Digital Commons Network^™

Renewable Bio-Based Intermediates, Monomers And Polymeric Materials From Plant Oils, Liang Yuan

Theses and Dissertations

In the dissertation work, new chemical intermediates, monomers and thermoplastic polymers were derived from renewable soybean oil. Elastomers were further developed using monomers and polymers from soybean oil. The properties of these polymeric materials were characterized and discussed.

In Chapter 1, the overall background and recent development polymers from renewable biomass, especially plant oils, is introduced. Major research objectives of my doctoral research were described.

The first section of the dissertation, on the preparation of renewable intermediates, novel monomers and homopolymers, is provided in Chapter 2 and Chapter 3. In Chapter 2, amidation of soybean oil with amino alcohols was …

Surface Chemistry And Transport Properties Of Ii-Vi Semiconductor Nanowires, Pravin Paudel

Theses and Dissertations

Semiconductor nanowires have been widely studied due to their unique properties such as width comparable to critical length-scales, high aspect ratio, and high carrier mobility. These unique properties make them a suitable candidate for various optical and electronic devices like photovoltaics, photodetectors, and field effect transistors. The nanowire surface plays an important role in the performance of these devices because of their high surface to volume ratio. The larger surface area of nanowires may provide better charge separation than planar heterostructures in photovoltaics by providing shorter distance to move for carrier before separation, however, presence of surface states may lead …

Issues In Laser Induced Breakdown Spectroscopy For Measurements In The Deep Ocean And Other High-Pressure Environments, Joseph C. Bonvallet

Theses and Dissertations

This dissertation describes fundamental and applied studies that have advanced the understanding and application laser induced breakdown spectroscopy (LIBS) to the deep-ocean environment and to operation on a deep-ocean submersible. Chapter one is an overview of LIBS including a brief history, LIBS theory, the instrumentation typically used, and a specific application. Chapter two analyzes the effect that monodisperse suspended particles have on LIBS emission intensity and on the formation of a LIBS plasma. This chapter demonstrates that for particle concentrations similar to those found in the neutrally buoyant regions around hydrothermal vents there is little effect on the LIBS emission …

Contribution Of New Thiol Antioxidant In The Treatment Of Acetaminophen Toxicity, Ahdab Naeem Khayyat

Doctoral Dissertations

"Acetaminophen (N-acetyl-p-aminophenol, APAP) is one of the most widely used over-the-counter antipyretic analgesic medications. It is safe at therapeutic doses, but an overdose can result in severe hepato-nephrotoxicity, a leading cause of drug-induced acute liver failure in the U.S. Although a few different mechanisms have been proposed for APAP-induced toxicity, a significant amount of evidence has pointed to the potential involvement of oxidative stress in acetaminophen toxicity. Depletion of glutathione (GSH) is one of the initiating steps in APAP-induced toxicity; therefore, one strategy for restricting organ damage is to restore GSH levels by using GSH prodrugs like N-acetylcysteine (NAC). Although …

Synthesis And Characterization Of Transition Metal Phosphide Nanoparticles For Catalytic Applications: Model Catalysts For Hydrodesulfurization And Electrocatalysts For The Oxygen Evolution Reaction, Don Malinda Ruchira Liyanage

Wayne State University Dissertations

Transition metal phosphides are emerging as efficient catalysts for different processes. Although binary phases have been extensively studied recently researchers have explored the synergism afforded by bimetallic ternary transition metal phosphides. The conventional catalyst preparation methods (temperature programmed reduction or solvothermal synthesis) yield inhomogeneous samples, preventing a detailed understanding of how active site density impacts catalytic activity and mechanism. In contrast, solution-phase arrested-precipitation reactions produce uniform nanoparticles with an excellent control on size, morphology and composition.

