Chemistry Commons^™

The 5'-7-Methylguanosine Cap On Eukaryotic Mrnas Serves Both To Stimulate Canonical Translation Initiation And To Block An Alternative Pathway, Sarah F. Mitchell

Chemistry and Biochemistry Faculty Works

Translational control is frequently exerted at the stage of mRNA recruitment to the initiating ribosome. We have reconstituted mRNA recruitment to the 43S preinitiation complex (PIC) using purified S. cerevisiae components. We show that eIF3 and the eIF4 factors not only stabilize binding of mRNA to the PIC, they also dramatically increase the rate of recruitment. Although capped mRNAs require eIF3 and the eIF4 factors for efficient recruitment to the PIC, uncapped mRNAs can be recruited in the presence of eIF3 alone. The cap strongly inhibits this alternative recruitment pathway, imposing a requirement for the eIF4 factors for rapid and …

Ribosome Recycling Step In Yeast Cytoplasmic Protein Synthesis Is Catalyzed By Eef3 And Atp, Sarah F. Mitchell

Chemistry and Biochemistry Faculty Works

After each round of protein biosynthesis, the posttermination complex (PoTC) consisting of a ribosome, mRNA, and tRNA must be disassembled into its components for a newround of translation. Here, we show that a Saccharomyces cerevisiae model PoTC was disassembled by ATP and eukaryotic elongation factor 3 (eEF3). GTP or ITP functioned with less efficiency and adenosine 5γ′-(β,γ-imido)triphosphate did not function at all. The kcat of eEF3 was 1.12 min-1, which is comparable to that of the in vitro initiation step. The disassembly reaction was inhibited by aminoglycosides and cycloheximide. The subunits formed from the yeast model PoTC remained separated under …

Observations Of Elevated Formaldehyde Over A Forest Canopy Suggest Missing Sources From Rapid Oxidation Of Arboreal Hydrocarbons, Nicole Bouvier-Brown

Chemistry and Biochemistry Faculty Works

To better understand the processing of biogenic VOCs (BVOCs) in the pine forests of the US Sierra Nevada, we measured HCHO at Blodgett Research Station using Quantum Cascade Laser Spectroscopy (QCLS) during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) of late summer 2007. Four days of the experiment exhibited particularly copious HCHO, with midday peaks between 15–20 ppbv, while the other days developed delayed maxima between 8–14 ppbv in the early evening. From the expansive photochemical data set, we attempt to explain the observed HCHO concentrations by quantifying the various known photochemical production and loss terms in its …

Synthesis, Characterization And Biological Activity Of Copper (Ii) And Zinc (Ii) Complexes Of Thiosemicarbazones And Their N(4)-Substituted Derivatives Derived From 2,4-Dihydroxybenzaldehyde., Tan Kong Wai

Student Works (2010-2019)

Four thiosemicarbazones ligands (1-4) have been prepared with good yield by refluxing 2,4-dihydroxybenzaldehyde with thiosemicarbazide or N(4)-substituted thiosemicarbazide in ethanol or methanol. From these four ligands, 16 new ternary metal complexes (5-20) with the general formulation of M(B)L have been prepared from the reactions of metal acetates with 2,4-dihydroxybenzaldehyde N(4)-substituted thiosemicarbazone in the presence of N,N-heterocyclic base (M2+ = Zn2+ or Cu2+; B = 2,2'-bipyridine, (bpy); 1,10-phenanthroline, (phen); L2- = doubly deprotonated thiosemicarbazones = 2,4-dihydroxybenzaldehyde thiosemicarbazonato, (HT); 2,4-dihydroxybenzaldehyde 4-methylthiosemicarbazonato, (HM); 2,4-dihydroxybenzaldehyde 4-ethylthiosemicarbazonato, (HE) and 2,4-dihydroxybenzaldehyde 4-phenylthiosemicarbazonato, (HP)) These compounds have been characterized by elemental analyses, IR, UV-Vis, NMR and magnetic …

Mapping The Reactivity Surface Of Metal-Olefin Reactions, Joshua Davis, Stephen A. Matchett

Student Summer Scholars Manuscripts

Our overall goal of our project was to map susceptibility for nucleophilic attack on a series of metal-olefin compounds as a function of their geometry. The scope of this paper, however, is directed toward stabilizing our reactants in solution and the developing methods to test the reaction. In order to measure the susceptibility on the series we must know three things: the initial concentration of the nucleophile and the metal-olefin as well as a way measure the rate of reaction. In order to take these measurements, the solvent used must not interact with either reactant, must not interfere with the …

