Chemistry Commons^™

Chemistry 104 Laboratory Manual, Boris Kalmatsky

Open Educational Resources

No abstract provided.

Using Electrocoagulation To Remove Perfluoroalkyl And Polyfluoroalkyl Substances (Pfas) From Contaminated Water, Amy Yanagida

UCARE: Research Products

Perfluoroalkyl and Polyfluoroalkyl substances (PFAS) are a family of manmade chemicals that are used to improve the quality of several commercial products by making them resistant to heat, oil, stains, grease and water. Unfortunately, the chemical properties that make PFAS useful from an industrial perspective also make them mobile and recalcitrant once released into the environment. We used electrocoagulation to run a direct current through contaminated water to generate a zinc floc to precipiate PFAS out of water.

Mathematical And Physical Description Of Conical Intersections, Nicholas Dewey

Honors Projects

Conical intersections (CIs) are points of degeneracy between two or more potential energy surfaces. Due to the intersection point, it is much easier for molecules to transition their electronic, vibrational, and rotational energies between surfaces. Therefore, CIs are critical to the study of excited states, particularly in the context of photochemistry. However, they are difficult to study because they interfere with traditional thermodynamics and deviate from the Born-Oppenheimer approximation. The purpose of this review is to explain why that is the case by exploring the foundation for the mathematics and physics behind CIs. Also included is an application of how …

Senior Project: An Investigative Study Into The Bacterial Contamination Of Little Black Creek, Margaret I. Brenneman

Honors Projects

An investigation of Escherichia coli concentrations in a west Michigan stream was conducted to determine sources of fecal contamination that impact water quality. Little Black Creek (LBC) is located in Muskegon County and discharges into Lake Michigan at the P.J. Hoffmaster Campground Beach. Often referred to as an “indicator bacteria,” water contaminated with E. coli has a high probability to contain other enteric pathogens as well. Beach water testing in 2020 using Colilert-18 methods revealed E. coli levels of 579 cfu/100mL in the creek discharge area that exceeded total body contact criteria of 300 cfu/100mL. A follow-up study of the …

Catalytic Carbon–Carbon Bond Activation Of Saturated And Unsaturated Carbonyl Compounds Via Chelate-Assisted Coupling Reaction With Indoles, Nuwan Asanka Pannilawithana, Chae S. Yi

Chemistry Faculty Research and Publications

The chelate assistance strategy was devised to promote a highly regioselective catalytic C–C bond activation reaction of saturated and unsaturated carbonyl compounds. The cationic Ru–H complex 1 was found to be an effective catalyst for mediating the coupling reaction of 1,2-disubstituted indoles with α,β-unsaturated aldehydes and ketones, in which the regioselective C_α–C_β activation of the carbonyl substrates has been achieved in forming the 3-alkylindole products. The analogous coupling reaction of indoles with saturated aldehydes and ketones directly led to the C_α–C_β cleavage of the carbonyl substrates in forming the 3-alkylindole products. The coupling reaction …

Using Surface-Enhanced Raman Scattering Of Gold Nanostars For Encoding Molecular Information, Samantha E. Curry

Honors Thesis

Increases in the selling of illicit goods warrant a subsequent need for even more sophisticated methods to prevent counterfeit products from being sold. Surface-enhanced Raman spectroscopy (SERS) has the potential to be a powerful tool to thwart counterfeiters because the unique security tags fabricated with this method are difficult to reproduce without knowing the “secret” recipes used in their preparation. In this work, gold nanostars are used as SERS active substrates since their branched structure allows for strong coupling between the light and plasmonic nanoparticles. As a result, Raman signals of trace amount of chemicals can be easily detected. The …

Characterization Of Influenza A Virus Full Length Matrix Protein 1 (M1) In Order To Probe M1-M2 Interaction, Elizabeth A. Erler , '20

Senior Theses, Projects, and Awards

Influenza remains a serious global health threat and further characterization of key viral proteins is necessary in order to develop novel drugs and vaccines. Matrix protein 1 (M1) and matrix protein 2 (M2) of Influenza A Virus play key roles in the assembly and release of new infectious viral particles. The cytoplasmic tail of M2 has been shown to be critical for inducing membrane curvature in order to facilitate budding. M1 has multiple roles, including packaging viral RNA and recruiting it to the budozone through interactions with M2 and other viral membrane proteins. In this role as an adaptor protein, …

A Public Health Perspective On Gen X Contamination In Drinking Water, Allison Stevens

Honors Capstone Enhancement Presentations

No abstract provided.

