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45th Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 45th annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-endorsed by the Colorado Section of the American Chemical Society and the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, July 27-31, 2003.

Amino Acids Glu323, Tyr324, Glu330, And Val331 Of Factor Va Heavy Chain Are Essential For Expression Of Cofactor Activity, Lisam S. Singh, Michael A. Bukys, Daniel O. Beck, Michael Kalafatis

Chemistry Faculty Publications

We have recently demonstrated that amino acid region 323-331 of factor Va heavy chain (9 amino acids, AP4') contains a binding site for factor Xa (Kalafatis, M., and Beck, D. O. (2002) Biochemistry 41, 12715-12728). To ascertain which amino acids within this region are important for the effector and receptor properties of the cofactor with respect to factor Xa, we have synthesized three overlapping peptides (5 amino acids each) spanning the amino acid region 323-331 and tested them for their effect on prothrombinase complex assembly and function. Peptide containing amino acids 323EYFIA327 alone was found to increase the catalytic efficiency …

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

Chemistry and Physics Faculty Articles

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, five …

Trace Gas Measurements In Nascent, Aged, And Cloud-Processed Smoke From African Savanna Fires By Airborne Fourier Transform Infrared Spectroscopy (Aftir), Robert J. Yokelson, Issac T. Bertschi, Ted J. Christian, Peter V. Hobbs, Darold E. Ward, Wei Min Hao

Chemistry and Biochemistry Faculty Publications

[1] We measured stable and reactive trace gases with an airborne Fourier transform infrared spectrometer (AFTIR) on the University of Washington Convair-580 research aircraft in August/September 2000 during the SAFARI 2000 dry season campaign in Southern Africa. The measurements included vertical profiles of CO₂, CO, H₂O, and CH₄ up to 5.5 km on six occasions above instrumented ground sites and below the TERRA satellite and ER-2 high-flying research aircraft. We also measured the trace gas emissions from 10 African savanna fires. Five of these fires featured extensive ground-based fuel characterization, and two were in the …

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. Kirchstetter, Tihomir Novakov, Peter Pilewskie

Chemistry and Physics Faculty Articles

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 species, …

Global Geometry Optimization Of Silicon Clusters Described By Three Empirical Potentials, S. Yoo, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

The “basic-hopping” global optimization technique developed by Wales and Doye is employed to study the global minima of silicon clusters Si_n (3<nnnn=17, as opposed to n=19. For larger SW clusters (20<n n =20. In particular, the overall structural features of SW Si₂₁, Si₂₃, Si₂₅, and Si₂₈ are nearly identical to the MSW counterparts. With the SW Si₂₁ as the starting structure, a geometric optimization at the B3LYP/6-31G(d) level of density-functional theory yields an isomer similar to the ground-stateisomer of Si₂₁ reported by Pederson et …

Untangling The Web: The National Digital Libraries Initiative, Dean Johnston

Chemistry Faculty Scholarship

A report on the National Digital Libraries Initiative is presented. To facilitate access to the vast resources of the Internet, the National Science Foundation has created the Digital Libraries Initiative. Several sites have come online recently that index and catalog materials in a way similar to a library, providing additional information about each site. The official National Science Digital Library Web site has the potential to become a one-stop site for a wide range of educational science material.

Multidentate Sulfur-Containing Ligands, David A. Atwood, Brock S. Howerton, Matthew Matlock

Chemistry Faculty Patents

Novel sulfur-containing ligands for binding of heavy metals are disclosed.

To read the remainder of this abstract, please download this patent.

