Chemistry Commons^™

Dielectric Constant And Proton Order And Disorder In Ice Ih: Monte Carlo Computer Simulations, Steven W. Rick

Chemistry Faculty Publications

The dielectric properties of ice Ih are studied using a Monte Carlo algorithm for sampling over proton configurations. The algorithm makes possible the calculation of the dielectric constant and other properties of the proton-disordered crystal. Results are presented for three classical models of water, two commonly used nonpolarizable models (SPC/E and TIP4P) and a polarizable model
(TIP4P-FQ).

Characterisation Of Polymer-Modified Electrodes, Karl Crowley

Doctoral

In this work, two contrasting polymer-modified electrodes are investigated. Electroanalysis of lead in aqueous solutions was performed with an electrode coated with Nafion and the redox behaviour of the electronically conducting polymer, polypyrrole, was characterised. In the first study, a glassy carbon electrode coated with Nafion was used in the determination of lead through anodic stripping voltammetry (ASV). Initially the work consisted of optimising the preparation of the electrode and the experimental conditions resulting in a reproducible Nafion-modified electrode (NME) with a lifetime of several weeks. Two different stripping techniques were examined. High frequency square wave ASV was found to …

Effect Of Petrochemical Industrial Emissions Of Reactive Alkenes And NoX On Tropospheric Ozone Formation In Houston, Texas, T. B. Ryerson, M. Trainer, W. M. Angevine, C. A. Brock, R. W. Dissly, F. C. Fehsenfeld, G. J. Frost, P. D. Goldan, J. S. Holloway, G. Hübler, R. O. Jakoubek, W. C. Kuster, J. A. Neuman, D. K. Nicks, D. D. Parrish, J. M. Roberts, D. T. Sueper, E. L. Atlas, Stephen G. Donnelly Ph.D., F. Flocke, A. Fried, W. T. Potter, S. Schauffler, V. Stroud, A. J. Weinheimer, B. P. Wert, C. Wiedinmyer, R. J. Alvarez, R. M. Banta, L. S. Darby, C. J. Senff

Chemistry Faculty Publications

Petrochemical industrial facilities can emit large amounts of highly reactive hydrocarbons and NOx to the atmosphere; in the summertime, such colocated emissions are shown to consistently result in rapid and efficient ozone (O3) formation downwind. Airborne measurements show initial hydrocarbon reactivity in petrochemical source plumes in the Houston, TX, metropolitan area is primarily due to routine emissions of the alkenes propene and ethene. Reported emissions of these highly reactive compounds are substantially lower than emissions inferred from measurements in the plumes from these sources. Net O3 formation rates and yields per NOx molecule oxidized in these petrochemical industrial source plumes …

Newtonian Cosmology, Ronald Lovett

Topics in Quantum Mechanics

No abstract provided.

Preparation Of 2s,3s-N-Isobutyl-N-(2-Hydroxy-3-Amino-4-Phenylbutyl)-P-Nitrobenzenesulfonylamide Hydrochloride And Other Derivatives Of 2-Hydroxy-1,3-Diamines, Aslam A. Malik, Hasan Palandoken, Joy A. Stringer, Roland P. Carlson, John Leach, Thomas G. Archibald, Robert G. Miotke

Chemistry and Biochemistry

The present invention provides a new process for the preparation of 2S,3S-N-isobutyl-N-(2-hydroxy-3-amino-4phenylbutyl)- p-nitrobenzenesulfonylamide hydrochloride, wherein this compound is prepared directly from the chloromethylalcohol. Importantly, the process of the present invention results in higher yields of 2S,3S-N-isobutyl-N-(2hydroxy -3 -amino -4-phenylbutyl) -pnitrobenzenesulfonylamide hydrochloride without sacrificing its purity. The processes of the present inventin can be used to prepare not only the 2S,3S-derivative, but also the 2R,3S-, 2S,2R- and the 2R,3R-derivatives.

