Chemistry Commons^™

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.

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 …

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 …

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 …

Synthesis And Characterization Of Polymer Nanomaterials Using Controlled Radical Polymerization, Lei Wang

Theses and Dissertations

This research focuses on creating and investigating polymer/organic bound interfaces on nanoparticles with advanced architectures to tailor the properties of polymer nanocomposites for various applications. Reversible addition-fragmentation chain transfer (RAFT) polymerization and a toolbox of surface functionalization from the simple to the advanced were developed to prepare the polymer nanomaterials.

In the first part (Chapter 2), a variety of RAFT agents (xanthate, dithiocarbamate and trithiocarbonate) were used to mediate the polymerizations of several classes of free radical polymerizable monomers. These monomers consist of styrene, methyl acrylate, methyl methacrylate, vinyl acetate and isoprene, which have different activities and require different classes …

Photochemical Elimination Reactions That Proceed Via Triplet Excited State Electrocyclic Ring Closures, Himali Devika Jayasekara

Master's Theses (2009 -)

Cage compounds have become an important tool for the study of biological processes. The research focuses on new cage compounds that can unmask functional groups present in biologically important molecules such as proteins, peptides, and oligonucleosides. The project focuses on certain functional groups that are often difficult to release photochemically. These are the thiolate groups present in cysteine residues of proteins and peptides. Thiolate groups are fairly basic leaving groups, unlike the more labile groups such as the carboxylates that are present in proteins and peptides, or the phosphate groups present in nucleosides. The research takes advantage of the ability …

Hitting Pause On Organic Chemistry, Jenny B. Vu

Interdisciplinary STEM Teaching & Learning Conference (2012-2019) (Archived)

Written procedures for performing organic chemistry experiments are replaced by visual demonstrations that allow students to watch these videos at home and/ or in the laboratory. These previously recorded demonstrations allow students to watch, pause, and rewind the video to better understand laboratory techniques.

Less Cookbook And More Research! Synthetic Efforts Toward Jbir-94 And Jbir-125: A Student-Designed Research Project In A Sophomore Organic Chemistry Lab, Mike A. Christiansen, C. L. Crawford, C. D. Mangum

Chemistry and Biochemistry Faculty Publications

In light of the meaningful learning gains that can be obtained through a genuine research experience, chemistry educators have had a longstanding interest in making teaching labs less “cookbook-like” and more research-driven [1]. With this mindset, we recently restructured our two-semester sophomore organic chemistry lab course to include a synthesis project that was chosen, designed, and carried out by students. This led to progress toward the syntheses of JBIR-94 and JBIR-125, two antioxidative/anticancer natural products that have yet to be assembled through organic chemistry. The major drawback of our course redesign is that it requires close supervision by an instructor …

Advancements In The Design, Synthesis, And Application Of Polybenzimidazoles, Alexander Lanier Gulledge

Theses and Dissertations

The overall goal of the work presented within this thesis is to investigate, understand, and develop structure-property relationships in regards to polymer structure, membrane stability, and device performance. Previous work has shown that material properties such as acid loading, proton conductivity, mechanical integrity, and device performance can be attributed to polymer structure, chemical functionality, and polymer architecture (homo, random, co-polymer etc.). Developing and understanding these relationships is critical to the advancement of fuel cell technology. Within this thesis, several of these relationships are investigated and reported.

Novel polymers and copolymer systems have been developed in this research and have significantly …

Design, Synthesis, And Evaluation Of Molecular Inhibitors For Biologically Relevant Enzymes, Sarah Emma St. John

Open Access Dissertations

The work in this thesis details the design, synthesis, and biological evaluation of molecular inhibitors for the inhibition of biologically relevant enzymes. The first three chapters of this thesis concern the polyphenol resveratrol and its inhibition of the quinone reductase 2 (QR2) enzyme. The work on this subject resulted in the complete design, synthesis, biological and structural evaluation of a second generation library of resveratrol analogues. From this work we identified a novel resveratrol analogue that inhibits QR2 in a previously unknown binding orientation. The fourth chapter of this thesis details the de novo design of molecules for the inhibition …

Synthetic Approaches To Organometallic Complexes For Electronics Applications, Ilya V. Vinogradov

Kaleidoscope

No abstract provided.

