Chemistry Commons^™

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 …

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 …

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 …

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 …

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 …

The Synthesis And Purification Methodology Of An Intermolecular Pyrophosphate Sensor: Applications For The Quantitative Polymerase Chain Reaction, Ethan Gevedon

Honors Projects

The optimized synthesis and purification methodology for an intermolecular pyrophosphate sensor scaffold molecule was performed: high performance liquid chromatography afforded the scaffold in excellent purity and yield. The applications of the sensor assembly in the quantitative polymerase chain reaction were discussed, and preliminary results show that

Simplified Synthesis Of Conjugated Polymers Enabled Via 1,4-Dihydropyrrolo[3,2-B]Pyrrole, Kenneth-John Jack Bell

Master of Science in Chemical Sciences Theses

Conjugated polymers have attracted significant attention as the active layer material in organic electronics, such as organic photovoltaics and light-emitting diodes, partly due to the ability to influence a broad range of properties through structural design motifs. However, high performance conjugated polymers suffer from numerous synthetic steps, generation of toxic waste, and harsh reaction conditions all of which impart additional costs that inhibit their widespread utilization. Therefore, an emphasis on reducing synthetic complexity and utilizing abundant, commercially available starting materials is needed for organic electronics to reach their full potential. Dihydropyrrolo[3,2-b]pyrrole (H₂DPP) chromophores offer a simple one-pot synthesis …

Fast Photochemical Oxidation And Footprinting Of Proteins Via Trifluoromethyl Radical Chemistry, Elaine Morrow

Honors Theses

Fast photochemical oxidation of proteins (FPOP) is a useful tool in proteomics because of the ability for modifications to occur on the scale of microseconds which reduces the modifications to tertiary and quaternary structure allowing for more accurate labeling of the protein. Labels for FPOP are generated from various radicals in our experiments which include hydroxyl radicals and trifluoromethyl radicals. Hydroxyl radicals are easily generated by using an excimer laser (KrF laser, 248 nm) or a UV flash lamp (as a part of the Fox™ System) by the photolysis of hydrogen peroxide. Trifluoromethyl radicals, however, need hydroxyl radicals to be …

X-Ray Crystallographic Analysis Of Quinoline N-Oxide And Isoquinoline N-Oxide With Zinc Halides, Nitrates, Perchlorates., Erin N. Groneck

GS4 Student Scholars Symposium

We have worked to analyze the chemistry between aromatic N-oxides, Quinoline N-oxide and Isoquinoline N-oxide, with zinc halides, nitrates, and perchlorates by X-ray crystallography. These structures were formed by reaction of the aromatic N-oxides with an equivalent of the zinc halide, nitrate, or perchlorate. These N-oxides had been chosen due to being the focus of this study. We will present the crystallographic X-ray structures of the synthesized novel complexes of the N-oxides with either a zinc halide, zinc nitrate, and zinc perchlorate.

New Synthetic Reactions Enabled By Protected Oxyallyl And Amidoallyl Cations, Binod Nepal

LSU Doctoral Dissertations

This dissertation entails design and development of two new synthetic methodologies made possible through the generation of cationic species, namely oxyallyl and amidoallyl cations. Chapter 1 involves literature survey on generation and trapping of oxyallyl cations. Mostly known for cycloaddition reactions with these elusive species, the most recent approach of direct nucleophilic capture of oxyallyl cations are discussed. Apt design of substrates and reaction conditions by Kartika Group to access a-electrophilic carbon towards the synthesis of a variety of value-added compounds, i.e., 1,4- and 1,6-dicarbonyls, carbazoles, densely substituted pyrroles and furans are elaborated.

Chapter 2 focuses on our discovery of …

Synthesis And Characterization Of A Novel Reaction-Based Azaborine Fluorescent Probe Capable Of Selectively Detect Carbon Monoxide Based On Palladium-Mediated Carbonylation Chemistry, Samuel Moore, Carl Jacky Saint-Louis

Symposium of Student Scholars

Azaborines are fascinating compounds because they possess valuable properties such as photochemical stability, have high molar absorption coefficient and high fluorescent quantum yields, as well as large Stokes shifts and tunable absorption/emission spectra. Here, we designed, synthesized, and will examine a novel reaction-based azaborine fluorescent probe capable of selectively detect carbon monoxide (CO) based on palladium-mediated carbonylation chemistry. This novel azaborine fluorescent probe will exhibit high selectivity for CO and display a robust turn-on fluorescent response in the presence of CO in aqueous buffer solution.

