Digital Commons Network^™

Predicting The Reactions Of Cs2, Ocs, And Co2 With Group Iv And Group Vi Transition Metal Oxides, Marissa Shea Blair, Zachary Ryan Lee Phd, David A. Dixon Phd

Posters-at-the-Capitol

Building on a recent serious of high level electronic structure studies of Lewis acid gas reactions with metal oxide sorbents, DFT (B3LYP and ωB97X-D) and CCSD(T) methods are being used to predict the Lewis acid-base addition (physisorption) and formation of metal oxide carbonate/thiocarbonate formation (chemisorption) reactions of CS2, OCS, and CO2 of CS2, OCS, and CO2 with Group IV (MO2)n and Group VI (MO3)n (n = 1 - 3) nanoclusters. For the Group IV oxides, chemisorption to form terminal carbonates and thiocarbonates is predicted to be the most favored, with thiocarbonate ligand binding energies slightly more exothermic than their carbonate …

Determination And Comparison Of Freely Dissolved Pahs Using Different Types Of Passive Samplers In Freshwater, Na Yeong Kim, Bommanna G. Loganathan, Gi Beum Kim

Faculty & Staff Research and Creative Activity

Polycyclic aromatic hydrocarbons (PAHs) are well-known for their recalcitrant properties and biotoxicity in organisms, leading to serious environmental and health problems. Despite various analytical methods available, accurate determination of the bioavailable fraction is warranted in order to evaluate the precise toxic potentials of these compounds. Currently, the passive sampler is used worldwide to measure the bioavailable PAHs in the environment using the equilibrium partitioning principle. In this study, we co-deployed different types of passive samplers, which are linear low-density polyethylene (LLDPE) and low-density polyethylene (LDPE), to determine freely dissolved concentrations (Cfree) of PAHs using the performance reference compounds (PRCs) in …

Swelling Studies Of Poly(Ionic Liquids) In Different Solvents And Salt Solutions, Pierson Perdue, Ali Alshaikh, Creighton Baltier, Jason E. Bara, Sourav Chatterjee

Scholars Week

Poly(ionic liquid)s (PILs) represented a special class of polymers, which comprised of a polymeric backbone and ionic liquids (ILs) species in each monomeric repeating units. PILs has properties that combined the properties of ionic liquids (ILs) (i.e., high conductivity, better thermal and chemical stability, and tailor-made functionality) with the intrinsic properties of polymer (i.e., mechanical stability). This synergistic property makes PILs a good candidate for various applications such as stable-ion conductors, membranes for gas separations and sorbents. In the past, it was shown that PILs are capable of swelling when dissolved in different ILs but there are few literature reported …

Synthesis And Characterization Of Semi-Interpenetrating And Double Networks Of Sulfonimide- And Imidazolium-Containing Poly(Ionic Liquids), Jeremiah Coughlon, Seth Taylor, Jason Bara, Kevin Miller, Sourav Chatterjee

Scholars Week

In recent years, there has been increased research interest in creating electrically conductive polymer membranes with materials that are widely available and environmentally safe. Herein, we report how polymeric membranes comprised of unique combinations of ionenes and poly(ionic liquids), including a recently developed sulfonimide- and imidazolium-containing methacryloxy-based monomer, were produced via UV photopolymerization. These membranes were specifically tailored to exhibit both ionic conductivity and an affinity for carbon dioxide, which are both crucial characteristics in such applications as electron transport in lithium-ion batteries and gas sorbency in separation techniques. Monomers, such as the aforementioned methacryloxy-based ionic liquid (IL) and C4VIm, …

Synthesis And Properties Of Bio-Based 3d Printable Resins, Cameron Woods, Seth Taylor, Jeremiah Coughlon, Turner Perdue, Sourav Chatterjee, Jason E. Bara

Scholars Week

A photopolymer resin is a monomer that, when introduced to light of a certain wavelength, starts to polymerize into a solid. This has become a growing part of the 3D printing industry. There have been many advancements in the field of 3D printing, however, a lot of these resins are not environmentally friendly and even harmful if not handled in the correct manner. Plant based resins are becoming more and more popular because of their biodegradability and for the possibility of using renewable resources. Glycerol is a plant-based compound that is produced in excess in industry. Glycerol obtained from bioethanol …

Physiochemical Properties Of Urethane-Containing Ionic Liquids And Ionenes From A Non-Isocyanate Synthetic Approach, George Timmermann

