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Mohan Invested As Hess Professor Of Chemistry, Kim Hill

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Antimicrobial Activity And Mechanistic Study For The Poly(Phenylene Ethynylene) (Ppe)-Based Cationic Conjugated Polyelectrolytes And Oligo-Phenylene Ethynylenes, Ying Wang

Chemistry and Chemical Biology ETDs

My dissertation work focuses on recent progress made in elucidating the intermolecular interactions between a novel class of synthetic phenylene ethynylene (PPE)-based conjugated polyelectrolyte polymers (CPEs) and oligomers (OPEs) and multiscale cellular targets that give rise to their remarkable broad spectrum biocidal activity. We studied the interactions and self-assembly behaviors of the CPEs and OPEs with a set of vital biomolecules, including lipids, proteins and nucleic acids, that reveal the potential pathways by which the synthetic biocidal agents could exert toxicity. Then, we explored the antimicrobial effects and mechanisms of the CPEs and OPEs on multiple clinically relevant pathogens, with …

Does Pegylation Increase The Thermodynamic Stability Of The Ww Domain Of Pin1 Via Hydrogen Bonding? A Molecular Dynamics Simulation, Chad Torgerson, Dr. Joshua Price

Journal of Undergraduate Research

Proteins are complex molecules that have the potential to treat diseases and illnesses that small molecule drugs cannot. However, a significant problem with protein medications is that proteins tend to have short serum half-lives and can be difficult to store for extended periods of time due to their often unstable nature.1 One widely used strategy to circumvent these problems and increase the serum half-life of protein drugs is to attach polyethylene glycol (PEG) oligomers to amino acid residues (i.e., PEGylation) of protein structures.2 The thermodynamic effects of PEGylation are not always positive, however, and currently difficult to predict.3 In order …

Investigate The Function Of The 5′ Leader In The Human At1 Angiotensin Receptor, Erik J. Petersen, Dr. Terry S. Elton

Journal of Undergraduate Research

A comparison of several published hAT1R cDNA sequences revealed that, although these clones shared an identical open reading frame, they differed in portions of their 5′-UTRs.1 Therefore these data suggest that alternative splicing events combine various 5′-UTR exons with the exon that harbors the hAT I R coding region.

Translational Control Of Poly(A)-Binding Protein Expression, Eliott Spencer, Dr. Roger Kaspar

Journal of Undergraduate Research

Poly(A)-binding protein or PABP is found in high concentrations in all eukaryotic cells. Cell biologists have speculated for a long time that PABP plays an important role in stabilizing the fragile MRNA molecule so that it can be more effectively translated into its final gene product. PABP does this by binding to the Poly(A) tail at the 3′ end of the MRNA. 1,2

A Novel Mglur5 Antagonist, Mfz 10-7, Inhibits Cocaine-Taking And Cocaine-Seeking Behavior In Rats, Thomas Keck, Mu-Fa Zou, Gui-Hua Bi, Hai-Ying Zhang, Xiao-Fei Wang, Hong-Ju Yang, Ratika Srivastava, Elliott L. Gardner, Zheng-Xiong Xi, Amy Hauck Newman

College of Science & Mathematics Departmental Research

Pre-clinical studies suggest that negative allosteric modulators (NAMs) of the metabotropic glutamate receptor subtype 5 (mGluR5), including 2-methyl-6-(phenylethynyl)pyridine (MPEP), 3-[(2-methyl-1,3-thiazol-4-yl)ethynyl]pyridine (MTEP) and fenobam are highly effective in attenuating drug-taking and drug-seeking behaviors. However, both MPEP and MTEP have no translational potential for use in humans because of their off-target effects and short half-lives. Here, we report that 3-fluoro-5-[(6-methylpyridin-2-yl)ethynyl]benzonitrile (MFZ 10-7), a novel mGluR5 NAM, is more potent and selective than MPEP, MTEP and fenobam in both in vitro binding and functional assays. Similar to MTEP, intraperitoneal administration of MFZ 10-7 inhibited intravenous cocaine self-administration, cocaine-induced reinstatement of drug-seeking behavior and …