Heavy-Atom Tunneling, Samuel Powell

Honors Capstone Enhancement Presentations

No abstract provided.

Structure-Activity Relationship Of Novel Diphenyl Ureas Targeting Mycobacterium, Piper Burghduf

Student Scholars Day Posters

In 2017, the World Health Organization reported that 10 million people were infected with tuberculosis, 1.6 million of whom died. Tuberculosis is caused by a bacterium called Mycobacterium tuberculosis, which primarily infects an individual’s lungs. Unfortunately, failure to adhere to the long and arduous drug regimen has contributed to the emergence of antibiotic-resistant strains of M. tuberculosis. Therefore, the need for novel antibiotics is imperative to saving millions of lives. Our lab has recently developed a family of diphenyl ureas that exhibited increased antimicrobial activity toward Mycobacterium. Reported herein is the continuation of our previous research involving the synthesis of …

Structural And Functional Characterization Of New Clinically Relevant Enzymes Involved In Antibiotic Resistance, Violet Ruiz

Student Scholars Day Posters

The rise of antibiotic resistance is a global health threat requiring development of novel treatments. β-lactamase enzymes found in many multi-drug resistant bacteria contribute to resistance of β-lactam antibiotics. The enzyme cleaves the β-lactam ring, preventing the drug from reaching its cellular target. A class of β-lactamases, Acinetobacter-derived cephalosporinases (ADCs) are found in the multi-drug resistant bacteria Acinetobacter baumannii. Specific ADCs were selected from a group of antibiotic-resistant infections. With no known structures of these newly identified ADCs, it is key to discern how minor differences in sequences between ADCs contribute to drug resistance. In this project, structural …

Investigating The Role Of Iron-Sulfur Signaling In Yeast Transcriptional Regulation, Malini Gupta

Theses and Dissertations

As an essential cofactor in a myriad of cellular processes, uptake and mobilization of iron must be tightly controlled. Iron homeostasis in fungi involves balancing iron uptake and storage with iron utilization to achieve adequate, non-toxic levels of this essential nutrient. Extensive work in the non-pathogenic yeasts Saccharomyces cerevisiae and Schizosaccharomyces pombe have uncovered unique iron regulation networks for each organism that control iron metabolism via distinct molecular mechanisms. The activities of all fungal iron-sensing transcription factors characterized to date are regulated via iron-sulfur cluster signaling.

In Saccharomyces cerevisiae, expression of iron uptake, utilization and storage genes is primarily regulated …

Current And Future Applications Of 3d Printing Using Custom-Made Materials, Bridger T. Irons

Honors Thesis

The use of 3D printers has increased exponentially from its inception in the 1980s. Recently, the ability to design and create detailed objects has drawn the attention of many who wish to capitalize on this highly customizable process. With much of the focus in this industry being placed on finding new printable materials, many are overlooking the possibility of modifying existing materials. The aim of our research was to modify the materials already being used by 3D printers to alter their properties and explore future possible applications. We examined the addition of graphene powder, carbon microfibers, and other nanoparticles to …

A Hybrid Lipid Membrane Coating “Shape-Locks” Silver Nanoparticles To Prevent Surface Oxidation And Silver Ion Dissolution, Thomas J. Miesen, Arek M. Engstrom, Dane C. Frost, Ramya Ajjarapu, Rohan Ajjarapu, Citlali Nieves Lira, Marilyn R. Mackiewicz

Chemistry Faculty Publications and Presentations

The controlled synthesis of stable silver nanoparticles (AgNPs), that do not undergo surface oxidation and Ag⁺ ion dissolution, continues to be a major challenge. Here the synthesis of robust hybrid lipid-coated AgNPs, comprised of L-α-phosphatidylcholine (PC) membranes anchored by a stoichiometric amount of long-chained hydrophobic thiols and sodium oleate (SOA) as hydrophobic binding partners, that do not undergo surface oxidation and Ag+ ion dissolution, is described. UV-Visible (UV-Vis) spectroscopy, transmission electron microscopy (TEM), and inductively coupled plasma mass spectrometry (ICP-MS) demonstrate that in the presence of strong oxidants, such as potassium cyanide (KCN), the hybrid lipid-coated AgNPs are stable …