High-Temperature Fiber Matrices: Electrospinning And Rare-Earth Modification, W. Kataphinan, R. Teye-Mensah, Edward A. Evans, R. D. Ramsier, D. H. Reneker, D. J. Smith

Chemical, Biomolecular, and Corrosion Engineering Faculty Research

We demonstrate the production of nonwoven mats of high-temperature organic and inorganic fibers by electrospinning. Specifically, glass/ceramic (tetraethylorthosilicate-SiO) and fire-blanket (polydiphenoxyphosphazene-PDPP) precursors are electrospun, and the resulting fibers are characterized by scanning electron microscopy, thermogravimetric analysis, and infrared (IR) spectroscopy. We find that the SiO fibers are smaller in diameter and more uniform than the PDPP fibers, and stable to higher temperatures. We also coat these fiber systems with several rare-earth nitrates, and find that these coatings can be used to selectively modify the near-IR spectra of the fibers. This work extends the use of electrospinning into two new classes …

Nanoscale Oxidation Of Zirconium Surfaces: Kinetics And Mechanisms, N. Farkas, G. Zhang, Edward A. Evans, R. D. Ramsier, J. A. Dagata

Chemical, Biomolecular, and Corrosion Engineering Faculty Research

We show that atomic force microscope-induced oxide features can be formed reproducibly on both Zr and ZrN surfaces, and that the growth rate decreases rapidly with increasing time. There is an increase in oxide-feature height with humidity for both systems, and an approximately linear dependence of the height of the structures on the applied voltage for all films for short exposure times. As the anodization time increases, only the thinnest (6 nm) films show a large enhancement in oxide-feature height, demonstrating the role of the film/substrate interface. Under the same conditions, the height of features grown on ZrN films is …

One-Step Processing Of Spinel Ferrites Via The High-Energy Ball Milling Of Binary Oxides, V. G. Harris, D. J. Fatemi, J. O. Cross, E. E. Carpenter, V. M. Browning, J. P. Kirkland, Amitabh Mohan, Gary J. Long

Chemistry Faculty Research & Creative Works

MnZn ferrites have been produced via the high-energy ball milling of binary oxide precursors. The milled ferrites have a nonequilibrium cation site distribution, with an unusually high population of Zn cations on the octahedral sites. The particle size distribution drops precipitously with milling time from 60±1 to ∼14±1 nm at 10 h, but increases to 18.5±1 nm after long durations (20–40 h) concurrent with the formation of nearly pure ferrite. A 1 h anneal at 673 K facilitates a redistribution of cations to their near equilibrium sites. This processing approach circumvents the need for deleterious high-temperature heat treatments that often …

Markov Chains And Dynamic Geometry Of Polygons, Jiu Ding, L. Richard Hitt, Xin-Min Zhang

Faculty Publications

In this paper we construct sequences of polygons from a given n-sided cyclic polygon by iterated procedures and study the limiting behaviors of these sequences in terms of non-negative matrices and Markov chains. (C) 2003 Elsevier Science Inc. All rights reserved.

Bulk And Interfacial Properties Of A Dipolar-Quadrupolar Fluid In A Uniform Electric Field: A Density-Functional Approach, V.B. Warshavsky, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

We have studied the bulk and interfacial properties of a dipolar-quadrupolar fluid based on an extended modified mean-field density-functional theory. Effects of a uniform electric field on the bulk and interfacial properties are also studied. Results of the coexisting vapor-liquid densities, interfacial profiles of the density and orientation order parameters, the surface tension, and their dependence on the temperature, magnitude of molecule dipole and quadrupole moment, and the applied field are obtained. In general, we find that the applied field increases the critical temperature, broadens the vapor-liquid coexistence curves, and reduces the surface tension. We also find that if the …

E1-E2 Interference In The Vuv Photoionization Of He, E. P. Kanter, B. Krassig, S. H. Southworth, Renaud Guillemin, Oliver Hemmers, Dennis W. Lindle, R. Wehlitz, M. Ya Amusia, L. V. Chernysheva, N. L. S. Martin

Environmental Studies Faculty Publications

We have measured the forward-backward asymmetry of photoelectron angular distributions produced in the vacuum ultraviolet photoionization of helium. This asymmetry, a consequence of the breakdown of the dipole approximation, measures the real part of the ratio of the quadrupole and dipole matrix elements. In the autoionization region, the strong energy dependence of the asymmetry permits an experimental separation of the ratio of those magnitudes from their phase difference. We experimentally determined the Fano parameters of the 2p²¹D₂ quadrupole resonance, and report improved values of the width Γ and line profile parameter q from those previously available …