This dissertation describes the synthesis of ternary transition metal phosphide nanoparticles (Ni2-xCoxP and Ni2-xRuxP) by solution-phase arrested-precipitation reactions and evaluation of their composition-dependent catalytic …

Facile Synthesis Of Tertiary Aliphatic Amine– Containing Cyclic Motif Via Neutral Aminyl Radical Cyclization, Heng Chen

Wayne State University Theses

Tertiary amine–containing cyclic motifs are prevalent in natural products and pharmaceutical lead targets. Inspired by these biological active molecules, one focus in our lab is the development of neutral aminyl radical chemistry in the synthesis of tertiary aliphatic amine–containing cyclic compounds. In this project, I investigated the mono- and tandem cyclization of aminyl radical with different types of olefins (terminal olefin, enone, and styrenyl). The effect of the hydrogen atom donor and the limitation of the reaction will be discussed.

In Vitro And In Vivo Measurments Of Serotonin For Ecological And Mental Health Via Fast Scan Cyclic Voltammetry, Matthew Nicholas Jackson

Wayne State University Theses

Fast Scan Cyclic Voltammetry has been proven to be a highly valuable technique in analysis and detection of neurotransmitters. With this technique, two novel applications are being explored to protect natural water sources as well as furthering the efficacy of antidepressants. Despite setbacks, promising data has been collected to further understand the mechanisms involved in the phototactic response observed in Daphnia Magna. Electrochemical modification of carbon fiber microelectrodes has proven to be inefficient as a means to effectively differentiate between serotonin and its metabolite. As such, this unsuccessful attempt has further narrowed down the list of candidates to electrochemically differentiate …

Targeted Delivery Of Nrf2 Sirna Using Modular Polymeric Micellar Nanodelivery System For Efficient Target Gene Knockdown In Hepatocellular Carcinoma, Shaimaa Mohamed Ibrahim Yousef

Wayne State University Theses

Tumor selective drug delivery as well as chemotherapy associated multi drug resistance (MDR) pose tremendous hurdles for effective cancer therapy. In this regard, designing multifunctional nanocarriers loaded with drug/gene payloads and engineered with tumor targeting ligands can serve as a modular platform for targeted drug/gene delivery. In this study we undertook the synthesis of a self-assembling block copolymer constructed using poly(styrene-co-maleic anhydride, partial iso-octyl ester) (SMAPIE) and branched polyethylenimine (PEI) as building blocks and evaluated its micelle forming ability, siRNA complexation and siRNA delivery potentials. In addition, we engineered galactosamine decorated nanomicelles using modular “click” chemistry based approaches for evaluating …

X-Ray Structure And Properties Of The Ferrous Octaethylporphyrin Nitroxyl Complex, Nagabhushanam Kundakarla, Sergey V. Lindeman, Hafiz Md. Rahman, Michael D. Ryan

Chemistry Faculty Research and Publications

The preparation and characterization of the iron octaethylporphyrin nitroxyl ion, [Fe(OEP)(NO)⁻], is reported. The complex was synthesized by the one-electron reduction of Fe(OEP)(NO) using anthracenide as the reducing agent. The compound was isolated as the potassium (2.2.2)cryptand salt. The anion was characterized using X-ray analysis with visible and infrared spectroscopy. The spectral features of the iron nitroxyl complex were consistent with previous literature reports. The important structural changes upon reduction were a significant decrease in the Fe–N–O bond angle from 142° to 127° and an increase in the N–O bond length from that in the starting nitrosyl moiety. …

I Want To Be The Inquiry Guy! How Research Experiences For Teachers Change Beliefs, Attitudes, And Values About Teaching Science As Inquiry, Deborah Herrington, Senetta F. Bancroft, Molly M. Edwards, Caroline J. Schairer

Peer Reviewed Articles

This qualitative study examined how and why a research experiences for teachers (RET) influenced middle and high school science teachers’ beliefs, attitudes, and values about teaching science as inquiry. Changes teachers reported after participating in the RET ranged from modifying a few lessons (belief change) to a comprehensive revision of what and how they taught to better reflect inquiry (attitude change). Some teachers who described comprehensively changing their instruction also described implementing actions meant to change science education within their respective schools, not just their own classrooms (value change). We present how and why teachers went about changes in their …

One-Pot Synthesis Of Biocompatible Silver Nanoparticle Composites From Cellulose And Keratin: Characterization And Antimicrobial Activity, Chieu D. Tran, Franja Prosenc, Mladen Franko, Gerald Benzi

