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 …

Antibacterial Activity, Structure-Activity Relationships, And Scale-Up Reaction Of 1,3,4-Oxadiazoles, Olivia Marie Smith

Undergraduate Honors Thesis Projects

Oxadiazoles are compounds in the field of organic chemistry that have been gathering interest in the medicinal chemistry and microbiology communities for their biological properties, which range from anti-inflammatory agents, to chemotherapy drugs, to antibiotics. The synthesis of oxadiazoles can be difficult due to the expensive and complex nature of the techniques used as well as the volatile reagents and elevated temperatures that are often required in organic synthesis. The Grote lab has recently developed a new method for the synthesis of 1,3,4-oxadiazoles under mild conditions. The goals of this thesis were thus twofold: to develop a viable scale-up procedure …

Access To Nitrogen Heterocycles Via Borrowing Hydrogen Catalysis, Robert P. Reynolds, Kellen P. Mcguire, Conor T. Mccormick, Kyle M. Lambert

Undergraduate Research Symposium

Nitrogen heterocycles are ubiquitous motifs which occur as the core structure of several alkaloid natural products exhibiting inherent biological activity against an array of bacteria, fungi, viruses, and cancer cell lines. These azacycles serve as key synthetic building blocks for medicinal chemists to access more structurally complex and diverse compounds with tunable biological properties. A synthetic approach to these valuable motifs employing intramolecular borrowing hydrogen catalysis has been developed. The utility of the developed chemistry will be applied to synthetic efforts towards the recently isolated Cylicomorphins A-E.

Oxidation Of Thiols To Disulfides Using An Environmentally “Green” Organocatalyst And New Mechanistic Insights, Kosta V. Vlasakakis, Olivia M. White, Robert P. Reynolds, Shayne M. Weierbach, Shannon M. Weaver, Ramsey T. Ritter, Nishi H. Patel, Eric C. Hayes, Sydney Dunmire, Kyle M. Lambert

Undergraduate Research Symposium

The selective oxidation of thiols to disulfides is an area of great importance in the areas of materials and medicinal chemistry research. The production of polymers, rubber, pharmaceuticals, and the folding of proteins in biological systems all rely on the formation of disulfide bonds. Herein, we introduce a stoichiometric and electrocatalytic method for the oxidation of various pharmaceutically and biologically relevant thiols into their respective disulfides in more environmentally benign solvents such as water and alcohol solvents. The scope of the transformation was evaluated and a detailed mechanistic study involving control experiments, experimental kinetic studies, and computational investigations led to …

Growth Kinetics Determine The Polydispersity And Size Of Pbs And Pbse Nanocrystals, Michael P. Campos, Jonathan De Roo, Matthew W. Greenberg, Brandon M. Mcmurtry, Mark P. Hendricks, Ellie Bennett, Natalie Saenz, Matthew Y. Sfeir, Benjamin Abecassis, Sanjit K. Ghose, Jonathan S. Owen

Advanced Science Research Center

A library of thio- and selenourea derivatives is used to adjust the kinetics of PbE (E = S, Se) nanocrystal formation across a 1000-fold range (kr = 10−1 to 10−4 s−1), at several temperatures (80–120 °C), under a standard set of conditions (Pb : E = 1.2 : 1, [Pb(oleate)2] = 10.8 mM, [chalcogenourea] = 9.0 mM). An induction delay (tind) is observed prior to the onset of nanocrystal absorption during which PbE solute is observed using in situ X-ray total scattering. Density functional theory models fit to the X-ray pair distribution function (PDF) support a Pb2(μ2-S)2(Pb(O2CR)2)2 structure. Absorption spectra …

Developing Efficient Transition Metal Catalyzed C-C & C-X Bond Construction, Chiyu Wei

USF Tampa Graduate Theses and Dissertations

This dissertation mainly contains three parts: 1) The synergistic Pd/enamine catalysis for asymmetric hydrocarbon functionalization of unactivated alkenes with ketones; 2) Gold redox catalysis with a selenium cation as mild oxidant; 3) HFIP promoted disulfidation and diselenation of alkyne, alkene, and allene.

Palladium-catalyzed alkene activation has its intrinsic limitation: 1) the requirement of a pre-functionalized alkene to form a Pd π-allyl complex; 2) problematic reversible β-H elimination. It always leads to limited reaction scope and losing of the stereochemical control. Synergistic palladium and enamine catalysis was conducted to promote ketone addition to unactivated olefins. A secondary amine-based organocatalyst was identified …

4,6-O-Phenylethylidene Acetal Protected D-Glucosamine Carbamate-Based Gelators And Their Applications For Multi-Component Gels, Pooja Sharma, Guijun Wang

Chemistry & Biochemistry Faculty Publications

The self-assembly of carbohydrate-based low molecular weight gelators has led to useful advanced soft materials. The interactions of the gelators with various cations and anions are important in creating novel molecular architectures and expanding the scope of the small molecular gelators. In this study, a series of thirteen new C-2 carbamates of the 4,6-O-phenylethylidene acetalprotected D-glucosamine derivatives has been synthesized and characterized. These compounds are rationally designed from a common sugar template. All carbamates synthesized were found to be efficient gelators and three compounds are also hydrogelators. The resulting gels were characterized using optical microscopy, atomic force microscopy, …

