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Novel “Acid Tuned” Deep Eutectic Solvents Based On Protonated L-Proline, Patrycja Janicka, Andrzej Przyjazny, Grzegorz Boczkaj

Natural Sciences Publications

The paper presents new types of deep eutectic solvents (DESs) based on L-proline protonated using three different acids (hydrochloric, sulfuric and phosphoric)and playing the role of a hydrogen bond acceptor(HBA). Glucose and xylitol were used as hydrogen bond donors (HBD). A series of deep eutectic solvents with various mole ratios were obtained for the systems L-proline: glucose and L-proline: xylitol. Density, melting point, pH and viscosity of the synthesized DESs were determined along with the effect of water content, mole fraction of the HBA in DES and temperature on properties of the DESs. A wide range of densities (1343–1606 kg/m3), …

Functionalized Ionic Liquids For Improved Co2 Hydrogenation Catalysts, Amol Nanduji Jaybhaye

Masters Theses & Specialist Projects

Climate change is one of the biggest problems we are facing today, and anthropogenic greenhouse gases contribute significantly to it. Among greenhouse gasses, carbon dioxide emission is increased drastically and affecting majorly for increasing global temperature, and anything we can do to mitigate carbon dioxide emission will be helpful. A carbon dioxide hydrogenation reaction is a promising technique that can convert carbon dioxide into value-added chemicals, but the reaction rate is slow, and for that, we can use catalysts that will accelerate the reaction rate. Platinum-based nanoparticles have sparked research related to energy and environmental catalysts. Catalytic properties are depending …

Design Of Antioxidant Monomer, Augustine Osilamah Yusuf

Masters Theses & Specialist Projects

Reactive oxygen species such as hydrogen peroxide are present at the sites of inflammation in the body. Degradable polymeric nanoparticles have shown great promise in a range of biomedical applications which include preferential delivery of therapeutics to such inflamed sites. We are working towards a new class of materials expected to have tunable degradation rates in the presence of hydrogen peroxide. These new materials consist of three parts: degradable linkages, antioxidant groups, and unreactive filler monomers such as methylmethacrylate. We have synthesized a polymerization initiator with a degradable linkage, and we have shown that using this initiator to synthesize another …

Nanozymes—Hitting The Biosensing “Target”, Yingfen Wu, Diane Darland, Julia Zhao

Biology Faculty Publications

Nanozymes are a class of artificial enzymes that have dimensions in the nanometer range and can be composed of simple metal and metal oxide nanoparticles, metal nanoclusters, dots (both quantum and carbon), nanotubes, nanowires, or multiple metal-organic frameworks (MOFs). They exhibit excellent catalytic activities with low cost, high operational robustness, and a stable shelf-life. More importantly, they are amenable to modifications that can change their surface structures and increase the range of their applications. There are three main classes of nanozymes including the peroxidase-like, the oxidase-like, and the antioxidant nanozymes. Each of these classes catalyzes a specific group of reactions. …

College Of Natural Sciences Newsletter, July 2021, College Of Natural Sciences

College of Natural Sciences Newsletters and Reports

Volume 2, Issue 7.

Page 1 Dean's Message
Page 2 Celebrating Three Years
Page 3 Summer School Travel
Page 4 Media Coverage of CNS
Page 5 Chemistry Teachers Visit
Page 5 Remembering Dr. Warren Hein
Page 6 Research Spotlights: Undergraduate Summer Experiences
Page 7 Open PRAIRIE Data; Grants Awarded in CNS

Ahr Expression On Rorc-Expressing Immune Cells Is Essential For I3c-Mediated Protection Against Colitis, Michal C. Williams

Senior Theses

Colitis is an inflammatory bowel disorder (IBD) whose etiology is attributed to modification in the luminal microbiota and dysregulation in the immune response. Indole is a signaling molecule which is naturally produced by gut luminal microbiota. Indole-3- carbinol (I3C) is a compound commonly found in vegetables and a ligand for the aryl hydrocarbon receptor (AhR). Previous studies have detected decreased expression and activation on the AhR receptor in colitis patients, thought to possibly alter gut microbiota metabolism, subsequently promoting colitis. 1 AhR, expressed in a variety of immune and epithelial cells, contributes to gut homeostasis by affecting vital mediators such …

Structure And Reactivity Of The First Row Transition Metals Bearing Redox-Active Ligands And Tunable H-Bonding Interactions, Khashayar Rajabimoghadam

