Organic Chemistry Commons^™

Dicyanobenzothiadiazole-Based Organic Dye As A Visible Light Absorbing Strong Photoinduced Oxidant With A 16 Microsecond Long-Lived Excited State, Ivy Li

Honors Theses

Strong photoinduced oxidants are important to organic synthesis and solar energy conversion to chemical fuels or electric. For these applications, visible light absorption is important to solar energy conversion and long-lived excited states are needed to drive catalysis. With respect to these desirable qualities, a series of five 5,6-dicyano[2,1,3]benzothiadiazole ((CN)₂BTD) dyes are examined as organic chromophores that can serve as strong photooxidants in catalytic systems. The series utilizes a ((CN)₂BTD) core with aryl groups on the periphery varying electron donation strengths relative to the core. The dyes are studied via both steady-state and transient absorption and …

Analysis Of The Light Responsive Azobenzene Peptide Nucleic Acid Duplexes, Kat Nguyen

Honors College Theses

Peptide nucleic acids (PNAs) are oligonucleotide analogues in which the sugar-phosphate backbone has been replaced by a pseudopeptide skeleton. Since PNAs use the natural nucleobases (Adenine, Thymine, Cytosine, Uracil, and Guanine) found in either DNA and/or RNA, they are able to hybridize according to Watson-Crick base-pairing to form duplexes. PNA is a promising therapeutic agent because they can function as antigene or antisense chemical agents. To further enhance their utility, we aim to incorporate a photoswitchable moiety using azobenzene. Here, we report the results of the synthesis and purification of a photoswitchable 11 mer PNA along with initial characterization efforts.

Surface-Functionalized Chemiresistive Films That Exploit H-Bonding, Cation-Pi, And Metal-Halide Interactions., Prasadanie Karunarathna Adhihetty

Electronic Theses and Dissertations

The development of gas sensors for detection of volatile organic compounds (VOCs) has been of interest in the sensing field for decades. To date, the use of metal nanoparticle-based chemiresistors for trace VOC detection, particularly gold nanoparticle-based sensors, is of great interest due to their high chemical stability, ease of synthesis, unique optical properties, large surface to volume ratio, and high level of conductivity. Much effort has been devoted towards gold monolayer protected clusters (Au MPCs) as chemiresistors to detect harmful VOCs. The present thesis documents the results of our efforts to exploit the advantages of functionalized Au MPCs chemiresistors …

Development And Novel Applications Of Halogenating Agents., Sagar Ravso Mudshinge

Electronic Theses and Dissertations

Organic halides are extensively utilized as synthetic intermediates in areas such as pharmaceuticals, agrochemicals, and material polymers. While many halogenating agents have been developed, they continue to have low efficiency or selectivity, are difficult to handle, and often have limited substrate scope. To address this issue, our laboratory has developed novel halogenating agents with improved stability and efficiency. In these studies, we demonstrated a novel application of halogenating reagent, HCl·DMPU, in the nitrile synthesis. We developed a novel method for C−SCF₃/SeCF₃ cross-coupling reactions using gold redox catalysis. We developed a novel trifluoromethylating agent in a cost-effective and …

Investigation Of The Analytical Utility Of The Inductively Coupled Plasma Mass Spectrometer (Icp-Ms) For The Quantification Of Proteins Via Lanthanide Labeling, Caitlin Elizabeth Dunlap

Undergraduate Honors Thesis Collection

The discovery and ability to provide an absolute concentration of biomarkers in the body can facilitate early diagnoses of diseases. This information can also be used for more accurate and unique treatments for those patients. While major advances in molecular mass spectrometry allows for a sensitive identification of these biomarkers, they are limited to only four orders of magnitude in their dynamic ranges. Due to this, detection and quantitation of low abundant proteins, which tend to make up these vital biomarkers, is very difficult. On the other hand, ICP-MS offers a wider dynamic range (up to 12 orders of magnitude) …

