generated, it also has limitations. Namely, semisynthesis requires the use of complex starting materials that have fixed absolute stereochemistry and often sparse functionality. One approach to address the inherent limitations with semisynthesis is through de novo synthesis. Recently, our …

Knowledge Management Of Historical Data: Ontology Development For Chemical Reactions, Quynh D. Tran, Alexander Harding Bradley, Balashanmuga Priyan Rajamohan, Jonathan E. Gordon, Van D. Tran, Kiefer Lin, Erika I. Barcelos, Laura S. Bruckman, Roger H. French

Researchers, Instructors, & Staff Scholarship

Knowledge management of the literature and historical data is critical to accelerated drug and materials discovery. Currently, literature knowledge is scattered in journal articles in various formats: diagrams, texts, plots, etc. Historical data from past experiments are saved in a number of local computers under confusing folder structures with ambiguous file names. To manage and organize historical data and knowledge, our group (SDLE) at CWRU follows FAIR (Findable, Accessible, Interoperable, Reusable) principles, which outline the best practices for data stewardship and data provenance, and ontology, a formal representation of terms and concepts and their relationships, as a tool to improve …

I. Degradable Polymers And Networks Based On Furan-Maleimide Diels-Alder Reactions Of Silyl Ether Derivatives And Maleimides, And Ii. The Michael Addition Of Amines To 1,3,5-Triacryloylhexahydro-1,3,5-Triazine (Tat) As A Synthetic Route To Novel Chelating Agents, Reyad Alkhazalah

Chemistry Theses and Dissertations

Degradable Polymers and Networks Based on Furan-Maleimide Diels-Alder Reactions of Silyl Ether Derivatives and Maleimides. I.

I. Part 1. Two groups of silyl ether monomers, A and B, were synthesized, each containing four different monomers. The monomers of group A were obtained by reacting furfuryl alcohol with four dichlorosilanes with varying siloxane spacers. The monomers of group B were obtained by reacting n-(2-hydroxyethyl)maleimide (HEMI-1c) with the same four dichlorosilanes. Each monomer from group A was individually reacted with each monomer from group B via a Diels-Alder reaction to produce a series of sixteen degradable linear polymers with a variety …

Investigating The Applications Of Peps To The Measurement Of The Stabilities Of Staphylococcal Nuclease (Stw) And Human Acidic Fibroblast Growth Factor (Hfgf1), Motolani Omolade Matthew

Graduate Theses and Dissertations

This dissertation presents a detailed investigation into the applications of Protein Equilibrium Population Snapshot H/D Exchange Electrospray Ionization Mass Spectrometry (PEPS-H/D exchange or PEPS) method. This method is based on protein equilibrium unfolding, and its fundamental capability is to capture a "snapshot" of the protein's state, allowing us to monitor the ratio of the unfolded to folded populations at different chemical denaturant concentrations. First, to increase the accuracy of PEPS data analysis for assessing protein stability, the traditional linear extrapolation method (LEM) was replaced. Instead of using LEM, which calculates free energy change based on the peak ratio of unfolded …

Quantum Modeling & Experimental Studies Of Radical Chemistry, Justin Michael Barrett

Graduate Theses and Dissertations

This work describes two projects centered around radical chemical mechanisms. The first investigation generalized the utility of a C-N bond homolysis followed by a [1,3] – rearrangement synthetic strategy found possible in N-alkylated thiazole & benzothiazole species onto analogous systems. Computational investigation guided the inquiry on structurally analogous systems that would favor a radical, [1,3] – rearrangement. Herein, we describe the implementation of that mechanism to transform Breslow Intermediate-like substrates into tertiary alcohol and amide products under facile conditions. We confer on the proficiency of this strategy with 2-pyridinemethanol and the problematic implementation with 2-(aminomethyl)pyridine. The second investigation solved a …

Application Of Functionalized Organosilicas In Adsorption Of Nitrates, Stephen Amoako

Electronic Theses and Dissertations

This study addresses the critical environmental issue of elevated nitrate levels in water bodies, primarily due to excessive use of nitrogenous fertilizers and improper waste disposal. It focuses on reducing nitrate concentrations in polluted water to permissible levels through the effectiveness of hybrid materials in nitrate adsorption. We synthesized nine amino-functionalized adsorbents using grafting and sol-gel techniques. Batch adsorption tests confirmed the high nitrate adsorption capacities of these adsorbents, with sol-gel materials showing the highest efficiency due to their abundant amino group contents. Among these, the surfactant-free, sol-gel adsorbent was the most effective, combining ease of synthesis with cost-efficiency. Our …

We Think, We Smell, We Remember: The Effect Of Smell On Memory For Chemistry Lab Learning, Michael A. Marino, Francine Wisnewski, Catherine Reilly, Andre Alexis

BCES: Faculty Presentations

The traditional five senses are the primary receptors of external stimuli for the brain. While tactile learning and visual observations are integral to the chemistry laboratory, olfaction is a sense that should be considered part of an educator's repertoire. Previous studies have discovered that our sense of smell plays a significant role in triggering memories. Moreover, specific scents like vanillin can prompt anamneses to recall previous experiences. A sample of 61 college students was employed for a three-week pretest-posttest control group experimental design. In the first week, participants conducted a chemical reaction to synthesize isoamyl acetate, the familiar and nontoxic …

Synthesis Of Portions Of An Acinetobacter Baumannii Lipooligosaccharide (Los), Brandon Conrad

