Organic Chemistry Commons^™

Synthesis Of Stimuli-Responsive Programmable Polymers Through Ring-Opening–Metathesis Cross-Metathesis (Rom-Cm), Courtney S. Dziewior, Sharon M. S. Strickland, Ping Li, Ken D. Shimizu

Journal of the South Carolina Academy of Science

Stimuli-responsive polymers can change their physical and/or chemical properties in response to external stimuli. These polymers have found great success in a number of important areas including molecular gels and biomedical engineering, as well as success in applications such as targeted drug delivery and biosensors. We have been working toward the development of programmable polymers that remember the response after a stimulus is withdrawn. To this end, we set out to synthesize specific functional monomers. While different types of reactions could potentially result in the desired target monomer, we studied the ring-opening metathesis–cross-metathesis reaction (ROM-CM). Previous work of ours synthesized …

Chronic Exposure To Complex Metal Oxide Nanoparticles Elicits Rapid Resistance In Shewanella Oneidensis Mr-1, Stephanie L. Mitchell, Natalie V. Hudson-Smith, Meghan S. Cahill, Benjamin N. Reynolds, Seth D. Frand, Curtis M. Green, Chenyu Wang, Mimi N. Hang, Rodrigo Tapia Hernandez, Robert J. Hamers, Z. Vivian Feng, Christy L. Haynes, Erin E. Carlson

Faculty Authored Articles

Engineered nanoparticles are incorporated into numerous emerging technologies because of their unique physical and chemical properties. Many of these properties facilitate novel interactions, including both intentional and accidental effects on biological systems. Silver-containing particles are widely used as antimicrobial agents and recent evidence indicates that bacteria rapidly become resistant to these nanoparticles. Much less studied is the chronic exposure of bacteria to particles that were not designed to interact with microorganisms. For example, previous work has demonstrated that the lithium intercalated battery cathode nanosheet, nickel manganese cobalt oxide (NMC), is cytotoxic and causes a significant delay in growth of Shewanella …

Visualizing The Fate And Distribution Of Pahs In Spartina And Avicennia Tissues From Barataria Basin, La, Kristina Jeannette Sebastian

LSU Master's Theses

During crude oil spill events, vegetation in marsh environments sequester polycyclic aromatic hydrocarbons (PAHs) from the crude oil by partitioning from the air phase through the waxy cuticle on the leaf surface. Recent studies from Macondo oil-impacted marshes have demonstrated that cycling of low molecular weight petrogenic PAHs occurs through the cuticle and other leaf tissue. At present, our understanding of how PAHs travel through the cuticle is coarse and limited by grab samples across the entire leaf, which preventing a full understanding the dynamics of PAH cycling in this environment. Multiphoton (MP) confocal microscopy visualizes the distribution of PAHs …

Synthesis And Evaluations Of “1,4-Triazolyl Combretacoumarins” And Desmethoxy Analogs, Tashrique A. Khandaker, Jessica D. Hess, Renato Aguilera, Graciela Andrei, Robert Snoeck, Dominique Schols, Padmanava Pradhan, Mahesh K. Lakshman

Publications and Research

1,4-Triazolyl combretacoumarins have been prepared by linking the trimethoxyarene unit of combretastatin A4 with coumarins, via a 1,2,3-triazole. For this, 4-azidocoumarins were accessed by a sequential two-step, one-pot reaction of 4-hydroxycoumarins with (benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate (BOP), followed by reaction with NaN₃. In the reaction with BOP, a coumarin-derived phosphonium ion intermediate seems to form, leading to an O⁴-(benzotriazolyl)coumarin derivative. For the CuAAC reaction of azidocoumarins with 5-ethynyl-1,2,3-trimethoxybenzene, catalytic [(MeCN)₄Cu]PF₆ in CH₂Cl₂/MeOH with 2,6-lutidine, at 50 ^oC, was suitable. The 4-azidocoumarins were less reactive as compared to PhN₃ and …

The Roundtable Of Scientific Communication: From Classroom To Course Creation, Back To Classroom And Beyond, Sean P. Hickey

LSU New Orleans Theses and Dissertations

This research encompasses many aspects of chemical education research including curriculum and pedagogical changes to the freshman and sophomore courses. Curriculum changes included the addition of recitations to the general chemistry and organic chemistry lectures and the creation of four new classes, CHEM 1001, 1002, 3091, and 3092. The addition of recitations was not limited to but was focused on improving DFW rates for these courses.

