Physical Sciences and Mathematics Commons^™

Development Of A Systems Engineering Model Of The Chemical Separations Process: Quarterly Progress Report 5/16/02- 8/15/02, Yitung Chen, Randy Clarksean, Darrell Pepper

Separations Campaign (TRP)

Two activities are proposed in this Phase I task: the development of systems engineering model and the refinement of the Argonne code AMUSE (Argonne Model for Universal Solvent Extraction). The detailed systems engineering model is the start of an integrated approach to the analysis of the materials separations associated with the AAA Program. A second portion of the project is to streamline and improve an integral part of the overall systems model, which is the software package AMUSE. AMUSE analyzes the UREX process and other related solvent extraction processes and defines many of the process streams that are integral to …

Polymer-Supported 14-Crown-4 And Bifunctional Resins For Selective Metal Ion Complexation: Synthesis And Characterization, Christy L. Stine

Doctoral Dissertations

Polymer-supported 14-crown-4 and bifunctional resins containing amine and phosphonate ester ligands were synthesized and characterized. Complexation studies were performed to evaluate the metal ion selectivity of the resins.

The immobilization of 14-crown-4 onto crosslinked polymer supports for the complexation of Li(l) from aqueous solutions was studied. M any methods were attempted, but etherification of the hydroxymethyl form of 14-crown-4 was found to be the most successful. The polymers examined were poly(vinylbenzyl chloride), poly(vinylbenzyl chloride)-co-acrylamide and poly(glycidyl methacrylate). The amount of Li(l) complexed by the crown ether supported polymers was affected by the polarity (i.e., hydrophilicity) of the polymer matrix. The …

Stabilization Of Rutile-Related Thin Film On Tio2 Substrates, Youngnam Cho

Electronic Theses and Dissertations

Conducting metal oxide thin films are of broad interest because they have a wide variety of magnetic and electronic properties. Materials exist that range from superconducting to insulating, are ferromagnetic and are ferroelectric. These properties make thin conducting oxide films attractive for many industrial applications. A class of metal oxides exists that adapt the rutile crystal structure; the structure of the mineral rutile, TiO₂. These metal oxides have the general formula MO₂ where M is a metal cation of valence +4. Metal oxides crystallizing in the rutile structure also display a wide variety of physical properties. The …

Studies Towards Anti-Bredt Ring Systems Of Natural Products, Ulf Peters

Masters Theses

Different ways for the synthesis of anti-Bredt ring systems of natural products have been explored.

An intended Favorskii rearrangement-divinylcyclopropane rearrangement to lead to the bicyclo[4.3.1] decadiene ring system was not accomplished. An envisioned tandem cyclopropanation-divinycyclopropane rearrangement of 2,3-divinyhex-2-enol did not furnish the desired bicyclo[4.4.1]undecadiene system, either, because cyclopropane occurred on the exocyclic double bond.

In the course of cyclopropanation studies on various cyclohexenols, an α-silyl-α-diazoethyl acetate was employed as tether. It could be removed by protodesilylation or oxidative cleavage to give a 1-(carboxylic ester)-cyclopropane or a 1-(carboxylic easter)-1-hydroxy cyclopropane derivative, respectively. Cyclopropanation general occurred on the less substituted more …

Simulation Of Structure, Dynamics And Electron Diffraction Patterns Of Heterogeneous Clusters Armn2N, W. H. Jinasena

Electronic Theses and Dissertations

The nitrogen-argon system provides a useful paradigm for studying segregation and mixing behavior in heterogeneous clusters. Using three realistic pair potentials corresponding to argon-argon, nitrogen-nitrogen and argon-nitrogen interactions, the structures and thermodynamics of Ar_m(N₂)_n, clusters are investigated. Comparison of these results to previous simulation results on neat argon and nitrogen clusters is made. The initial focus of the study is the series of thirteen particle clusters of Ar_m(N₂)_13-m (0 ≤ m ≤ 13); molecular dynamics in the microcanonical ensemble is the principle simulation tool. The icosahedral nitrogen-argon clusters …

Corrosion Of Steel By Lead Bismuth Eutectic: Quarterly Report For May-June-July 2002, John Farley

Transmutation Sciences Materials (TRP)

The goal of this project is to understand the basic science of corrosion in the steel/LBE system.