The Synthesis Of A Homologous Series Of Alkyl Lumazines And Their Application To The Dispersion Of Carbon Nanotubes, William P. Kopcha

Master's Theses

In this thesis, the synthesis of a series of alkyl lumazine surfactants (LC_n) is reported. Their application to the dispersion of both CoMoCAT and HiPco single-walled carbon nanotubes (SWNTs) is examined in detail and the thermal stability and chirality selection properties of dispersions made with these surfactants were compared both between themselves and with an alkyl flavin surfactant (FC₁₂). Lumazine alkyl chain length exhibited some control over the quality and the quantity of SWNTs dispersed. LC₁₀ was deemed most appropriate for comparison with FC₁₂ based on considerations of solubility and nanotube individualization. …

Polymers Used In Medicine: Common Types And Benefits Of Drug Delivery Systems, Camille Andrews

Natural Sciences Student Research Presentations

This poster describes the common types and benefits of drug delivery systems.

Design, Synthesis, And Biological Evaluation Of Novel Polyamine Transport System Probes And Their Application To Human Cancers, Aaron Muth

Electronic Theses and Dissertations

The mammalian polyamine transport system (PTS) has been of interest due to its roles in cancer and maintaining cellular homeostasis. Polyamines are essential growth factors which are tightly controlled via a balance of biosynthesis, metabolism, import, and export. This work focused on the development and biological testing of polyamine transport probes to help understand the molecular requirements of the PTS. This was mediated through the use of a CHO (PTS active) and CHO-MG* (PTS deficient) screen, where compounds demonstrating high toxicity in CHO and low toxicity in CHO-MG* were considered PTS selective. The first chapter focused on the development of …

Nmr And Computational Studies Of Nad(P)(H) Cofactor Binding, Junghwa Kim

Master's Theses (2009 -)

Tuberculosis (TB) is one of the most dangerous diseases in a sense of spread method. According W.H.O., one third of world population has this disease and annual one of these infected people spreads 10 -15 people unintentionally. To protect human from this bacterial, the unique feature of mycrobacterial [sic] TB was studied previously. The unique cell wall, peptidoglycan, has high content of DAP (diaminopimelic acid). The disruption of synthesis DAP results in cell death due to instability of cell wall. One way to inhibiting synthesis of DAP is to modify cofactor which acts with dehydrogenase. To do that the study …

Student-Faculty Research In Organic Chemistry, Timo V. Ovaska

Honors and Awards Speeches and Programs

Timo Ovaska remarks that the clothes we wear, the colors we see, the foods we eat, the fuels that power our cars, the medicines that make us heal and feel better, even the biochemical reactions that happen in our bodies are all manifestations of the importance of organic chemistry in daily life.

He also praises his students who chose to do research, as there is no mandatory research component for the chemistry major at Connecticut College, who have gone on to successful careers. Students chose to get involved not because it was going to be easy, but because they were …

Integrating Formative Feedback Into Individual And Group Assessments In A First Year Organic Chemistry Module, Barry Ryan, Julie Dunne

Conference papers

It is common for science undergraduates, particularly first year students, to remark that they do not receive appropriate support in their transition from second level to third level education; particularly in effective scientific laboratory report writing, new subject area preparedness and technical ‘know-how’ [1]. This is compounded by the insufficient, or inappropriate, feedback offered to students in these problem areas. The pedagogical emphasis often focuses on quantity rather than quality; both in report writing and content delivered. This publication describes an assessment methodology redesign to, firstly, incorporate on-line formative feedback and; secondly, to introduce one-to-one and one-to-group lab report feedback …

Access To Nmr Spectroscopy For Two-Year College Students: The Nmr Site At Trinity University, Nancy S. Mills, M. Shanklin

Chemistry Faculty Research

Students at two-year colleges and small four-year colleges have often obtained their exposure to NMR spectroscopy through "canned" spectra because the cost of an NMR spectrometer, particularly a high-field spectrometer, is prohibitive in these environments. This article describes the design of a NMR site at Trinity University in which spectral data from student samples from community colleges and several four-year colleges are obtained on a 300 MHz NMR spectrometer. The unprocessed free induction decay (FID) is distributed to the students via the Internet and then processed by the students at their local institutions. The success of the NMR site at …