Chemistry Theses and Dissertations

Metalloenzymes, as natural catalysts, can break a reaction with high activation energy to multiple small reactions with lower activation energies; in these small reactions, multiple bonds form and dissociate rapidly, some metalloenzymes use redox-active ligands in their active site to provide the needed electrons for these multiple small reactions. Additionally, in the secondary coordination sphere in the vicinity of the metalloenzymes, the hydrogen bonding interactions facilitate the transfer and interaction of the substrates and the stabilization of the active intermediates. These unique features in metalloenzymes inspired chemists to design molecular models that can partially mimic the structure and reactivity of …

The Effects Of Sugar Osmolytes On Reverse Micelle Systems, Jenna Deckard, Bridget Gourley Phd

Annual Student Research Poster Session

Reverse Micelles (RM) are nanoscopic pools of water encapsulated by an amphipathic surfactant molecule that allows the water pool to be suspended in a nonpolar solvent. We use RM systems because they allow for the study of water and dissolved osmolyte interactions in confinement. Gaining an understanding of how sugars interact with water in confinement has significant implications for biological systems. This project seeks to understand the effects of galactose as an osmolyte on the interactions, loading limits, and size of RMs when compared to RMs containing only water and RMs containing glucose. Galactose and glucose have slight structural differences, …

Effect Of A Hexylamine Derivative On Cancer Cell Viability, Rachel Delancey, Bamlak Deju, Jeff Hansen Phd, Nipun Chopra Phd

Annual Student Research Poster Session

2-[(p-Chlorophenyl)hydroxymethyl]-1-[(methylamino)hexyl]cyclohexanol is a drug produced by hexyl amine and an epoxide through an aldol epoxidation reaction. Motifs of β-amino alcohols and nonpolar R groups in organic compounds have been found to have cytotoxic properties. Past studies in Dr. Hansen’s lab has shown that this hexylamine derivative has similar LC50 values to other antitumor agents. They also found that the drug was cytotoxic to HL-60 cancer cells. No other cell lines have been tested with this drug. Our study investigates the effect of our compound on varying cell lines to further determine its anticancer properties. Mouse NIH/3T3, Human HEK293, and Human …

Diversity Oriented Synthesis Of Furan Epoxide, Yuhui Wei, Jeff Hansen Phd

Annual Student Research Poster Session

In this project, we are doing the Diversity Oriented Synthesis of Furan Epoxide. There are two main reactions we are trying to accomplish with the epoxide which are the Achmatowicz reaction with the furan ring, and the epoxide ring opening reaction with amine. During this summer, we are able to make the amino alcohol and the Achmatowicz product has been made from the previous semester. We were also trying to get Achmatowicz reaction happening with the amino alcohol product. However, the result doesn't show the expected structure and still needs further research. Besides organic chemistry synthesis, we also tested the …

Awegnn: Auto-Parametrized Weighted Element-Specific Graph Neural Networks For Molecules., Timothy Szocinski, Duc Duy Nguyen, Guo-Wei Wei

Mathematics Faculty Publications

While automated feature extraction has had tremendous success in many deep learning algorithms for image analysis and natural language processing, it does not work well for data involving complex internal structures, such as molecules. Data representations via advanced mathematics, including algebraic topology, differential geometry, and graph theory, have demonstrated superiority in a variety of biomolecular applications, however, their performance is often dependent on manual parametrization. This work introduces the auto-parametrized weighted element-specific graph neural network, dubbed AweGNN, to overcome the obstacle of this tedious parametrization process while also being a suitable technique for automated feature extraction on these internally complex …

Harnessing Surface Chemistry And Instabilities In Silicone Elastomers To Synthesize Adaptive Systems With Mechanically Tunable Surface Properties And Functionality, Ali Jamal Mazaltarim

Department of Chemistry: Dissertations, Theses, and Student Research

Material interfaces are of critical importance to numerous fields, including nanomaterials, electronics, microfluidics, synthesis, bioanalysis, pharmaceuticals, and catalysis, and they have been extensively researched. The materials used in these fields are often rigid/hard (such as silicon wafers) resulting in static surface properties. Consequently, the chemical/morphological properties of a surface may be modified using synthetic or mechanical means to tailor the interfacial properties of a material (i.e., surface energy, adhesion, topography, and reactivity). Recently, emphasis has been placed on designing dynamic materials with adaptive interfacial properties that respond to a variety of environmental stimuli. To this end, the surface chemistry and …

Computational Analysis Of Type 3 Iodothyronine Deiodinase: Potential Inhibitors, Substrate Binding, And Dimer Structure, Eric Scott Marsan