CHEM 3091 and 3092 are chemistry internship and undergraduate teaching assistant classes. These courses were necessary to offer outside internship opportunities and training for undergraduate teaching assistants, respectively. CHEM 1001 and 1002 are chemistry …

Synthesis, Characterization And Biological Evaluation Of Novel (S,E)-11-[2-(Arylmethylene) Hydrazono] Pyrrolo [2,1-C] [1,4] Benzodiazepine Derivatives, David Mingle

Electronic Theses and Dissertations

Pyrrolo [2,1-c] [1,4] benzodiazepine (PBD) is a class of natural products obtained from various actinomycetes which have both anti-tumor and antibiotic activities and can bind to specific sequences of DNA. PBD-dilactam was initially produced using isatoic anhydride and (L)-proline which was then converted to the PBD-thiolactam using Lawesson's reagent. Reaction of thiolactam with hydrazine in ethanol afforded PBD-11-hydrazinyl. Condensation of 11-hydrazinyl PBD with aldehydes possessing various substitutions was performed to obtain (S,E)-11-[2-(arylmethylene) hydrazono] pyrrolo [2,1-c] [1,4] benzodiazepine derivatives. ¹HNMR, ¹³C-NMR, DEPT, IR, GC-MS and X-ray crystallography were used for the characterization. Inhibition activity of the products …

Design And Synthesis Of Stable Aminyl And Nitroxide Radical Precursors, Joshua Bryan Lovell

Department of Chemistry: Dissertations, Theses, and Student Research

Aminyl diradicals with sterically-hindered tert-butyl groups have yet to be fully investigated for their increased stability due to their difficulty in synthesis. The first chapter of this thesis details design and synthesis towards sterically-hindered aminyl radical and diradical precursors.

Structural features effecting nitroxide radical stability have been well investigated except for the impact on the ring-size of stability of nitroxides towards reduction by ascorbate. Two 7-membered nitroxides derived from TEMPONE and TEMPOL have been synthesized and characterized. The alcohol nitroxide shows increased stability towards reduction by ascorbate compared to the corresponding TEMPOL, while the other nitroxide shows decreased stability compared …

Synthesis Of Diazonium N-(Perfluoroalkyl) Benzenesulfonimide Polymers For Proton Exchange Membrane Fuel Cells (Pemfcs), Helal Alharbi

Electronic Theses and Dissertations

The objective of the research is to synthesize the diazonium N-(perfluoroalkyl) benzenesulfonimide (PFSI)zwitterionicpolymers as electrolytes in polymerelectrolyte membrane (PEM) fuel cells. The proposed diazoniumPFSI zwitterionic polymer (I) is expected to enhance the thermal and chemical stability, increase the proton conductivity of electrolytes, and improve the catalyst efficiency for PEM fuel cells. Synthesis of the perfluorobenzoyl peroxide initiator, homopolymerization of perfluoro (3-oxapent-4-ene) sulfonyl fluoride,coupling reaction with4-sulfamonylacetanilide, couplingreaction with 4-nitrobenzene sulfonyl amide, n-deacetylation reaction, and diazotization reactionhave been carried outsuccessfully in the lab. The intermediate chemicals are characterized by GC-MS, IR, NMR, and GPC spectroscopies.