Scholars Week

Ionic polymers that are designed to contain ionic liquids (ILs) in their backbones have been shown to exhibit a high degree of variability through changing the type of ionic character and the location of the ionic region within the molecule. This large amount of variability in both the structure and characteristics of ILs allows researchers to design task-specific ionic polymers and ILs for a variety of applications including gas separation membranes and solid polymer electrolytes. The synthesis of a specific class of ILs and ionenes through the incorporation of urethane groups with imidazolium rings by reacting carbonyl diimidazole with various …

Dual Ionic Liquid-Functionalized Cellulosic Materials: Thermal, Mechanical And Conductive Properties, Elizabeth Mcgrew, Kevin M. Miller Phd

Posters-at-the-Capitol

Cellulose, an inexpensive and renewable biomacromolecule, represents an intriguing synthetic foundation for new materials with task-specific properties. Here, we wish to report a synthetic route for functionalizing cellulose with a side chain containing two ionic liquid functional groups using azide-alkyne ‘click’ cyclization strategy, followed by quaternization of the two resulting heterocycles (1,2,3-triazole and imidazole). Through this functionalization strategy, the resulting cellulosic materials exhibited significant softening, with several glass transition (T_g) values observed below room temperature, indicating the amorphous nature of the materials, with the T_g dependent on both the length of the side chain and the …

Strategies For Identifying Important Residues In The Trna Modification Protein Trm732, Alex K. Mullins, Natalie N. Creech, Holly Funk, Michael Guy

Posters-at-the-Capitol

Post-transcriptional tRNA modifications are required for efficient protein translation. In yeast, the Trm7 methyltransferase forms a complex with Trm732 to modify tRNA at position 32. In humans, lack of the human homolog for Trm7, FTSJ1, causes intellectual disability. Little is known about the function of Trm732, although we have shown that one conserved motif in Trm732 is important for tRNA modification. We have identified other residues important for function using two strategies. First, we compared Trm732 proteins of different organisms using protein alignments to determine conserved regions to mutate for testing. We have generated four new Trm732 variants and have …

Spatial And Temporal Varitations In Dissolved Calcium In The Kentucky Lake Watershed In Relation To Zebra Mussel Colonization, Kelsie Meystedt

Murray State Theses and Dissertations

Calcium is the fifth most abundant element on earth’s crust. Plants and animals require calcium for structure and intracellular metabolism. Recent studies have shown that dissolved calcium (Ca2+) freshwater ecosystems is of growing concern as the increasing concentrations of this element are implicated in altering the natural environment and biota. Elevated levels of dissolved calcium and sporadic re-emergence of an invasive species, namely zebra mussels (Dreissena polymorpha) in Kentucky Lake in the recent years served as a motivation for this study. The objective of this study was to determine spatial and temporal variations in dissolved calcium in selected streams, Kentucky …

The Use Of Hallucinogens In The Treatment Of Mental Health Disorders, Brianna Gagen

Honors College Theses

The percent of people with mental health disorders in the United States have skyrocketed over the past decade. With stigma surrounding the discussion of mental health and the symptoms associated with it, often those that are suffering do not receive sufficient treatment, as they might with a physical illness. The current, common treatment options for common psychological disorders, like depression, anxiety, and post-traumatic stress disorder, are sometimes not effective in patients, due to resistance or poor response outcomes. Consequently, in order to research alternative therapeutic approaches for mental health disorders, scientists are researching the effects of several hallucinogenic drugs in …

Temporal Changes And Possible Sources Of Dissolved Calcium Levels In Stream, River, And Lake Waters In Western Kentucky, Kelsie Meystedt

Scholars Week

ABSTRACT

Zebra Mussels (Dreissena polymorpha) are an exotic and invasive mollusk that spread extensively over various rivers and lakes in the United States. These mussels are known for being notorious in their “biofouling” capabilities, costing the U.S. government billions of dollars in removal operations. Recently, zebra mussel colonies were found in Kentucky Lake possibly due to human activities increasing the salinity of today’s freshwater resources. The increase in salinity from human activities may have adversely affected the ecosystems and water supplies. The Specific aim of this study was to determine the temporal trend of dissolved calcium in Kentucky Lake …

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.