Enantioselective Synthesis Of Hasubanan Alkaloids, Daniel Nielsen, Laura Nielsen, Dr. Steven L. Castle

Journal of Undergraduate Research

In nature, many molecules exist in two different forms, referred to as enantiomers. These forms are structurally identical, yet they are mirror images of each other. One simple example of this is our hands. While both hands are structurally identical, there is no way that they can be superimposed. Our hands are enantiomers, and interact differently with certain objects. For instance, a left hand cannot fit a right-handed glove. Such a phenomenon occurs on the molecular level as well. A left-handed enantiomer of a drug might react with the receptors in the body in a beneficial way, while the right-handed …

The Planar Ion Trap, Ivan Miller, Dr. Daniel Austin

Journal of Undergraduate Research

Mass spectrometry has been a common analytical procedure for over fifty years. Today it is most commonly used to characterize and quantify unknown solutions, solids, and vapors in chemical and biochemical environments by determining the specific masses of atoms and molecules. Ion traps have become standard methods in analysis as they have dramatically improved the selectivity and resolution of mass spectrometers. Ion traps use applied voltages to create electrical fields in a small trapping volume. These fields interact with the molecules in the mass analyzer by trapping ionized molecules over a broad mass range. The trapped ions are eventually ejected …

Myeloperoxidase, Paraoxonase-1, And Hdl Form A Functional Ternary Complex, Ying Huang, Zhiping Wu, Meliana Riwanto, Shengqiang Gao, Bruce S. Levison, Xiaodong Gu, Xiaoming Fu, Matthew A. Wagner, Christian Besler, Gary Gerstenecker, Renliang Zhang, Xin Min Li, Anthony J. Didonato, Valentin Gogonea, W.H. Wilson Tang, Jonathan D. Smith, Edward F. Plow, Paul L. Fox, Diana M. Shih, Aldons J. Lusis, Edward A. Fisher, Joseph A. Didonato, Ulf Landmesser, Stanley L. Hazen

Chemistry Faculty Publications

Myeloperoxidase (MPO) and paraoxonase 1 (PON1) are high-density lipoprotein–associated (HDL-associated) proteins mechanistically linked to inflammation, oxidant stress, and atherosclerosis. MPO is a source of ROS during inflammation and can oxidize apolipoprotein A1 (APOA1) of HDL, impairing its atheroprotective functions. In contrast, PON1 fosters systemic antioxidant effects and promotes some of the atheroprotective properties attributed to HDL. Here, we demonstrate that MPO, PON1, and HDL bind to one another, forming a ternary complex, wherein PON1 partially inhibits MPO activity, while MPO inactivates PON1. MPO oxidizes PON1 on tyrosine 71 (Tyr71), a modified residue found in human atheroma that is critical for …

Cloning And Characterization Of Ef-Tu And Ef-Ts From Pseudomonas Aeruginosa, Stephanie O. Palmer, Edna Y. Rangel, Alberto E. Montalvo, Alexis T. Tran, Kate C. Ferguson, James M. Bullard

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

We have cloned genes encoding elongation factors We have cloned genes encoding elongation factors EF-Tu and EF-Ts from Pseudomonas aeruginosa and expressed and purified the proteins to greater than 95% homogeneity. Sequence analysis indicated that P. aeruginosa EF-Tu and EF-Ts are 84% and 55% identical to E. coli counterparts, respectively. P. aeruginosa EF-Tu was active when assayed in GDP exchange assays. Kinetic parameters for the interaction of EF-Tu with GDP in the absence of EF-Ts were observed to be = 33 μM, = 0.003 s−1, and the specificity constant was  s−1 μM−1. In the presence of EF-Ts, these values were …

Hypothesis Driven Single Nucleotide Polymorphism Search (Hydn-Snp-S), Rebecca J. Swett, Angela Elias, Jeffrey A. Miller, Gregory E. Dyson, G. AndréS Cisneros