Ketal-Azaborine Versus Ketal-Azaborine With A Spacer: Structural Effects On The Photophysical Properties Of Tunable Heteroaromatic Polycyclic Chromophores, Albert Campbell, Janiyah Riley, Samuel Moore, Albert Campbell

Symposium of Student Scholars

Flat-structured heteroaromatic polycyclic compounds with extended conjugated π-systems such as azaborines are in high demand in the material and imaging technology markets because of their unique features such as simultaneous tunability of fluorescence color and intensity. We have designed, synthesized, and investigated a series of novel conjugated thermally stable ketal-azaborine chromophores that contain a phenyl ring as a spacer between electronic moieties and the ketal-azaborine core as easily tunable high-luminescent organic materials. We investigated the impact of the phenyl spacer on the ketal-azaborine unit. We examined the structural effects on their photophysical properties by incorporating electron –donating and –withdrawing substituents …

Azaborine Versus Azaborine With A Spacer: Structural Effects On The Photophysical Properties Of Tunable Azaborine Chromophores, Kaia Ellis, Janiyah Riley, Lyric Gordon, Janiyah Riley

Symposium of Student Scholars

Azaborines are fascinating compounds because of their valuable and interesting optical properties making them suitable to be utilized in many optoelectronic devices. We have designed, synthesized, and investigated a series of novel conjugated thermally stable azaborine chromophores by incorporating a phenyl ring as a spacer linking the chromophore to different electronic moieties as easily tunable high-luminescent organic materials. We investigated the effect of the phenyl spacer on the azaborine unit. The substituent effects of different electronic moieties were investigated by the insertion of electron –withdrawing and –donating moieties to the phenyl spacer. We examined the role of the electron –donating …

Organic Chemistry Through Dance, Holly Gibson

Undergraduate Research Conference

This research project explores representing organic chemistry mechanisms using dance. Dancers represent molecules, electrons, and atoms in demonstrating the movement of electrons and bonds created and broken by the movement. It was concluded that some organic mechanisms and ideas can be easily transferred to a dance concept, while others take more time and exploration. Additionally, dancers representing the atoms and electrons were able to have a better grasp of what was occurring, regardless of chemical education background. This leads to the conclusion of a new way to implement kinesthetic learning into the chemistry classroom. The purpose of the videos are …

Asymmetric Synthesis Of 𝜸-Borylated Amines Via Rhodium-Catalyzed Hydroboration Of Allylamine Derivatives, Rukshani Wickrama Arachchi, Shekhar Kc, Arun Suneja, James Takacs

UNL Student Research Days Posters, Graduate

The Takacs group has explored different dimensions of Catalytic Asymmetric Hydroboration (CAHB) reaction mainly focusing on variety of amide, oxime ether and phosphonate directing groups. Inspired by the results obtained with BINOL- and TADDOL- derived chiral catalysts along with pinacolborane, we explored the potential of acyclic N-acyl allylamines as substrates for direct-hydroboration to prepare chiral amine derivatives bearing g-boronic ester functionality, yields up to 90% with 98:2 enantioselectivity. The major enantiomer obtained is independent of starting alkene geometry, revealing that rhodium-catalyzed cis/trans-alkene isomerization occurs prior to hydroboration. In this poster, we will discuss the generation of active catalysts …

Comparing And Contrasting Therapeutic Drugs Vs. Lifestyle Changes That Combattype-Ii Diabetes, Alexander Cline Helmuth

Chemistry & Biochemistry Student Projects

In this thesis, I will be presenting various preventive approaches to combat type-II diabetes. The focus of this paper will be comparing and contrasting therapeutic drug targets such as Metformin and Sulfonylureas that are prescribed for type-II diabetic patients versus taking preventative steps such as making lifestyle changes including weight management, physical activity, and having a balanced diet that prevents onset of type-II diabetes or helps patients manage type-II diabetes. From this paper, one will gain insight on how there are multiple approaches to combat type-II diabetes that are not in the form of the pill.