Methyl And T-Butyl Group Reorientation In Planar Aromatic Solids: Low-Frequency Nuclear Magnetic Resonance Relaxometry And X-Ray Diffraction, Peter A. Beckmann, Carylon Buser, Kathleen Gullifer, Frank B. Mallory, Clelia W. Mallory, Gene M. Rossi, Arnold L. Rheingold

Chemistry Faculty Research and Scholarship

We have synthesized 3-t-butylchrysene and measured the Larmor frequency omega/2pi (= 8.50, 22.5, and 53.0 MHz) and temperature T (110-310 K) dependence of the proton spin-lattice relaxation rate R in the polycrystalline solid [low-frequency solid state nuclear magnetic resonance (NMR) relaxometry]. We have also determined the molecular and crystal structure in a single crystal of 3-t-butylchrysene using x-ray diffraction, which indicates the presence of a unique t-butyl group environment. The spin-1/2 protons relax as a result of the spin-spin dipolar interactions being modulated by the superimposed reorientation of the t-butyl groups and their constituent methyl groups. The reorientation is successfully …

Environment-Induced Degradation And Crack-Growth Studies Of Candidate Target Materials: Annual Progress Report (May 2002 – May 2003), Ajit K. Roy, Brendan O'Toole

Transmutation Sciences Materials (TRP)

As indicated in the original proposal, the primary objective of this task is to evaluate the effect of hydrogen on environment-assisted cracking of candidate target materials for applications in spallationneutron- 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 aqueous environments of interest using tensile specimens under constant load and slow-strain-rate (SSR) conditions. …

Perilipin A Is Essential For The Translocation Of Hormone-Sensitive Lipase During Lipolytic Activation. J Cell Biol, John Tansey

Chemistry Faculty Scholarship

A key step in lipolytic activation of adipocytes is the translocation of hormone-sensitive lipase (HSL) from the cytosol to the surface of the lipid storage droplet. Adipocytes from perilipin -null animals have an elevated basal rate of lipolysis compared with adipocytes from wild-type mice, but fail to respond maximally to lipolytic stimuli. This defect is downstream of the -adrenergic receptor–adenylyl cyclase complex. Now, we show that HSL is basally associated with lipid droplet surfaces at a low level in perilipin nulls, but that stimulated translocation from the cytosol to lipid droplets is absent in adipocytes derived from embryonic fibroblasts of …

A 59-Cobalt Nmr Investigation Of The Hydrogen/Deuterium Exchange Kinetics In Cobalt(Iii) Complexes, Michelle Mccombs

Masters Theses & Specialist Projects

Currently, the hydrogen/deuterium exchange kinetics in cobalt(III) complexes are being investigated. In the presence of deuterated solvents, (e.g. D2 0 and CH3CH20D) the amine hydrogens in the complexes are exchanged for deuteriums. For the hexaamminecobalt(III) ion, 19 isotopmers (H18D0 to HOD 18) are possible. For the tris(ethylenediammine)cobalt(III) ion, 13 isotopmers (HI 2D0 to HOD 12) are possible. Each hydrogen/deuteruim exchange causes a shift in the observed 59Co resonance of approximately 6 ppm. The rate constant of the hydrogen-deuterium exchange for the first H-D exchange has been determined as a function of solvent. When the chosen solvent is D20, the rate …

Thickness Dependence Of Magnetic Blocking In Granular Thin Films With Interacting Magnetic Particles, Jian Qing Wang, Zhi Dong Zhao, Scott L. Whittenburg