Synthesis Of Phosphonate-Based Diimide Ligands, Kenya V. Medina

Honors Program Theses and Research Projects

There has been a resurged interest in the synthesis of metal-organic frameworks because of their potential applications in energy production and drug delivery. Although diimides are insoluble in aqueous solutions, the addition of phosphonic acid allows the complex to be water soluble, which greatly increases their application. Therefore, the creation of a hybrid metal-organic complex by the addition of phosphonic groups to diimide ligands can result in a polar porous compound. In this project the ligand design included the use of dianhydrides including pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, and biphenyl-tetracarboxylic acid dianhydride. These dianhydride precursors were refluxed under argon …

Speciation Of Diaryliodonium Salts In Solution And Their Reactivity Towards N-Nucleophiles (Phthalimide And Amines) And O-Nucleophiles (Phenols And Phenoxide), Souradeep Basu

Dissertations and Theses

Benzenoid rings are prevalent in pharmaceutical drug molecules, agrochemical molecules and even in some polymers used in electronic device. Aryl rings are often installed using metal catalysis, however, metal free arylations are known but limited. Diaryliodonium salts are novel electrophilic arylating agents. Herein, metal free N-arylation of phthalimide and diarylether formation using aryl(TMP)iodonium salts is described.

The structure of diaryliodonium salts has been primarily studied in either the solid state or in-silico. The structure and speciation of diaryliodonium salts in solution is not well explored. In this work evidence of dimer formation of aryl(Mes)iodonium salts in chloroform using …

Methanol Decomposition On Ni(111) And O/Ni(111), Henrik Öström, Bingjie Zhang, Tiffany Vallejo, Bryn Merrill, Jeremy Huang, Jerry Larue

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Methanol decomposition on Ni(111) surfaces has been studied in the presence and absence of oxygen using temperature-programmed desorption and temperature-dependent sum frequency generation spectroscopy. Under both conditions the C–H and O–H bonds break, forming carbon monoxide and atomic hydrogen on the surface. No C–O bond scission was observed, limiting the number of reaction pathways. The O–H bonds break first (>150 K), forming surface methoxy, followed by C–H bond breakage (>250 K). All atomic hydrogen desorbs from the surface as H2 through H+H recombinative desorption. H2 desorbs at a higher temperature in the presence of oxygen (>300 K) …

One-Pot Conversion Of Carboxylic Acids To Aldehydes, Hannah Khan, Michael Nantz, Saurin Sutaria

Posters-at-the-Capitol

There are many different ways to convert a carboxylic text acid to an aldehyde. A common way to accomplish this transformation is to use multiple steps (e.g., reduction of the carboxylic acid to the corresponding alcohol followed by selective oxidation to the aldehyde). Our success in reducing the diacid muconic acid (1) to muconaldehyde (4) in a relatively mild, one-pot process has led us to examine whether the method can be expanded to other carboxylic acids. We report here our findings using benzoic acid as a representative substrate.

A Core–Shell Au@Tio2 And Multi-Walled Carbon Nanotube-Based Sensor For The Electroanalytical Determination Of H2o2 In Human Blood Serum And Saliva, Ayman Ali Saeed, Mohammed Nooredeen Abbas, Waheed Fathi El-Hawary, Yousry Moustafa Issa, Baljit Singh

Articles

A hydrogen peroxide (H2O2) sensor was developed based on core–shell gold@ titanium dioxide nanoparticles and multi-walled carbon nanotubes modified glassy carbon electrode (Au@TiO2/MWCNTs/GCE). Core–shell Au@TiO2 material was prepared and characterized using a scanning electron microscopy and energy dispersive X-ray analysis (SEM/EDX), transmission electron microscopy (TEM), atomic force microscopy (AFM), Raman spectroscopy, X-ray diffraction (XRD) and Zeta-potential analyzer. The proposed sensor (Au@TiO2/MWCNTs/GCE) was investigated electrochemically using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The analytical performance of the sensor was evaluated towards H2O2 using differential pulse voltammetry (DPV). The proposed sensor exhibited excellent stability and sensitivity with a linear concentration …

Lipophilic Probes For Cellular Ethylene Detection, Morgan R. Brown

Electronic Theses and Dissertations

The structure of ethylene is simple, yet its biological effects are significant. When considering its role in biology it is almost exclusively regarded as a plant hormone. Research on ethylene from plants was progressed by several advancements in analytical instrumentation, from its discovery to elucidation of its signaling pathway. There is currently limited understanding of ethylene’s role in mammals, but evidence suggests that it may be a biomarker for oxidative stress! Additional tools and technology are crucial to study this surprising and important signaling role in mammals. Our group has developed molecular ethylene probes as a strategy to detect ethylene …

Esipt-Enabled Alkyne Migration Provides Rapid Access To Benzoxazinones, Andrés G. Muñoz

