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Observation Of The Low-Frequency Spectrum Of The Water Trimer As A Sensitive Test Of The Water-Trimer Potential And The Dipole-Moment Surface, Raffael Schwan, Chen Qu, Devendra Mani, Nitish Pal, Gerhard Schwaab, Joel M. Bowman, Gregory S. Tschumper, Martina Havenith

Faculty and Student Publications

© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. Intermolecular interactions in bulk water are dominated by pairwise and non-pairwise cooperative interactions. While accurate descriptions of the pairwise interactions are available and can be tested by precise low-frequency spectra of the water dimer up to 550 cm−1, the same does not hold for the three-body interactions. Here, we report the first comprehensive spectrum of the water trimer in the frequency region from 70 to 620 cm−1 using helium-nanodroplet isolation and free-electron lasers. By comparison to accompanying high-level quantum calculations, the experimentally observed intermolecular bands can be assigned. …

A Diverse View Of Science To Catalyse Change, César A. Urbina-Blanco, Safia Z. Jilani, Isaiah R. Speight, Michael J. Bojdys, Tomislav Friščić, J. Fraser Stoddart, Toby L. Nelson, James Mack, Renã A.S. Robinson, Emanuel A. Waddell, Jodie L. Lutkenhaus, Murrell Godfrey, Martine I. Abboud, Stephen O. Aderinto, Damilola Aderohunmu, Lučka Bibič, João Borges, Vy M. Dong, Lori Ferrins, Fun Man Fung, Torsten John, Felicia P. L. Lim, Sarah L. Masters, Dickson Mambwe, Pall Thordarson, Maria Magdalena Titirici, Gabriela D. Tormet-González, Miriam M. Unterlass, Austin Wadle, Vivian W. W. Yam, Ying Wei Yang

Faculty and Student Publications

© 2020 Croatian Chemical Society. All rights reserved. Valuing diversity leads to scientific excellence, the progress of science and, most importantly, it is simply the right thing to do. We must value diversity not only in words, but also in actions.

Pyridyl Co2Fixation Enabled By A Secondary Hydrogen Bonding Coordination Sphere, Jacqueline N. Gayton, Qing Li, Lakeeta Sanders, Roberta R. Rodrigues, Glake Hill, Jared H. Delcamp

Faculty and Student Publications

Copyright © 2020 American Chemical Society. Reversible CO2 binders under ambient conditions are of significant interest for multiple applications in sensing and capture technologies. In this paper, a general systematic way to evaluate CO2 receptors with π-systems is put forward. A series of receptors (five pyridine-based and one triazine-based) are evaluated as CO2 binders in terms of number of hydrogen bonding sites, strength of hydrogen bond donors, and number of nucleophilic sites. The binding of CO2 to the receptors was probed by computational models, absorption spectroscopy, fluorescence spectroscopy, cyclic voltammetry, and 1H NMR studies. Multiple solvents with varying ionic strength …

Silver-Catalyzed Synthesis Of Disubstituted Fluorinated Isoxazoles, Micah Stewart

Honors Theses

The presence of fluorine can provide organic compounds with useful biological properties, such as increased metabolic stability and drug uptake. Because of these advantages, fluorinated compounds make up about 30% of the drug industry. However, fluorination of complex molecules is difficult due to fluorine’s high electronegativity.

Fluorinated isoxazoles are of particular interest in the pharmaceutical industry. Isoxazoles are five-membered heterocycles with oxygen and nitrogen in the 1, 2 positions that are able to engage in interactions unavailable to other ring structures, conferring advantageous biological properties upon compounds containing them. However, there are limited synthetic routes for fluorinated isoxazoles, and those …

Study Of Pharmaceutical Tablets Using Raman Mapping, Kyle Joseph Pauly

Honors Theses

Covalent bonds are the strongest type of bonds holding molecules together. Based on the pattern of bonding of the molecule, the atoms associated with the bond will vibrate at a specific frequency. Utilizing vibrational spectroscopy, such as Raman spectroscopy, these unique vibrational frequencies can be used to detect the presence of analytes over a selected area. Furthermore, the intensities of the vibrational modes can be tracked to comparatively quantify the concentration of analytes at various locations. This is a method of great importance due to its ability to compare pharmaceutical tablets synthesized with different techniques. Here, the presence and concentration …

Approaches Towards The Synthesis Of Ketamine Metabolites, Ann K. Patrick

Honors Theses

Major Depressive disorder (MDD) plagues society and stands at the forefront of research as MDD affects approximately 16% of the population. Pharmaceutical drugs, including the selective serotonin reuptake inhibitors (SSRIs), have been used for MDD treatment and remain a popular option today. However, current antidepressant treatments have proven to be ineffective in just less than half of the patients. Research continues with the goal to better understand the mechanisms of the pathology of depression and to search for other treatment options. For example, the stress-neurogenesis hypothesis investigates the role of stress and decreased neuroplasticity within MDD.

