Chemistry Commons^™

Classification Of Biorenewable Multiblock Copolymers, Sean Pickthorn

Celebrating Scholarship & Creativity Day (2011-2017)

Recent advances in polymer production sciences have led to an increase in research in sustainable practices. Our efforts intended to produce a toughened biorenewable multiblock copolymer. Polylactide has been noted to be produced by sustainable practices but is limited because of the fragile structure. To improve the brittle behavior of polylactide, preparation of polylactide-b-polybutadiene-b-polylactide multiblock copolymers were synthesized with a fixed weight of dihydroxyl polybutadiene (~3000 and ~2000g/mole series) and variable volume percent (50-90%) of both semicrystalline poly(L-lactide) and amorphous poly(D,L-lactide). Producing a multiblock copolymer intended to strengthen the mechanical properties by bridging and gapping over several domains. Initially, triblock …

Ring-Opening Polymerization Of Lactones And Lactides: An Organic Chemistry Lab Synthesis, Erin Wissler

Celebrating Scholarship & Creativity Day (2011-2017)

This project analyzed the ring opening chemistry of D, L- lactide, γ – butyrolactone, valerolactone, dodecalactone and caprolactone. Starting with each of the above monomers, Sn(Oct)2,SnCl2, Zn(acac)2, ZnCL2, and AlCl3 were used as catalysts in the polymerization process. Initiators included benzyl alcohol, 2-phenylethanol and 1-butanol. The results of each reaction were analyzed by 1H-NMR and IR spectroscopy and dynamic light scattering (DLS). The results were collated to determine the most promising candidates for a student project in the teaching laboratory.

Splicing Of Chicken Cyclooxygenase-2, Matthew Lelegren

Journal of Undergraduate Research

As described in the proposal, my goal was to further understand the mechanisms of mRNA processing of the chicken gene called Cyclooxygenase (COX)-2. There are many mechanisms by which mRNA molecules are modified in order to produce proteins that fulfill the needs of a given cell. The mechanism I chose to study was called alternative splicing, a process through which sequences are removed from the mRNA thereby altering the structure and function of the protein to be translated from its sequence. In brief summary splicing mechanisms, the cells possess machinery that recognize certain sequences, called splice sites, as a guide …

Estrogen Signaling In Migraine Pathogenesis, Sarah Bahr, Dr. Emily Bates

Journal of Undergraduate Research

Migraine is a disorder that can include aura, headache, nausea, and hypersensitivity to all sensory modalities. It affects over thirty million people in the US. Migraines affect men and women equally until puberty, but overall migraines affect 3x more women than men. They also increase in frequency and severity during periods of estrogen fluctuation and often subside after menopause. Moreover, hormone supplements and birth control can affect migraine patterns. These correlations of migraine episodes to the menstrual cycle and increased pain sensitivity in response to estrogen suggest that differences in estrogen signaling contribute to migraine. We hypothesized that estrogen receptor …

Acetylation Of Sod1 As A Regulator Of The Tumor Stress Response, Matthew Whited, Dr. Joshua L. Andersen

Journal of Undergraduate Research

In cancer patients, a lack of cell apoptosis (programmed cell death) coupled with increased levels of cell proliferation leads to the formation of a tumor. Among the available treatment options, cytotoxic chemotherapy is the most common. The primary purpose of this treatment is to induce tumor cell apoptosis. In many cases, tumor cells develop chemoresistance, rendering chemotherapy ineffective as a method to activate apoptosis. Understanding the mechanisms that lead to chemoresistance is a critical step toward developing methods to increase the effectiveness of chemotherapy treatments.

The Fenzian Unit: Applications To Physical Therapy And Beyond, Jeshua Paul Spadino Mr.

Senior Honors Theses

The field of physical therapy includes many different treatment options in the form of exercises and modalities. The development of a low electrical stimulation signal through the Fenzian unit has provided a new outlook on healing. This device gives information to and receives information from the central nervous system (CNS) through electro-biofeedback and is separated into its own category of modalities. The device can be used to treat a wide range of ailments, all with no adverse effects. This makes it a promising tool in the medical field. It is currently being validated as an authentic medical device through clinical …

Investigation Of The 4-Amino-Α,Α-Dihydroxy-3,5-Dichloroacetophenone Impurity In The Synthesis Of Clenbuterol Hydrochloride, Kerry Moore