Microfluidic Paper Analytical Devices, Madison Page

Chemistry & Biochemistry Student Projects

Microfluidic paper analytical devices (µPADs) are small, paper-based matrices similar to Lab-on-a-Chip (LOC). They are capable of semi-quantitative analysis, with applications ranging from medical to environmental to food and beverage testing. Important to improving point-of-care devices (POCs), various techniques have been integrated into µPADs to customize analysis and fit different clinical situations.

The Application Of Biological Processes To Increase Energy Potential In Landfills, Ashlyn Eisenhart

Chemistry & Biochemistry Student Projects

There has been a dramatic increase in the amount of waste that we humans have created. This has been due to population growth, an increase in industrial manufacturing, along with urbanization and modernization.⁸ The number of tons of municipal solid waste entering landfills has increased from 82.5 million tons in 1960 to 146.1 million tons in 2018.¹⁷ However, thanks to recycling, composting, and energy recovery from combustion, the percentage of solid waste going to landfills has dramatically decreased, from around 93.6 to about 65.4 percent.¹⁷

Chemistry Of Toothpaste, Kayla Blanche Kirtley

Chemistry & Biochemistry Student Projects

The chemistry of toothpaste is explained, with a description of the chemical components and their mode of action in the role of toothpaste.

Towards Semiconductor Nanorods With Nickel/Iron Cocatalyst., Kehinde Ayorinde

Masters Theses & Specialist Projects

The adverse effects associated with the utilization of fossil fuels has led to the need to provide an alternative cleaner energy. Photocatalytic hydrogen evolution reaction via water splitting provides a renewable pathway to generating energy. Our photocatalyst system includes a semiconductor component (CdSe/CdS core/shell nanorods) to capture light and an attached metal (cocatalyst) for the hydrogen evolution reaction. Platinum is an effective metal catalyst for this reaction due to strong proton binding energy that easily facilitates the reduction of water to produce hydrogen gas. However, due to the high cost of platinum, there is a need to find a less …

Synthetic, Photophysical, And Catalytic Studies Of Light-Harvesting Macrocyclic Complexes, Fox Bratcher

Masters Theses & Specialist Projects

Chromophores are an important class of compounds in Nature and industry, with several hundred thousand tons produced annually as dyes and pigments. Alone, these compounds absorb light unto themselves; however, several of these compounds can be combined to produce a beneficial cascading transfer of energy to a core chromophore.

In this study, photophysical properties of several covalent and axially borondipyrromethene (BODIPY)-conjugated complexes of porphyrin and salphen scaffolds have been evaluated in a series of emission and catalytic studies. In the porphyrin systems, a beneficial excited energy transfer (EET) from the BODIPY moieties to the porphyrin core was observed; however, only …

Sulfondiimidamides Unlocked As New S(Vi) Hubs For Synthesis And Drug Discovery, Nicholas Ball

Pomona Faculty Publications and Research

Despite their promise as drug targets, access to nitrogen-rich S(VI) compounds has been a significant synthetic challenge. In this issue of Chem, Zhang and Willis explore a new class of S(VI) compounds-sulfondiimidamides-providing robust strategies toward their synthesis, derivation, and promise as new sulfonamide bioisosteres.

A Quantitative Analysis Of The Efficacy Of Various Essential Oils Against The Sars Cov-2 Virus, Elizabeth Wagstaff, Chandrelyn Kraczek, Jack Brandon Lopez

Annual Research Symposium

A poster presentation and abstract for the Roseman Symposium. The project focuses on testing 3 essential oil blends and two disinfectants containing an essential oil blend against SARS CoV-2 in response to the COVID-19 pandemic. The project procedure involves plaque assays, disinfection, and neutralization techniques.

Effects Of Dibutyltin Exposures On Translation Regulatory Factor S6 In Human Immune Cells, Meaghan Lewis, Amanda Ruff, Margaret Whalen

Student Research

Dibutyltin is an organotin contaminating the environment through its use as a stabilizer in polyvinylchloride, PVC plastics. DBT has been found in drinking water and beverages, such as beer and wine, due to leaching from the PVC plastics used during the distribution of these drinks. Along with PVC plastics, DBT has been used as a deworming agent in poultry, infiltrating additional food products and increasing the exposure of the toxin to humans. Due to its multiple uses, it has entered the food chain and has been detected in human blood at levels as high as 0.3μM. Inflammatory cytokines are important …