Chemistry Faculty Research and Publications

A novel, simple method was developed to synthesize biocompatible composites containing 50% cellulose (CEL) and 50% keratin (KER) and silver in the form of either ionic (Ag⁺) or Ag⁰ nanoparticles (Ag⁺NPs or Ag⁰NPs). In this method, butylmethylimmidazolium chloride ([BMIm⁺Cl^–]), a simple ionic liquid, was used as the sole solvent and silver chloride was added to the [BMIm⁺Cl^–] solution of [CEL+KER] during the dissolution process. The silver in the composites can be maintained as ionic silver (Ag⁺) or completely converted to metallic silver (Ag …

A Flipped Classroom Redesign In General Chemistry, Scott A. Reid

Chemistry Faculty Research and Publications

The flipped classroom continues to attract significant attention in higher education. Building upon our recent parallel controlled study of the flipped classroom in a second-term general chemistry course (J. Chem. Educ., 2016, 93, 13–23), here we report on a redesign of the flipped course aimed at scaling up total enrollment while keeping discussion sizes small (i.e.,students), and maintaining equivalent contact hour load for faculty and workload for students. To that end, the course format featured lecture contact pushed outside of the classroom in the form of video lectures (mean duration 13 minutes) paired with online …

A Disease Spectrum For Itpa Variation: Advances In Biochemical And Clinical Research, Nicholas E. Burgis

Chemistry and Biochemistry Faculty Publications

Human ITPase (encoded by the ITPA gene) is a protective enzyme which acts to exclude noncanonical (deoxy) nucleoside triphosphates ((d)NTPs) such as (deoxy)inosine 5′-triphosphate ((d)ITP), from (d)NTP pools. Until the last few years, the importance of ITPase in human health and disease has been enigmatic. In 2009, an article was published demonstrating that ITPase deficiency in mice is lethal. All homozygous null offspring died before weaning as a result of cardiomyopathy due to a defect in the maintenance of quality ATP pools. More recently, a whole exome sequencing project revealed that very rare, severe human ITPA mutation results in early …

Uv Light-Induced Aggregation Of Titania Submicron Particles, Can Zhou, Yashar Bashirzadeh, Timothy A. Bernadowsky Jr., Xiaoyu Zhang

Mechanical & Aerospace Engineering Faculty Publications

In this study, aggregation of TiO₂ (rutile and anatase) submicron particles in deionized (DI) water under ultra-violet (UV) light irradiation was investigated. While no aggregation was observed in the dark, rutile and anatase submicron particles started aggregating upon application of UV light and ceased aggregation in about 2 and 8.4 h, respectively. It has been demonstrated that UV light directly mitigated the particle mobility of TiO₂, resulting in a neutralization effect of the Zeta potential. It was also observed that rutile particles aggregated much faster than anatase particles under UV radiation, indicating that the Zeta potential of …

Carinata Fame Production Process And Biofuel Oxidation, Benoit Kindo

Honors College Theses

In this experiment, the contribution of a standard production method for biofuels on their oxidative stability was investigated. Peroxide values were measured at different steps of the production process of Brassica carinata and peanut-based biofuels. The washing and drying steps in this production method showed significant increases in peroxide values for both biofuels and was identified as a major contributor of biofuel oxidation. Further analyses of the physical and thermal properties showed a more pronounced affect in the biofuel from Bassica carinata, and indicated an unusual composition much higher in saturated fatty acids much longer than those found in peanut. …

The Nobel Prize In Chemistry 2015: Exciting Discoveries In Dna Repair By Aziz Sancar, David K. Orren

Toxicology and Cancer Biology Faculty Publications

On October 7, 2015, the Nobel Prize in Chemistry for 2015 was awarded to three deserving scientists for their pioneering research on DNA repair. Tomas Lindahl was recognized for studies that uncovered the inherent instability of DNA as well as the mechanism of the base excision repair pathway, Paul Modrich for characterization of the mismatch repair pathway, and Aziz Sancar for mechanistic elucidation of the nucleotide excision repair (NER) pathway. For me, the announcement of these awards in my area of research was extremely gratifying, particularly so because Aziz was my mentor during my Ph.D. studies that examined the steps …