Purification Of Dna Origami Nanostructures Using Capillary Electrophoresis, Janan Hui , '20

Senior Theses, Projects, and Awards

DNA origami are nanostructures designed based on Watson-Crick base-pairing that fold a scaffold into non-arbitrary morphologies using an excess of linear single-stranded DNA "staples". As an engineered nanomaterial (ENM) with great customizability, DNA origami also enjoys the benefit of naturally encoded and well-studied structural and functional properties. The flexibility of different folding patterns allows for construction of a wide variety of shapes and sizes of DNA origami, showing potential applications in fields such as medicine, biocomputing, biomedical engineering , and measurement science. Despite the successes as a functional nanomaterial, a major barrier to the applicability of DNA origami rests in …

Photophysical Properties And Excited State Dynamics Of Porous Organic Materials, Korlan Duisenova

Master's Theses (2009 -)

Charge transfer complexes are charge separated states that are formed at donor - acceptor interfaces and play significant role in charge photogeneration. One of the main criteria for efficient charge transfer is suppression of charge recombination process. Previous experiments show that one of the most effective ways to inhibit recombination is an introduction of bridge molecules between donor and acceptor or increase the number of electron donating and withdrawing groups. These solutions are inspired by photosynthetic reaction centers where charge transfer occurs over long distances. Covalent Organic Frameworks (COFs) are advanced porous crystalline materials that can be constructed of multiple …

Mechanistic Investigations Of Isothiourea Catalyzed Silylations Of Secondary Alcohols Using Reaction Progress Kinetic Analysis, Brandon Kane Redden

Theses and Dissertations

The primary focus of this research is in expanding the knowledge and scope of the asymmetric silylation of alcohols. Since it was discovered in 2011 that chiral isothioureas can selectively silylate alcohols through kinetic resolution reactions, the Wiskur group has been working to increase the applications of the methodology. Understanding the kinetics behind the mechanism of the reaction is fundamental in the designing both improved kinetic resolutions and other silylation methodology. Chapter 2 focuses on using reaction progress kinetic analysis to monitor silylations of secondary alcohols with thiourea catalysts in real time using in situ IR to determine the rate …

Development Of Natural Product-Derived Cationic Polymers For Biomaterial Applications, Moumita Sharmin Jui

Theses and Dissertations

In this thesis, multicyclic natural products and metallocene-containing polymers were synthesized for biomedical applications.

Chapter 1 describes the overall background, the recent development of natural product-based antimicrobial biomaterial and metallocene containing polymer for biomedical application. Afterward, the primary research objectives of my research are illustrated.

In chapter 2, a multicyclic natural product derived guanidine-based facially amphiphilic homopolymers and copolymers were synthesized. Cholic acid is one of the bile acid derivatives used to prepare facially amphiphilic moieties. A neutral polyethylene glycol (PEG) component was used to prepare copolymers with cholic acid. Reversible-addition fragmentation chain transfer (RAFT) polymerization technique was used to …

Quantitative Analysis Of Silver Nanoparticle Dissolution Kinetics In Complex Matrices Using Point-Of-Use And End-Of-Use Models, Daniel J. Boehmler , '20

Senior Theses, Projects, and Awards

Engineered nanomaterials (ENMs) have become increasingly popular for use in both industrial and consumer settings in recent years. Of the myriad of materials used to synthesize ENMs, silver is one of the most common. Silver nanoparticles (AgNPs) undergo dynamic transformations in biological environments, leading to modifications in their reactivity, surface interactions, and speciation. In particular, release of ionic silver (Ag(I)(aq)) through AgNP dissolution can have significant impacts on ecological and human health. Thus, quantifying AgNP dissolution rates in biologically relevant matrices can provide valuable information regarding their potential cytotoxic effects. Linear sweep stripping voltammetry (LSSV) is a technique …

Scanning Electron Microscopy (Sem) Investigation Of Morphology Changes In The Reduction Of Silica Nanoparticles To Elemental Silicon, Allison M. Cairns

