Chemistry Commons^™

Analyzing The Catalytic Role Of Asp97 In The Methionine Aminopeptidase From Escherichia Coli, Sanghamitra Mitra, Kathleen M. Job, Lu Meng, Brian Bennett, Richard C. Holz

Physics Faculty Research and Publications

An active site aspartate residue, Asp97, in the methionine aminopeptidase (MetAPs) from Escherichia coli (EcMetAP-I) was mutated to alanine, glutamate, and asparagine. Asp97 is the lone carboxylate residue bound to the crystallographically determined second metal-binding site in EcMetAP-I. These mutant EcMetAP-I enzymes have been kinetically and spectroscopically characterized. Inductively coupled plasma–atomic emission spectroscopy analysis revealed that 1.0 ± 0.1 equivalents of cobalt were associated with each of the Asp97-mutated EcMetAP-Is. The effect on activity after altering Asp97 to alanine, glutamate or asparagine is, in general, due to a ∼ 9000-fold decrease in k_ca towards …

Linear Dichroism In Resonant Inelastic X-Ray Scattering To Molecular Spin-Orbit States, Renaud Guillemin, Stephane Carniato, Wayne C. Stolte, Loic Journel, Richard Taieb, Dennis W. Lindle, Marc Simon

Chemistry and Biochemistry Faculty Research

Polarization-dependent resonant inelastic x-ray scattering (RIXS) is shown to be a new probe of molecular-field effects on the electronic structure of isolated molecules. A combined experimental and theoretical analysis explains the linear dichroism observed in Cl 2p RIXS following Cl 1s excitation in HCl and CF₃Cl as due to molecular-field effects, including singlet-triplet exchange, indicating polarized-RIXS provides a direct probe of spin-orbit-state populations applicable to any molecule.

Inverse Velocity Dependence Of Vibrationally Promoted Electron Emission From A Metal Surface, N. H. Nahler, J. D. White, Jerry L. Larue, Daniel J. Auerbach, Alec M. Wodtke

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

All previous experimental and theoretical studies of molecular interactions at metal surfaces show that electronically nonadiabatic influences increase with molecular velocity. We report the observation of a nonadiabatic electronic effect that follows the opposite trend: The probability of electron emission from a low–work function surface—Au(111) capped by half a monolayer of Cs—increases as the velocity of the incident NO molecule decreases during collisions with highly vibrationally excited NO(X²π_½, V = 18; V is the vibrational quantum number of NO), reaching 0.1 at the lowest velocity studied. We show that these results are consistent with a vibrational …

An Extended Multireference Study Of The Electronic States Of Para-Benzyne, Carol A. Parish, Evan B. Wang, Hans Lischka

Chemistry Faculty Publications

A state-averaged, multireference complete active space (CAS) approach was used for the determination of the vertical excitation energies of valence and Rydberg states of para-benzyne. Orbitals were generated with a 10- and 32-state averaged multiconfigurational self-consistent field approach. Electron correlation was included using multireference configuration interaction with singles and doubles, including the Pople correction for size extensivity, multireference averaged quadratic coupled cluster (MR-AQCC) and MR-AQCC based on linear response theory. There is a very high density of electronic states in this diradical system—there are more than 17 states within 7 eV of the ground state including two 3s …

50th Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 50th 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 Breckenridge, Colorado, July 27-31, 2008.

Simpol.1: A Simple Group Contribution Method For Predicting Vapor Pressures And Enthalpies Of Vaporization Of Multifunctional Organic Compounds, James F. Pankow, William E. Asher

Physics Faculty Publications and Presentations

The SIMPOL.1 group contribution method is developed for predicting the liquid vapor pressure p^o_L (atm) and enthalpy of vaporization Δ H_vap (kJ mol^-1) of organic compounds as functions of temperature (T). For each compound i, the method assumes log₁₀p^o_L,i (T)=∑_kν_k,ib_k(T) where ν_k,i is the number of groups of type k, and b_k (T) is the contribution to log₁₀p^o_L,i (T) by each group of type k. A …

Real-Time Plasma Controlled Chemistry In A Two-Frequency, Confined Plasma Etcher, Vladimir Milosavljevic, Albert R. Ellingboe, Cezar Gaman, John V. Ringwood

Articles

The physics issues of developing model-based control of plasma etching are presented. A novel methodology for incorporating real-time model-based control of plasma processing systems is developed. The methodology is developed for control of two dependent variables (ion flux and chemical densities) by two independent controls (27 MHz power and O2flow). A phenomenological physics model of the nonlinear coupling between the independent controls and the dependent variables of the plasma is presented. By using a design of experiment, the functional dependencies of the response surface are determined. In conjunction with the physical model, the dependencies are used to deconvolve the sensor …