Molecular Dynamics Simulations Of Human Quadruplexes In K+ Solution And The Role Of The Carboxyl Terminus Of Bacteriorhodopsin In Protein Stability, Farah Rezae

Seton Hall University Dissertations and Theses (ETDs)

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Thermal And Electrochemical Characterization Of Cathode Materials For High Temperature Lithium-Ion Batteries In Ionic Liquids, Jodie R. Shoaf

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Finding a cathode material to operate a high-temperature Li-ion battery in the presence of an ionic liquid has become an attractive area of research. Three cathode materials, LiCoO2, Li4Ti5O12, and LiFePO4, were received from Electrochemical Systems Inc. of Knoxville, TN. Three ionic liquids were synthesized using a 1-alkyl-3-methylimidazolium (XMI+) cation, where the alkyl group was either ethyl, pentyl or hexyl, and contained a bis(pentafluoroethylsulfonyl)imide (Beti-) anion. The thermal and electrochemical properties of each ionic liquid, of each cathode material, and each combination of cathode material in the presence of ionic liquid were studied. All of the ionic liquids were found …

Exploration Using Reaction Temperature To Tailor The Degree Of Order In Micro-Block Copolymer Proton Exchange Membranes, John Quentin Buquoi Iii

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The ability to control the self-assembly of sulfonated poly(arylene ether) sulfones (s-PAESs) was explored by tailoring rate coefficients, via temperature, in an A₂ + B₂ + B₂' Nucleophilic Aromatic Substitution (S_NAr) approach. The reactivity of various electrophilic sites were studied and tuned, via temperature control, to elicit a range of more ordered and disordered polymers of equivalent monomeric composition. These polymers were characterized by ¹H and ¹³C NMR spectroscopy and found to have highly disordered polymer configuration at higher temperatures while having a more regular configuration at lower temperatures.

1-Alkyl-3-Methylimidazolium Bis(Trifluoromethylsulfonyl)Imide Based Ionic Liquids: A Study Of Their Physical And Electrochemical Properties, Charles William Dutton

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Ionic liquids are of interest because of their electrochemical and thermal properties and their possible use as electrolytes in batteries. In this work five ionic liquids were synthesized. They consisted of a 1-alkyl-3-methylimidazolium (RMI⁺) cation, where the alkyl group was ethyl, propyl, butyl, pentyl, or hexyl, and a bis(tri-fluoromethylsulfonyl)imide (NTf2^-)anion. The decomposition temperatures, melting points, conductivities, viscosities, densities, absorption and desorption of water, diffusion coefficients, and electrochemical properties were studied. It was found that these ionic liquids were thermally stable up to ~310 °C, and that EMINTf₂ had a melting point at -18.26 °C. Conductivities …

A Comparison Of Atmospheric Pahs In Pine Needles And High-Volume Sampler Filters In The Dayton Metro Area, Timothy A. Tomashuk

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Samples of filters from High-volume (HiVol) samplers of particulate matter (PM) with a size of 10 micrometers or less were deployed for five months in Moraine and Yellow Springs, OH, by the Regional Air Protection Control Agency and analyzed for the Environmental Pollution Agency (EPA) 16 polycyclic aromatic hydrocarbons (PAHs). Pine needles on trees near the HiVol samplers were also collected and analyzed for a comparison with the active samplers to estimate atmospheric PAH concentrations. Pine needles were found to collect lower molecular weight (LMW) compounds far more than HiVol sampler and thus their profiles shown to compliment the HiVol …

Electrochemical Deposition Of Molybdenum And Tungsten From Trinuclear Metal Clusters (M3O2(Oac)6(H2O)3(Cf3So3)2) In 1-Ethyl-3-Methylimidazolium Tetrafluoroborate Ionic, Charles Woods

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Electrochemical properties of Mo₂WO₂(O₂CCH₃)₆(H₂O)₃(CF₃SO₃)₂ and W₃O₂(O₂CCH₃)₆(H₂O)₃(CF₃SO₃)₂ clusters in 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF₄) ionic liquid was investigated. Cyclic voltammograms using a platinum electrode indicated that deposition of metal had occurred. Constant potential electrolysis of Mo₂WO₂(O₂CCH₃)₆(H₂O)₃(CF₃SO₃)₂ at -1.9 V using a platinum foil electrode …

Routes To Sydno[3,4-A]Quinoxalines, Erik Dihrkop

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In the present work, the reactivity of alkyl and aryl sydnoquinoxalines was studied. Using a previously developed method, triphenylphosphine-2-(3-sydnonyl)phenylimide was prepared in a two-step process via a diazotization / azidation process of 3-(2-aminophenyl)sydnone, followed by treatment with triphenylphosphine. Due to the inability to achieve previously reported yields, a new, one-step method using Mitsunobu conditions was employed to synthesize the iminophosphorane in a good yield. A similar, brominated iminophosphorane was synthesized using the same conditions in a good yield. Treatment of both the brominated and non-brominated iminophosphoranes with alkyl and aryl isocyanates or isothiocyanates in an aza-Wittig process, gave the corresponding …