Solvent And Method For Extraction Of Triglyceride Rich Oil, Shubhender Kapila, Paul Ki-Souk Nam, V. J. Flanigan

Chemistry Faculty Research & Creative Works

The present invention relates to a solvent for use in extracting oil from an oil bearing material, such as soybeans, with the solvent resulting in the selective extraction of a triglyceride rich oil, which contains 95% or greater triglycerides and non-polar constituents, with the solvent comprised of a hydrocarbon, preferably hexane, and a fluorocarbon, so that the solvent has a viscosity less than 2.6 centipoise and a polarity of less than 0.1. The present invention also relates to a method of using the solvent to extract the triglyceride rich oil, with the method including preferably extracting the oil at a …

Clean, High-Yield Preparation Of S,S- And R,S- Amino Acid Isosteres, Aslam A. Malik, Todd E. Clement, Hasan Palandoken, James Robinson Iii, Joy A. Stringer

Chemistry and Biochemistry

The present invention provides compounds and methods that can be used to convert the intermediate halomethyl ketones (HMKs), e.g., chloromethyl ketones, to the corresponding S,S- and R,S-diastereomers. More particularly, the present invention provides: (1) reduction methods; (2) inversion methods; and (3) methods involving the epoxidation of alkenes. Using the various methods of the present invention, the R,S-epoxide and the intermediary compounds can be prepared reliably, in high yields and in high purity.

Tropospheric Carbon Monoxide Measurements From The Scanning High-Resolution Interferometer Sounder On 7 September 2000 In Southern Africa During Safari 2000, W. W. Mcmillan, M. L. Mccourt, H. E. Revercomb, R. O. Knuteson, Ted J. Christian, B. G. Doddridge, Peter V. Hobbs, J. V. Lukovich, P. C. Novelli, S. J. Piketh, L. Sparling, D. Stein, R. J. Swap, Robert J. Yokelson

Chemistry and Biochemistry Faculty Publications

[1] Retrieved tropospheric carbon monoxide (CO) column densities are presented for more than 9000 spectra obtained by the University of Wisconsin-Madison (UWis) Scanning High-Resolution Interferometer Sounder (SHIS) during a flight on the NASA ER-2 on 7 September 2000 as part of the Southern African Regional Science Initiative (SAFARI 2000) dry season field campaign. Enhancements in tropospheric column CO were detected in the vicinity of a controlled biomass burn in the Timbavati Game Reserve in northeastern South Africa and over the edge of the river of smoke in south central Mozambique. Relatively clean air was observed over the far southern coast …

Chemistry & Biochemistry Newsletter, Department Of Chemistry & Biochemistry, South Dakota State University

Chemistry & Biochemistry Newsletter: 2002-2015

Inside:

Page 2 2003 Graduates; Bonneman Scholarship in Medical Technology Awarded; Dean’s List–Spring 2003

Page 3 Update of Sophomore Organic Chemistry Lab; Halaweish Receives Governor’s Grant

Page 4 A Mini-sized Antarctic in Shepard Hall

Page 5 Alumni News; Faculty and Staff News; Foundation Donors

Page 6 Recent Faculty Publications

Teachers' Resource For Materials And Environmental Chemistry, Carnetta Skipworth

Masters Theses & Specialist Projects

In many secondary education chemistry classrooms, teachers have a difficult time introducing chemistry topics in a way that will be interesting to the high school student. The development of a materials and environmental chemistry teacher's manual will help teachers introduce a variety of selected topics in an interesting fashion to the students. This manual focuses on the subjects covered for freshman and sophomore level students. The manual uses five separate experiments to introduce topics such as the electromagnetic spectrum and solubility. The five experiments include a test on tennis shoe stiffness and energy dissipation ability, pesticides in water, grease in …

Peptide−Protein Interactions: Photoinduced Electron-Transfer Within The Preformed And Encounter Complexes Of A Designed Metallopeptide And Cytochrome C, Robin C. Lasey, Liu Liu, Ling Zang, Michael Y. Ogawa