Wastewater-Based Estimation Of Substances Discharged At The Rest Areas Along The State Highways In Kentucky, Katherine E. Gray, Eugene Shin, Tyler Whitt, Andrew Windhorst, Houston Hampton, Chris Delcher, Bikram Subedi

Posters-at-the-Capitol

The availability of licit and illicit stimulants and its adverse consequences on public health has emerged as a major drug threat to communities in the United States. Despite several drug-involved traffic incidents along the interstate highways, this report represents the first comprehensive and quantitative report of drugs discharged at the rest areas along the interstate highways. In this National Institute of Justice-funded study, the amount of several discharged drugs focusing on stimulants but also including opioids and prescription antipsychotics are being measured in raw wastewater collected from five rest areas and a truck servicing facility using a state-of-the-art mass …

Synthesis Of Functional Chalcone Library For Use In Aza- Dipyrromethene Dye Systems, Kendal Crawley

Murray State Theses and Dissertations

Over the past decade, Aza-Bodipy dyes (ADPs), a derivative of the extensively studied BF₂-dipyrromethene (BODIPY), have become a growing field of research due to their unique photophysical properties, high yielding synthesis, and relative stability. They possess a unique spectral window of 600 to 750 nm which is the red to near-IR region, evidenced by the blue color of many of these dyes. Increasing interest in these dyes is due to this near-IR window which is important for many applications.^1-4 ADP chromophores also have a common core motif to that of phthalocyanines which allow for coordination at their …

Exploring The Geometric And Electronic Properties Of Palladium Doped Silicon Clusters, Madison Winkeler, Ciara N. Richardson

Scholars Week

Transition metal-doped silicon clusters have unique properties and have been studied as building blocks for nanomaterials and microelectronics. Here, the structure and properties of candidate palladium doped silicon clusters (SinPd2: n=1-17) were determined using global optimization techniques on a high performance computing cluster at the San Diego Supercomputing Center. Then geometric structures were further optimized utilizing the B3LYP method with 6-311+G(d) basis sets for silicon and lanl2dz pseudopotential for palladium, followed by the larger DSDPBEP86 method with 6-311+G(2d) basis sets for silicon and SDD pseudopotential for palladium, as implemented in the Gaussian 16 program package. The energetics for each cluster …

Structure Determination Of Pd2sin (N = 1 - 9) Clusters, Ryan Carlin

Honors College Theses

The geometry and relative stability of small Pd2Sin (n = 1 - 9) clusters are determined using the B3LYP hybrid density functional theory method. Candidate structures are identified by the utilization of unbiased global optimization procedures. From the lowest energy geometries, binding energy, fragmentation energy, second-order energy difference, and frontier orbital gap energy are calculated to determine cluster stability. Pd2Sin (n = 8 and 9) adapts new lowest energy geometric configurations that have previously not been considered. Pd2Si5 is determined to have a high relative stability of the clusters within this size range.

Effect Of Precise Control Of Crosslink Density On The Thermal, Mechanical, And Conductive Properties Of Covalently Crosslinked Ionene Networks, Alexander Thome

Honors College Theses

Ionic liquids (ILs), besides being well known as environmentally friendly solvents, have attracted attention for a wide variety of other applications, including gas separation, 3D-printing and electrochemical actuators. However, for many such applications, incorporation of the IL moiety into a polymeric material eliminates the use of mechanically unstable free ILs while maintaining many of their electrochemical benefits. Such polymers can take two basic forms: poly(ionic liquid)s are ion-containing polymers in which the IL group is attached pendant to the polymeric backbone, while ionenes are ion-containing polymers in which the IL group is anchored directly into the backbone of the repeating …

Thermal, Mechanical, And Rehealing Properties Of Cross-Linked Ionene Networks, Katelyn Lindenmeyer

Honors College Theses

Polymers which contain ionic liquid groups have numerous applications in a wide variety of fields. Past research from our group has shown that IL-containing polymers which exist in covalently crosslinked networks can exhibit good ionic conductivities despite the hindrance in polymer chain mobility and relaxation. In part one of this thesis, efforts to create ionic networks which have the capability of being rehealed after exposure to an external stimulus are discussed. Thermoreversible maleimide-furan chemistry was incorporated into an imidazolium-containing ionene network. Maleimide-terminated, imidazolium-containing monomers were coupled with furan-functionalized monomers, prepared from commercially available multifunctional acrylates. Thermal, mechanical and rheological characterization …

Designing Ionic Liquid-Derived Polymer Composites From Poly(Ionic Liquid)–Ionene Semi-Interpenetrating Networks, Kathryn E. O'Harra, George E. Timmerman, Jason E. Barra, Kevin Miller

Faculty & Staff Research and Creative Activity

While the solvating power of ionic liquids (ILs) for a variety of solute types including polymers is well-known, the use of ILs as solvents for ionenes—charged polymers with cationic moieties within the backbone—has only recently begun to be explored. IL–ionene combinations offer vast possibilities to make iongels and perhaps even use ILs to exert control over ionene organization (i.e., coil or rod). If the IL solvent is also polymerizable, then poly(IL)–ionene semi-interpenetrating networks (semi-IPNs) can be achieved. This study reports, for the first time, examples of poly(IL)–ionene semi-IPNs formed by dissolving an ionene in a vinyl-functionalized imidazolium IL followed by …