We are taking more data, typically using the newly installed X-ray Photoelectron Spectrometry (XPS) apparatus, and analyzing our existing data. Undergraduate students Denise Parsons and Julia Manzerova have helped a great deal in the analysis of the data. We can obtain the elemental composition as a function of position within the sample. This gives clues to the migration of materials, the composition of the protective oxide layer, and the basic science of the corrosion process. We found dramatic differences between the exposed and …

The Use Of Native And Modified Cyclodextrins For Method Development In Capillary Electrophoresis And Chemical Sensor Applications, Mustafa Culha

Doctoral Dissertations

The development and design of novel methods and materials for separation and sensing systems have critical importance for the analysis of complex mixtures. In these systems, molecular recognition is the key element for desired selectivity and it can only be achieved using rationally designed, chemically selective reagents. Cyclodextrins (CDs) are a group of macro-cyclic molecules that can recognize certain analytes depending on their shape and size. In this work, the primary goal was the design and development of CD-based separation and sensing systems. Native and derivatized CDs were utilized to develop methods for separation of a complex mixture containing six …

Metal Ion Separation Mediated By Organized Molecular Assemblies, Hong Cao

Masters Theses

We have investigated the separation of Co(II), Ni(II), Cu(II) and Zn(II) by the ligands 8-hydroxyquinoline- 5-sulfonic acid and 7-iodo-8-hydroxy-quinoline- 5-sulfonic acid in the presence of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant octyltrimethylammonium bromide (OTAB) . Baseline separations have been achieved by HPLC employing an octadecylsilanized silica (ODS) column. The underlying mechanisms of separation have been determined.

The significant new results of our studies are: (1) separation is not possible without the presence of surfactants and hence organized assemblies; (2) separations can be achieved under submicellar concentrations; (3) the separations are not driven by micelles; and …

The Biophysical Basis Of Triplet Repeat Dna Expansion In Genetic Disease, Anthony M. Paiva

Seton Hall University Dissertations and Theses (ETDs)

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The 1.20 Å Resolution Crystal Structure Of The Aminopeptidase From Aeromonas Proteolytica Complexed With Tris: A Tale Of Buffer Inhibition, William Desmarais, David L. Bienvenue, Krzysztof P. Bzymek, Richard C. Holz, Gregory A. Petsko, Dagmar Ringe

Chemistry Faculty Research and Publications

The aminopeptidase from Aeromonas proteolytica (AAP) is a bridged bimetallic enzyme that removes the N-terminal amino acid from a peptide chain. To fully understand the metal roles in the reaction pathway of AAP we have solved the 1.20 Å resolution crystal structure of native AAP (PDB ID = 1LOK). The high-quality electron density maps showed a single Tris molecule chelated to the active site Zn²⁺, alternate side chain conformations for some side chains, a sodium ion that mediates a crystal contact, a surface thiocyanate ion, and several potential hydrogen atoms. In addition, the high precision of the atomic …

The Enthalpy Of Vaporization And Sublimation Of Corannulene, Coronene, And Perylene At T = 298.15 K, James S. Chickos, Paul Webb, Gary Nichols, Tetsu Kiyobayashi, Pei-Chao Cheng, Lawrence Scott

James Chickos

No abstract provided.

Determination Of Barbituric Acid, Utilizing A Rapid And Simple Colorimetric Assay, Ronald Bartzatt

Chemistry Faculty Publications

Barbituric acid is widely used in the manufacturing of plastics, textiles, polymers, and pharmaceuticals. Three assay methods are presented, which can utilize either aqueous or solid samples. The detection of as little as 10 μg of barbituric acid can be accomplished, either as an aqueous or solid sample, when using micro reaction tubes. The red–violet endpoint is easily discerned and results upon the formation of a violuric acid derivative. A Spot Test protocol is described which allows for a positive/negative indication of barbituric acid presence. The Spot Test is sensitive to as little as 18.75 μg/ml of barbituric acid. The …

44th Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 44th annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-endorsed by the Colorado Section of the American Chemical Society and the Society for Applied Spectroscopy. Held in Denver, Colorado, July 28 - August 1, 2002.

