Chemistry Commons^™

How Does Water Freeze Inside Carbon Nanotubes?, Kenichiro Koga, G.T. Gao, Hideki Tanaka, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Phase behavior of quasi-one-dimensional water confined inside a carbon nanotube is studied in the thermodynamic space of temperature, pressure, and diameter of the cylindrical container. Four kinds of solid-like ordered structures—ice nanotubes—form spontaneously from liquid-like disordered phases at low temperatures. In the model system that comprises of TIP4P water molecules interacting with each other via short-range Lennard–Jones and long-range Coulomb site–site potentials under a periodic boundary condition in the axial direction, the phase change occurs either discontinuously or continuously depending on the path in the thermodynamic space. That the isotherms for a given diameter are found to be similar to …

Strontium Isotopic Signatures Of The Streams And Lakes Of Taylor Valley, Southern Victoria Land, Antarctica: Chemical Weathering In A Polar Climate, W. B. Lyons, Carmen A. Nezat, Larry V. Benson, Thomas D. Bullen, Elizabeth Y. Graham, Jesicca Kidd, Kathleen A. Welch, James M. Thomas

United States Geological Survey: Staff Publications

We have collected and analyzed a series of water samples from three closed-basin lakes (Lakes Bonney, Fryxell, and Hoare) in Taylor Valley, Antarctica, and the streams that flow into them. In all three lakes, the hypolimnetic waters have different ⁸⁷Sr/⁸⁶Sr ratios than the surface waters, with the deep water of Lakes Fryxell and Hoare being less radiogenic than the surface waters. The opposite occurs in Lake Bonney. The Lake Fryxell isotopic ratios are lower than modern-day ocean water and most of the whole-rock ratios of the surrounding geologic materials. A conceivable source of Sr to the system …

University Of Nevada, Las Vegas Transmutation Research Program Annual Report 2001, Anthony Hechanova, Elizabeth Johnson, Gary Cerefice

Transmutation Research Program Reports (TRP)

The UNLV Transmutation Research Program was established in March 2001 as part of the national Advanced Accelerator Applications program to develop the technologies necessary for the ecological and economical treatment of spent nuclear fuel.

The primary role of the UNLV program in the national effort is the training of graduate and undergraduate students in nuclear engineering and other related fields to support the augmentation of the U.S. human infrastructure for transmutation technologies.

To accomplish this role, UNLV has developed the TRP with the primary focus of supporting student research into transmutation and supporting technologies. This focus is realized through the …

Experimental Investigation Of Steel Corrosion In Lead Bismuth Eutectic (Lbe): Characterization, Species Identification, And Chemical Reactions, John Farley, Dale L. Perry, Allen L. Johnson

Transmutation Sciences Materials (TRP)

The goal of the present research is to achieve a basic understanding of corrosion of steels by Lead Bismuth Eutectic (LBE). Liquid LBE is under consideration in the transmuter as both a spallation target and as a blanket coolant. There have been previous studies of LBE, especially by the Russians, who have over 80 reactor-years experience with LBE coolant in their Alpha-class submarine reactors. However, a fundamental understanding and verification of its role in the corrosion of steels is still very incomplete. We have begun a program of post-experiment testing and analysis on steel samples that have been in intimate …

Corrosion Of Steel By Lead Bismuth Eutectic, John Farley, Dale L. Perry, Allen L. Johnson

Transmutation Sciences Materials (TRP)

This research program will analyze various steel samples that have been exposed to LBE as part of the national program to develop LBE and transmutation technologies. This information will be paramount in developing engineering efforts to control, avoid, and/or minimize the effect of corrosion of steels by LBE in transmuter and LBE systems. Additionally, this program provides UNLV researchers with hands-on experience that will be crucial in developing the UNLV LBE program, supporting the University’s mission with the ISTC target complex, and the future development of additional facilities to examine LBE systems.

The research group plans to test the hypothesis …

Corrosion Of Steel By Lead Bismuth Eutectic: Year 1 Annual Report, John Farley

Transmutation Sciences Materials (TRP)

The goal is to investigate the corrosion of stainless steel by lead-bismuth eutectic (LBE), which has been proposed for use as a blanket coolant and a spallation target in the transmuter.