Chemistry & Biochemistry Theses & Dissertations

Thyroid hormones (THs) in mammalian tissues are crucial for development and maintaining metabolic homeostasis. Iodothyronine deiodinases (Dios) remove iodines from THs by a selenocysteine (Sec) residue, which either activates or inactivates them. Halogen bonding (XB) has been proposed to describe the interaction between the Se and I atoms of the T4-Dio complex. Disruption of TH homeostasis by xenobiotics, such as polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) can cause deleterious effects on the endocrine system. Experimental studies have indicated that PBDEs and PCBs could disrupt TH homeostasis by inhibiting Dio through XB formation. However, no current quantitative study exists …

Improvement Of Biochar Through Ozonization And Biosafety Of Genetically Engineered Cyanobacteria, Oumar Sacko

Chemistry & Biochemistry Theses & Dissertations

Through the innovative technique of biochar post-production surface oxygenation by ozonization, we were able to improve certain properties of biochar. In project one, the incubation of an insoluble phosphate rock material (hydroxyapatite) with the wet ozonized pine 400 biochar and its filtrate resulted in a solubilization of 80 times more phosphate from hydroxyapatite (569.0 mg/L ± 6.4) compared to the pure water-hydroxyapatite control (7.2 mg/L ± 0.3). The ozonized biochar may provide a new possible way to unlock the phosphorus from insoluble phosphate mineral phases. The cation exchange capacity (CEC) is a key property of biochar when used as a …

Molecular Dynamics Simulations Of Ion Transport Through Electrically Stressed Biological Membranes, Federica Castellani

Biomedical Engineering Theses & Dissertations

The cell membrane is a selectively permeable barrier that controls the transport of ions, molecules, and other materials into and out of a cell. The manipulation of the cell membrane permeability is the basis for several biotechnological and biomedical applications, including electroporation. Electroporation (or electropermeabilization) occurs when the application of an external electric pulse causes water intrusion into the membrane interior and the formation of conductive transmembrane electropores. These electropores allow drugs, genetic material, and other normally impermeant molecules to enter a cell. Despite years of study, the complex mechanisms underlying this process are still not well understood. Molecular dynamics …

The Development Of Novel Carbohydrate-Based Gelators And Their Applications As Advanced Soft Materials, Joedian Morris

Chemistry & Biochemistry Theses & Dissertations

Low molecular weight gelators (LMWGs) are attractive molecules that have been explored extensively due to their practical applications in many disciplines. These small molecules self-assemble forming solid-like gels via three-dimensional cross-linked networks with the solvent as the key component within the matrix. Carbohydrate-based LMWGs are small molecules that can form solid-like gels in water, organic solvents, and aqueous solutions. They have great potential to be utilized in different applications because carbohydrates are biocompatible and can be made from easily accessible and renewable resources. Designing gelators is still a challenge within the field, even though researchers have developed tools to predict …

Bioethanol Production: Glucose Testing And Quantification Using Dns Analysis And Addition Analytical Methods, Dineen Vogler, Barnabas Gikonyo

McNair Scholars Program

The search for alternative ways to create a more sustainable and environmentally friendly source of energy, other than fossil fuels, has been ongoing for many years. Particularly, the production of biofuels has become of interest. One effort has been through the creation of first-generation biofuels that curb greenhouse gas emissions, unlike fossil fuels. However, first generation biofuels lead to the increase in food prices which negatively impacts developing countries, as they use food sources to produce biofuel. To mitigate this issue, second generation biofuels are considered as a better alternative. Instead of hindering the food supply, second generation biofuels aim …

Mechanisms Of Spontaneous Curvature Inversion In Compressed Graphene Ripples For Energy Harvesting Applications Via Molecular Dynamics Simulations, James M. Mangum, Ferdinand Harerimana, Millicent N. Gikunda, Paul M. Thibado

Physics Faculty Publications and Presentations

Electrically conductive, highly flexible graphene membranes hold great promise for harvesting energy from ambient vibrations. For this study, we built numerous three-dimensional graphene ripples, with each featuring a different amount of compression, and performed molecular dynamics simulations at elevated temperatures. These ripples have a convex cosine shape, then spontaneously invert their curvature to concave. The average time between inversion events increases with compression. We use this to determine how the energy barrier height depends on strain. A typical convex-to-concave curvature inversion process begins when the ripple’s maximum shifts sideways from the normal central position toward the fixed outer edge. The …

Machine Learning Using Host/Guest Energy Histograms To Predict Adsorption In Metal–Organic Frameworks: Application To Short Alkanes And Xe/Kr Mixtures, Zhao Li, Benjamin J. Bucior, Haoyuan Chen, Maciej Haranczyk, J. Ilja Siepmann, Randall Q. Snurr