Chemistry Faculty Publications

Photoinduced electron-transfer (ET) occurs between a negatively charged metallopeptide, [Ru(bpy)2(phen-am)-Cys-(Glu)(5)-Gly](3-) = RuCE(5)G, and ferricytochrome c = Cyt c. In the presence of Cyt c, the triplet state lifetime of the ruthenium metallopeptide is shortened, and the emission decays via biexponential kinetics, which indicates the existence of two excited-state populations of ruthenium peptides. The faster decay component displays concentration-independent kinetics demonstrating the presence of a preformed peptide-protein complex that undergoes intra-complex electron-transfer. Values of K-b = (3.5 +/- 0.2) x 10(4) M-1 and k(ET)(obs) = (2.7 +/- 0.4) x 10(6) s(-1) were observed at ambient temperatures. The magnitude of k(ET)(obs) decreases …

Einstein Oscillators In Thallium Filled Antimony Skutterudites, Raphaël P. Hermann, Rongying Jin, Werner Schweika, Fernande Grandjean, David G. Mandrus, Brian C. Sales, Gary J. Long

Chemistry Faculty Research & Creative Works

Heat capacity measurements were performed on Tl_0.8Co₄Sb₁₁Sn. An Einstein vibrating behavior for the thallium atoms was found. The inelastic neutron scattering measurements on T_0.8Co₄Sb₁₁Sn, Tl_0.5Co_3.5Fe_0.5Sb₁₂, and Tl_0.8Co₃FeSb₁₂ showed a localized vibrational mode, which confirmed this Einstein vibrational behavior. Furthermore, the 56±2 K temperature of the Einstein vibrational mode obtained from the heat capacity measurements showed excellent agreement with the 5 meV energy or 57±2 K values obtained from the neutron scattering measurements.

Properties Of A Mixed-Valent Iron Compound With The Kagomé Lattice, Chintamani Nagesa Ramachandra Rao, Geo L. Paul, Amitava Choudhury, Echur Varadadesikan Sampathkumaran, Arup Kumar R. Raychaudhuri, Suryanarayanasastry Ramasesha, Indranil Rudra

Chemistry Faculty Research & Creative Works

An organically templated iron sulfate of the formula [HN(CH₂)₆NH][Fe^III Fe₂ ^IIF₆(SO₄)₂] ·[H₃O] possessing the kagomé lattice has been prepared and characterized by single-crystal crystallography and other techniques. This mixed-valent iron compound shows complex magnetic properties including spin-glass behavior and magnetic hysteresis. The low-temperature specific heat data show deviation from the T² behavior found in two-dimensional frustrated systems. Simple calculations have been carried out to understand the properties of this kagomé compound.

Measurement Of Proton Transfer Reaction Rates In A Microwave Cavity Discharge Flowing Afterglow, George M. Brooke Iv

Physics Theses & Dissertations

The reaction rate coefficients between the hydronium ion and the molecules ethene (C₂H₄), propene (C₃H₆), 1-butene (C₄H₈) and hydrogen sulfide (H₂S) were measured at 296 K. The measured reaction rates were compared to collision rates calculated using average dipole orientation (ADO) theory. Reaction efficiency depends primarily upon the proton affinity of the molecules. All the measurements were obtained using the newly developed microwave cavity discharge flowing afterglow (MCD-FA) apparatus. This device uses an Asmussen-type microwave cavity discharge ion source that is …

Regio- And Stereoselective Ruthenium Catalyzed Hydrovinylation Of 1,3-Dienes: Application To The Generation Of A 20s-Steroidal Sidechain, Zhengjie He, Chae S. Yi, William A. Donaldson

Chemistry Faculty Research and Publications

The addition of ethylene to 1,3-dienes and 1-vinylcycloalkenes, catalyzed by two ruthenium complexes, proceeds in a regioselective fashion to afford 3-methyl-1,4-dienes as products. For a steroidal-based 1-vinylcycloalkene, the addition is stereospecific, giving a product with a 20(S) configuration.