Theses and Dissertations

Clenbuterol Hydrochloride is a bronchodilator marketed as Spirospent® for Human Pharmaceuticals and as Ventipulmin® for Veterinary Pharmaceuticals by Boehringer Ingelheim.1 This research investigates formation of the 4-amino-α,α-dihydroxy-3,5-dichloroacetophenone impurity (Dihydroxy Impurity) in the synthesis of Clenbuterol Hydrochloride. The Dihydroxy Impurity has increased three-fold since the process was transferred to Boehringer Ingelheim Chemicals, Inc. in 1999.1 The Dihydroxy Impurity is proposed to be produced during an amination/reduction step from a reaction of water with the starting material.2 Additionally, the Dihydroxy Impurity can be formed by the reaction of water with an impurity, 4-amino-α,α-didibromo-3,5-dichloroacetophenone (Dibromo Impurity), that is generated in the previous step.2 …

Synthesis Of A Soluble Thiopheneanthrone Organic Semiconductor: Thiopheneanthrone-1-Thioglycoliccarboxylic Acid, Denise M. Page

Senior Honors Theses

Organic semiconductors are currently being researched for various uses, both electronic and biologic. They are less expensive than current inorganic semiconductors and do not require doping. They are useful in many areas including thin film transistors, photovoltaic cells, and Light Emitting Diodes (LED). However, synthesizing soluble organic semiconductors has been difficult. As a result, this study undertakes the synthesis of a specific organic semiconductor aiming at increased solubility following an adapted literature protocol. Tests for solubility, fluorescence, and conductivity potential will be used to assess the potential of this molecule as a semiconductor. Synthesis of anthraquinone-1,8-bisthioglycoliccarboxylic acid as an intermediate …

Communication: Conical Intersections Between Vibrationally Adiabatic Surfaces In Methanol, Mahesh B. Dawadi, David S. Perry

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

A set of seven conical intersections (CI’s) in methanol between vibrationally adiabatic surfaces is reported. The intersecting surfaces represent the energies of the two asymmetric CH stretch vibrations regarded as adiabatic functions of the torsion and COH bend angles. The ab initio data are well described by an extended Zwanziger and Grant (E ⊗ e) model [J. W. Zwanziger and E. R. Grant, J. Chem. Phys. 87, 2954 (1987)] that might also be regarded as an extension of the XHL model [L.-H. Xu, J. T. Hougen, and R. M. Lees, J. Mol. Spectrosc. 293–294, 38 (2013)]. …

Environmental Impact Assessment Of The Missouri Mine, Christian Laursen, Waco Holve-Burk

College of Arts and Sciences Presentations

Gold mining in Idaho and other western states has left a legacy of heavy metal contamination. These metals enter the food chain via plants and water, and are toxic to living organisms. There is a need to identify and map the heavy metal contamination, and to track the fate and transport of heavy metals from one mine site to another via surface waters. Our hypothesis is that the severe contamination in the area of the Missouri Mine is not all from that site, but includes heavy metals transported in surface water from another mine to the northeast, in the Summit …

Dioxygen Reactivity Of Biomimetic Fe(Ii) Complexes With Noninnocent Catecholate, O-Aminophenolate, And O-Phenylenediamine Ligands, Michael M. Bittner, Sergey V. Lindeman, Cordina V. Popescu, Adam T. Fiedler

Chemistry Faculty Research and Publications

This study describes the O₂ reactivity of a series of high-spin mononuclear Fe(II) complexes each containing the facially coordinating tris(4,5-diphenyl-1-methylimidazol-2-yl)phosphine (^Ph2TIP) ligand and one of the following bidentate, redox-active ligands: 4-tert-butylcatecholate (^tBuCatH^–), 4,6-di-tert-butyl-2-aminophenolate (^tBu2APH^–), or 4-tert-butyl-1,2-phenylenediamine (^tBuPDA). The preparation and X-ray structural characterization of [Fe²⁺(^Ph2TIP)(^tBuCatH)]OTf, [3]OTf and [Fe²⁺(^Ph2TIP)(^tBuPDA)](OTf)₂, [4](OTf)₂ are described here, whereas [Fe²⁺(^{Ph2 …}

Computational Study Of The Nitric Oxide Autoxidation Mechanism Using Quantum Chemistry Methods, Yazen Abusad