Light Harvesting And Electrically Conducting Metal-Organic Frameworks, Monica Gordillo Varela

All Dissertations

Composed of metal clusters nodes and organic linkers, metal-organic frameworks (MOFs) have emerged as versatile platforms with unparalleled chemical and structural tunability, synthetic facility, permanent porosity, and size-selective guest encapsulation capability. These features make them potential candidates for a variety of applications such as gas storage,drug delivery, catalysis,and sensing. In recent years, the introduction of redox- and photoactive components have yielded stimuli-responsive electronic and photonic MOFs and expanded their utility in molecular electronics and energy storage devices/technologies.

Chapter one describes the light-harvesting ability of a porphyrin-based MOF. Herein, we have demonstrated spontaneous solvothermal growth of [100]-oriented uniform pillared-porphyrin framework-11 (PPF-11) …

Sustainable Nanocatalysis In Water For C–C And C–N Cross-Couplings., Tharique Ahammed Ansari Nalakath

Electronic Theses and Dissertations

The development and application of various micelle-enabled nanopalladium-catalyzed organic transformations are discussed in this dissertation. These methodologies primarily harness the “micellar effect” imparted by the custom-designed amphiphile PS-750-M. Modern spectroscopic and imaging techniques were employed to systematically study the metal-micelle interactions and answer the fundamental questions regarding the operational nature of micellar catalysis. Chapter 1 reviews the history and evolution of organic synthesis, providing a critical outlook regarding the alarming inefficiency of contemporary synthetic practices indicating an inevitable transition to more sustainable synthetic techniques. In this context, the development of micellar catalysis is discussed, emphasizing its basic principles, applications, and …

Nucleic Acid Editing By Adenosine Deaminase Enzymes, Josey Rae Mckinley

Undergraduate Honors Thesis Collection

RNA editing is crucial to the genetic diversity and structural complexity of organisms. ADAR (adenosine deaminase acting on RNA) is an RNA editing enzyme that creates a mutation of adenosine to inosine. The human ADAR2 (hADAR2) enzyme is known to edit RNA; however, it contains minor sequence homology with the cytidine deaminase enzymes, APOBEC and AID, which are known to edit both DNA and RNA (11 & 12). The ability of hADAR2 to edit DNA was tested through transformation into the Saccharomyces cerevisiae yeast strain BY4741. DNA editing was tested by determining if the transformed yeast became resistant to the …

Friedel-Crafts Alkylation Of Benzene With A Superacid Catalyst, Josh T. Cutright

Undergraduate Honors Theses

Long-chain alkylbenzenes are industrially synthesized precursors to commercial surfactants such as laundry detergent. The currently used catalysts in the processes of their synthesis are corrosive and harmful to the environment. These problems can be avoided utilizing heterogeneous highly acidic catalysts. Solid catalysts do not corrode equipment and are relatively simple to remove from the post-reaction mixture. Phosphotungstic acid (PTA) supported on silica gel could be a possible catalyst due to its high acidity with an estimated pKa ≈ -13. The catalyst PTA-SiO₂ was prepared via the sol-gel method to covalently embed it in a silica support. The catalyst was …

Valorization Of Biopolymers And Biomass To Produce Materials For A More Circular Economy, Moira Lauer

All Dissertations

With a globally increasing population and largely unchecked consumption of raw materials, human society is on track for devastating consequences. Two industries responsible for utilizing massive amounts of raw materials and generating equally gargantuan quantities of waste are the packaging and infrastructure sectors. In 2017 in Europe, for example, packaging reached a record 173 kg of packaging waste per capita. One of the largest packaging consumers is the food industry, in which 40% of packaging is made of petroleum-derived single-use plastic, leading to a massive carbon imbalance. “The Built Environment,” on the other hand, is responsible for about 50% of …

The Design Of A Efficient Production And Purification Of Fibroblast Growth Factor 2, Mandeep Kaur