Electrochemical Oxidation Of Ethanol In Ionic Liquids And Its Possible Use In Fuel Cells, Ashley M. Mason

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Electrochemical properties of EtOH in EMImBF4 ionic liquid were investigated and compared to the electrochemical properties of EtOH in 0.1M HClO4/H2O. As was shown earlier, oxidation of EtOH in HClO4/H2O involves formation of PtO on the electrode surface, which makes the electrode poisoned. We have found that the best procedure for removal of PtO from the Pt electrode is heating the electrode in concentrated H2SO4. Cyclic voltammograms obtained after cleaning several Pt electrodes conforms that this treatment gives clean Pt electrodes without any PtO. Electrochemical oxidation of EtOH in EMImBF4 ionic liquid show that is poisoning of Pt electrode by …

Skeletal Pathology Of Tibiotarsi In Chick Embryos Exposed To Platinum Group Metals By Micro-Raman Spectroscopy, Jennifer L. Monahan

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Platinum group metals (PGMs) have been shown to accumulate in various tissues of organisms but their toxicity is not well-known. Raman spectroscopy is a powerful analytical technique that enables direct and non-destructive chemical characterization of bone tissues. PGMs were injected into chick embryos in the following concentrations: 0.1, 1.0, 5.0, or 10.0 ppm solutions of Pt^(IV), Rh^(III), Pd^(II) or PGMs mixtures (0.1 ppm or 1.0 ppm of each metal). The micro-Raman maps recorded on the paraffin embedded tibiotarsus cross-sections showed significant changes in the chemical composition and structure of the bone tissue as a result …

Temperature And Ph Responsive Polyethylenimine Systems As Potential Nonviral Gene Vectors, S. Chad Skidmore

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Modified HPEI was used to determine if the LCST could be controlled by varying multiple variables, including: percent modification, pH, salt solution concentration, and weight percent. Two modifications were done with butylene oxide (Butox) and isobutyryl amide (IBAm). Specifically, 100% (HPEI-Butox1.00)butoxylated and 10% (HPEI-IBAm0.10), 54% (HPEI-IBAm0.54), and 70% (HPEI-IBAm0.70) amidated samples were synthesized. Additionally, HPEI-IBAm0.54 was further modified with hydroxyl ethyl groups (HPEI-IBAm0.54 Eox0.46) and ethyl groups (HPEI-IBAm0.54-Et0.44). The LCSTs of all amidated systems were below body temperature, 37 °C, at pH = 7.4. This indicates an ability of these systems to be used as a vector for gene delivery. …

Novel Synthesis Of Polyhydrogenated Fullerenes, Angela Campo

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Hydrogenated fullerenes are of interest as a starting material in metal fulleride synthesis. By reacting C₆₀H₂ with various metals, alloyed metal fullerides could be produced. To achieve this goal, first a reliable synthesis of C₆₀H₂ must be determined. C₆₀H₂ is difficult to synthesis exclusively; C₆₀H₄ and C₆₀H₆ are also produced. Reduction of C₆₀ with NaBH₄ produced a mixture of products as well as excessive unreacted C₆₀. Attempts to modify this reaction to achieve C₆₀H₂ exclusively were unsuccessful. A …

Small Molecule Caspase Inhibitors Using Isatin And Oxindole Scaffolds And A Combinatorial Approach, Hagar Mahmoud Abdallah

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Quinolyl-valyl-O-methylaspartyl-[2,6-difluorophenoxy]-methyl ketone (Q-VD-OPh) is a next generation broad spectrum caspase inhibitor, the effectiveness and reduced toxicity of which can be partially attributable to the carboxyterminal O-phenoxy group as well as the amino terminal quinolyl groups. We seek to incorporate some of these unique recognition elements onto small molecule derived protease inhibitors with drug like properties. Specifically, heterocyclic scaffolds such as isatins and oxindoles. Thus, isatins bearing electron withdrawing groups on C-5 and 2,6-difluorobenzyl moieties have been prepared by analogy to the well studied N-substituted 5-pyrrololidinylsulfonyl isatins. Moreover, 3-benzylidene oxindole derivatives bearing these structural motifs have also been prepared and their …