LSU Doctoral Dissertations

Glycoconjugate vaccines have become an effective strategy for protection against an array of globally persistent diseases resulting from pathogenic bacteria such as Haemophilus influenzae type b (Hib), Neisseria meningitidis, and Salmonella enterica serotype Typhi. Comprised of a carbohydrate (referred to as glycan) covalently inked to a carrier protein, these vaccines can initiate adaptive immunity by inducing B and T cell responses once in the lymphatic system. This is particularly relevant for infants two years of age and younger whose immune systems are not fully developed. A continuously emerging threat in clinical settings, Acinetobacter baumannii is a Gram-negative bacterium …

Novel Approaches To The Activation Of Chalcogenoglycosides For O-Glycosylation, Tiffany Duong

LSU Doctoral Dissertations

Carbohydrates are integral to various biological processes such as cell signaling, function and regulation. Carbohydrates also play critical roles in various disease and metastatic pathways. This has garnered considerable attention to the field of glycoscience, however, the study of carbohydrate-containing compounds remains a challenge due to the difficulty in obtaining pure samples from natural sources. As a result, the biological evaluation of carbohydrates relies on synthetic chemistry to produce pure compounds in significant quantities. However, the synthesis of carbohydrates present their own challenges owing to the complexity in controlling stereochemistry and regiochemistry. The most significant of these challenges is controlling …

Advances In Stereoselective Glycosylation: Electron-Withdrawing Groups, Benzyne-Mediated Stereoinversion, And Visible-Light Photochemistry For 1,2-Cis O-Glycosylation, Erik Giovanni Alvarez Valenzuela

LSU Doctoral Dissertations

The symbiotic relationship between humans and their microbiota is essential for health, with imbalances in the complex microbiota ecosystem linked to a variety of disorders ranging from neurodegenerative to gastrointestinal diseases. Bacteria within the human microbiota, comprising over 1000 known species, are densely and diversely coated with oligosaccharides crucial for functions like cell recognition, communication, signaling, adhesion, proliferation, and pathogenic inhibition. However, studying the structure-activity relationships of these sugars which are also secreted by bacteria is challenging due to difficulties in obtaining homogenous samples from natural sources.

Chemical synthesis offers a solution by enabling the production of well-defined oligosaccharides in …

Response To Replication Stress And Maintenance Of Genome Stability By Wrn, The Werner Syndrome Protein, David K. Orren, Amrita Machwe

Markey Cancer Center Faculty Publications

Werner syndrome (WS) is an autosomal recessive disease caused by loss of function of WRN. WS is a segmental progeroid disease and shows early onset or increased frequency of many characteristics of normal aging. WRN possesses helicase, annealing, strand exchange, and exonuclease activities and acts on a variety of DNA substrates, even complex replication and re- combination intermediates. Here, we review the genetics, biochemistry, and probably physiological functions of the WRN protein. Although its precise role is unclear, evidence suggests WRN plays a role in pathways that respond to replication stress and maintain genome stability particularly in telomeric regions.

The Asymmetric Total Synthesis Of Membranolide And Efforts Towards The Oxeatamides, Sean Bradley

USF Tampa Graduate Theses and Dissertations

Total synthesis is a discipline within organic chemistry that is a constant force that propels the field forward. In our lab, we have immersed ourselves within the field of total synthesis to gain access to complex natural products, perform SAR studies, as well as highlight interesting methodology. Within these endeavors, we have completed the first asymmetric synthesis of membranolide. This has allowed us to explore potential biofilm eradication in our efforts to develop novel therapeutics to combat the ESKAPE pathogens and multi-drug resistance. We have also begun to pursue the first asymmetric total synthesis of the oxeatamides. By utilizing our …

Nanoparticles As Antioxidant Agents: A Comprehensive Review, Sulyman Olalekan Ibrahim, Halimat Yusuf Lukman, Fatimat Ronke Abdulkadir, Monsurat Yemisi Bello, Yusuf Oloruntoyin Ayipo, Halimah Funmilayo Babamale, Marili Funmilayo Zubair, Olubunmi Atolani

Al-Bahir

This study seeks to provide a comprehensive overview of the latest progress in the antioxidant properties of nanoparticles. Nanoparticles (NPs) have emerged as a promising tool in several domains of science and industry, including their application as antioxidant agents. The main knowledge gaps seem to be in correctly identifying the make-up of the naturally occurring phytochemicals that give these nano-antioxidants their extraordinary pharmacology and drug-like properties. In many instances, that characterization is done using spectroscopy instrumentation such as fourier-transform Infrared (FT-IR), scanning electron microscope (SEM), and X-ray diffraction analysis (XRD). From literature appraisals, it was discovered that a lot of …

Mechanistic, Biochemical, And Theoretical Studies Of Phototoxicity And Photobluing, Lloyd M. Lapoot

Dissertations, Theses, and Capstone Projects

This thesis consists of four chapters as detailed below:

Chapter 1 discusses the photoconversion of heptamethine to pentamethine cyanines and of pentamethine to trimethine cyanines. Here, we report mechanistic studies and initial experimental evidence for a previously unexplored 4-carbon truncation reaction that converts the simplest heptamethine cyanine to the corresponding trimethine cyanine. We propose a DFT-supported model describing a singlet oxygen (¹O₂) mediated formation of an allene hydroperoxide intermediate and subsequent 4-carbon loss through a retro-Diels-Alder process. Fluorescence and mass spectrometry measurements provide evidence for this direct conversion process. This 4-carbon truncation reaction adds to growing …