Chemistry & Biochemistry Undergraduate Honors Theses

Chronic wounds pose a major problem in the United States with an estimate of twenty-five million dollars a year spent on associated treatments. Growth factors can be used as a potential treatment for chronic wounds since they promote cell proliferation and angiogenesis. This study employs one specific growth factor, fibroblast growth factor 2 (FGF2) so that it could potentially be used in future treatment. Wild-type FGF2 is thermally unstable, and it has a mean elimination time of 7.6 hours. This study attempted to improve upon its stability through a mutation on the heparin binding loop. The mutation performed was K134E. …

Ketone Hydrosilylation Studies Using A Carbodiphosphorane Catalyst, Liam Sullivan, Allegra Liberman-Martin

Student Scholar Symposium Abstracts and Posters

The objective of this research is to discover an effective, safe, and low-cost catalyst for ketone hydrosilylation reactions, which involve the addition of a silicon–hydrogen bond across a C=O double bond. Improving catalyst efficiency could benefit the organic synthesis industry, as carbonyl hydrosilylation is used industrially in the synthesis of alcohol products. Use of the carbodiphosphorane catalyst as a replacement for toxic heavy-metal-containing catalysts could reduce waste and emissions harmful to the environment, while also providing an alternative means for accomplishing ketone reduction. Using a cyclic carbodiphosphorane catalyst, we have compared catalytic activity toward acetophenone hydrosilylation for a range of …

Understanding The Transition From General To Organic Chemistry, Hannah Chan

Student Scholar Symposium Abstracts and Posters

Organic chemistry is commonly known to have high failure rates and regarded as one of the most difficult courses offered in undergrad. This study assessed whether a modified general chemistry curriculum allowing for more time focused on foundational organic chemistry concepts in general chemistry can improve students’ grade outcome and/or self efficacy when transitioning from general to organic chemistry courses. Two separate variables were tested: grade outcome and self efficacy. Using an independent sample t-test, a comparison of the two groups (modified versus traditional general chemistry) was performed. Grades were assessed by giving students four questions (out of 4 points …

Fabrication Of Mof Films Of Uio Or Pcn Type Through Layer-By-Layer Molecular Deposition As Well As Bulk Deposition For Catalytic Applications, John Ozdemir

Graduate Theses and Dissertations

Metal-organic frameworks (MOFs) are crystalline, porous materials comprised of symmetric organic linkers coordinated to positively charged metal atoms or metal oxide nodes. This dissertation uses strategies in crystal engineering to advance the study of functional MOFs with emphasis on thin film deposition. The first chapter of this dissertation will introduce the field of reticular chemistry to the reader and describe synthetic efforts to develop useful building blocks for MOF materials: namely porphyrin macrocycles and carboxylate capped zirconium-oxo and hafnium-oxo clusters. The building blocks for MOFs developed in the first chapter will be employed in the second and third chapters through …

Understanding Interfacial Reactions Initiating On Electrode Materials For Energy Storage Technologies, Jingnan Li

Graduate Theses and Dissertations

Since the first generation of lithium-ion batteries featured lithium cobalt oxide cathode and carbon anode commercialized in the 1990s, the high-capacity materials with lower cost are in demand to further increase the battery energy density. Lithium metal and silicon anode are promising high-capacity anode materials to achieve next-generation lithium batteries. However, both the materials actively react in electrolytes and suffer from dramatic volume change. Therefore, a reliable passivation layer at the electrolyte/electrode interphase (i.e., solid electrolyte interphase, or “SEI”) is required to support the long-term cycling of both materials. Cetrimonium hydro fluoride (CTAHF2) has been proposed and synthesized as an …

Introduction Of Human Acidic Fibroblast Growth Factor (Fgf1) Variant With Increased Stability And Bioactivity, Azadeh Tavousi Tabatabaei