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

A machine learning (ML) methodology that uses a histogram of interaction energies has been applied to predict gas adsorption in metal–organic frameworks (MOFs) using results from atomistic grand canonical Monte Carlo (GCMC) simulations as training and test data. In this work, the method is first extended to binary mixtures of spherical species, in particular, Xe and Kr. In addition, it is shown that single-component adsorption of ethane and propane can be predicted in good agreement with GCMC simulation using a histogram of the adsorption energies felt by a methyl probe in conjunction with the random forest ML method. The results …

Characterization Of Ph – Responsive Nanocage Based On The Ferritin Iron Storage Protein, Satyam Singh

Theses and Dissertations

The iron-storage protein ferritin (Ftn) assembles into a protein cage structure with 24 subunits and octahedral (4-fold, 3-fold, 2-fold) symmetry. Each monomeric subunit contains a robust four-helix bundle fold. The fully assembled Ftn structure has a high degree of thermal stability (up to 100°C), a mono dispersed size (12 nm in diameter), and a large central cavity (7-8 nm in diameter). The central cavity stores ferric iron in phylogenetically diverse group of organisms, including humans. The central cavity has been used for encapsulation of cargoes such as other metals, contrast agents for imaging, small molecule drugs for therapy, …

Characterization Of A High Affinity Glutathione Transporter And Its Impact On Glutathione Depleted Saccharomyces Cerevisiae, Tirthankar Bandyopadhyay

Theses and Dissertations

Thiol-disulfide redox homeostasis is integral for maintaining the redox status of proteins and other thiol-containing molecules within the cell. Among the many antioxidants and detoxifying enzymes and small peptides, glutathione (GSH) has proven to be critical for the preservation of function and structural integrity of the cell due to its functionality in areas like oxidative protein folding, thiol redox control, reactive oxygen species (ROS) and xenobiotics removal as well as iron regulation and Fe-S cluster biogenesis. Therefore, our studies are aimed at elucidating the factors that control GSH trafficking and metabolism in the model eukaryote Saccharomyces cerevisiae (baker’s yeast). Using …

Exploration Of Vase As An Extraction Method For Emerging Disinfection By-Products And Acidic Methanol As A Safe And Effective Derivatization Method For Haloacids, Madison Leigh Kilpatrick

Theses and Dissertations

This project aims to create an environmentally friendly, robust, and efficient extraction and preconcentration method in both the detection and quantification of various disinfection by-products (DBPs). Vacuum assisted sorbent extraction (VASE) is a newly developed method in the extraction of both volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs). This extraction method is paired with a Thermo Scientific TSQ Quantum Triple Quadrupole GC-MS system for the quantification of DBPs. VASE outperforms current DBP extraction methods, with liquid-liquid extraction (LLE) being the most used alternative, because of its minimal use of solvent, high level of automation, and over-all ease of …

Colloidal Semiconductor Quantum Dots: Solution Processing And Heterostructure-Based Optoelectronics, Mathew L. Kelley

Theses and Dissertations

Colloidal semiconductor quantum dots (QDs) are attractive candidates for high-efficiency solar cells and uncooled multiplexed photodetectors due to their favorable characteristics including large absorption cross-sections, size-tunable bandgap energies spanning the ultraviolet (UV) to short wave infrared, and solution processability. These QD-based optoelectronic devices operate on the basis of efficient photogenerated charge migration within QD solids and charge separation and recombination at electrical junctions, underscoring the need for (1) processing strategies that facilitate charge transport and (2) characterization techniques that robustly interrogate charge separation at QD interfaces. Here, my work on the post-synthetic processing and surface modifications of several semiconductor QDs, …

Plasmonic Metallic And Semiconductor Nanomaterials, Mengqi Sun

Theses and Dissertations

The earliest account of localized surface plasmon resonance (LSPR) has to date back to the ancient age of Rome in 400 A.D. The famous glass of Lycurgus cup told the story of unique light-and-matter interaction at the nanoscale that confines the electromagnetic field resonance at its surface and therefore allows LSPR feature to noticeably arise. The conventional metallic LSPR nanomaterials, like Au and Ag nanoparticles attract constant attentions due to their synthetic simplicity, chemical robustness, and visible spectral response. Its ability to generate sensitive dielectric sensing of the surroundings, strong electromagnetic field and active charge carriers upon optical excitation triggered …

Alkyne Cyclization Involving A Zwitterionic Hexaruthenium Carbido Carbonyl Complex And The Synthesis Of The First-Nitrido Heterometallic Carbonyl Cluster Complexes, Nutan Damodhar Wakdikar

Theses and Dissertations

Chapter 1 introduces two related topics with the primary focus on the background of zwitterions and the conceptual understanding of a metal-complexed zwitterion. It also discusses the potential of a metal-complexed zwitterion for a carbon-carbon bond formation reaction. Synthesis of the metal carbonyl cluster, Ru6(µ6-C)(µ-CO)(CO)16, is also discussed in detail. Then, the background with the importance of heterometallic cluster complexes is discussed with the help of various examples used for catalysis.