Biophysical Characterization Of A Proline Mutant Of Neural Cadherin, Keshia S. Dykes

Electronic Theses and Dissertations

Cadherins are calcium dependent glycoproteins whose homophilic interactions mediate cell-cell adhesion in solid tissues. They are comprised of an extracellular region, a transmembrane region and a cytoplasmic region. The extracellular region plays a critical role in cadherin-mediated cell adhesion, and has five tandemly repeated ectodomains (ec1-ec5), with three calcium binding sites situated in each interface between the domains. Dimerization of cadherin occurs through formation of adhesive interactions between extracellular domains of cadherins from neighboring cells. Adhesive interaction occurs at the interfaces of ec1 domains of two molecules originating from different cell surfaces. Dimerization is critically dependent on the binding of …

Studies On Hydroxyl Radical Formation And Correlated Photoflocculation Process Using Degraded Wood Leachate As A Cdom Source, Luni Sun, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

In this study, we examined hydroxyl radical (•OH) formation with respect to photoreactivity of colored dissolved organic matter (CDOM), the Fenton reaction, and photoflocculation using leachate from decaying wood. The relationship between •OH photoproduction rate and leachate optical properties (UV-visible absorption and fluorescence excitation-emission matrices (EEMS)) was studied during irradiation using a UV solar simulator. The results showed that the •OH photochemical formation rate is strongly related to humic-like fluorescence as characterized by parallel factor analysis (PARAFAC), and that these fluorescence components are more photolabile than most of the other CDOM components. Fourier transform infrared spectroscopy (FT-IR) indicated the photodegradation …

The Role Of Microbial Exopolymers In Determining The Fate Of Oil And Chemical Dispersants In The Ocean, Antonietta Quigg, Uta Passow, Wei-Chun Chin, Chen Xu, Shawn Doyle, Laura Bretherton, Manoj Kamalanathan, Alicia K. Williams, Jason B. Sylvan, Zoe V. Finkel, Anthony H. Knap, Kathleen A. Schwehr, Saijin Zhang, Luni Sun, Terry L. Wade, Wassim Obeid, Patrick G. Hatcher, Peter H. Santschi

Chemistry & Biochemistry Faculty Publications

The production of extracellular polymeric substances (EPS) by planktonic microbes can influence the fate of oil and chemical dispersants in the ocean through emulsification, degradation, dispersion, aggregation, and/or sedimentation. In turn, microbial community structure and function, including the production and character of EPS, is influenced by the concentration and chemical composition of oil and chemical dispersants. For example, the production of marine oil snow and its sedimentation and flocculent accumulation to the seafloor were observed on an expansive scale after the Deepwater Horizon oil spill in the Northern Gulf of Mexico in 2010, but little is known about the underlying …

Measurement Of Antioxidant Activity Toward Superoxide In Natural Waters, D. Whitney King, Emma Berger, Zachary Helm, Eleanor Irish, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Antioxidants are a class of molecules that provide a protective function against reactive oxygen species (ROS) in biological systems by out competing physiologically important molecules for ROS oxidation. In natural waters, the reactivity of antioxidants gives an estimate of oxidative stress, and may determine the reactivity and distribution of reactive oxidants. We present an analytical method to measure antioxidant activity in natural waters through the competition between ascorbic acid, an antioxidant, and MCLA, a chemiluminescent probe for superoxide. A numerical kinetic model of the analytical method has been developed to optimize analytical performance. Measurements of antioxidant concentrations in pure and …

Anticancer, Biophysical And Computational Investigations Of Half-Sandwich Ruthenium(Ii) Thiosemicarbazone Complexes: The Effect Of Arene Versus Thiacrown Face-Cap, Floyd A. Beckford, Alyssa Stott, P. Canisius Mbarushimana, Marc-Andre Leblanc, Kinsey Hall, Samantha Smith, Jimmie L. Bullock, Dennis J. Houghton, Alvin A. Holder, Nikolay Gerasimchuk, Antonio Gonzalez-Sarrías