Hydrogen-Induced Embrittlement Of Candidate Target Materials For Applications In Spallation-Neutron-Target Systems, Ajit K. Roy, Brendan O'Toole, Zhiyong Wang, David W. Hatchett

Transmutation Sciences Materials (TRP)

Spallation-neutron-sources, such as those under investigation for use in accelerator-driven transmutation systems, generate neutrons through the collision of high-energy protons, or charged hydrogen atoms, with heavy metal targets such as lead. As a result, these systems also tend to deposit a significant amount of hydrogen in the materials of the transmuter target and superstructure. This can result in accelerated corrosion and changes in the properties of the exposed materials. Of particular importance is a phenomenon called hydrogen embrittlement, in which materials lose their ductility (ability to deform under stress) and become brittle (more susceptible to fracture) after reacting with hydrogen. …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics: Task V 4th Quarterly Report, Samir Moujaes

Transmutation Sciences Materials (TRP)

The project is moving on target with the newly realigned objective set for the Phase I. Through close communications with Dr. Li and Dr. Jinsuo Zhang from LANL a realignment of the simulation work has been recommended. The reason for that is the vendor of STAR-CD/CHEMKIN had not perfected yet the final coupling of the post processing of output for any potential surface chemistry reaction taking place on the inside pipe surface of the LBE loop. This is because the coupling of CHEMKIN and STAR-CD has been done fairly recently.

Our final effort has been to generate using an innovative …

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

Many of the international efforts to develop transmutation technology, including the U.S., Russian, and European scientific communities, have determined that lead bismuth eutectic (LBE) is a potential material for use as a both a spallation target and a coolant. To exploit this potential, a more thorough understanding of the effect and rates of corrosion on steels, particularly non-Russian alloys, inside the LBE systems is required. Properly controlling the oxygen content in LBE systems has been observed to drastically reduce the corrosion of structural steels in LBE. However, the transport of oxygen and formation of corrosion products is not well understood; …

Development Of Dose Conversion Coefficients For Radionuclides Produced In Spallation Neutron Sources, Phillip W. Patton, Mark Rudin

Transmutation Sciences Physics (TRP)

For the first year of this effort, the UNLV research team set out four objectives. First, the university and laboratory consortium had to be established. This consortium was tasked with helping to determine the methodology for determining the dose coefficients, and to ensure that the resulting DCs will be of use to the national programs developing accelerator-driven nuclear systems (such as the SNS or an accelerator-driven transmutation system) and to the health physics community as a whole. The second goal of this program was to determine a methodology and then prioritize the radionuclides so that the research effort would address …

Development Of Dose Coefficients For Radionulides Produced In Spallation Neutron Sources: Annual Report, Phillip W. Patton, Mark Rudin

Transmutation Sciences Physics (TRP)

The University of Nevada, Las Vegas (UNLV) Transmutation Research Program has been tasked to support U.S. Department of Energy (DOE) efforts to assess the health risks associated with the operation of each of their accelerator-driven nuclear facilities for both NEPA and PSAR development. Quantifying the radiological risks to workers will have to be addressed during the design and siting of each of these facilities. U.S. Environmental Protection Agency (EPA) Federal Guidance Report No. 11 “Limiting Values of Intake and Air Concentration and Dose Conversion Factors for Inhalation, Submersion, and Ingestion”, developed two derived guides, Annual Limit on Intake (ALI) and …

Nuclear Criticality, Shielding, And Thermal Analyses Of Separations Processes For The Transmutation Fuel Cycle, William Culbreth, Denis Beller

Separations Campaign (TRP)

The remediation of nuclear waste created by conventional fission reactors will rely upon the separation of the waste products for further treatment. The UREX+ process now under review will involve the use of an aqueous chemical process to separate out depleted uranium resulting in a product containing minor actinides, fission products, cesium, strontium, technetium, and iodine. The radioactive decay of strontium and cesium produces roughly half of the thermal and gamma production in spent fuel and the relatively short halflife of isotopes of both of these elements requires storage for about 300 years before heat and radiation decreases to safe …

Nuclear Criticality Analyses Of Separations Processes For The Transmutation Fuel Cycle, William Culbreth, Pang Tao, Denis Beller

Separations Campaign (TRP)

The separation and partitioning of used commercial reactor fuel is a vital component of any reprocessing or transmutation strategy. To process the high actinide fuels required for a transmutation effort, the Chemical Technology Division (CMT) at Argonne National Laboratory (ANL) is developing a pyrochemical separations process. Currently, this work is being done via small experiments. While this is more than sufficient to develop the technologies required to process actinide-bearing fuels, it does not allow for the direct investigation of criticality concerns that would be present in larger systems. As the volume of waste to be treated increases, a higher probability …