Collection of Engaged Learning

Nitric oxide (NO) is a critical cell-signaling messenger in the immune, cardiovascular, and nervous systems. It is linked to several diseases, and due to its high reactivity, and toxicity as a free radical, NO possesses a controversial effect on cell viability. The S-nitrosylation of protein thiol groups is a key mechanism in NO redox signal transduction, and lends a mechanistic basis for NO as a cell regulator. Numerous experiments have shown that the rate-limiting step of S-nitrosylation is NO autoxidation, independent of thiol concentration. Due to the transient nature, and structural variety of reactive nitrogen species, very little is known …

A Small Molecule That Binds And Inhibits The Etv1 Transcription Factor Oncoprotein, Marius C. Pop, Nicolas Stransky, Colin W. Garvie, Jean-Philippe Theurillat, Emily C. Hartman, Timothy A. Lewis, Cheng Zhong, Elizabeth K. Culyba, Fallon Lin, Douglas S. Daniels, Raymond Pagliarini, Lucienne Ronco, Angela N. Koehler, Levi A. Garraway

Chemistry Faculty Publications

Members of the ETS transcription factor family have been implicated in several cancers, where they are often dysregulated by genomic derangement. ETS variant 1 (ETV1) is an ETS factor gene that undergoes chromosomal translocation in prostate cancers and Ewing's sarcomas, amplification in melanomas, and lineage dysregulation in gastrointestinal stromal tumors. Pharmacologic perturbation of ETV1 would be appealing in these cancers; however, oncogenic transcription factors are often deemed “undruggable” by conventional methods. Here, we used small-molecule microarray (SMM) screens to identify and characterize drug-like compounds that modulate the biological function of ETV1. We identified the 1,3,5-triazine small molecule BRD32048 as a …

Hydration Of The Sulfuric Acid−Methylamine Complex And Implications For Aerosol Formation, Danielle J. Bustos, Berhane Temelso, George C. Shields

Faculty Journal Articles

The binary H₂SO₄−H₂O nucleation is one of the most important pathways by which aerosols form in the atmosphere, and the presence of ternary species like amines increases aerosol formation rates. In this study, we focus on the hydration of a ternary system of sulfuric acid (H₂SO₄), methylamine (NH₂CH₃), and up to six waters to evaluate its implications for aerosol formation. By combining molecular dynamics (MD) sampling with high-level ab initio calculations, we determine the thermodynamics of forming H₂SO₄(NH₂CH₃)(H …

Determination Of The Factors That Affect The Gas-Phase Reactivity Of Metal-Centered Cyclopropanation Catalysts And Examination Of The Properties Of Their Reaction Products, Jamal Aldajaei

Theses and Dissertations

Gas phase studies of organometallic systems have provided deep insight into reaction mechanisms and reaction intermediates. In this thesis, several metal/ligand systems were examined in an effort to form metal carbenes in the gas phase. With cobalt and iron porphyrins, the carbene undergoes metal-ligand insertion. With copper bis-oxazolines, metal carbenes tend to undergo metal-ligand insertion and a Wolff rearrangement. To avoid insertions, we turned to a rigid ligand, 1, 10-phenanthroline. Under ESI conditions, a copper (I) complex with phenanthroline can be formed. When treated with diazoacetate esters, the dominant product results from addition with loss of nitrogen followed by loss …

Synthesis And Characterization Of Cobalt Carbide Based Nanomaterials, Zachary Huba

Theses and Dissertations

Permanent magnets are used heavily for multiple applications in industry and current electronic technologies. However, the current permanent landscape is muddled by high cost of materials and insufficient magnetic or thermal properties. The primary focus of this dissertation work is the synthesis and optimization of a new permanent magnetic material, in the form of cobalt carbide nanomaterials. The optimization revolved around controlling the crystal phase and particle shape of synthesized cobalt carbide particles; these parameters have significant impact on the observed magnetic properties of magnetic nanoparticles. Co₃C was identified to be the preferred crystal phase, leading to better …

The Development And Characterization Of Dual Electrodes For Use With Scanning Electrochemical Microscopy, Colleen Leonard, Melinda Baur, Faculty Advisor

John Wesley Powell Student Research Conference

Scanning Electrochemical Microscopy (SECM) utilizes electrode probes that can be positioned just abutting cells and can detect the presence of small quantities of chemicals known as neurotransmitters. In order to detect neurotransmitter release from PC12 cells, used as model neurons, the electrode must be positioned very close to the cell surface to detect the change in current that accompanies the oxidation/reduction of the neurotransmitters released. The peaks in current were analyzed in order to detect differences in release mechanisms, such as slow or fast-release. Furthermore, dual electrodes were made and characterized in order to monitor two different locations on a …

Asymmetric Reactions Of N-Heterocyclic Carbenes Using Green Chemistry Principles, James J. J. Kiddle

Faculty Research and Creative Activities Award (FRACAA)

No abstract provided.