Chemistry Faculty Research Publications

The advent of complete-genome genotyping across phenotype cohorts has provided a rich source of information for bioinformaticians. However the search for SNPs from this data is generally performed on a study-by-study case without any specific hypothesis of the location for SNPs that are predictive for the phenotype. We have designed a method whereby very large SNP lists (several gigabytes in size), combining several genotyping studies at once, can be sorted and traced back to their ultimate consequence in protein structure. Given a working hypothesis, researchers are able to easily search whole genome genotyping data for SNPs that link genetic locations …

Shared Mycobacterium Avium Genotypes Observed Among Unlinked Clinical And Environmental Isolates, M. Ashworth Dirac, Kris M. Weigel, Mitchell A. Yakrus, Annie L. Becker, Hui-Ling Chen, Gina Fridley, Arthur Sikora, Cate Speake, Elizabeth D. Hilborn, Stacy Pfaller, Gerard A. Cangelosi

Chemistry and Physics Faculty Articles

Our understanding of the sources of Mycobacterium avium infection is partially based on genotypic matching of pathogen isolates from cases and environmental sources. These approaches assume that genotypic identity is rare in isolates from unlinked cases or sources. To test this assumption, a high-resolution PCR-based genotyping approach, large-sequence polymorphism (LSP)-mycobacterial interspersed repetitive unit–variable-number tandem repeat (MIRU-VNTR), was selected and used to analyze clinical and environmental isolates of M. avium from geographically diverse sources. Among 127 clinical isolates from seven locations in North America, South America, and Europe, 42 genotypes were observed. Among 12 of these genotypes, matches were seen in …

Toward An Understanding Of The Retinal Chromophore In Rhodopsin Mimics, Mark M. Huntress, Samer Gozem, Konstantin R. Malley, Askat E. Jailaubekov, Chrysoula Vasileiou, Mikas Vengris, James H. Geiger, Babak Borhan, Igor Schapiro, Delmar S. Larsen, Massimo Olivucci

Chemistry Faculty Publications

Recently, a rhodopsin protein mimic was constructed by combining mutants of the cellular retinoic acid binding protein II (CRABPII) with an all-trans retinal chromophore. Here, we present a combine computational quantum mechanics/molecular mechanics (QM/MM) and experimental ultrafast kinetic study of CRABPII. We employ the QM/MM models to study the absorption (lambda(a)(max)), fluorescence (lambda(f)(max)), and reactivity of a CRABPII triple mutant incorporating the all-trans protonated chromophore (PSB-KLE-CRABPII). We also study the spectroscopy of the same mutant incorporating the unprotonated chromophore and of another double mutant incorporating the neutral unbound retinal molecule held inside the pocket. Finally, for PSB-KLE-CRABPII, stationary fluorescence spectroscopy …

Assessment Of Density Functional Theory For Describing The Correlation Effects On The Ground And Excited State Potential Energy Surfaces Of A Retinal Chromophore Model, Miquel Huix-Rotllant, Michael Filatov, Samer Gozem, Igor Schapiro, Massimo Olivucci, Nicolas Ferré

Chemistry Faculty Publications

In the quest for a cost-effective level of theory able to describe a large portion of the ground and excited potential energy surfaces of large chromophores, promising approaches are rooted in various approximations to the exact density functional theory (DFT). In the present work, we investigate how generalized Kohn-Sham DFT (GKS-DFT), time-dependent DFT (TDDFT), and spin-restricted ensemble-DFT (REKS) methods perform along three important paths characterizing a model retinal chromophore (the penta-2,4-dieniminium cation) in a region of near-degeneracy (close to a conical intersection) with respect to reference high-level multiconfigurational wave function methods. If GKS-DFT correctly describes the closed-shell charge transfer state, …

Norm, University Of North Dakota. Energy And Environmental Research Center

EERC Brochures and Fact Sheets

Fact sheet about naturally occurring radioactive material (NORM). Gives fundamental information on radiation and discusses how NORM is regulated and disposed of. [This item is an outdated or superseded version and retained for historical purposes only. It may no longer reflect current information, policies, or practices.]