Phosphonate-Directed Catalytic Asymmetric Hydroboration: Synthesis Of Functionalized Chiral Secondary And Tertiary Boronic Esters And Mechanistic Insights, Suman Chakrabarty

Department of Chemistry: Dissertations, Theses, and Student Research

Over the past 30 years, catalytic asymmetric hydroboration (CAHB) of alkenes has emerged as a leading methodology to access chiral primary and secondary boronic esters. However, it wasn’t until 2015 that directed-CAHB was for the first time shown to efficiently access chiral tertiary boronic esters. The latter are excellent precursors to synthetically challenging structural motifs such as chiral tertiary alcohols, carbinamines and all-carbon quaternary stereocenters via stereospecific C-B bond substitutions. This dissertation focuses on phosphonate-directed CAHB of diverse alkene substrates, including challenging stereodefined trisubstituted alkenes, to efficiently access multifunctional chiral secondary and tertiary boronic esters. Mechanistic insights obtained via deuterium …

Development Of Ni-Catalyzed Alkene Dicarbofunctionalization Reactions, Shekhar Kc

Chemistry and Chemical Biology ETDs

Alkenes serve as one of the most important feedstocks for organic synthesis, having two vicinal sites for bond formation. In alkenes, both vicinal sites can be functionalized with two reagents in a process commonly known as alkene difunctionalization, which results in the formation of two new bonds. A number of alkenes difunctionalization reactions, such as diamination, dioxygenation, carboamination and carbooxygenation, are known. However, difunctionalization of alkenes with two carbon-based entities, termed alkene dicarbofunctionalization, is relatively less common. Development of such a process could provide a powerful method to introduce two different carbon fragments across an alkene in a regioselective manner, …

Acid-Mediated N-Iodosuccinimide-Based Thioglycoside Activation For The Automated Solution-Phase Synthesis Of Α-1,2-Linked-Rhamnopyranosides, Victoria R. Kohout, Alyssa L. Pirinelli, Nicola L.B. Pohl

Chemistry Publications

Carbohydrate structures are often complex. Unfortunately, synthesis of the range of sugar combinations precludes the use of a single coupling protocol or set of reagents. Adapting known, reliable bench-chemistry reactions to work via automation will help forward the goal of synthesizing a broad range of glycans. Herein, the preparation of di- and tri-saccharides of alpha 1→2 rhamnan fragments is demonstrated using thioglycoside donors with the development for a solution-phase-based automation platform of commonly used activation conditions using N-iodosuccinimide (NIS) with trimethylsilyl triflate. Byproducts of the glycosylation reaction are shown to be compatible with hydrazine-based deprotection conditions, lending broader functionality …

Organic Chemistry With A Biographical Emphasis: Solutions To In-Chapter Exercises, Timothy Soderberg

Chemistry Publications

The solutions to the in-chapter exercises of Organic Chemistry with a Biological Emphasis volume 1 and 2.

Organic Chemistry With A Biological Emphasis: Solutions To Selected End-Of-Chapter Problems, Timothy Soderberg

Chemistry Publications

The solutions to the in-chapter exercises of Organic Chemistry with a Biological Emphasis volume 1 and 2.

Organic Chemistry With A Biological Emphasis Volume Ii, Timothy Soderberg

Chemistry Publications

The traditional approach to teaching Organic Chemistry, taken by most of the textbooks that are currently available, is to focus primarily on the reactions of laboratory synthesis, with much less discussion - in the central chapters, at least - of biological molecules and reactions. This is despite the fact that, in many classrooms, a majority of students are majoring in Biology or Health Sciences rather than in Chemistry, and are presumably taking the course in order to learn about the chemistry that takes place in living things.

In an effort to address this disconnect, I have developed a textbook for …

Organic Chemistry With A Biological Emphasis Volume I, Timothy Soderberg

Chemistry Publications

The traditional approach to teaching Organic Chemistry, taken by most of the textbooks that are currently available, is to focus primarily on the reactions of laboratory synthesis, with much less discussion - in the central chapters, at least - of biological molecules and reactions. This is despite the fact that, in many classrooms, a majority of students are majoring in Biology or Health Sciences rather than in Chemistry, and are presumably taking the course in order to learn about the chemistry that takes place in living things.