Chemical Investigation Of The Antarctic Marine Invertebrates Austrodoris Kerguelenensis & Dendrilla Membranosa And The Antarctic Red Alga Gigartina Skottsbergii, John Alan Maschek

USF Tampa Graduate Theses and Dissertations

The marine realm and, in particular, the Antarctic benthos is largely unexplored and understudied. The chemical investigation reported herein reveals not only the biodiversity, but how that biodiversity manifests remarkable chemical diversity. In our continuing study of the nudibranch Austrodoris kerguelenensis, we have isolated a diverse suite of diterpenoid glyceride esters, palmadorins D - S (2.32 - 2.47), one of which is the first reported halogenated diterpene from a dorid nudibranch. Utilizing genomic data from collaborators, we have investigated the chemical diversity from phylogenetically unique specimens collected in close proximity to one another. Chemical groupings based on comparison of LC/MS …

Molecular Orbitals And Organic Chemical Reactions (Book Review), Jeffrey H. Glans

Chemistry & Physics Faculty Publications

Book review by Jeffrey Glans.

Fleming, Ian. Molecular Orbitals and Organic Chemical Reactions. Wiley-Blackwell, 2010, c2009.

ISBN: 9780470746608; 9780470746592 (pbk.)

Chemical Investigation Of The Antarctic Marine Invertebrates Synoicum Adareanum And Artemisina Plumosa, Jaime Heimbegner Noguez

USF Tampa Graduate Theses and Dissertations

Of the small percentage of organisms chemically investigated over the years as potential sources of natural products, much less is known about those from the marine realm. Despite the lack of attention they have received in comparison to terrestrial organisms, marine life have recently been found to represent a valuable source for novel bioactive compounds. Cold water marine habitats are home to a plethora of organisms that have the ability to produce secondary metabolites that exhibit a great deal of diversity in both their chemical structures and biological activities. The chemical investigation of these unique and relatively unstudied ecosystems is …

Trimethylsilyl Trifluoromethanesulfonate- Accelerated Addition Of Catalytically Generated Zinc Acetylides To Aldehydes, C. Wade Downey, Brian D. Mahoney, Vincent R. Lipari

Chemistry Faculty Publications

In the presence of TMSOTf, a wide variety of terminal acetylenes add rapidly and efficiently to aldehydes via a catalytically generated zinc acetylide. In the absence of TMSOTf, no reaction is observed under otherwise identical conditions.

Arrow Pushing In Organic Chemistry: An Easy Approach To Understanding Reaction Mechanisms (Book Review), Jeffrey H. Glans

Chemistry & Physics Faculty Publications

A book review by Jeffrey Glans.

Levy, Daniel E. Arrow Pushing in Organic Chemistry: An Easy Approach to Understanding Reaction Mechanisms. New York: Wiley, 2008.

ISBN 9780470171103

Pressure Perturbation Calorimetry And Guest-Host Chemistry Of Ndmg And N-Map With P-Sulfonatocalix[6]Arene, Cassandra Newell

Honors Theses

The aim of this project is to provide an explanation for recently obtained binding constants for two similar guest molecules, NDMG and N-MAP, with a p-sulfonatocalix[6]arene host in ammonium acetate buffer. This work was done primarily using pressure perturbation calorimetry, which is a technique that determines the coefficient of thermal expansion, α, which is in turn related to the solute molecule's effect on the order of the surrounding water molecules. A series of experiments were designed to test the effects of suspected confounding variables on the validity of PPC data. PPC was then used to study NDMG and N-MAP in …

A Series Of Vertically Integrated Nanotechnology Experiments For The Undergraduate Curriculum, Kevin W. Kittredge, Lesley E. Russell, Michael C. Leopold

Chemistry Faculty Publications

We have designed three nanotechnology experiments that are vertically integrated for an undergraduate chemistry curriculum. They are an evolving set of experiments for sequential courses in an undergraduate chemistry program. These experiments are designed to match the student's level of understanding for each particular course. The participating student is involved in a "research" project that progresses in both theory and experimental technique. Students benefit from these vertically integrated experiments by being involved in multiple facets of a simulated research project. This mimics a traditional research project under an advisor's supervision without the undesired drawback of an unknown outcome.