Characterization And Interactions Of Mercury, Dissolved Organic Matter And Organic Sulfur In Surface Waters Of The Florida Everglades, Maria Asuncion Calero Sheils

FIU Electronic Theses and Dissertations

Two sampling stations in the Florida Everglades were selected based on the results from US Environmental Protection Agency and Florida International University Mercury Project. In both sites, most of the methylmercury is associated with the truly dissolved organic matter fraction (

A Model For Mechanochemical Transformations: Applications To Molecular Hardness, Instabilities, And Shock Initiation Of Reaction, Tadeusz Luty, Piotr Ordon, Craig J. Eckhardt

Craig J. Eckhardt Publications

A basic theoretical structure for mechanochemical transformations based on prior models for solid-state reactions and HOMO–LUMO (highest occupied molecular orbital–lowest unoccupied molecular orbital) gap closing produces the concept of distortion-induced molecular electronic degeneracy (DIMED) of the highest occupied and lowest unoccupied molecular orbitals of an energetic molecule. Both intermolecular and intramolecular charge transfer are involved. The resulting distortion-induced local instability, a mechanochemical effect, leads to chemical transformations and can be analyzed by renormalization of the molecular hardness through the molecular deformation energy. Linear combinations of normal modes are shown to be useful for description of the mechanically induced reaction path. …

Heterogeneous Nucleation On Mesoscopic Wettable Particles: A Hybrid Thermodynamic/Density-Functional Theory, T.V. Bykov, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

A hybrid thermodynamic and density-functional theory for heterogeneous nucleation on mesoscopic wettable particles is developed. The nonlocal density-functional theory (DFT) is on basis of the weighted-density approximation (WDA) of Tarazona. The model system consists of a Lennard-Jones (LJ) fluid and a 9–3 LJ wall for the solid particle. Effects of the droplet curvature and compressibility are accounted for in the theory. A by-product of this work is the calculation of the Tolman length using the WDA-DFT (Appendix A). Important characteristics of the heterogeneous nucleation, including the chemical potential of the liquid condensate, the free energy of droplet formation, and the …

A New Accelerator Mass Spectrometry System For 14c-Quantification Of Biochemical Samples, Ted J. Ognibene, Graham Bench, Tom A. Brown, Graham F. Peaslee, John S. Vogel

Faculty Publications

A compact accelerator mass spectrometry (AMS) system that meets our requirements for View the MathML source-quantification of biochemical samples is described. The spectrometer occupies approximately 5 m2 of floor space and can measure >300 samples per day with 3% precision. A long diffuse gas cell is used to destroy interfering molecules and to charge exchange injected negative ions. System sensitivity is <1 amol View the MathML source/mg carbon on milligram-sized samples with a dynamic range that extends over 4 orders magnitude. All components, with the exception of the ion source, are commercially available and the system operates reliably with low maintenance.

Non-Dipolar Electron Angular Distributions From Fixed-In-Space Molecules, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, E. Shigemasa, K. Le Guen, D. Ceolin, C. Miron, N. Leclercq, P. Morin, Marc Simon, P. W. Langhoff

Environmental Studies Faculty Publications

The first indication of nondipole effects in the azimuthal dependence of photoelectron angular distributions emitted from fixed-in-space molecules is demonstrated in N₂. Comparison of the results with angular distributions observed for randomly oriented molecules and theoretical derivations for the nondipole correction first order in photon momentum suggests that higher orders will be needed to describe distributions measured in the molecular frame.