The reaction of hexaruthenium carbido carbonyl cluster, Ru6(µ6-C)(µ-CO)(CO)16, with C2H2 and Me3NO yielding first examples of two new zwitterionic complexes, Ru6C(CO)15(μ−η2−C2H2NMe3), 2.2, and Ru6C(CO)14(μ3−η4−C4H4NMe3), 2.3, are presented in Chapter …

Resonant Two-Photon Ionization And Velocity Mapped Ion Imaging Studies Of Aromatic Van Der Waals Complexes, James T. Makuvaza

Dissertations (1934 -)

The study of van der Waals complexes provides a means for understanding the nature and strength of non-covalent interactions. Non-covalent interactions including C-H/, C-H/O, C-H/N, C-H/F, halogen and chalcogen bonding are found in important intermediates that regulate chemical and biological processes in many forefront areas of science including molecular self-assembly, drug substrate interactions, supramolecular chemistry, crystal engineering and biochemistry. To better understand these interactions, laser spectroscopic techniques that include mass selected two color resonant two photon ionization (2CR2PI) and velocity mapped ion imaging spectroscopy in combination with complementary ab initio calculations were used to probe the electronic structure, geometries, and …

Microfabrication And Electrochemical Characterization Of A Novel Su-8 Probe With An Array Of Individually Addressable Electrodes Suitable For Redox Cycling Experiments In Ultra-Small Volumes, Mahsa Lotfi Marchoubeh

Graduate Theses and Dissertations

Redox cycling is an electrochemical technique that utilizes closely spaced generator and collector electrodes to cycle reversible redox species between their oxidative states. With advantages in signal amplification, selectivity of species based on their electrochemical reaction mechanism, and limited or no background subtraction, this technique is well suited for selective detection of important electrochemically active molecules such as dopamine at basal or slowly changing levels.

Miniaturized medical devices have become an area of great interest for measurement of chemicals in limited volumes with low concentrations or in sensitive tissues. A probe on a polymeric SU-8 substrate with suitable dimensions and …

Investigation Of Factors Influencing Recombination Versus Disproportionation Of Complex Radicals Formed By C-N Homolysis Of Breslow Type Intermediates And Related Compounds, Taylor Burnett

Graduate Theses and Dissertations

Electron rich enamines are capable of C-N bond homolysis and subsequent recombination and/or disproportionation. It is unclear what causes these radicals to undergo recombination or disproportionation. Density Functional Theory (DFT) calculations do not provide a transition state for the recombination and disproportionation processes and therefore they cannot be used to predict the favorable reaction. Breslow intermediates formed by deprotonation of thiazolium salts and reaction with aromatic aldehydes are examples of electron rich enamines. These breslow intermediates can undergo C-N bond homolysis to form a radical pair the either recombine or disproportionate. Upon investigation of the factors influencing recombination and disproportionation, …

Implications Of The Links Between Demography And Ecology For The Economy Of The Republic Of Karakalpakstan, Keunimjay Allanazarov, Gulya Khodjaeva, Katherine Shields

Karakalpak Scientific Journal

This article analyzes the impact of demographic factor on territorial organization of production in rural areas of the Republic of Karakalpakstan and reveals the main trends in production development. The analysis of statistical data of rural areas is given and proposals to improve the negative situation are given. More than 1306.8 thousand people live in rural areas of the Republic of Karakalpakstan, where they are concentrated in 1187 settlements, 26 urban settlements, and 11 towns of district subordination. All this testifies to the presence of large undeveloped production reserves and huge human potential. However, due to reduction of Amudarya water …

Investigation Of The Twist Of A Yarn With A Square Structure, Liza Toreniyazova, R. Orazbayeva, D. Kadirova, R. Rakhimkhodzhaev

Karakalpak Scientific Journal

The article presents the results of a study of the effect of yarn twist on the surface density of clothing fabrics with a square structure and the filling calculation of the fabric depending on the weave. The tension in the process of weaving square fabric on a loom with short overlaps is higher relative to weaving of fabric with long overlaps. With an increase in the twist of the yarn, the surface density of the fabric, the coefficient of filling (CST) and the coefficient of connectivity of the fabric (FTC) of the square structure increase.