Thermodynamic Characterization Of Five Key Kinetic Parameters That Define Neuronal Nitric Oxide Synthase Catalysis, Mohammad Mahfuzul Haque, Jesus Tejero, Mekki Bayachou, Zhi-Qiang Wang, Mohammed Fadlalla, Dennis J. Stuehr

Chemistry Faculty Publications

NO synthase (NOS) enzymes convert L-arginine to NO in two sequential reactions whose rates (kcat1 and kcat2) are both limited by the rate of ferric heme reduction (kr). An enzyme ferric heme –NO complex forms as an immediate product complex and then undergoes either dissociation (at a rate that we denote as kd) to release NO in a productive manner, or reduction (kr) to form a ferrous heme –NO complex that must react with O2 (at a rate that we denote as kox) in a NO dioxygenase reaction that regenerates the ferric enzyme. The interplay of these five kinetic parameters …

Structure, Theoretical Studies And Coupling Reactions Of Some New Cyclic Boronic Esters, Andrew Kuttler, Sravanthi Durganala, Albert Fratini, Alexander Morgan, Vladimir Benin

Chemistry Faculty Publications

The present report describes the X-ray structural and theoretical studies of some new pinacolboronate esters, and it also outlines the use of the target structures in Suzuki coupling reactions to produce new aromatic or heteroaromatic esters and amides. X-ray structural analysis of the studied compounds revealed that the pinacolborane ring's position with respect to the benzene ring varies, depending on the particular environment. An ortho-positioned carboxylic ester (methyl ester) causes a nearly perpendicular orientation of the pinacolborane unit with respect to the benzene ring, whereas an ortho-positioned amide (N,N-dimethylamide) causes the pinacolborane unit to orient itself nearly coplanar. A plausible …

Eerc Laboratory Capabilities, University Of North Dakota. Energy And Environmental Research Center

EERC Brochures and Fact Sheets

Brochure about the Energy & Environmental Research Center (EERC) laboratory facilities, equipment, and capabilities. Includes information on Analytical Research Laboratory, Natural Materials Analytical Research Laboratory, Applied Geology Laboratory, and Environmental Chemistry Laboratory. [This item is an outdated or superseded version and retained for historical purposes only. It may no longer reflect current information, policies, or practices.]

Preparation Of Cyclohexenones From Acyclic (Pentadienyl)Iron(1+) Cations: Synthesis Of Carvone Metabolites And Synthetic Studies Directed Toward Dihydrotachysterols, Charles Felix Manful

Dissertations (1934 -)

ABSTRACT

PREPARATION OF CYCLOHEXENONES FROM ACYCLIC (PENTADIENYL)IRON(1+) CATIONS: SYNTHESIS OF CARVONE METABOLITES AND SYNTHETIC STUDIES DIRECTED TOWARD DIHYDROTACHYSTEROLS

Charles Felix Manful, BSc.

Marquette University, 2013

Six-membered carbocycles are abundant in natural products. This structural feature is present in terpenes, secosteroids, antibiotics, and even imbedded in the polycyclic framework of complex alkaloids. A wide variety of methodologies have been utilized for the preparation of six-membered carbocycles including Robinson annulation, Diels-Alder cycloaddition, Dieckmann condensation, ring closing metathesis, photochemical carbonylation of alkenylcyclopropanes, addition of soft nucleophiles to acyclic (ç5-pentadienyl)iron cations, etc.

Acyclic (ç5-pentadienyl)iron(+1) cations were first prepared about 50 years ago. The reactivity …

Supramolecular Polysaccharide Composite Materials: Green And Recyclable Synthesis, Characterization, Analytical And Biomedical Applications, Simon Duri

Dissertations (1934 -)

A simple novel recyclable synthetic method was successfully developed for the synthesis of polysaccharide composite materials. The method involves the use of 1-butyl-3-methylimidazolium chloride [BMIm+Cl-], a simple ionic liquid, as the sole solvent. Naturally abundant and renewable materials such as cellulose (CEL) and chitosan (CS) were used for the preparation of the composite materials. CEL is the most abundant compound on earth, while CS is a product of deacetylation of chitin, which is the second most abundant material on earth. [BMIm+Cl-] is relatively non toxic, non volatile and stable over a wide range of temperature eliminating one of the major …