The Discovery-Oriented Approach To Organic Chemistry. 5. Stereochemistry Of E2 Elimination: Elimination Of Cis- And Trans-2-Methylcyclohexyl Tosylate, Ram Mohan, Marcus Cabay, Brad Ettlie, Adam Tuite, Kurt Welday

Scholarship

The E2 elimination is one of the most important reactions in organic chemistry and is discussed in considerable detail in a sophomore organic course. We have developed a discovery-oriented lab that illustrates the stereochemistry of the E2 elimination reaction and is a good exercise in 1H NMR spectroscopy. The added element of discovery insures that student interest and enthusiasm are retained.

The Discovery-Oriented Approach To Organic Chemistry. 4. Epoxidation Of P-Methoxy-Trans-Β-Methylstyrene. An Exercise In 1H Nmr And 13C Nmr Spectroscopy For Sophomore Organic Laboratories, Ram Mohan, Rebecca Centko

Scholarship

Epoxidation of alkenes using peroxyacids is one of the most fundamental reactions in organic chemistry, yet there are very few examples of laboratory experiments that illustrate this important reaction. We have developed a discovery-oriented lab experiment that illustrates epoxidation of alkenes as well as the reactivity of epoxides toward acids. The experiment involves reaction of p-methoxy-trans-β-methylstyrene (trans-anethole) with m-chloroperoxybenzoic acid (MCPBA), in both the absence and presence of a buffer, followed by product identification using ¹H NMR, ¹³C NMR, and IR spectroscopy. The added element of discovery ensures that students' interest and enthusiasm are retained.

The Discovery-Oriented Approach To Organic Chemistry. 3. Boron-Trifluoride Catalyzed Rearrangement Of Cis- And Trans-Stilbene Oxides. An Exercise In 1H Nmr Spectroscopy For Sophomore Organic Laboratories, Ram Mohan, Erik Sgariglia, Regina Schopp, Kostas Gavardinas

Scholarship

Epoxides, or oxiranes, are among the most versatile intermediates in organic synthesis. Yet very few examples of laboratory experiments involving reactions of epoxides are to be found in lab texts. We have developed a discovery-oriented laboratory experiment that involves the rearrangement of both cis- and trans-stilbene oxides with boron trifluoride etherate. The identity of the product can be easily determined by ¹H NMR spectroscopy and, in case of the trans isomer, by preparation of the semicarbazone derivative as well. In spite of the simplicity of the experiment, the element of discovery ensures that student interest and enthusiasm are retained.

The Discovery-Oriented Approach To Organic Chemistry. 2. Selectivity In Alcohol Oxidation. An Exercise In 1H Nmr Spectroscopy For Sophomore Organic Laboratories, Ram Mohan, Steven Shadwick

Scholarship

We have developed a simple oxidation experiment that presents the student with a puzzle and is a good exercise in ¹H NMR spectroscopy. The experiment, which illustrates the important concept of selectivity in organic synthesis, involves selective oxidation of a mixture of 1-heptanol and 2-heptanol using commercial swimming pool chlorine. ¹H NMR analysis of the product mixture allows the student to determine the selectivity exhibited by the reagent.

The Discovery-Oriented Approach To Organic Chemistry 1. Nitration Of Unknown Organic Compounds. An Exercise In 1H Nmr And 13C Nmr Spectroscopy For Sophomore Organic Laboratories, Ram Mohan, Sonia Mcelveen, Kostas Gavardinas, Jean Stamberger

Scholarship

Nitration is one of the most fundamental reactions in organic chemistry. However, the majority of the nitration experiments found in the standard lab textbooks are of the "cookbook" variety and convey none of the excitement associated with discovery in experimental chemistry. We have developed two simple nitration experiments that present the student with a puzzle and are a good exercise in ¹H NMR and ¹³C NMR spectroscopy. ¹³ C NMR spectroscopy is a powerful structure elucidation tool and yet not many examples of the use of ¹³C NMR spectroscopy in organic lab experiments can be found. The …