Supporting the stress-neurogenesis hypothesis, …

Isolation, Identification, And Investigation Of A Novel Bioactive Furanocoumarin From Leaves Of Amyris Elemifera, Amy K. Bracken

Honors Theses

Plants produce biologically active compounds that humans have utilized for many agricultural applications. Amyris elemifera was investigated due to the known bioactivity of its family, Rutaceae, and its use in medicines in tribes of the Bahamas. Biotage® and TLC guided fractionation of the EtOAc, hexane, and MeOH extracts of the leaves of Amyris elemifera yielded bioactive compounds. Most significantly, a novel furanocoumarin, 8-(3-methylbut-2-enyloxy)-marmesin acetate (1), and its analog 8-(3-methylbut-2-enyloxy)-marmesin (2), were isolated. The structures were identified via NMR and X-ray crystallography techniques; the X-ray crystal structure for 1 was reported for the first time, and the …

13c Nmr Substituent Effects On Para-Substituted Tolans: Using Deuteration To Assign 13c Signals In Methyltolan, Reece Crumpler

Honors Theses

Substituents are capable of affecting their molecules via induction, resonance, and field effects. Using the Hammett equation, the effect a range of substituents has on different properties of a molecule can be quantified.¹ Hammett’s parameters have been correlated with the substituent effects on ¹H NMR chemical shifts in different molecules, including experiments on substituted chalcones (1,3-diarylpropenones).² The effect a substituent has on a molecule can also be observed using ¹³C NMR. The chemical shifts of carbons throughout the molecule may be affected by the substituent. This was shown to be true by Wilson and Zehr in …

Synthesis Of Polyethylene Glycol - Trifluoromethyl Sulfonamide And Analysis Of Its Ion-Transport Properties, Andrew Groneck

Honors Theses

This project investigates the synthetic pathway to develop a polyethylene glycol – trifluoromethyl sulfonamide compound to be used as an electrolyte in a proton exchange membrane fuel cell. The inspiration to develop a trifluoromethyl sulfonamide compound tethered to a polyethylene glycol polymer was inspired by the work of David P. Siska and D. F. Shriver in their studies of polysiloxane – trifluoromethyl sulfonamide electrolytes.

In this thesis, I have developed the synthesis of MePEG7-Trifluoromethyl sulfonamide (MePEG7-NHSO2CF3) from monomethylpolyethylene glycol (MePEG7OH). Unfortunately, due to the COVID-19 pandemic, I was unable to complete the depronation and ion-exchange to the Li+ and H+ …

Detection And Characterization Of Delta-9-Tetrahydrocannabinol And Novel Synthetic Cannabinoid Metabolites Using Human Liver Microsomes, Seema Murugan

Honors Theses

Marijuana and synthetic cannabinoids are the most commonly used and trafficked illicit drug. ∆⁹-tetrahydrocannabinol (THC) is the primary active compound in marijuana. Synthetic cannabinoids were created as a method to study the effects of cannabinoids on the endocannabinoid system, which consists of endogenous cannabinoids, cannabinoid receptors, and the synthetic and degrading enzymes responsible for the synthesis and degradation of endocannabinoids. Cannabinoids activate the same receptors as endocannabinoids. Synthetic cannabinoids gained popularity as recreational drugs due to their ability to avoid detection. Synthetic cannabinoids have been found to have a greater binding affinity to the cannabinoid CB₁ receptor …

Comparison Of The Vibrational Modes Of Thiolated Gold Nanoparticles Undergoing Core-Conversions Via Raman Spectroscopy, William Gregory Cannella Jr.