Co-Catalytic Metallopeptidases As Pharmaceutical Targets, Richard C. Holz, Krzysztof P. Bzymek, Sabina I. Swierczek

Chemistry Faculty Research and Publications

Understanding the reaction mechanism of co-catalytic metallopeptidases provides a starting point for the design and synthesis of new molecules that can be screened as potential pharmaceuticals. Many of the enzymes that contain co-catalytic metallo-active sites play important roles in cellular processes such as tissue repair, protein maturation, hormone level regulation, cell-cycle control and protein degradation. Therefore, these enzymes play central roles in several disease states including cancer, HIV, stroke, diabetes, bacterial infections, neurological processes, schizophrenia, seizure disorders, and amyotrophic lateral sclerosis. The mechanism of AAP, an aminopeptidase from Aeromonas proteolytica, is one of the best-characterized examples of a metallopeptidase …

Water-Soluble Organic Components In Aerosols Associated With Savanna Fires In Southern Africa: Identification, Evolution, And Distribution, Song Gao, Dean A. Hegg, Peter V. Hobbs, Thomas W. Kirchstetter, Brian I. Magi, Martin Sadilek

Chemistry and Physics Faculty Articles

During the SAFARI 2000 field campaign, both smoke aerosols from savanna fires and haze aerosols in the boundary layer and in the free troposphere were collected from an aircraft in southern Africa. These aerosol samples were analyzed for their water-soluble chemical components, particularly the organic species. A novel technique, electrospray ionization-ion trap mass spectrometry, was used concurrently with an ion chromatography system to analyze for carbohydrate species. Seven carbohydrates, seven organic acids, five metallic elements, and three inorganic anions were identified and quantified. On the average, these 22 species comprised 36% and 27% of the total aerosol mass in haze …

Emissions Of Trace Gases And Particles From Savanna Fires In Southern Africa, Parikhit Sinha, Peter V. Hobbs, Robert J. Yokelson, I. T. Bertschi, Donald R. Blake, Isobel J. Simpson, Song Gao, Thomas W. Kirschsetter, Tica Novakov

Chemistry and Biochemistry Faculty Publications

[1] Airborne measurements made on initial smoke from 10 savanna fires in southern Africa provide quantitative data on emissions of 50 gaseous and particulate species, including carbon dioxide, carbon monoxide, sulfur dioxide, nitrogen oxides, methane, ammonia, dimethyl sulfide, nonmethane organic compounds, halocarbons, gaseous organic acids, aerosol ionic components, carbonaceous aerosols, and condensation nuclei (CN). Measurements of several of the gaseous species by gas chromatography and Fourier transform infrared spectroscopy are compared. Emission ratios and emission factors are given for eight species that have not been reported previously for biomass burning of savanna in southern Africa (namely, dimethyl sulfide, methyl nitrate, …

Chlorine Budget And Partitioning During The Stratospheric Aerosol And Gas Experiment (Sage) Iii Ozone Loss And Validation Experiment (Solve), S. M. Schauffler, E. L. Atlas, Stephen G. Donnelly Ph.D., A. Andrews, S. A. Montzka, J. W. Elkins, D. F. Hurst, P. A. Romashkin, G. S. Dutton, V. Stroud

Chemistry Faculty Publications

The amount of chlorine in the stratosphere has a direct influence on the magnitude of chlorine-catalyzed ozone loss. A comprehensive suite of organic source gases of chlorine in the stratosphere was measured during the NASA Stratospheric Aerosol and Gas Experiment (SAGE) III Ozone Loss and Validation Experiment (SOLVE) campaign in the arctic winter of 2000. Measurements included chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), halon 1211, solvents, methyl chloride, N2O, and CH4. Inorganic chlorine contributions from each compound were calculated using the organic chlorine measurements, mean age of air, tropospheric trends, and a method to account for mixing in the stratosphere. Total organic …

Concerning The Stability Of Dichlorodiazene, Gregory S. Tschumper, Michael C. Heaven, Keiji Morokuma

Chemistry Faculty Research & Creative Works

The stability of N2Cl2 with respect to dissociation into N2 + 2Cl has been investigated using ab initio electronic structure techniques. Triple-ζ basis sets with d- and f-functions were required to obtain qualitative agreement between multi-reference and highly correlated single reference methods regarding the stability of the cis- and trans-isomers. The CCSD(T) method predicts a barrier to dissociation of 7-8 kcal mol-1 for the two isomers. CASPT2 barrier heights are substantially smaller (≤1.5 kcal mol^-1), indicating that these species are barely bound. © 2003 Elsevier Science B.V. All rights reserved.