Probing Stability And Unfolding Of The N-Terminal Domains 5-6 Of Wilson Protein, Ibtesam Y. Alja'afreh, Ramakrishna Guda, David L. Huffman

Research and Creative Activities Poster Day

The Wilson protein (ATP7B) is a copper transporting P1b type ATPase found in the liver, brain, and other organs. The N-terminal end consists of six copper binding domains which have a ferrodoxin βαββαβ fold with a CxxC motif. Despite similarities in copper binding affinities they interact differently with the HAH1 metallochaperone. Studying the stability of these domains will help understanding the differences in their functions. The stability of WLN5-6 was probed using several different methods: Dynamic light scattering (DLS), Circular dichroism (CD) and Fluorescence spectroscopy methods.

Previous studies show that WLN5-6 has a spherical shape and CD chemical unfolding studies …

Two-Photon Absorption Spectroscopy To Differentiate Chromophore-Dna Binding Interactions, Saad H. Alotaibi, Kelly M. Usakoski, Mohammad Hatshan, Ramakrishna Guda

Research and Creative Activities Poster Day

The study of molecule-DNA binding interactions are vital as they are the principle components behind drug action, transcription and replication. Optical spectroscopic techniques are often used to study these interactions. However, the existing techniques cannot differentiate different binding motifs of intercalation and minor-grove binding. In the present study, we present a novel approach based on the two-photon absorption (2PA) cross-sections of chromophores to differentiate the intercalation and minor-grove binding interactions. The investigations are carried out using three cyanine derivatives Diethylthiacyanine iodide (DTI), 3,3′-Diethylthiacarbocyanine iodide (DTCI) and 3,3′- Diethylthiadicarbocyanine iodide (DTDCI). The chromophores were chosen as they are similar series of …

Multi-Electron Transfer From Charged Semiconductor Surfaces To Quantized Bimetallic Nanoparticles, Ali Bolandi, Sherine O. Obare

Research and Creative Activities Poster Day

Palladium-platinum bimetallic nanoparticles were prepared using a novel method of hydrothermal co-reduction of precursors. Elemental analysis, x-ray diffraction and electron microscopy indicated the formation of spherical bimetallic nanoparticles with a size distribution of 2.5 ± 0.5 nm. When the Pd/Pt bimetallic nanoparticles were brought in close contact with an electron-rich surface, the particles accepted and stored the electrons. Multiple electrons were found to be stored in the Pd/Pt bimetallic NPs.

Crystal And Molecular Structures Of New Metallocarboranes, Au25 Gold Cluster And Metal Sensor Molecules, Agozie N. Oyeamalu, Rathnayaka Madawala, Viraj Thanthirige, Ekkehard Sinn

Research and Creative Activities Poster Day

Introduction

Bragg’s equation has become one of the most trusted model used to calculate crystal structures.

2014 marks the 100th anniversary of Max von Laue’s Nobel Prize for discovering that X-Rays fired into a crystal of copper sulfate produced a characteristic diffraction pattern.

2015 will be the 100th anniversary of the Nobel Prize to Bragg and Bragg for their equation that ultimately led to X-ray crystallography.

Optical Properties Of Bi-Icosahedral Au25 And Au24 Clusters: Influence Of Central Gold Atom, Viraj Dhanushka Thanthirige, Ekkehard Sinn, Rongchao Jin, Guda Ramakrishna

Research and Creative Activities Poster Day

Temperature-dependent absorption and ultrafast luminescence measurements of [Au₂₄(PPh₃)₁₀(SC₂H₄Ph)₅Cl₂]+(bi-Au₂₄) were studied and compared with [Au₂₅(PPh₃)₁₀(C₆S)₅Cl₂]₂+ (bi-Au₂₅). The investigations are carried out on these two clusters as they are structurally similar except for the absence of central Au atom for bi-Au24. The objective of the work is to probe the influence of the central gold atom on the optical transitions and electron-phonon interactions in bi-icosahedral nanoclusters. The investigations are focused …