Honors Theses

In this project, the vibrational characteristics/vibrational modes are explored via Raman Spectroscopy for thiolated-gold nanoparticles. This class of compounds is also known as gold nanoparticles (AuNPs). They remain of great interest in research areas such as catalysis, gold dependent nanoelectronics, drug delivery, and sensing, due to their unique size-dependent optical, chiroptical, and electronic properties. Vibrational spectroscopy of thiolated gold nanoparticles are oftentimes considered nontrivial as the compounds strongly absorb light in the visible region of the electromagnetic spectrum, are generally considered weak scatterers, and give off large amounts of fluorescence. This combined with their black appearance, susceptibility to localized heating, …

Intrinsic Buffer Hydroxyl Radical Dosimetry For Hydroxyl Radical Protein Footprinting, Addison Roush

Honors Theses

Hydroxyl radical protein footprinting (HRPF) coupled to mass spectrometry is a powerful technique for the analysis of protein topography as it generates covalent mass labels that can survive downstream sample handling, and it is sensitive to the solvent accessibility of amino acid sidechains. Of the multiple platforms for HRPF, fast photochemical oxidation of proteins (FPOP) utilizes a pulsed 248 nm KrF excimer laser to label proteins by photolyzing hydrogen peroxide. FPOP is the most widely used HRPF platform because it labels proteins faster than unfolding can occur. Variations in FPOP sample conditions make it difficult to compare results between experiments …

Synthesis Of Fluorinated Pyrazoles Via Intra- And Intermolecular Cyclization Reactions, Matthew Saucier

Honors Theses

Pyrazole-based pharmaceuticals treat a wide array of diseases and conditions including obesity, diabetes, cancer, microbial and viral infections, pain and inflammation, and many neurological disorders. Syntheses for this biologically significant substrate have been well developed, but current methods to afford fluorinated pyrazoles are limited by variability and selectivity. By 2013, over 25% of all drugs available on the market contained the element fluorine due to its unique characteristics leading to improved target protein binding, bioavailability, and metabolic stability. In order to harness these pharmaceutical benefits of fluorine and overcome its difficulty in handling and stability, we set out to develop …

The Synthesis Of A Mepeg-Based Hydroxide Conducting Electrolyte And The Optimization Of The Mepeg-Tosylation Reaction, Andrew Ladner

Honors Theses

As society is becoming increasingly aware of the effects of climate change and the ever-looming threat of a fuel shortage, exploring green and renewable alternative energy production, such as fuel cells, is paramount. This project investigates the synthesis of a polyethylene glycol monomethyl ether (MePEG_n) based polymer as well as the optimization of the MePEG Tosylation reaction. The MePEG explored contains seven polymerized ethoxy groups (MePEG₇). The MePEG₇ polymer was modified by substituting a positively-charged trimethylamine group in the place of the alcohol functional group at the end of the PEG chain. The reason for …

The Histone Deacetylase Inhibitor Largazole: A Potential Chemotherapeutic Agent, Hannah Lynn Carson

Honors Theses

Histone deacetylase enzymes are known for their inherent activity as epigenetic modifiers. Although, they have become recognized for their role in cancer progression and other diseases. But also, histone deacetylases have other non-histone targets, for example, microtubules, which play important roles in cancer metastasis, apoptosis, and replication. With histone deacetylase inhibitors (HDACi), our research explored HDACi effects on breast cancer cell lines. The overall goal was to understand the potential of largazole, a class one histone deacetylase inhibitor on breast cancer cell lines. The research consisted of two parts: sulforhodamine B (SRB) viability assays under hypoxic and normoxic conditions. The …

Investigation Of The History Of Fingerprinting, Advancements In The Field, And Development Of Potential Methods That Could Improve The Detection Of Endogenous And Exogenous Drugs In Latent Prints, Kristen Malloy

Honors Theses

When someone thinks of fingerprinting, they are most likely going to picture how a latent print is matched to the fingerprint of a suspect based on ridge pattern analysis. However, there is much more information that can be obtained from a latent print. The work performed in this thesis focuses the detection of exogenous and endogenous drugs in latent prints. The experiments performed analyzed fingerprints from volunteers that were contaminated with one of three common painkillers: acetaminophen, acetylsalicylic acid (ASA), and ibuprofen. Three different instruments were tested for this purpose: MALDI-MS, ATR-FTIR, and LC-MS. Based on the results gathered, it …

Synthesis And Characterization Of Transition Metal Scorpionate Complexes For Redox Shuttle Applications In Dye-Sensitized Solar Cells, Chase Lance