Electronic Theses and Dissertations

Benozoxazinones have long been of interest to agrochemical scientists and medicinal chemists because of their widespread biological activity. These scaffolds are also of interest to synthetic chemists, who recognize the utility of benzoxazinones for accessing functionalized heterocycles. The use of efavirenz, a benzoxazinone-based reverse transcriptase inhibitor used in the treatment of HIV-1, has brought increased attention to this privileged pharmacophore. While there exist numerous strategies for synthesizing benzoxazinones, methods that do not require the use of acutely toxic and environmentally hazardous reagents are lacking. Consequently, there is a need to develop new methods for constructing this valuable scaffold. Herein, we …

Modelling Quinones Using Density Functional Theory, David Ruiter, Madeleine Callan, Elijah Gruszecki, Maya Nambisan, Dr. K. V. Lakshmi

Summer Research

We modelled benzoquinone (BQ), dichlorobenzoquinone (DCBQ), and dimethylbenzoquinone (DMBQ) using the ORCA quantum chemistry computation suite. We obtained singlepoint energies, electron and spin densities, and the hyperfine coupling values for each molecule suspended in dimethyl sulfoxide (DMSO) and isopropyl alcohol (IPA). In most cases, we find close agreement with published literature values.

An Approach To The Synthesis Of 3-Quinazolinedione Carboxylic Acids: Putative Antibiotics, Colton J. Stonehouse, Michael Barbachyn

Summer Research

Bacterial resistance to antibiotics is a growing public health threat. Each year, more than 2.8 million antibioticresistant infections occur in the United States and 35,000 people die as a consequence. Fluoroquinolone (FQ) agents targeting the essential bacterial type II topoisomerases DNA gyrase and topoisomerase IV, exemplified by ciprofloxacin, have been in clinical use since the 1980’s and shown to be useful antibiotics. Unfortunately, heavy use of the FQs has inevitably led to the development of FQ-resistant pathogens

Development Of New Photochemical Tools For Applications In Cancer Research And Enzymatic Signaling, Nicholas Paul Toupin

Wayne State University Dissertations

Photochemical tools empower researchers to act with precision and control over the cellular environment through production of reactive oxygen species (ROS), targeted drug delivery, and modulation of enzymatic activity. These molecular tools use light as a readily available, biorthogonal reagent for initiating advantageous light-activated reactions. Using light in this way allows researchers to affect the cellular environment in specific ways with high spatio-temporal control. This dissertation focuses on expanding the applications of, mostly Ru(II)-based, photoactivated chemicals. Complexes of this type are able to act as photosensitizers in photodynamic therapy (PDT), as photocages (PCT), or as dual-action compounds capable of both …

Phenanthroline-Catalyzed 1,2-Cis Glycosylation: Scope And Mechanism, Jiayi Li

Wayne State University Dissertations

Phenanthroline, a rigid and planar organic compound with two fused pyridine rings, has been used as a powerful ligand for metals and a binding agent for DNA/RNA. We recently discovered that phenanthroline could be used as a nucleophilic catalyst to access high yielding and diastereoselective α-1,2-cis glycosides through the coupling of hydroxyl acceptors with α-glycosyl bromide donors. The utility of the phenanthroline catalysis is expanded to sterically hindered hydroxyl nucleophiles and chemoselective coupling of an alkyl hydroxyl group in the presence of a free C1-hemiacetal functionality. In addition, the phenanthroline-based catalyst has a pronounced effect on site-selective couplings of triol …

Whole Exome Sequencing Identifies A Novel Mutation In Aspm And Ultra-Rare Mutation In Cdk5rap2 Causing Primary Microcephaly In Consanguineous Pakistani Families, Ehtisham Ul Haq Makhdoom, Haseeb Anwar, Shahid Mahmood Baig, Ghulam Hussain

Department of Biological & Biomedical Sciences

Background & objectives: Primary Microcephaly (MCPH) is a rare neurogenetic disease, manifesting congenitally reduced head circumference and non-progressive intellectual disability (ID). To date, twenty-eight genes with biallelic mutations have been reported for this disorder. The study aimed for molecular genetic characterization of Pakistani families segregating MCPH.
Methods: We studied two unrelated consanguineous families (family A and B) presenting >2 patients with diagnostic symptoms of MCPH, born to asymptomatic parents. We employed whole-exome sequencing (WES) of probands to find putative causal mutations. The candidate variants were further confirmed and analyzed for co-segregation by Sanger sequencing of all available members of each …

Biomimetic Synthesis Of Palladium Nanoparticles For Catalytic Application, Emily A. Groover

College of Graduate Studies: Theses & Dissertations

The synthesis of palladium nanoparticles (Pd NPs) using materials-directed peptides is a novel, nontoxic approach which exerts a high level of control over the particle size and shape. This biomimetic technique is environmentally benign, featuring nonhazardous ligands and ambient conditions. Nanoparticles are extremely reactive catalysts, boasting a large surface-to-volume ratio when compared to their bulk counterparts. The rational design of these nanoparticles using peptides has been very successful in aqueous environments, but no research has been done to apply it in organic systems. As such, the biomimetic synthesis of Pd NPs in an organic system is here investigated, with ethanol …