Chemistry and Biochemistry Faculty Publications

Interparticle interaction among single domain nanosize magnetic particles embedded in nonmagnetic matrix was studied. Attention was paid to concentrated Cu–Co granular thin films with a fixed magnetic volume fraction (20%). By analyzing theoretical models and comparing with experimental results, a dimensional constraint on the magnetic properties was found. As the film thickness reduces toward the thin limit the interparticle interaction plays important roles in modifying the magnetic behavior. The dipolar interaction energy was calculated among magnetic particles including far-neighbor interaction for films with different thickness values. When magnetization variation is included in the calculation, the resulting calculated interaction energy versus …

Tools For The Automatic Identification And Classification Of Rna Base Pairs, Neocles B. Leontis, Huanwang Yang, Fabrice Jossinet, Li Chen, John Westbrook, Helen Berman, Eric Westhof

Chemistry Faculty Publications

Three programs have been developed to aid in the classification and visualization of RNA structure. BPViewer provides a web interface for displaying three-dimensional (3D) coordinates of individual base pairs or base pair collections. A web server, RNAview, automatically identifies and classifies the types of base pairs that are formed in nucleic acid structures by various combinations of the three edges, Watson-Crick, Hoogsteen and the Sugar edge. RNAView produces two-dimensional (2D) diagrams of secondary and tertiary structure in either Postscript, VRML or RNAML formats. The application RNAMLview can be used to rearrange various parts of the RNAView 2D diagram to generate …

Bis[Μ-1,2-Bis(2-Pyridyl)Ethyne-K2N:N']Bis[Aquadinitratocadmium(Ii)], Badruz Zaman Md., Matthew J. Davis, Mark D. Smith, Hans Conrad Zur Loye

Faculty Publications

Two twisted 1,2-bis(2-pyridyl)ethyne ligands bridge two Cd²⁺ centers in the C₂-symmetric title complex, [Cd₂(NO₃)₄(-C₁₂H₈N₂)₂(H₂O)₂]. The bridging ligands arch across one another creating a `zigzag loop' molecular geometry. Two nitrate ions and a water molecule complete the irregular seven-coordinate Cd-atom environment. The dihedral angles between the equivalent pyridyl ring planes of the two independent ligands are 67.2 (1)°. O_water-HO_nitrate hydrogen bonding creates two-dimensional layers parallel to the ab plane.

Formula: [Cd₂(NO₃)₄(C …

Non-Watson-Crick Basepairing And Hydration In Rna Motifs: Molecular Dynamics Of 5s Rrna Loop E, Neocles B. Leontis, Kamila Réblová, Nad'a Špačková, Richard Štefl, Kristina Csaszar, Jaroslav Koča, J Sponer

Chemistry Faculty Publications

Explicit solvent and counterion molecular dynamics simulations have been carried out for a total of > 80 ns on the bacterial and spinach chloroplast 5S rRNA Loop E motifs. The Loop E sequences form unique duplex architectures composed of seven consecutive non-Watson-Crick basepairs. The starting structure of spinach chloroplast Loop E was modeled using isostericity principles, and the simulations refined the geometries of the three non-Watson-Crick basepairs that differ from the consensus bacterial sequence. The deep groove of Loop E motifs provides unique sites for cation binding. Binding of Mg2+ rigidifies Loop E and stabilizes its major groove at an intermediate …

Thickness Dependence Of Magnetic Blocking In Granular Thin Films, Scott Whittenburg

Chemistry Faculty Publications

Interparticle interaction among single domain nanosize magnetic particles embedded in nonmagnetic matrix was studied. Attention was paid to concentrated Cu–Co granular thin films with a fixed magnetic volume fraction 20%. By analyzing theoretical models and comparing with experimental results, a dimensional constraint on the magnetic properties was found. As the film thickness reduces toward the thin limit the interparticle interaction plays important roles in modifying the magnetic behavior. The dipolar interaction energy was calculated among magnetic particles including far-neighbor interaction for films with different thickness values. When magnetization variation is included in the calculation, the resulting calculated interaction energy versus …

Afci Quarterly Input – Unlv April Through June, 2003, Harry Reid Center For Environmental Studies. Nuclear Science And Technology Division

Transmutation Research Program Reports (TRP)

The University of Nevada, Las Vegas supports the AFCI through research and development of technologies for economic and environmentally sound refinement of spent nuclear fuel. The UNLV program has four components: infrastructure, international collaboration, student-based research, and management and program support.