One-Pot Enol Silane Formation-Mukaiyama–Mannich Addition Of Ketones, Amides, And Thioesters To Nitrones In The Presence Of Trialkylsilyl Trifluoromethanesulfonates, C. Wade Downey, Carolyn M. Dombrowski, Erin N. Maxwell, Chelsea L. Safran, Odamea A. Akomah

Chemistry Faculty Publications

Ketones, amides, and thioesters form enol silanes and add to N-phenylnitrones in one pot in the presence of trimethylsilyl trifluoromethanesulfonate and trialkylamine. The reaction is general to a range of silyl trifluoromethanesulfonates and N-phenylnitrones. The b-(silyloxy)amino carbonyl products are stable to chromatography and can be isolated in 63-99% yield.

Statistical Analysis Of Aerosol Species, Trace Gases, And Meteorology In Chicago, Katrina Binaku, Timothy O'Brien, Martina Schmeling, Tinamarie Fosco

Chemistry: Faculty Publications and Other Works

Both canonical correlation analysis (CCA) and principal component analysis (PCA) were applied to atmospheric aerosol & trace gas concentrations and meteorological data collected in Chicago during the summer months of 2002, 2003, and 2004. Concentrations of ammonium, calcium, nitrate, sulfate, and oxalate particulate matter, as well as, meteorological parameters temperature, wind speed, wind direction, and humidity were subjected to CCA & PCA. Ozone and nitrogen oxide mixing ratios were also included in the data set. The purpose of statistical analysis was to determine the extent of existing linear relationship(s), or lack thereof, between meteorological parameters and pollutant concentrations in addition …

Facile, Green Synthesis Of Large Single Crystal Copper Micro And Nanoparticles With Ascorbic Acid And Gum Arabic, Preston B. Landon, Alexander H. Mo, Carlos T. Ramos, Jose J. Gutierrez, Ratnesh Lal

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

Large single crystal colloidal copper particles with diameters between 0.5 - 2 μm were created using a green synthesis process. The process used ascorbic acid to reduce Schweizer’s reagent created in situ using copper salts in the presence of various concentrations of gum arabic. The Schweizer’s reagents were created by varying the concentrations of ammonium hydroxide and copper nitrate solutions, copper hydroxide, or copper sulfate. The pH of the solution was controlled by the addition of ascorbic acid. Particle formation was favored at high temperature using copper sulfate at pH values ranging from 7.5 to 9, while the optimal formation …

Intramolecular Hydrogen Bonding In CuIi Complexes With 2,6-Pyridinedicarboxamide Ligands: Synthesis, Structural Characterization, And Physical Properties, Denan Wang, Sergey V. Lindeman, Adam T. Fiedler

Chemistry Faculty Research and Publications

The significance of second-sphere interactions in synthetic catalysts and metalloenzyme active sites has encouraged the development of ligand frameworks capable of supporting intramolecular hydrogen-bonding networks. With this approach in mind, we prepared a series of 2,6-pyridinedicarboxamide ligands (H₂L^X) that feature outer-sphere heterocyclic groups (pyridine, pyrimidine, or quinoline rings). Reaction with CuCl₂ yields complexes with the general formula [CuCl₂(L^X{H}₂)] (1^X), in which the pincer ligands coordinate to the Cu^II center in a tridentate fashion through the central pyridine and two amidato nitrogen atoms. The L^{X …}

Computational Study Of The Cyclization Of 5-Hexenyl, 3-Oxa-5-Hexenyl And 4-Oxa-5-Hexenyl Radicals, Albert Matlin, Matthew C. Leyden

Faculty & Staff Scholarship

The intramolecular cyclization of 5-hexenyl radicals continues to be an important synthetic method for the construction of five-membered rings. The synthetic utility arises from the high degree of regioselectivity to give predominantly cyclopentyl products in high yield under mild conditions. Recently we reported product cyclization studies on 4-oxa perturbed 5-hexenyl radical. In this paper we report our results from a computational study (UB3LYP and UCCSD(T)) of the cyclization of a series of 5-hexenyl and 3- and 4-oxa-5-hexenyl radicals. Three highly conserved cyclization transitions states (exo-chair, exo-boat and endo-chair) were located for 10 acyclic radicals. Activation en-ergies …