Synthetic Studies Directed Toward The Phorboxazoles: Preparation Of The C3–C15 Bisoxane Segment And Two Stereoisomers, Patrick Bernard Greer, William Donaldson

Chemistry Faculty Research and Publications

A synthetic approach to the C3–C15 segment of the cytotoxic marine metabolite phorboxazoles is described. This segment consists of a methylene linked bisoxane structure. The first pyran ring was constructed by a Lewis acid catalyzed diene–aldehyde cyclocondensation. The β-C-glucoside substitution pattern of this ring was established by a stereoselective allylation. Ozonolysis of vinyl group and enantioselective allylation of the racemic aldehyde generated two separable homoallylic alcohols (−)-22 and (+)-23. The Mosher's esters of each alcohol were determined to be >90% de. Reaction of (−)-22 with acryloyl chloride, followed by ring closing metathesis gave the …

In-Situ X-Ray-Absorption Spectroscopy Study Of Hydrogen Absorption By Nickel-Magnesium Thin Films, B. Farangis, Ponnusamy Nachimuthu, T. J. Richardson, J. L. Slack, Rupert C. Perera, Eric M. Gullikson, Dennis W. Lindle, M. Rubin

Chemistry and Biochemistry Faculty Research

Structural and electronic properties of co-sputtered Ni-Mg thin films with varying Ni to Mg ratio were studied by in-situ x-ray absorption spectroscopy in the Ni L-edge and Mg K-edge regions. Co-deposition of the metals led to increased disorder and decreased coordination around Ni and Mg compared to pure metal films. Exposure of the metallic films to hydrogen resulted in formation of hydrides and increased disorder. The presence of hydrogen as a near neighbor around Mg caused a drastic reduction in the intensities of multiple scattering resonances at higher energies. The optical switching behavior and changes in the x-ray spectra varied …

Preprogramming Of Porphyrin-Nucleic Acid Assemblies Via Variation Of The Alkyl/Aryl Substituents Of Phosphonium Tetratolylporphyrins, Pavel Kubat, Kamil Lang, Vladimir Kral, Pavel Anzenbacher Jr.

Chemistry Faculty Publications

Cationic alkyl/arylphosphonium meso-tetratolylporphyrins aggregate in an aqueous solution to form H-aggregates, J-aggregates, and long-range assemblies. The ratio between the monomer and various types of aggregates can be controlled by the substitution in the phosphonium units and by the ionic strength. A trimethylphosphonium derivative is predominantly monomeric, dimethylphenylphosphonium forms monomers as well as low-molecular-weight H- and J-aggregates, triphenylphosphonium forms mainly H- and J-aggregates, and tri(n-butyl)phosphonium forms mainly long-range assemblies. Porphyrin monomers associate with calf thymus DNA (binding constant Kb approximate to 10(7) M-1) and oligonucleotides (K-b approximate to 10(5-)10(6) M-1). The large size of the meso-substituents prevents the intercalation between base …

Electron Hopping Conductivity And Vapor Sensing Properties Of Flexible Network Polymer Films Of Metal Nanoparticles, Francis P. Zamborini, Michael C. Leopold, Jocelyn F. Hicks, Pawel J. Kulesza, Marcin A. Malik, Royce W. Murray

Chemistry Faculty Publications

Films of monolayer protected Au clusters (MPCs) with mixed alkanethiolate and ω-carboxylate alkanethiolate monolayers, linked together in a network polymer by carboxylate-Cu2+-carboxylate bridges, exhibit electronic conductivities (σEL) that vary with both the numbers of methylene segments in the ligands and the bathing medium (N2, liquid or vapor). A chainlength-dependent swelling/contraction of the film's internal structure is shown to account for changes in σEL. The linker chains appear to have sufficient flexibility to collapse and fold with varied degrees of film swelling or dryness. Conductivity is most influenced (exponentially dependent) by the chainlength of the nonlinker (alkanethiolate) ligands, a result consistent …

Synthesis Of The Abc Ring System Of Azaspiracid. 2. A Systematic Study Into The Effect Of C16 And C17 Substitution On Bis-Spirocyclization, Rich G. Carter, David E. Graves, Melissa A. Gronemeyer, Gregory S. Tschumper

Chemistry Faculty Research & Creative Works

(matrix presented) A systematic study into the effect of C16 and C17 substitution on the stereochemical outcome of bis-Spiro cyclization to form the ABC ring system of azaspiracid is disclosed. Successful construction of the natural 10R,13R bis-spirocyclic stereochemistry has been accomplished on the C16 benzyloxy-containing precursor.