Graduate Theses and Dissertations

Human acidic Fibroblast Growth Factor 1 (FGF-1) involves in a broad spectrum of biological processes, including cell growth, proliferation, differentiation, migration, angiogenesis, wound healing, and embryonic development. hFGF1 non-selectively binds to cell surface hFGF receptor isoforms to elicit these cell-signaling processes. Since hFGF1 plays a significant role in tissue repair activity, that is a prime candidate for novel wound healing therapeutics. However, hFGF1 has been found to unfold near physiological temperature due to a strong electrostatic repulsion created by a dense cluster of positively charged amino acids near the c-terminus. The problem not only leads to proteolytic degradation of the …

Bis(Tryptophan) Amphiphiles: Design, Synthesis And Efficacy As Antimicrobial Agents, Michael Mckeever

Dissertations

Amphiphiles play important roles in nature. These molecules contain both hydrophilic and hydrophobic regions, leading to some astonishing properties. The lipid bilayer of the cell membrane is a fascinating organization of amphiphilic phospholipids. Natural and synthetic amphiphiles, such as antimicrobial peptides, interact with the cell membrane. Such interactions can impact transport of molecules across the cell membrane, disrupting cell functions. In this work, a library of tryptophan-containing amphiphiles was synthesized and their antimicrobial properties were explored.

First, a library of bis(tryptophan) amphiphiles was synthesized. Preparation included a coupling reaction of a diamine with tryptophan residues, via their carboxy-termini, at …

Design, Synthesis, And Analysis Of Paired Coiled-Coil Peptidic Molecular Building Blocks Used For Linearly Controlled Self-Assembly Of Α-Helical Coiled-Coil Heterodimer Peptide Pairs, Jason Distefano

Chemistry Theses

Molecular building blocks are fundamental to biological synthesis and processes and have been utilized in advanced materials, drugs and drug delivery systems, and biotechnology. Proteins have been used as molecular building blocks for the construction of complex, well-ordered structures. Coiled-coil protein domains are essential subunits used for the oligomerization of protein complexes, gene expression, and structural elements of biological materials. The synthesis and assembly of proteins utilizing coiled-coil motifs are of great scientific interest due to their potential applications in disease treatment, biomechanical motors, nanoscale delivery systems, etc. However, assembling protein complexes with specific morphology is still challenging because …

Synthesis And Study Of Unsymmetrical Bidentate Bis(Phosphino)Pyrrole Ligands And Their Transition Metal Complexes, Julia F. Vidlak

Honors Theses

Our laboratory has reported the synthesis and characterization of a broad library of unsymmetrical bidentate bis(phosphino)pyrrole (BPP) ancillary ligands for use in nickel-catalyzed cross-coupling reactions. The electronic and steric properties of nickel complexes bearing these ligands are examined, and our data support the hypothesis that these ligands produce nickel complexes with electron-deficient metal centers. The syntheses of (BPP)Ni(o-tolyl)Cl precatalysts for utilization in nickel-catalyzed Buchwald-Hartwig Amination are described, and preliminary reactivity studies reveal that (BPP)Ni(o-tolyl)Cl precatalysts are effective in promoting C–N cross-coupling reactions. Finally, we report steric measurements and electronic properties obtained from computed (BPP)NiCl2 and (BPP)Ni(CO)2 complexes, respectively. Additional reactivity …

New Chemoselective Dehydration And Cyclization Strategies Enabled By Triphosgene, Moshood Oreofeoluwa Ganiu

LSU Doctoral Dissertations

Since Friedrich Wöhler’s synthesis of urea in 1828, the techniques of organic synthesis have developed and advanced greatly. This advancement has facilitated the discovery of new organic synthetic methods, and enabled access to a more expansive chemical space. The purpose of this dissertation is to present the development of new organic synthetic reactions that were uncovered through previous discoveries. Additionally, the main theme of this work relies on exploiting the versatility of triphosgene in organic synthesis. To this end, the developed chemistries rely on the ability of triphosgene to serve as an activating agent, and a chloride source.

Chapter 1 …