University Honors Theses

The application of silicon nanoparticles varies from energy storage materials, to drug-delivery, and molecular recognition. Various chemical and physical properties of the Si nanoparticles arise from their morphology. This paper aims to reveal the morphology of Si nanoparticles following magnesiothermic reduction of silica (SiO₂) nanoparticles. Two sets of SiO₂ nanoparticles were used, commercially available NanoXact nanoparticles and laboratory-synthesized Stöber nanoparticles. A Zeiss Sigma VP FEG SEM was used to examine the morphology. Following the magnesiothermic reduction, the nanoparticles were etched with HF. Ten sets of images were taken of both Stöber and NanoXact nanoparticles: 1,2: the SiO …

Visible-Light Photooxidation In Water By 1o2-Generating Supramolecular Hydrogels, Sankarsan Biswas, Mohit Kumar, Andrew Levine, Ian Jimenez, Rein V. Ulijn, Adam Braunschweig

Advanced Science Research Center

We report supramolecular photocatalytic hydrogels, produced by the enzymatically driven self-assembly of low molecular weight gelators (LMWGs). These LMWG precursors are composed of the organic chromophore diketopyrrolopyrrole (DPP), which is bi-functionalized with a series of amino acid (Phe, Tyr, Leu) methyl esters. In situ enzymatic hydrolysis of these photoactive precursors results in supramolecular hydrogels that provide a high density of photocatalytic sites. Under visible light irradiation these hydrophobic fibers recruit the reaction substrates and also produce ¹O₂, which is used here for the photooxidation of thioanisole (aromatic substrate) and cyclohexyl methyl sulfide (aliphatic substrate), with yields as …

Versatile Bismuth Salts-Induced Reactions From Our Laboratory: A Perspective, Debasish Bandyopadhyay, Bimal Krishna Banik

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

Bismuth salts-mediated reactions are developed for the synthesis of diverse organic molecules of medicinal significance. Reactions conducted with bismuth salts are environmentally friendly and these may proceed due to the release of acids in the media. Bismuth salt may also act as a Lewis acid in these reactions. Versatile organic molecules in chiral and achiral forms are synthesized using bismuth salts-induced reactions at our research laboratory.

Structure–Activity Relationship Of Rgd-Containing Cyclic Octapeptide And Αvβ3 Integrin Allows For Rapid Identification Of A New Peptide Antagonist, Aaron Silva, Wenwu Xiao, Yan Wang, Wei Wang, Heng Wei Chang, James B. Ames, Kit S. Lam, Yonghong Zhang

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

The αvβ3 integrin, a receptor for many extracellular matrix proteins with RGD-sequence motif, is involved in multiple physiological processes and highly expressed in tumor cells, therefore making it a target for cancer therapy and tumor imaging. Several RGD-containing cyclic octapeptide (named LXW analogs) were screened as αvβ3 antagonists with dramatically different binding affinity, and their structure–activity relationship (SAR) remains elusive. We performed systematic SAR studies and optimized LXW analogs to improve antagonistic potency. The NMR structure of LXW64 was determined and docked to the integrin. Structural comparison and docking studies suggested that the hydrophobicity and aromaticity of the X7 amino …

Glutaminyl-Trna Synthetase From Pseudomonas Aeruginosa: Characterization, Structure, And Development As A Screening Platform, Yaritza Escamilla, Casey A. Hughes, Jan Abendroth, David M. Dranow, Samantha Balboa, Frank B. Dean, James M. Bullard

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

Pseudomonas aeruginosa has a high potential for developing resistance to multiple antibiotics. The gene (glnS) encoding glutaminyl-tRNA synthetase (GlnRS) from P. aeruginosa was cloned and the resulting protein characterized. GlnRS was kinetically evaluated and the KM and kcatobs , governing interactions with tRNA, were 1.0 μM and 0.15 s-1 , respectively. The crystal structure of the α2 form of P. aeruginosa GlnRS was solved to 1.9 Å resolution. The amino acid sequence and structure of P. aeruginosa GlnRS were analyzed and compared to that of GlnRS from Escherichia coli. Amino acids that interact with ATP, glutamine, and tRNA are well …

Structural, Functional And Immunological Studies Of Group 1 And 2 House Dust Mite And Profilin Allergens For The Development Of Allergen Specific Diagnostics And Immunotherapy, Anyway B. Kapingidza