Stability And Equation Of State Of A Nanocrystalline Ga-Ge Mullite In A Vitroceramic Composite: A Synchrotron X-Ray Iffraction Study, Kristina E. Lipinska-Kalita, Patricia Kalita, Cedric Gobin, Oliver Hemmers, Thomas Hartmann, Gino Mariotto

Environmental Studies Faculty Publications

Synchrotron x-ray diffraction and diamond anvil cell techniques were used to characterize the phase transformations and to evaluate the structural stability at elevated pressures of a developed nanocrystalline composite. The optically transparent material was built of a germanium oxide-based amorphous host matrix with homogeneously dispersed 13±3 nm Ga-Ge mullite-type nanocrystals, which had a structure similar to the conventional Al₂O₃-SiO₂ mullite. The equation of state of the nanocrystals and the overall structural integrity of the nanocomposite were investigated in quasihydrostatic conditions on compression to 36 GPa and on the following decompression to ambient conditions. The overall …

Volume 01, Jessica Fields, Stephanie Neeley, Derek W. Hambright, Mary E. Lehman, Andrew R. Grzankowski, Zachary Johnson, Boone M. Prentice, Ashley M. Swandby, Victoria Morgan, Katie Williamson, Kristine G. Bender, Katelyn N. Romaine, D. Nicole Swann, Jessica Fox, Mike Mcateer, Alex Grabiec, Laura Nodtvedt, Nick Costa, Rachel Wolfe, Zack Dalton

Incite: The Journal of Undergraduate Scholarship

Introduction from Dean Dr. Charles Ross

Three Decades of Digging: Undergraduate Archeology at Longwood by Jessica Fields and Stephanie Neeley

Interactions of Allelopathy and Heat Stress in Plants by Derek W. Hambright and Mary E. Lehman

Inertial Electrostatic Confinement D-D Fusion Device: Construction and Simulation by Andrew R. Grzankowski

Shackled Nim by Zachary Johnson

Development of GC-MS and Chemometric Methods for the Analysis of Accelerants in Arson Cases by Boone M. Prentice

A Comparison of Image Analysis Methods in cDNA Microarrays by Ashley M. Swandby

Perceived Sexual Activity of Short and Long-Term Relationships by Victoria Morgan and Katie Williamson

Elderly …

Equation Of State Of Gallium Oxide To 70 Gpa: Comparison Of Quasihydrostatic And Nonhydrostatic Compression, Kristina E. Lipinska-Kalita, Patricia Kalita, Oliver Hemmers, Thomas Hartmann

Environmental Studies Faculty Publications

Synchrotron x-ray diffraction and diamond-anvil cell techniques were used to characterize pressure induced structural modifications in gallium oxide. Gallium oxide was studied on compression up to 70 GPa and on the following decompression. The effect of the pressure-transmitting medium on the structural transformations was investigated in two sets of compression and decompression runs, one with nitrogen as a quasihydrostatic pressure-transmitting medium and the other in nonhydrostatic pressure conditions. The x-ray diffraction data showed gradual phase transition from a low-density, monoclinic β-Ga₂O₃ to a high-density, rhombohedral α-Ga₂O₃. With the use of nitrogen as a …

The Decomposition Of Yba₂Cu₃O₇₋Δ Doped Into Ba₂Yruo₆, H. A. Blackstead, William B. Yelon, M. Kornecki, M. P. Smylie, P. J. Mcginn, Jinbo Yang, Qingsheng Cai, William Joseph James

Physics Faculty Research & Creative Works

One of the persistent criticisms of claims for observation of superconductivity in Ba2YRu1−uCuuO6 (O6) is that the diamagnetism is actually due to the decomposition of the material into YBa2Cu3O7−delta and other phases. We report a series of experiments in which YBa2Cu3O7−delta is doped into Ba2YRuO6 and carried through a series of sintering steps which were followed by magnetization, neutron diffraction, and scanning electron microscopy/microprobe measurements. It was found that the dopant YBa2Cu3O7−delta decomposed and failed to reform with cooling. It is concluded that the O6 phase is the stable high-temperature phase. The Cu released from the Y123 decomposition doped the …

Evaluation Of Cs/Sr Waste Form For Long Term Storage And Disposal, Gary Cerefice

Waste Forms Campaign (TRP)

The goal of this project is to examine the potential long term performance of the proposed aluminosilicate waste/storage form for the isolation and eventual direct disposal of the cesium and strontium separated from recycled nuclear fuel. In the first phase of this work, researchers will investigate the sintering procedure to prepare the drum-like aluminosilicate waste/storage form from the as-received aluminosilicate powder, and then examine the basic physical properties, phase structure and microstructure of the sintered aluminosilicate with /without mixing solution with several ppm Cs/Sr. In the second phase, researchers will evaluate the interaction of the proposed waste form with structural …