In an effort to address this disconnect, I have developed a textbook for …

Photoswitchable Self-Complementary Hydrogen Bond Arrays, Suendues Noori, James A. Wisner

Western Research Forum

Background: Photochromism is the reversible transformation of a chemical material to another form by the absorption of electromagnetic radiation (light), where the two metastable forms have distinct absorption spectra and other properties. Photochromism in materials allows for the switching of their function solely based on irradiation with light. Polymers are used frequently as the building blocks for materials as they are versatile, multifunctional, can carry charge and be processed by solution-based deposition methods. Supramolecular polymers share the same definition as polymers with the exception that they are held together by reversible and directional non-covalent interactions such as hydrogen bonds. Synthesizing …

Additive-Free Palladium-Catalyzed Decarboxylative Cross-Coupling Of Aryl Chlorides, Ryan A. Daley, En Chih Liu, Joseph J. Topczewski

Chemistry Faculty Research & Creative Works

The cross-coupling of sodium (hetero)aryl carboxylates with (hetero)aryl chlorides proceed with 1 mol % palladium catalyst and does not require inorganic base, silver salts, or copper salts. This coupling uses two low energy partners, and the only stoichiometric byproducts are carbon dioxide and sodium chloride. The substrate scope includes less activated aryl chlorides and carboxylates (>25 examples). The palladium loading could be reduced to 0.1 mol %, and Buchwald-style precatalysts could be used.

Chemosensors Based On Higher Energy Gap Control Of Fluorescence In Conjugated Polymers, Chun-Han Wang

LSU Doctoral Dissertations

Conjugated polymers (CPs) have been widely investigated for their remarkably high sensitivity towards various chemical detection applications. CPs can exhibit effective transduction of certain analyte binding events through changes in fluorescence. These changes include amplified fluorescence quenching ("turn-offmechanism") or an appearance of a fluorescent emission ("turn-onmechanism"). Whereas turn-offsensors can be readily designed and are widely used, amplifying turn-onsensors, from a practical standpoint, are more convenient to use but are more challenging to design.

This dissertation primarily focuses on the development and study of conjugated polymer based amplifying turn-onfluorescence chemosensors utilizing the novel “higher …

Kinetic Resolution Of Cyclic Secondary Azides, Using An Enantioselective Copper-Catalyzed Azide-Alkyne Cycloaddition, Juliana R. Alexander, Amy A. Ott, En Chih Liu, Joseph J. Topczewski

Chemistry Faculty Research & Creative Works

An enantioselective copper-catalyzed azide-alkyne cycloaddition (E-CuAAC) is reported by kinetic resolution. Chiral triazoles were isolated in high yield with limiting alkyne (up to 97:3 enantiomeric ratio (er)). A range of substrates were tolerated (>30 examples), and the reaction was scaled to >1 g. The er of a triazole product could be enhanced by recrystallization and the recovered scalemic azide could be racemized and recycled. Recycling the azide allows efficient use of the undesired azide enantiomer.

Crystal Structure Of Zymonic Acid And A Redetermination Of Its Precursor, Pyruvic Acid, Dominik Heger, Alexis J. Eugene, Sean R. Parkin, Marcelo I. Guzman

Chemistry Faculty Publications

The structure of zymonic acid (systematic name: 4-hy­droxy-2-methyl-5-oxo-2,5-di­hydro­furan-2-carb­oxy­lic acid), C₆H₆O₅, which had previously eluded crystallographic determination, is presented here for the first time. It forms by intra­molecular condensation of parapyruvic acid, which is the product of aldol condensation of pyruvic acid. A redetermination of the crystal structure of pyruvic acid (systematic name: 2-oxo­propanoic acid), C₃H₄O₃, at low temperature (90 K) and with increased precision, is also presented [for the previous structure, see: Harata et al. (1977). Acta Cryst. B33, 210–212]. In zymonic acid, the hy­droxy­lactone ring …