Stress Corrosion Cracking Of Type 422 Stainless Steel For Applications In Spallation-Neutron-Target Systems, Ramprashad Prabhakaran

Transmutation Sciences Materials (TRP)

Introduction

• This research program is aimed at evaluating different types of environment-induced degradation of candidate target materials for applications in transmutation of spent nuclear fuels (SNF).

• Transmutation refers to the elimination of long-lived actinides and fission products from SNF.

Objectives

• Evaluate susceptibility of candidate target materials to stress corrosion cracking (SCC) and localized corrosion (pitting and crevice) in neutral and acidic aqueous environments at ambient and elevated temperatures

• Determine the extent and morphology of cracking in tested materials as functions of experimental and environmental variables including pH, temperature, loading conditions and specimen geometry

• Develop mechanistic …

Method Of Solubilizing Carbon Nanotubes In Organic Solutions, Robert C. Haddon, Mark A. Hamon

Chemistry Faculty Patents

Carbon nanotubes are dissolved in organic solutions by attaching an aliphatic carbon chain (which may contain aromatic residues) so as to render the carbon nanotubes soluble.

Evolution Of Gases And Particles From A Savanna Fire In South Africa, Peter V. Hobbs, Parikhit Sinha, Robert J. Yokelson, Ted J. Christian, Donald R. Blake, Song Gao, Thomas W. Kirschsetter, Tica Novakov, Peter Pilewskie

Chemistry and Biochemistry Faculty Publications

[1] Airborne measurements of particles and gases from a 1000-ha savanna fire in South Africa are presented. These measurements represent the most extensive data set reported on the aging of biomass smoke. The measurements include total concentrations of particles (CN), particle sizes, particulate organic carbon and black carbon, light-scattering coefficients, downwelling UV fluxes, and mixing ratios for 42 trace gases and 7 particulate species. The ratios of excess nitrate, ozone, and gaseous acetic acid to excess CO increased significantly as the smoke aged over ∼40–45 min, indicating that these species were formed by photochemistry in the plume. For 17 other …

Analysis Of Heme Structural Heterogeneity In Mycobacterium Tuberculosis Catalase-Peroxidase (Katg), Salem Chouchane, Stefania Girotto, Sofia Kapetanaki, Johannes Schelvis, Shengwei Yu, Richard S. Magliozzo

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Mycobacterium tuberculosis catalase-peroxidase (KatG) is a heme enzyme considered important for virulence, which is also responsible for activation of the anti-tuberculosis pro-drug isoniazid. Here, we present an analysis of heterogeneity in KatG heme structure using optical, resonance Raman, and EPR spectroscopy. Examination of ferric KatG under a variety of conditions, including enzyme in the presence of fluoride, chloride, or isoniazid, and at different stages during purification in different buffers allowed for assignment of spectral features to both five- and six-coordinate heme. Five-coordinate heme is suggested to be representative of "native" enzyme, since this species was predominant in the enzyme examined …

Magnetic And Mössbauer Spectral Study Of Erfe₁₁Ti And Erfe₁₁Tih, Cristina Piquer, Raphäel P. Hermann, Fernande Grandjean, Gary J. Long, Olivier Isnard

Chemistry Faculty Research & Creative Works

The influence of the insertion of hydrogen into the crystal lattice of ErFe₁₁Ti upon its spin reorientation was investigated. It was found that the insertion of hydrogen into ErFe₁₁Ti to form ErFe₁₁TiH expanded the lattice by 1% and increased the Curie temperature by 56 K. The presence of one titanium near neighbor in the environment of an iron site decreased the hyperfine field by ~2T and changed the isomer shift by ~0.05 mm/s.