Hydrogen-Induced Embrittlement Of Candidate Target Materials For Applications In Spallation-Neutron-Target Systems: Annual Progress Report (May 2001 – May 2002), Ajit K. Roy, Brendan O'Toole

Transmutation Sciences Materials (TRP)

The primary objective of this task is to evaluate the effect of hydrogen on environment-assisted cracking of candidate target materials for applications in spallation-neutron-target (SNT) systems such as accelerator production of tritium (APT) and accelerator transmutation of waste (ATW). The materials selected for evaluation and characterization are martensitic stainless steels including Alloy HT-9, Alloy EP 823 and Type 422 stainless steel. The susceptibility to stress corrosion cracking (SCC) and hydrogen embrittlement (HE) of these materials are being evaluated in environments of interest using tensile specimens under constant load and slow-strain-rate (SSR) conditions. Further, the localized corrosion behavior of these alloys …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics: Quarterly Progress Report 03/16/02- 06/15/02, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The Lead-Bismuth eutectic (LBE) has been determined from previous experimental studies by the Russians and the European scientific community to be a potential material that can be used as a spallation target and coolant for the AAA proposed application. Properly controlling the oxygen content in LBE can drastically reduce the LBE corrosion to structural steels. However, existing knowledge of material corrosion performance was obtained from point-wise testing with very limited density. Scientists have noticed that the concentration of oxygen dissolved in the liquid alloy could control the corrosion rate of steels exposed to Pb or Pb-Bi. At high oxygen concentration, …

Evaluation Of Fluorapatite As A Waste-Form Material, Dennis W. Lindle, Dale L. Perry

Separations Campaign (TRP)

Fluorapatite, fluorinated calcium phosphate, has been identified as a potential matrix for the entombment of the zirconium fluoride fission product waste stream from the proposed FLEX process. If the efficacy of fluorapatite based waste-storage can be demonstrated, then new and potentially more-efficient options for handling and separating high-level wastes, based on fluoride-salt extraction, will become feasible. This proposal will develop a dual-path research project to develop a process to fabricate a synthetic fluorapatite waste form for the ZrF₄, FP waste stream, characterize the waste form, examine its performance under environmental conditions, and correlate the behavior of the waste …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix, 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 sorbtion materials and processes, such as natural organic matter (NOM) and other promising alternatives. …

Organic Geochemical Analysis Of Late-Glacial And Early-Holocene Ecosystem Changes: A Case Study From Northern New England Lakes, Michael A. Kruge, Andrea Lini

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The lacustrine sedimentary archive of organic remains provides important evidence for the reconstruction of the environmental histories of lakes and their watersheds, recording the response of the Earth's biota to changes on scales varying from the local to the global. The last Glacial-Interglacial transition presents an opportunity to investigate how, and at what rates, watershed and lake ecosystems were established on once glaciated, carbon and nutrient-poor landscapes. The small lakes of northern Vermont (USA) provide an appropriate setting in which to investigate such changes.

As part of a multidisciplinary study of three Vermont lake sediment cores, samples ranging in age …

Weinreb Amides : Novel Titanium Enolate Reagents, Andrew J. Leyhane

Honors Theses

The amides of N-methoxy-N-methylamine or "Weinreb amide" have earned an important role in synthetic chemistry as both a protective group and as synthetic intermediates. We have discovered that the Weinreb amide of acetic acid, N-methoxy-N-methylacetamide adds to aldehydes to afford classic aldol products in good to excellent yields. The scope of this novel aldol reaction will be discussed.

Inclusion Chemistry Of Neutral Nonlinear Optical Dyes Within Organically Modified Silicates, Ian Saratovsky

Honors Theses

The field of photonics involves the use of light to acquire, store, process, and transmit information. Nonlinear optical (NLO) materials are crucial for success in the advancement of photonic devices. Laponite and hectorite host assemblies have been shown previously by our group to induce I -aggregation of nonlinear optical (NLO) dyes and offer facile routes to film fabrication. Head-to-tail alignment (J-aggregation) of the NLO chromophores is a required condition for photonic applications. In this study, tetrabutylammonium, triethylhexylammonium, trimethyldodecylammonium, and trimetylcetylarunonium surfactants were utilized to render the smectic intergallery region organophilic thus facilitating chromophore intercalation and an increased J-aggregated dye fraction. …