Quarterly Report For The Trp Project, March–June 2003, Samir Moujaes, Yitung Chen, Kanthi Kiran Daiska, Chao Wu

Transmutation Sciences Materials (TRP)

The MTL is assumed to be a 5m long rectangular loop with a circular cross-section. Because of the non-symmetry, and due to the active participation of the secondary flows due to the elbows present in the rectangular loop model, the geometry is considered as a 3D model.

When the regions of maximum corrosion and precipitation are compared, they fall in the same zone for both the analytical and simulated models. The reason for a larger concentration flux in the case of turbulent flow than for the laminar flow can be explained by the concept of higher lateral diffusion in the …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quarterly Report April-June 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. …

The Role Of The Dielectric Barrier In Narrow Biological Channels: A Novel Composite Approach To Modeling Single-Channel Currents, Artem B. Mamonov, Rob D. Coalson, Abraham Nitzan, Maria G. Kurnikova

Chemistry Faculty Research and Publications

A composite continuum theory for calculating ion current through a protein channel of known structure is proposed, which incorporates information about the channel dynamics. The approach is utilized to predict current through the Gramicidin A ion channel, a narrow pore in which the applicability of conventional continuum theories is questionable. The proposed approach utilizes a modified version of Poisson-Nernst-Planck (PNP) theory, termed Potential-of-Mean-Force-Poisson-Nernst-Planck theory (PMFPNP), to compute ion currents. As in standard PNP, ion permeation is modeled as a continuum drift-diffusion process in a self-consistent electrostatic potential. In PMFPNP, however, information about the dynamic relaxation of the protein and the …

Pharmacophore Derivation Using Discotech And Comparison Of Semi-Emperical, Ab Initio And Density Functional Comfa Studies For Sigma 1 And Sigma 2 Receptor-Ligands, Dawoon Jung

Dissertations

This study describes the development of pharmacophore and CoMFA models for sigma receptor ligands. CoMFA studies were performed for 48 bioactive sigma 1 receptorligands using [H³ ](+) pentazocine as the radioligand, for 30 PCP derivatives for sigma 1 receptor-ligands using [³H](+)SK-F 10047 as the radioligand and for 24 bioactive sigma 2 receptor-ligands using the radioligand [H³](+)DTG in the presence of pentazocine. Distance Comparisons (DISCOtech) was used as the starting point for CoMFA studies. The conformers, derived by DISCOtech were optimized using AMi, or HF/3-21G* in Gaussian 98. The optimized geometries were aligned with the pharmacophore, …

Evaluation Of Fluorapatite As A Waste-Form Material: Third Quarter Report, March 1 - May 31 2003, 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 form …

Rnase L Mediates Transient Control Of The Interferon Response Through Modulation Of The Double-Stranded Rna-Dependent Protein Kinase Pkr, Khalid S.A. Khabar, Yunus M. Siddiqui, Fahad Al-Zoghaibi, Latifa Al-Haj, Mohammed Dhalla, Aimin Zhou, Beihua Dong, Mark Whitmore, Jayashree Paranjape, Mohammed N. Al-Ahdal, Futwan Al-Mohanna, Bryan R.G. Williams, Robert H. Silverman

Chemistry Faculty Publications

The transient control of diverse biological responses that occurs in response to varied forms of stress is often a highly regulated process. During the interferon (IFN) response, translational repression due to phosphorylation of eukaryotic initiation factor 2α, eIF2α, by the double-stranded RNA-dependent protein kinase, PKR, constitutes a means of inhibiting viral replication. Here we show that the transient nature of the IFN response against acute viral infections is regulated, at least in part, by RNase L. During the IFN antiviral response in RNase L-null cells, PKR mRNA stability was enhanced, PKR induction was increased, and the phosphorylated form of eIF2α …