Chemistry & Biochemistry Faculty Publications

A series of half-sandwich ruthenium complexes, two containing an arene face-cap and the other a thiacrown ether face-cap were synthesized to investigate the necessity of the arene for anticancer activity in this class of compounds. The complexes are formulated as [(h⁶-p-cymene)Ru(dmabTSC)Cl]PF₆, [(h⁶-benzene)Ru(dmabTSC)Cl]PF₆ (arene complexes), and [([9]aneS₃(dmabTSC)Cl]PF₆ (dmabTSC = dimethylaminobenzaldehye thiosemicarbazone). It was observed that none of the complexes showed good anticancer activity in vitro against HCT-116 and Caco-2 (colon adenocarcinoma) cells. All three complexes can bind strongly to calf-thymus DNA with binding constants on the order of 10 …

Synthesis And Characterization Of Azo-Guanidine Based Alcoholic Media Naked Eye Dna Sensor, Ataf A. Altaf, Uzma Hashmat, Muhammad Yousaf, Bhajan Lal, Shafiq Ullah, Alvin A. Holder, Amin Badshah

Chemistry & Biochemistry Faculty Publications

DNA sensing always has an open meadow of curiosity for biotechnologists and other researchers. Recently, in this field, we have introduced an emerging class of molecules containing azo and guanidine functionalities. In this study, we have synthesized three new compounds (UA1, UA6 and UA7) for potential application in DNA sensing in alcoholic medium. The synthesized materials were characterized by elemental analysis, FTIR, UV-visible, ¹H NMR and ¹³C NMR spectroscopies. Their DNA sensing potential were investigated by UV-visible spectroscopy. The insight of interaction with DNA was further investigated by electrochemical (cyclic voltammetry) and hydrodynamic (viscosity) studies. …

Detailed Source-Specific Molecular Composition Of Ambient Aerosol Organic Matter Using Ultrahigh Resolution Mass Spectrometry And H Nmr, Amanda S. Willoughby, Andrew S. Wozniak, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Organic aerosols (OA) are universally regarded as an important component of the atmosphere that have far-ranging impacts on climate forcing and human health. Many of these impacts are related to OA molecular characteristics. Despite the acknowledged importance, current uncertainties related to the source apportionment of molecular properties and environmental impacts make it difficult to confidently predict the net impacts of OA. Here we evaluate the specific molecular compounds as well as bulk structural properties of total suspended particulates in ambient OA collected from key emission sources (marine, biomass burning, and urban) using ultrahigh resolution mass spectrometry (UHR-MS) and proton nuclear …

Degradation Of Hexachlorobenzene, Pentachlorophenol And Pentachloroanisole Using Activated Magnesium In An Acidified Ethanol/Ethyl Lactate Cosolvent System, Amel Garbou

Electronic Theses and Dissertations

For many centuries, chemists have dedicated many labor-intensive hours to improving the quality of life for mankind by developing synthetic methods for the production of compounds which fulfill the needs and meet the demands of society. However, the innovation of such compounds has frequently come at the cost of detrimental side-effects that do not always present themselves until many years, or even decades, following their initial application. Many compounds in this category come in the form of globally-distributed halogenated molecules which are toxic to many living organisms, susceptible to bioaccumulation and resistant to biodegradation processes. Such compounds are classified as …

Analysis Of Benzopyrenes And Benzopyrene Metabolites By Fluorescence Spectroscopy Techniques, Bassam Al-Farhani

Electronic Theses and Dissertations

Polycyclic aromatic hydrocarbons (PAHs) are some of the most common and toxic pollutants encountered worldwide. Presently, monitoring is restricted to sixteen PAHs, but it is well understood that this list omits many toxic PAHs. Among the "forgotten" PAHs, isomers with molecular weight 302 are of particular concern due to their high toxicological properties. The chromatographic analysis of PAHs with MW 302 is challenged by similar retention times and virtually identical mass fragmentation patterns. The first original component of this dissertation evolves from a high-resolution spectroscopic approach specifically developed to fulfil this gap. Herein, 4.2 K Laser-Excited Time-Resolved Shpol'skii Spectroscopy (4.2K …

Sialyltransferase Inhibition And Recent Advances, Libo Wang, Ying Liu, Lijun Wu, Xue-Long Sun