Progress Towards The Synthesis Of Type B Polycyclic Polyprenylated Acylphloroglucinol 7-Epi-Clusianone, Pushpa Suresh Jayasekara Mudiyanselage

University of Kentucky Doctoral Dissertations

Plants of the family Guttiferae produce polycyclic polyprenylated acylphloroglucinols (PPAPs), which have interesting biological activities including anticancer and antibacterial properties. The main structural features of PPAPs comprise of bicyclo[3.3.1]nonane-2,4,9-triketone with one acyl group together with prenyl, geranyl, or other C₁₀H₁₇ groups. 7-epi-Clusianone, a type B PPAP with C-7 endo stereochemistry, is being approached by establishing the cis relationship with C(4) allyl group and C(2) methyl ester in the early stage of the synthesis. Then C(2) methyl ester is converted to alkyne aldehyde and syn reduction followed by intramolecular aldol reaction to give bicyclo[3.3.1]nonane structure with …

Isomer Identification And Resolution In Small Gold Clusters, Wei Huang, Rhitankar Pal, Lei-Ming Wang, Xiao Cheng Zeng, Lai-Sheng Wang

Xiao Cheng Zeng Publications

A variety of experimental techniques are used to resolve energetically close isomers of Au_{7 ⁻} and Au_{8 ⁻} by combining photoelectron spectroscopy and ab initio calculations. Two structurally distinct isomers are confirmed to exist in the cluster beam for both clusters. Populations of the different isomers in the cluster beam are tuned using Ar-tagging, O₂-titration, and isoelectronic atom substitution by Cu and Ag. A new isomer structure is found for Au_{7 ⁻}, which consists of a triangular Au₆ unit with a dangling Au atom. Isomer-specific photoelectron spectra of Au_{8 ⁻} are obtained …

Improved Arene Fluorination Methodology For I(Iii) Salts, Bijia Wang, Linlin Qin, Kiel D. Neumann, Shriharsha Uppaluri, Ronald Cerny, Stephen G. Dimagno

Ronald Cerny Publications

The use of low polarity aromatic solvents (benzene or toluene) and/or the removal of inorganic salts results in dramatically improved yields of fluorinated arenes from diaryliodonium salts. This methodology is shown to “scale down” to the conditions used typically for radiotracer synthesis.

Concave Cubic Gold Nanocrystals With High-Index Facets, Jian Zhang, Mark R. Langille, Michelle L. Personick, Ke Zhang, Shuyou Li, Chad A. Mirkin

Department of Chemistry: Faculty Publications

A new class of gold nanostructures, concave nanocubes, enclosed by 24 high-index {720} facets, have been prepared in a monodisperse fashion by a modified seed-mediated synthetic method. The Cl− counterion in the surfactant plays an essential role in controlling the concave morphology of the final product. The concave nanocubes exhibit higher chemical activities compared with low-index {111}-faceted octahedra.

Includes Supporting Information.

Corrosion Of Steel Shipwrecks In The Marine Environment: Uss Arizona—Part 2, Donald L. Johnson, Brent M. Wilson, James D. Carr, Matthew A. Russell, Larry E. Murphy, David L. Conlin

Department of Chemistry: Faculty Publications

This article is a continuation of Part 1 (October 2006 MP) on the USS Arizona hull. It discusses additional methods being investigated for use in determining corrosion rates with a minimal impact on the existing structure. Marine biofouling (concretion) has accumulated on the hull. Concretion samples have been studied using x-ray diffraction, environmental electron microscopy, and corrosion potential (E_corr) to characterize the relationship between concretion and the steel substrate. The data presented in this study confirm the viability of concretion analysis as a minimum-impact procedure to estimate the corrosion rate of mild steel in seawater.

Corrosion Of Civil War Era Sub Marine Explorer—Part 2, Donald L. Johnson, James D. Carr, Brent M. Wilson, Larry E. Murphy, James P. Delgado

Department of Chemistry: Faculty Publications

The Sub Marine Explorer was designed and built by Julius H. Kroehl, who was born in Prussia in 1820. After migrating to the United States in 1838 and becoming a citizen, he served in the Union Navy (United States Navy during the Civil War) as an underwater demolitions expert. He left the Navy in 1863 and began designing a “sub-marine” that would facilitate Union forces’ mine removal and obstruction clearance. At the end of the Civil War, he became an engineer for the Pacific Pearl Co., an organization interested in using the craft to recover pearls from deep sea oyster …

Corrosion Of Civil War Era Sub Marine Explorer—Part 1, Donald L. Johnson, James D. Carr, Brent M. Wilson, Larry E. Murphy, James P. Delgado