Photochemical Generation And Chemistry Of Α-Acetoxycarbene, Jonathan Mann

Honors Theses

Efforts have been made at generating the parent α-acetoxycarbene from a non-nitrogenous precursor. Baeyer-Villiger oxidation of the ketone, 1-(1a,9b-dihydro-lHcyclopropa[1] phenanthren-1-yl)-ethanone, available in two steps from phenanthrene, led to the ester, 1-(1 a,9b-dihydro-lH-cyclopropa[/]phenanthren-l-yl)-acetate, which is a photochemical precursor of the parent α-acetoxycarbene intermediate. Photolysis of the ester in cyclohexene afforded an isomeric mixture of endo and exo acetates resulting from the carbene adding to the α-bond. Photolysis of the ester in trans-3-hexene yielded a single trans-cis acetate, a product of the same cycloaddition process. The formation of methyl glyoxal, via the l,2-acyl shift of the carbene, is observed through its derivatives. …

Investigations Of Intramolecular Copper (I)-Arene Interactions Using A Ns2-Macrocyclic Ligand With Different Pendant Aryl Arms, Paul J. Lee

Honors Theses

Two macrocyclic ligands with a pendant phenyl group -N-[2-(l-phenyl)ethyl]-1-aza-4,8di thiacyclodecane (L1) and N-[2-0-phenyl)propyl]-1-aza-4,8-dithiacyclodecane, (L2) has been synthesized and characterized. The copper(I)-triphenylphosphine complex [LICu(PPhJ)]OTf , (2) was synthesized from L1 1/2(C6H6)[CuOTf]2, and PPh3. The complexes [LICu]OTf 1 and [L2Cu]OTf 3 were also synthesized and characterized using DC and IH NMR, UV-vis and lR spectroscopy, and ESI-MS. In CD2Cl2, 1 was found to have a fluxional behavior with the barrier ΔG to the process estimated at 9-11 kcal/mol. Variable temp. NMR spectroscopy of 1 gave compelling evidence that the phenylappended group is bound in an intramolecullar η2-fashion with the copper center. At …

Temperature And Pressure Dependence Of Excitation Spectra As A Probe Of The Solution Structure And Equilibrium Thermodynamics Of A Eu(Iii) Complex Containing A Modified Dota Ligand, Gilles Muller, S. D. Kean, D. Parker, J. P. Riehl

Faculty Publications, Chemistry

No abstract provided.

Precursors For Copper Chemical Vapor Deposition, Muna Bufaroosha

LSU Doctoral Dissertations

The main objective of this study was to synthesize precursors that are capable of producing copper films of high quality by chemical vapor deposition (CVD). We investigated some copper(I) and copper(II) complexes as precursors for chemical or photochemical vapor deposition. In chapter 2, we synthesized a series of Cu(hfac)₂(amine) adducts, where hfac^- is hexafluoroacetylacetonate and the amines are: dimethylamine, isopropylamine, allylamine, pyrrolidine, and piperidine. The efficiency of these adducts compared to Cu(hfac)₂(H₂O) as Cu-CVD precursors was examined under hydrogen. We found that among these amine adducts, Cu(hfac)₂(allylamine)₂ gave the best …

Mode Specific Photoionization Dynamics In Polyatomic Molecules, Gerald Jeffery Rathbone

LSU Doctoral Dissertations

The work presented in this dissertation presents new work on polyatomic photoionization. In these investigations, the broad range behavior of both allowed and forbidden vibrational modes in linear triatomic systems were studied to understand mode specific aspects of photoionization. The current study is made possible by the experimental strategy of exploiting high resolution photoelectron spectroscopy and the high brightness of third generation synchrotron radiation sources. The data is taken typically tens of eV’s past the ionization potential. The strategy that I employ is to probe alternative vibrational modes which are frequently affected differently following resonant ionization. Such vibrationally resolved data …

Capillary And Microdevice Electrophoretic Tools For Genetic Analyses: Heteroduplex Analysis For Tuberculosis Drug Susceptibility And Ligase Detection Reaction For Colorectal Cancer Detection, Gloria Thomas

LSU Doctoral Dissertations

The traditional format of electrophoresis, the slab gel, is quickly being replaced by capillary and microdevice platforms, which offer improvements in cost, resolution, speed, quantitation and automation in genetic analyses. These techniques also employ a variety of separation matrices while the slab gel is limited to agarose and polyacrylamide. The research presented here explores the use of these electrophoretic formats for the detection of single nucleotide mutations using two genetic models associated with human disease. Slab gel based heteroduplex analysis (HDA), a popular mutation scanning method, uses a specially designed universal heteroduplex generator (UHG) containing controlled variation to enhance the …

Molecular Structures Of The Metastable Charge-Transfer Complexes Of Benzene (And Toluene) With Bromine As The Pre-Reactive Intermediates In Electrophilic Aromatic Bromination, Alexandr V. Vasilyev, Sergey V. Lindeman, Jay K. Kochi