Honors Theses

Given the rising global energy demands, alternative renewable energy sources are currently being investigated. The most appealing renewable energy source is solar energy, and dye-sensitized solar cells (DSSCs) in particular are an attractive technology. DSSCs have traditionally utilized iodide/triiodide as the redox mediator couple, which exhibits high efficiencies and fast regeneration of the oxidized dye with little recombination. Recently, the use of alternative redox couples based on transition metal complexes has been studied as a promising substitute due to the tunable design of these complexes. In this study, tridentate tris(pyrazolyl)borate and tris(pyrazolyl)methane ligands with first-row transition metals were designed and …

Raman Spectroscopy Study Of Delta-9-Tetrahydrocannabinol And Cannabidiol And Their Hydrogen-Bonding Activities, Kalee Sigworth

Honors Theses

Cannabis and products containing its cannabinoids have grown rapidly in acceptance and use in recent years with legalization of cannabis in many countries and US states. Cannabidiol and Delta-9-Tetrahydrocannabinol are two primary cannabinoids in Cannabis that have been shown to produce analgesic effects along with many other positive side effects for the user. These two cannabinoids interact with receptors in the Central and Peripheral Nervous Systems. No spectroscopic study to our knowledge has been performed to analyze the hydrogen bonding effects of interactions between these two cannabinoids and solvents. Here, we employ theoretical Raman spectra through computational methods to study …

Gold Nanoparticles: Core Conversion Of Au144(Sch2ch2ph)60 To Au99(Sph-Ch3)42 Using Aromatic Thiolate Ligands And Crystallization Of Au99(Sph-Ch3)42, Elizabeth Turnage

Honors Theses

The purpose of this thesis is to synthesize Au₁₄₄(SCH₂CH₂Ph)₆₀ using a two-step synthesis reaction, and then using this product to conduct a core conversion from Au₁₄₄(SCH₂CH₂Ph)₆₀ to Au₉₉(SPh-CH₃)₄₂. The Au₉₉(SPh-CH₃)₄₂ product will then be used to attempt to form crystals using five different crystal set-up methods. Au₁₄₄(SCH₂CH₂Ph)₆₀ is made with aliphatic thiolate ligands, and when it is placed in a mixture containing excess para-methyl benzenethiol, it undergoes a …

Raman Spectroscopic And Quantum Chemical Investigation Of The Effects Of Tri-Methylamine N-Oxide (Tmao) On Hydrated Urea, Hydrated Guanidinium, And Hydrogen Bonded Networks, Genevieve Verville

Honors Theses

Trimethylamine N-Oxide (TMAO), guanidinium, and urea are three important

osmolytes with their main significance to the biophysical field being in how they

uniquely interact with proteins. TMAO is known to stabilize and counteract the

destabilizing effects of both urea and guanidinium. The exact mechanisms by which

TMAO stabilizes and both guanidinium and urea destabilize folded proteins continue

to be debated in the literature. Some studies suggest that solvent interactions do not

play a large role in TMAO’s stabilizing effects and therefore advocate direct

stabilization, whereas others suggest that TMAO counteracts denaturation primarily

through an indirect effect of strong solvent interactions. …

Spectroscopic And Computational Studies Of The Agricultural Active Ingredient Dicamba, James Johnson

Honors Theses

3,6-dichloro-2-methoxy benzoic acid, more commonly known as Dicamba, is the active ingredient in an array of pesticides used on farmlands across the globe. Dicamba’s mode of action works by mimicking the plant hormone auxin, which is synonymous to growth hormones in mammals. The mimicking of auxin results in excessive elongation and growing, which is eventually fatal for plants when the rate of growth can no longer be sustained. Dicamba has risen in prominence in recent years due to drift damage as a result of Dicamba’s high volatility. Having the ability to identify Dicamba is crucial for the agricultural industry. The …

A Diverse View Of Science To Catalyse Change: Valuing Diversity Leads To Scientific Excellence, The Progress Of Science And, Most Importantly, It Is Simply The Right Thing To Do. We Must Value Diversity Not Only In Words, But Also In Actions, César A. Urbina-Blanco, Safia Z. Jilani, Isaiah R. Speight, Michael J. Bojdys, Tomislav Friščić, J. Fraser Stoddart, Toby L. Nelson, James Mack, Renã A. S. Robinson, Emanuel A. Waddell, Jodie L. Lutkenhaus, Murrell Godfrey, Martine I. Abboud, Stephen O. Aderinto, Damilola Aderohunmu, Lučka Bibič, João Borges, Vy M. Dong, Lori Ferrins

Faculty and Student Publications

No abstract provided.