Influence Of Counteranion And Humidity On The Thermal, Mechanical And Conductive Properties Of Covalently Crosslinked Ionenes, Nicholas C. Bontrager, Samantha Radomski, Samantha P. Daymon, R. Daniel Johnson, Kevin M. Miller

Faculty & Staff Research and Creative Activity

Thiol-ene photopolymerization was used to generate a series of covalently crosslinked, imidazolium-containing ionene networks. A variety of counteranions were chosen so as to investigate the influence of size and basicity on the thermal, mechanical and conductive properties of the resulting networks. Anhydrous conductivities at 20 °C were found to be on the order of 10−6 to 10−10 S/cm and correlated to some degree with Tg; however, Tg-normalization of the curves indicated that this relationship between polymer structure and conductivity was more complex. VFT fitting, along with free ion concentration and ion mobility data, were investigated in order to …

Synthesis And Evaluation Of Cellulose-Based, 1,2,3-Triazolium-Functionalized Polymerized Ionic Liquids: Thermal Transitions, Ionic Conductivities, And Morphological Properties, Rose J. Miller, Vanessa M. Smith, Stacey A. Love, Sarah M. Byron, David Salas-De La Cruz, Kevin M. Miller

Faculty & Staff Research and Creative Activity

A series of 1,2,3-triazolium-functionalized cellulose derivatives were prepared using an azide–alkyne “click” cyclization strategy, followed by quaternization. As cellulose represents an inexpensive and sustainable biomacromolecule, the ability to functionalize the backbone with an ionic liquid and generate conductive materials is of great interest. Here, three different counteranions ([Br], [OTf], and [NTf2]) were employed to explore the interplay between thermal, conductive, and morphological properties using a diverse set of techniques including nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray scattering, and dielectric relaxation spectroscopy (DRS). Functionalization of native cellulose resulted in …

Gene Alteration In Zebrafish Exposed To A Mixture Of Substances Of Abuse☆, Bikram Subedi, Sydni Anderson, Tara L. Croft, Eric C. Rouchka, Mei Zhang, Dena Weinberger

Faculty & Staff Research and Creative Activity

A recent surge in the use and abuse of diverse prescribed psychotic and illicit drugs necessitates the surveillance of drug residues in source water and the associated ecological impacts of chronic exposure to the aquatic organism. Thirty-six psychotic and illicit drug residues were determined in discharged wastewater from two centralized municipal wastewater treatment facilities and two wastewater receiving creeks for seven consecutive days in Kentucky. Zebrafish (Danio rerio) larvae were exposed to the environmental relevant mixtures of all drug residues, all illicit drugs, and all prescribed psychotic drugs. The extracted RNA from fish homogenates was sequenced, and differentially …

Optimization Of The Mechanochemical Synthesis Of Several Distinct Compounds., Joseph Ryan Williams

Honors College Theses

Mechanochemical synthesis, as used in this work, is the mechanical milling of reagents to drive reaction. It is often considered a greener alternative to traditional solution-based methods of synthesis. This work will describe the mechanochemical synthesis of furan-2-yl(pyrrolidin-1-yl)methanethione and N-hexadecylfuran-2-carbothioamide, the optimization of the mechanochemical synthesis of 1,3-dibenzylbenzimidazolium bromide as well as the kinetics of this reaction, and finally the ongoing development of the mechanochemical synthesis of N,N′-dioctyl-2,2′-bipyridine-4,4′-dicarboxamide.

This work studied both the traditional method and mechanochemical method for synthesis of furan-2-yl(pyrrolidin-1-yl)methanethione, as well as the mechanochemical method for N-hexadecylfuran-2-carbothioamide. While initial work was promising, it was …

Root Cause Analysis And Method Development Of Calorimetry Experiments, Anya M. Deaton, Lydia R. Deaton, John M. Farrar Dr.