Chemistry Faculty Research and Publications

Successful crystallization and X-ray crystallographic analyses of the highly metastable (1∶1) complexes of bromine with benzene and toluene establish the unique (localized) structure B that differs in notable ways from the long-accepted (delocalized) structure A. Furthermore, we demonstrate the (highly structured) charge-transfer complexes [C₆H₆,Br₂] and [CH₃C₆H₅,Br₂] to be the pre-reactive intermediates that are converted (via an overall Br⁺ transfer) to the Wheland intermediates in electrophilic aromatic bromination. The role of the dative ion pairs [C₆H₆˙⁺ Br₂˙ …

Overexpression And Divalent Metal Binding Properties Of The Methionyl Aminopeptidase From Pyrococcus Furiosus, Lu Meng, Shane Ruebush, Ventris M. D'Souza, Alicja J. Copik, Susumu Tsunasawa, Richard C. Holz

Chemistry Faculty Research and Publications

The gene encoding for the methionyl aminopeptidase from the hyperthermophilic archaeon Pyrococcus furiosus (PfMetAP-II; EC 3.4.11.18) has been inserted into a pET 27b(+) vector and overexpressed in Escherichia coli. The new expression system resulted in a 5-fold increase in purified enzyme obtained from a 5 L fermentor growth. The as-purified PfMetAP-II enzyme, to which no exogenous metal ions or EDTA was added, was found to have 1.2 equiv of zinc and 0.1 equiv of iron present by ICP-AES analysis. This enzyme had a specific activity of 5 units/mg, a 60-fold decrease from the fully loaded Fe(II) …

Silicon-Methoxide-Modified Clays And Their Polystyrene Nanocomposites, Jin Zhu, Paul Start, Kenneth A. Mauritz, Charles A. Wilkie

Chemistry Faculty Research and Publications

Silicon-methoxide-containing modified clays were obtained through cationic exchange between the sodium clay and the ammoniumcation of [3-(trimethoxysilyl) propyl]octadecyldimethylammoniumchloride (Si18). The nanocomposites were prepared through bulk polymerization of styrene in which the Si18 clay was dispersed. The silicon-methoxide offers the possibility of reaction between the methoxide and a clay hydroxyl group to link together the cation and the clay. The nanocomposites were characterized by X-ray diffraction, transmission electron microscopy, and atomic force microscopy. Their thermal stability and flame retardancy were measured by thermogravimetric analysis (TGA) and cone calorimetry. Linkage between the silicon and the clay apparently occurs in the clay but …

Fire Retardant Halogen-Antimony-Clay Synergism In Polypropylene Layered Silicate Nanocomposites, Marco Zanetti, Giovanni Camino, Domenico Canavese, Alexander B. Morgan, Frank K. Lamelas, Charles A. Wilkie

Chemistry Faculty Research and Publications

Nanocomposites of polypropylene-graft-maleic anhydride with organically modified clays have been prepared and characterized by X-ray diffraction and transmission electron microscopy. Their combustion behavior has been evaluated using oxygen consumption cone calorimetry. Synergy is observed between the nanocomposite formed and conventional vapor phase fire retardants, such as the combination of decabromodiphenyloxide and antimony oxide. The presence of bromine and antimony does not affect the heat release rate curves of the virgin polymer.

A Comparison Of Various Methods For The Preparation Of Polystyrene And Poly(Methyl Methacrylate) Nanocomposites, Dongyan Wang, Jin Zhu, Qiang Yao, Charles A. Wilkie

Chemistry Faculty Research and Publications

Polymer−clay nanocomposites of styrene and methyl methacrylate have been prepared by bulk, solution, suspension, and emulsion polymerization as well as by melt blending. Two different organic modifications of montmorillonite have been used:  one contains a styryl monomer on the ammonium ion while the other has no double bond. The organic modification as well as the mode of preparation determines if the material will be exfoliated or intercalated. Exfoliation is more likely to occur if the ammonium ion contains a double bond which can participate in the polymerization reaction, but the mere presence of this double bond is not sufficient to …

Preparation Of Pvc- Clay Nanocomposites By Solution Blending, Dongyan Wang, Charles A. Wilkie

Chemistry Faculty Research and Publications

PVC-clay nanocomposites have been prepared by solution blending of the polymer with both sodium montmorillonite and an organically modified clay. The nanocomposites have been characterized by X-ray diffraction and transmission electron microscopy; in all cases the materials are best described as mixed immiscible—intercalated nanocomposites, Thermogravimetric analysis shows that, in some cases, the onset temperature of the degradation is enhanced, and the fraction of nonvolatile residue is always decreased. This decrease in the amount of char indicates a significant change in the degradation pathway of the polymer, caused by the presence of the clay. For some preparations, the tensile strength and …