Site-Specific Nitration Of Apolipoprotein A-I At Tyrosine 166 Is Both Abundant Within Human Atherosclerotic Plaque And Dysfunctional, Joseph A. Didonato, Kulwant Aulak, Ying Huang, Matthew A. Wagner, Gary Gerstenecker, Celalettin Topbas, Valentin Gogonea, Anthony J. Didonato, W.H. Wilson Tang, Ryan A. Mehl, Paul L. Fox, Edward F. Plow, Jonathan D. Smith, Edward A. Fisher, Stanley L. Hazen

Chemistry Faculty Publications

We reported previously that apolipoprotein A-I (apoA-I) is oxidatively modified in the artery wall at tyrosine 166 (Tyr166), serving as a preferred site for post-translational modification through nitration. Recent studies, however, question the extent and functional importance of apoA-I Tyr166 nitration based upon studies of HDL-like particles recovered from atherosclerotic lesions. We developed a monoclonal antibody (mAb 4G11.2) that recognizes, in both free and HDL-bound forms, apoA-I harboring a 3-nitrotyrosine at position 166 apoA-I (NO2-Tyr166-apoA-I) to investigate the presence, distribution, and function of this modified apoA-I form in atherosclerotic and normal artery wall. We also developed recombinant apoA-I with site-specific …

Synthesis And Purification Of The Glycosphingolipid Csa-13, Tyler Olsen, Dr. Paul Savage

Journal of Undergraduate Research

The need for novel antibiotic mechanisms is prevalent. Common antimicrobial medicines such as penicillin, ampicillin and vancomycin have started becoming obsolete as resistant strains of bacteria become more widespread. The main problem with antibiotics is the rapid mutations that bacteria undergo. Eventually one cell will develop resistance, and then have that mutation selected for as patients undergo antibiotic therapy. Bacteria are rapidly changing to combat the many new antibiotic variants that have come out.

Follicular Dendritic Cells And Activation Of T Cells Bearing Latent Hiv, Jared Huber, Dr. Gregory F. Burton

Journal of Undergraduate Research

Determine the pathway by which FDC cytokines activate HIV transcription in CD4+ T‐cells harboring latent HIV.

Searching For Nascent Peptides That Cause Ribosome Stalling, Shankar Parajuli, Dr. Allen Buskirk

Journal of Undergraduate Research

Ribosomes are molecular machines that synthesize all the proteins for all living cells. Ribosomes sometimes stall and cannot complete the synthesis of a given protein. Some peptides interact with the ribosome during their own translation and induce stalling.1 The SecM and TnaC peptides in E. coli, for example, have been found to play a key regulatory role in translation of genes found on the same mRNA.2

Electrospray Of Bacteria Intact And Viable, Sara Pratt, Dr. Daniel Austin

Journal of Undergraduate Research

In this project we wanted to see if bacteria can survive a process called electrospray ionization (ESI). While bacteria survival of ESI has not previously been demonstrated, viruses survivability has1. The process of ESI consists of spraying a solution of the desired analyte in a strong electric field. Solution flowing through a capillary forms a Taylor cone at the end from which charged droplets emit. As solvent evaporates, the droplets break apart. As solvent continues to evaporate, that process is repeated and eventually forms individually charged particles once all the solvent is evaporated. The ESI in this experiment is done …

Characterization Of Peptides That Cause Ribosome Stalling, Diana Valverde, Dr. Allen Buskirk

Journal of Undergraduate Research

The ribosome is a macromolecular machine found in all living cells. It catalyzes protein synthesis through a process known as translation. The ribosome reads messenger RNA that carries the blueprint for a protein product and brings in the appropriate amino acids to build a specific protein. Ribosomes are composed of two subunits (50S and 30S) that form three binding sites for transfer RNA. The A site of the ribosome accepts the incoming tRNA charged with an amino acid. This tRNA transfers its amino acid to a growing polypeptide chain held in the P site. After the transfer, the tRNA exits …

Bioactive Lipid Analysis Of Asthma-Induced Lung Tissue With A Focus On Biomarker Identification, Mackay Merrill, Dr. John Prince

Journal of Undergraduate Research

Initially, the goal of my project was to search for biologically active lipids in the lung tissue of mice with and without asthma (as opposed to those which simply form the membranes of cells) and determine if any of these lipids could serve as indicators of the disease. Over the course of experimentation, the focus shifted to these membrane (or structural) lipids. I planned to find indicative lipids (biomarkers) using mass spectrometry and statistical analysis.