Theses and Dissertations

Group 1 and 2 house dust mites (HDM) allergens elicit IgE response in more than 80% of sensitized individuals. These allergens affect 10-30% of the world’s population. Prolonged inhalation of low doses of allergens (microgram amounts inhaled over months or years) by genetically predisposed individuals leads to the induction of a Th2-type immune response induced by allergen-specific immunoglobulin E (IgE) produced by plasma cells resulting in allergic diseases like asthma, atopic dermatitis, and rhinitis. Group 1 and 2 HDM allergens, in particular, are associated with the development of the aforementioned allergic diseases. The goal of this research was to characterize …

An Examination Between Neighborhood Characteristics And Alzheimer’S Disease And Related Dementias And Caregiver Mental Health In South Carolina, Mohammad Jahirul Islam

Theses and Dissertations

Carboranes are of topical interest due to their unique structures and applications in the fields of catalysis, polymers, material sciences and supramolecular chemistry. Icosahedral closo-dicarbadodecaboranes are remarkably robust three-dimensional boron-carbon clusters with two slightly acidic C-H bonds. Moreover, coordinatively unsaturated transition-metal complexes containing C-functionalized ortho-carborane are considered as potential catalysts for activation of small molecules.

Recently, we reported the synthesis of a pyridine-backbone pincer complex {(C₅H₃N)(C₂B₁₀H₁₀)₂}Ni(CH₃CN) (1) in which two C-functionalized ortho-carborane clusters act as the arms of the pincer ligand. The complex …

Systematic Development Of Photocatalysts, Mary Victoria Bobo

Theses and Dissertations

Photocatalysis is a rapidly growing field and a powerful synthetic tool that has recently seen many advancements, showing immense promise to replace classic catalysis with a mild and elegant alternative methodology. Visible light driven catalysis relies on redox stable transition metal and organic based photoactive catalysts (photocatalysts) that absorb visible light efficiently and facilitate electron/energy transfer. The desire for greener and more renewable catalytic methods has caused research to shifted away from traditional transition metals (due to scarcity and environmental toxicity) and toward organic based photocatalysts. Due to similar photophysical and electrochemical characteristics of each of these classes of photocatalysts …

A Behavioral And Voltammetric Study Of The Effects Of Pb Exposure In Mice As A Model Of Autism Spectrum Disorder, Brenna Parke

Theses and Dissertations

Despite being a known toxin for several centuries, lead (Pb²⁺) is still utilized in commercial products including leaded gasoline, paint, and modern cosmetics. This presence has caused (Pb²⁺) to pollute the environment, including public drinking water sources. The recent outbreaks of elevated levels of (Pb²⁺) in the drinking water in Flint, Michigan and Washington D.C. have caused large populations to be exposed to the heavy metal for months at a time, raising a public health concern over the implications of widespread, long-term (Pb²⁺) exposure. Young children are most susceptible to the effects …

Synthesis, Characterization, Electronic Structure Of Reduced Graphene Oxide And Nh₂-Mil-125(Ti) Modified Binbo₄ And Their Photocatalytic Activities, Maram Yahya Bakiro

Chemistry Theses

The present thesis focuses on the design and synthesis of novel visible light photocatalysts for CO₂ utilization. In recent years, Bi-based materials have shown remarkable photocatalytic activity in the field of CO₂ reduction. Particularly, BiNbO₄ has many promising applications as a visible light-harvesting material due to its bandgap position and orbital hybridization. In this study, an intensive effort has been made to study the effect of different reaction parameters such as temperature and pH of the different synthetic methodologies applied. The new photocatalytic materials have been characterized using different characterization techniques including PXRD, BET, SEM, EDX, and UV-Vis DRS. Since …

Synthesis, Characterization, Electronic Structure Of Reduced Graphene Oxide Modified Fenbo₄, Nh₂-Mil-125(Ti) Modified Fenbo₄ Composities And Their Photocatalytic Activities, Salwa Abdelrahim Hussein

Chemistry Theses

The production of value-added products through CO₂ utilization using photocatalysis offers an alternative green route for CO₂ fixation. Wide bandgap photocatalysts allow the absorption of light in the UV region, which represents the lowest percentage of the sunlight irradiation. On the other hand, narrow bandgap photocatalysts absorb light in the visible region, though the recombination rate of the generated electron-hole pairs affects their activity. In this thesis, the narrow bandgap FeNbO₄ is synthesized, studied and efforts are made to reduce the recombination rate and enhancing the photocatalytic activity.

Moreover, three FeNbO₄/NH₂-MIL-125(Ti) composites with different mole ratios are prepared, characterized and …