Three-Dimensional Structure Of The Complexin/Snare Complex, Xiaocheng Chen, Diana R. Tomchick, Evgenii L. Kovrigin, Demet Araç, Mischa Machius, Thomas C. Südhof, Josep Rizo

Chemistry Faculty Research and Publications

During neurotransmitter release, the neuronal SNARE proteins synaptobrevin/VAMP, syntaxin, and SNAP-25 form a four-helix bundle, the SNARE complex, that pulls the synaptic vesicle and plasma membranes together possibly causing membrane fusion. Complexin binds tightly to the SNARE complex and is essential for efficient Ca²⁺-evoked neurotransmitter release. A combined X-ray and TROSY-based NMR study now reveals the atomic structure of the complexin/SNARE complex. Complexin binds in an antiparallel α-helical conformation to the groove between the synaptobrevin and syntaxin helices. This interaction stabilizes the interface between these two helices, which bears the repulsive forces between the apposed membranes. These results …

Hydrolysis Of Thionopeptides By The Aminopeptidase From Aeromonas Proteolytica:  Insight Into Substrate Binding, David L. Bienvenue, Danuta M. Gilner, Richard C. Holz

Chemistry Faculty Research and Publications

A series of l-leucine aniline analogues were synthesized that contained either a carbonyl or thiocarbonyl as a part of the amide bond. Additionally, the para-position on the phenyl ring of several substrates was altered with various electron-withdrawing or donating groups. The kinetic constants K_m and k_cat were determined for the hydrolysis of each of these compounds in the presence of the aminopeptidase from Aeromonas proteolytica (AAP) containing either Zn(II) or Cd(II). The dizinc(II) form of AAP ([ZnZn(AAP)]) was able to cleave both carbonyl and thiocarbonyl containing peptide substrates with similar efficiency. However, the dicadmium(II) form of AAP …

Steric Hindrance As A Mechanistic Probe For Olefin Reactivity:  Variability Of The Hydrogenic Canopy Over The Isomeric Adamantylideneadamantane/Sesquihomoadamantene Pair (A Combined Experimental And Theoretical Study), Rajendra Rathore, Sergey V. Lindeman, C.-J. Zhu, T. Mori, R. Schleyer, Jay K. Kochi

Chemistry Faculty Research and Publications

Access to each CC face of adamantylideneadamantane (AA) and sesquihomoadamantene (SA) is hindered by the hydrogenic canopy consisting of four β-hydrogens; otherwise, these olefins have quite normal environments. X-ray crystallography and density functional (DFT) calculations show a 0.5 Å larger annular opening in the protective cover of AA than that in SA. This contributes to the remarkable differences in reactivity toward various reagents, not only by limiting access to the olefin site in SA but also by inhibiting reactions which force these hydrogens closer together. Thus, AA is subject to typical olefin-addition reactions with bromine, …

Novel Bis-Arene (Sandwich) Complexes With No+ Acceptor. Isolation, X-Ray Crystallography And Electronic Structure, Sergiy V. Rosokha, Sergey V. Lindeman, Jay K. Kochi

Chemistry Faculty Research and Publications

The unusual charge-transfer complexes of various arene donors (ArH) with the nitrosonium cation (NO⁺) resulting from bimolecular [1 ∶ 1] associations can be extended at suitably high ArH concentrations to termolecular processes leading to the analogous [2 ∶ 1] complexes. Spectral analyses of the intense color changes accompanying the arene interaction with NO⁺ provide optimum conditions for the isolation of pure crystalline ternary complexes. Single crystal X-ray crystallographic determinations establish the unique sandwich structure consisting of the NO moiety interposed (parallel) between a pair of cofacial arene donors—reminiscent of the well-known transition metal sandwich complexes with aromatic …

Polystyrene/Graphite Nanocomposites: Effect On Thermal Stability, Fawn Marie Uhl, Charles A. Wilkie

Chemistry Faculty Research and Publications

Nanocomposites consisting of polymer and clay have been shown to exhibit a significant reduction in flammability and an increase in mechanical properties. This work examines the effect of thermal stability and mechanical properties of nanocomposites prepared from potassium graphite and styrene. Synthesis of nanocomposites was accomplished by using potassium graphite (KC₈) as the initiator in the polymerization of styrene. A slight increase in thermal stability is observed but mechanical properties are decreased.