Department of Chemistry: Faculty Publications

The Sub Marine Explorer is one of five submersibles (submarines) constructed prior to 1870 that have survived either in museums or as in situ archaeological sites around the world. Since 1869, the wreck of Explorer has emerged at low tide on the beach of Isla San Telmo, Archipiélago de las Perlas, Panama, located ~75 km southwest of Panama City in the Bay of Panama. In 2001, James Delgado visited the site. Locals described the wreck as a World War II-era Japanese midget submarine. Delgado consulted with Richard Wills, an expert on American Civil War submarines, and confirmed that the well-preserved …

Method For Monitoring The Stereoselectivity And Relative Rate Of Organic Chemical Reactions, David R. Berkowitz, Sangeeta Dey, Kannan R. Karukurichi, Weijun Shen

Department of Chemistry: Faculty Publications

A method for monitoring the stereoselectivity of at least one organic chemical reaction and the relative rate of at least one organic chemical reaction, wherein the reaction produces a product that can exist as at least two stereoisomers, is provided herein. Also disclosed are methods for identifying and preparing catalysts for the above reactions.

Regiospecific Reductive Elimination From Diaryliodonium Salts, Bijia Wang, Joseph W. Graskemper, Linlin Qin, Stephen G. Dimagno

Stephen DiMagno Papers

StereoElectronic Control of Unidirectional Reductive Elimination (SECURE) is provided by the cyclophane substituent on iodine(III). Computational and experimental studies demonstrate that out of plane steric bulk strongly destabilizes the reductive elimination transition state, and leads to regiochemical control. This approach should be general for high valent main group and transition metal ions.

Ni Doping Of Semiconducting Boron Carbide, Nina Hong, Marjorie Langell, Jing Liu, Orhan Kizilkaya, Shireen Adenwalla

Marjorie A. Langell Publications

The wide band gap, temperature stability, high resistivity, and robustness of semiconducting boron carbide make it an attractive material for device applications. Undoped boron carbide is p type; Ni acts as a n-type dopant. Here we present the results of controlled doping of boron carbide with Ni on thin film samples grown using plasma enhanced chemical vapor deposition. The change in the dopant concentration within the thin film as a function of the dopant flow rate in the precursor gas mixture was confirmed by x-ray photoelectron spectroscopy measurements; with increasing dopant concentration, current-voltage (I-V) curves clearly establish the trend from …

Immobilization Of The Aminopeptidase From Aeromonas Proteolytica On Mg2+/Al3+ Layered Double Hydroxide Particles, Steven T. Frey, Stephanie L. Guilmet, Richard G. Egan Iii, Alyssa Bennett, Sarah R. Soltau, Richard C. Holz

Chemistry Faculty Research and Publications

A novel biomaterial formed by the immobilization of the Aminopeptidase from Aeromonas proteolytica (AAP) on synthetic Mg²⁺ and Al³⁺ ion-containing layered double hydroxide (LDH) particles was prepared. Immobilization of AAP on the LDH particles in a buffered, aqueous mixture is rapid such that the maximum loading capacity, 1 × 10⁻⁹ moles of AAP/mg LDH, is achieved in a few minutes. X-ray powder diffraction of LDH samples before and after treatment with AAP indicates that the enzyme does not intercalate between the layers of LDH, but instead binds to the surface. Treatment of AAP/LDH with various amounts of …

Polymeric Paracest Mri Contrast Agents As Potential Reporters For Gene Therapy, Yunkou Wu, Christiane E. Carney, Michael Denton, Elaine Hart, Piyu Zhao, Daniel N. Streblow, A. Dean Sherry, Mark Woods

Chemistry Faculty Publications and Presentations

Gene therapy is a potentially powerful treatment approach that targets molecular remedies for disease. Among other challenges it remains difficult to monitor gene delivery and its downstream metabolic consequences. Approaches to MRI gene reporters have been reported but few have the potential for translation beyond isolated cell systems. Herein, we report a polycationic polymer MRI contrast agent that binds to DNA in a ratio of one monomer unit per phosphate group of DNA. Significantly, this binding event diminishes the MR contrast signal from the agent itself potentially providing a platform for imaging delivery and release of a gene into cells …

Nir Dyes For Bioimaging Applications, Jorge O. Escobedo, Oleksandr Rusin, Soojin Lim, Robert M. Strongin

Chemistry Faculty Publications and Presentations

Fluorescent dyes based on small organic molecules that function in the near infra red (NIR) region are of great current interest in chemical biology. They allow for imaging with minimal autofluorescence from biological samples, reduced light scattering and high tissue penetration. Herein, examples of ongoing NIR fluorophore design strategies as well as their properties and anticipated applications relevant to the bioimaging are presented.