Analysis Of Anion Distributions In The Developing Strata Of A Constructed Wetland Used For Chlorinated Ethene Remediation, Joshua D. Kovacic

Theses and Dissertations

Perchloroethene (PCE), Trichloroethene (TCE) and their degradation products are among the most common organic groundwater contaminants in the United States. Constructed wetlands utilizing upward flow harbor reduction-oxidation conditions that have demonstrated the potential to promote both partial and total mineralization of PCE and TCE through the process of natural attenuation. Organic acid and inorganic anion concentrations are indicative of reduction-oxidation processes that drive chlorinated ethene degradation. These analytes were investigated to assess their development within three vertically stratified regions of a constructed wetland cell at Wright-Patterson Air Force Base fed by groundwater contaminated with PCE and TCE. Data collected during …

Dynamics Of Adsorbed Poly(Methyl Acrylate) And Poly(Methyl Methacrylate) On Silica, Frank D. Blum, Wuu-Yung Lin, Crystal E. Porter

Chemistry Faculty Research & Creative Works

Deuterium NMR and modulated differential scanning calorimetry (MDSC) were used to probe the behavior of ultrathin adsorbed poly(methyl acrylate) (PMA). The spectra for the bulk methyl-labeled PMA-d3 were consistent with the motions of the polymer segments being spatially homogeneous. For the polymers adsorbed on silica, multicomponent line shapes were observed. The segmental mobility of the surface polymers increased with increased adsorbed amounts. In contrast to the behavior of the polymers in bulk, the adsorbed lower-molecular-mass PMA-d3 was less mobile than the adsorbed high-molecular-mass polymer. The presence of a polymer overlayer was sufficient to suppress the enhanced mobility of the more-mobile …

The Solvent Boundary Potential: A New Approach For Computer Simulation Of Large Systems, Valentin Gogonea

Chemistry Faculty Publications

The paper presents the theoretical framework for the development of a new solvent boundary method for computer simulations and its possible application to the simulation of nitric oxide synthase. Different approaches for the construction of a solvent boundary potential are reviewed and their strengths and weaknesses are discussed. A new solvent boundary potential is proposed which combines the mean field force approximation with the Green's function approach for treating long-range electrostatic interactions, and introduces a novel strategy to treat electrostriction effects due to ions crossing the solvent boundary. Finally, a series of computational tests are devised in order to assess …

Ab Initio Studies Of Quasi-One-Dimensional Pentagon And Hexagon Ice Nanotubes, Jaeil Bai, C.-R. Su, R. D. Parra, Xiao Cheng Zeng, H. Tanaka, K. Koga, J.-M. Li

Xiao Cheng Zeng Publications

Ab initio plane-wave total-energy calcuation is carried out to study the relative stability of the quasi-one-dimensional (Q1D) pentagon and hexagon ice nanotubes. Electronic structure calculations indicate the two Q1D ice nanotubes have nearly the same band structures and energy bandgap as those of proton-ordered bulk ice I_h . Ab initio molecular-orbital and density-functional theory calculations, as well as three classical potential models of water, are also employed to investigate the relative stability of the pentagon and hexagon water clusters (H₂O) ₃₀, (H₂O) ₆₀ , and (H₂O) ₁₂₀ . Clusters of this kind …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quarterly Report January-March 2003, Spencer M. Steinberg

Separations Campaign (TRP)

The recovery of iodine released during the processing of used nuclear fuel poses a significant challenge to the transmutation of radioactive iodine. This proposal will develop and examine the use of Fullerene Containing Carbon (FCC) compounds as potential sorbents for iodine release from the reprocessing of nuclear fuel. This work will also include the development of bench-scale testing capabilities at UNLV to allow the testing of the FCC material in a simulated process off-gas environment. This experimental capability will also be used to test other potential sorption materials and processes, such as natural organic matter (NOM) and other promising alternatives. …