Chemistry Faculty Publications

Sialic acids, existing as terminal sugars of glycoconjugates, play important roles in various physiological and pathological processes, such as cell–cell adhesion, immune defense, tumor cell metastasis, and inflammation. Sialyltransferases (STs) catalyze the transfer of sialic acid residues to non-reducing oligosaccharide chains of proteins and lipids, using cytidine monophosphate N-acetylneuraminic acid (CMP-Neu5Ac) as the donor. Elevated sialyltransferase activity leads to overexpression of cell surface sialic acids and contributes to many disease developments, such as cancer and inflammation. Therefore, sialyltransferases are considered as potential drug targets for disease treatment. Inhibitors of sialyltransferases thus are of medicinal interest, especially for the cancer …

Studies Of The Effectiveness Of Bisphosphonate And Vanadium-Bisphosphonate Compounds In Vitro Against Axenic Leishmania Tarentolae, Amy Christensen, Craig C. Mclauchlan, Anne Dolbecq, Pierre Mialane, Marjorie A. Jones

Faculty Publications – Chemistry

Leishmaniasis is a disease that is a significant problem for people, especially in tropical regions of the world. Current drug therapies to treat the disease are expensive, not very effective, and/or of significant side effects. A series of alkyl bisphosphonate compounds and one amino bisphosphonate compound, as well as alendronate and zoledronate, were tested as potential agents against Leishmania tarentolae. Also, two polyoxometalates (POMs) with nitrogen-containing bisphosphonate ligands, vanadium/alendronate (V5(Ale)2) and vanadium/zoledronate (V3(Zol)3), were tested against L. tarentolae and compared to the results of the alendronate and zoledronate ligands alone. Of the compounds evaluated in this study, the V5(Ale)2 …

Acridine Orange Staining Of Virus Infected Host Cells To Monitor Proliferation Of Viral Infection, Ronald Bartzatt

Chemistry Faculty Publications

Acridine orange staining is a methodology for nucleic acid selective metachromatic staining that is useful for following cell cycle determination. The interaction of acridine orange with target molecules (i.e. DNA and RNA) is by intercalation or electrostatic attraction, respectively. This work presents methodology and results of a cell staining that utilizes acridine orange fluoresence. It is possible to visualize under dark field ultraviolet microscope the actual viral infected host cells. The color production is stark and easily selected. This method appears to be versatile for a number of various cell types in tissue culture, including human lymphocytes. This methodology is …

Four Compounds Suppressing Growth Of Mycobacterium Tuberculosis, Ronald Bartzatt, Preeti Sule, Woojung Kim, Jeffrey D. Cirillo

Chemistry Faculty Publications

Aims: To demonstrate the efficacy of several small molecular weight compounds having hydrazide groups, for inhibiting the growth of Mycobacterium tuberculosis. To show these same compounds have favorable drug-likeness properties.

Study Design: To synthesize tuberculostats and test their antibacterial activity in-vitro.

Place and Duration of Study: University of Nebraska, Durham Science Center, 6001 Dodge Street, Omaha NE 68182, and Texas A&M Health Science Center, Department of Microbial Pathogenesis and Immunology, 8447 State Hwy 47, Medical Research and Education Building, Room #3012, Bryan, TX 7780. From January 2015 to June 2015.

Methodology: Hydrazide groups were formed by covalently bonding hydrazine …

A Novel Copper (Ii) Complex Identified As A Potent Drug Against Colorectal And Breast Cancer Cells And As A Poison Inhibitor For Human Topoisomerase Iiᶐ, Shayna Sandhaus, Rosella Taylor, Tiffany Edwards, Alexis Huddleston, Stephen J. Beebe, Alvin A. Holder

Bioelectrics Publications

A novel complex, [Cu(acetylethTSC)Cl]Cl · 0.25C₂H₅OH 1 (where acetylethTSC = (E)-N-ethyl-2-[1-(thiazol-2-yl)ethylidene]hydrazinecarbothioamide), was shown to have anti-proliferative activity against various colon and aggressive breast cancer cell lines. In vitro studies showed that complex 1 acted as a poison inhibitor of human topoisomerase IIᶐ which may account for the observed anti-cancer effects.