Posters-at-the-Capitol

First year chemistry students learn a broad range of concepts that are also proven out in the lab environment. These concepts are a basis for a solid foundation for future chemistry learning. When the lab experiments don’t produce the expected results, students understanding in these concepts diminish and overall confidence and grades suffer. Our project details the root cause analysis and subsequent method development work for two experiments related to calorimetry; heat of solution and freezing point depression. The team sought to refine these experiments after finding that many of the students were unable to generate the expected results for …

Near Real-Time Determination Of The Prevalence Of Cannabinoids, Cathinones, And Synthetic Opioids, Catherine O'Rourke, Bikram Subedi

Scholars Week

Unregulated new psychoactive substances (NPS) in “pure” or “preparation” forms are designed to mimic the effects of controlled substances, and are introduced and reintroduced in the market as a cheap substitute of established regulated drugs in quick succession to loophole the law enforcement efforts on combating drugs. For example, carfentanil, a synthetic opioid activates the opioid receptors similar to morphine but it is astoundingly potent compared to a typical drug of abuse (100 times more potent than fentanyl and 10,000 times more powerful than morphine). Based on the cost- and time-intensive forensic analysis, National Drug Early Warning System reported the …

Determination Of Cannabinoids, Cathinones, And Synthetic Fentanyls Using Wastewater-Based Epidemiology, Catherine O'Rourke, Bikram Subedi

Posters-at-the-Capitol

Unregulated new psychoactive substances (NPS) in “pure” or “preparation” forms are designed to mimic the effects of controlled substances, and are introduced and reintroduced in the market as a cheap substitute for established regulated drugs in quick succession to loophole the law enforcement efforts on combating drugs. For example, carfentanil, a synthetic opioid activates the opioid receptors similar to morphine but it is astoundingly potent compared to a typical drug of abuse (100 times more potent than fentanyl and 10,000 times more powerful than morphine). Based on the cost- and time-intensive forensic analysis, National Drug Early Warning System reported the …

Hour-Level Resolution On Consumption Pattern Of Substance Abuse, Jarrett Mauk, Rhiannon Huffines, Brittney Nelson, Tara Croft, Bikram Subedi

Scholars Week

Conventional survey-based approaches of determining the consumption statistics of drugs in communities are suffered from non-response biases, and typically underestimate the actual consumption. Time and cost-intensive conventional approaches, therefore, can’t be utilized to determine high-resolution temporal variability in drug consumption. In this study, the temporal trend of consumption of 10 illicit and 26 prescribed neuropsychiatric drugs was determined at hour-level resolution utilizing wastewater-based epidemiology. The hourly composite raw wastewater (every 10 minutes) samples were collected for three consecutive days in a typical week (total of 72 samples), analyzed for target drug residues using UPLC-MS/MS, and back-calculated the consumption rate of …

Uncertainties Treatment For Wastewater-Based Epidemiological Estimation Of The Consumption Of Illicit And Prescribed Neuropsychiatric Drugs In Two Urban Communities In Kentucky Using Ammonium Normalized Population And Monte Carlo Simulation, Rhinannon Huffines, Tara Croft, Manoj Pathak, Bikram Subedi

Scholars Week

The conventional estimation of the prevalence of substance use in a community based on self-reported surveys typically underestimates the actual consumption. Drug’s residues in raw wastewater collected from the centralized wastewater treatment plants were utilized – Wastewater-Based Epidemiology (WBE) – to determine the consumption rate of illicit and prescribed neuropsychiatric residues in two urban communities in eastern Kentucky and two rural communities in western Kentucky. The ammonical nitrogen content in raw wastewater samples was used to minimize the uncertainty associated with the population dynamicity. Uncertainties associated with the several WBE parameters to back-calculate the consumption rate of drugs such as …

Nucleophilic Phosphine Addition: Exploration Of Novel Alkyne Transformations, Brett Pierce

Murray State Theses and Dissertations

Nucleophilic phosphine catalysis has demonstrated its value in synthetic chemistry by allowing for mild carbon-carbon bond formation. Many phosphine-catalyzed reactions with electron-deficient alkynes have been reported in recent years, leading to an array of valuable products. Stemming from this field of study, phosphines can also be utilized as mild chemoselective reductants for alkynes, resulting in the corresponding alkenes. Herein, a mild, stereoselective, phosphine-mediated partial reduction of alkynes to (E)- and (Z)-alkenes is described. Specifically, a general method for the partial reduction of ynoates to the corresponding (E)- and (Z)-enoate, …

Properties And Applications Of Tetraalkylphosphonium Alkylsulfate Ionic Liquids And 3d Printed Polymerized Ionic Liquids, Mustafa Mohammed Alhussain

Murray State Theses and Dissertations

Ionic liquids (ILs) are defined as pure salts with a melting temperature below 100 °C with a subset called room-temperature ILs (RTILs) with melting temperatures at or below room temperature. The sizes of the cation and anion play a critical role in determining the properties, with smaller ions forming stronger ionic forces and packing better, raising viscosity and lowering conductivity of the IL. At the same time, intermolecular forces such as van der Waals and hydrogen bonding can play a role in IL properties as well. Our research described herein is focused on three tetraalkylphosphonium-based cations coupled with three alkylsulfate …