Carbon And Oxygen Isotope Study Of Carbonates From Watling's Blue Hole And Blue Hole Five, San Salvador, Bahamas, Elaine D. Flynn

Mahurin Honors College Capstone Experience/Thesis Projects

Carbonate platforms, such as the Bahamas, formed through deposition and sea level fluctuations. These platforms contain records of rapid interglacial climate change and are useful in studying the impacts of climate change on similar tropical carbonate environments. Blue holes are dissolution lakes that may be beneficial for understanding climate change and anthropogenic impact. A δ¹³C and δ¹⁸O study was conducted on lake sediment core samples from Watling’s Blue Hole and Blue Hole Five on San Salvador Island, Bahamas. These lakes are located in a failed housing development and Watling’s Blue Hole was once part of an …

Investigation Of The Structure Of Quinoa Saponins By Hplc And Mass-Spec, Samuel Swainhart, Dr. Steve Wood

Journal of Undergraduate Research

Quinoa is a grain grown mainly by Natives in diverse areas throughout Latin America that is considered by many nutritional scientists as possibly the most nourishing grain available. Its contents include high levels of protein, an exceptional composition of amino acids, and many carbohydrates. Unfortunately, quinoa is very climate sensitive, and currently can only be grown in certain areas of the world, due to a low tolerance for intense heat. For this reason, quinoa is not grown everywhere and its annual yields are nowhere near the enormous quantities of rice and grain harvested annually. There are many different known varieties …

Electrosynthesis Of Glycerol Carbonate From Co2 And Glycerol, Huan Wang, Mei-Xia Zhu, La-Xia Wu, Xiao-Ming Xu, Xue-Ru Zhao, Jia-Xing Lu

Journal of Electrochemistry

Glycerol carbonate was obtained from glycerol and carbon dioxide under room temperature and normal pressure by electrochemical method. The effects of synthesis conditions, such as cathode, charge, current density and temperature, on the reaction of glycerol and carbon dioxide have been investigated. The yields of 73% were produced by electrosynthesis of carbonate under the optimized condition, which is much higher than that by common catalysis method. The electrochemical behavior of the reaction system has been studied by cyclic voltammetry, through which the reaction process has been proposed.

Influence Of Pretreatment On Electrocatalytic Property For Methanol Oxidation Of Ptru/Wc, Xiao-Ling Lang, Mei-Qin Shi, Ye-Kun Jiang, Chun-An Ma

Journal of Electrochemistry

The surface of tungsten carbide (WC) was treated by potassium hydroxide (KOH) at different pH values for different time. The PtRu/WC composite was prepared by microwave-assisted polyol method. The phase structure of PtRu/WC composites were characterized by XRD. The electrocatalytic activity was tested by cyclic voltammetry and chronoamperometry. The results indicated that with different pH treatments WC became more readily supported on PtRu. When treating WC in KOH at pH = 14, PtRu exhibited the best degree of crystallinity on WC surface, leading to the highest electrocatalytic activity of PtRu/WC. Moreover, the optimized activity of PtRu/WC towards methanol oxidation was …

Synthesis And Electrochemical Properties Of Li(Ni0.5Co0.2Mn0.3)1-2xTiXNbXO2, Yong Tang, Qin-Lin Liao, Xiang-An Guo

Journal of Electrochemistry

The cathode-active materials of layered Li(Ni_0.5Co_0.2Mn_0.3)_1-2xTi_xNb_xO₂（x=0, 0.002, 0.005, 0.01, 0.02）composites were synthesized by the thermal treatment of the coprecipitated precursor at 900 ^oC in air. The effects of Ti-Nb co-dopants on the structural and electrochemical properties of Li(Ni_0.5Co_0.2Mn_0.3)O₂ were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical experiments. The results show that the small amounts of Ti-Nb co-dopants in Li(Ni_0.5Co_0.2Mn_0.3)O₂significantly decreased the degree of cation mixing in …