Constructing Explicit Magnetic Analogies For The Dynamics Of Glass Forming Liquids, Jacob D. Stevenson, Aleksandra M. Walczak, Randall W. Hall, Peter G. Wolynes

Collected Faculty Scholarship

By defining a spatially varying replica overlap parameter for a supercooled liquid referenced to an ensemble of fiducial liquid state configurations, we explicitly construct a constrained replica free energy functional that maps directly onto an Ising Hamiltonian with both random fields and random interactions whose statistics depend on the liquid structure. Renormalization group results for random magnets when combined with these statistics for the Lennard-Jones glass suggest that discontinuous replica symmetry breaking would occur if a liquid with short range interactions could be equilibrated at a sufficiently low temperature where its mean field configurational entropy would vanish, even though the …

Simultaneous Measurements Of Electronic Conduction And Raman Response In Molecular Junctions, Daniel R. Ward, Naomi J. Halas, James M. Tour, Jacob W. Ciszek, Yanpeng Wu, Peter Nordlander, Douglas Natelson

Chemistry: Faculty Publications and Other Works

Electronic conduction through single molecules is affected by the molecular electronic structure as well as by other information that is extremely difficult to assess, such as bonding geometry and chemical environment. The lack of an independent diagnostic technique has long hampered single-molecule conductance studies. We report simultaneous measurement of the conductance and the Raman spectra of nanoscale junctions used for single-molecule electronic experiments. Blinking and spectral diffusion in the Raman response of both para-mercaptoaniline and a fluorinated oligophenylyne ethynylene correlate in time with changes in the electronic conductance. Finite difference time domain calculations confirm that these correlations do not result …

Editorial, First Science And Policy Issue, Jscas

Journal of the South Carolina Academy of Science

No abstract provided.

A Call For A Statewide Bioinformatics Institute, John R. Rose

Journal of the South Carolina Academy of Science

No abstract provided.

With The Help Of South Carolina Research Universities, Scra Demonstrates Leadership In Applied Research And Commercialization Within Sc, Bill Mahoney

Journal of the South Carolina Academy of Science

No abstract provided.

Sc Inbre: A Catalyst For Biomedical Research Development In South Carolina, Lucia A. Pirisi-Creek M.D, Scott Little, Ph.D.

Journal of the South Carolina Academy of Science

No abstract provided.

Local Structures Surrounding Zr In Nanostructurally Stabilized Cubic Zirconia: Structural Origin Of Phase Stability, Y. L. Soo, P. J. Chen, S. H. Huang, T. J. Shiu, T Y. Tsai, Y. H. Chow, Y. C. Lin, S. C, Weng, S. L. Chang, G. Wang, Chin Li Cheung, Renat F. Sabirianov, Wai-Ning Mei, Fereydoon Namavar, Hani Haider, Kevin L. Garvin, J. F. Lee, H. Y. Lee, P. P. Chu

Physics Faculty Publications

Local environment surrounding Zr atoms in the thin films of nanocrystalline zirconia (ZrO₂) has been investigated by using the extended x-ray absorption fine structure (EXAFS) technique. These films prepared by the ion beam assisted deposition exhibit long-range structural order of cubic phase and high hardness at room temperature without chemical stabilizers. The local structure around Zr probed by EXAFS indicates a cubic Zr sublattice with O atoms located on the nearest tetragonal sites with respect to the Zr central atoms, as well as highly disordered locations. Similar Zr local structure was also found in a ZrO₂ nanocrystal …

Phonon Scattering Effects On Thermal Conductivity Of Tinisn-Based Half-Heusler Alloys, S. Bhattacharya, T. M. Tritt, M. J. Skove, M. Russell, S. J. Poon, V. Ponnambalam, Y. Xia, N. Thadhani

Journal of the South Carolina Academy of Science

No abstract provided.

Photofragmentation Of Sif4 Upon Si 2p And F 1s Core Excitation: Cation And Anion Yield Spectroscopy, Maria Novella Piancastelli, Wayne C. Stolte, Renaud Guillemin, A. Wolska, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We have studied the fragmentation dynamics of core-excited SiF₄ by means of soft-x-ray photoexcitation and partial positive and negative ion yield measurements around the Si L_2,3-shell and F K-shell ionization thresholds. All detectable ionic fragments are reported and we observe significant differences between the various partial ion yields near the Si 2p threshold. The differences are similar to our previous results from CH₃Cl showing more extended fragmentation in correspondence to transitions to Rydberg states. At variance with smaller systems, we observe negative ion production in the shape resonance region. This can be related …

Activation Energy Of Surface Diffusion And Terrace Width Dynamics During The Growth Of In (4×3) On Si (100) - (2×1) By Femtosecond Pulsed Laser Deposition, M. A. Hafez, H. E. Elsayed-Ali

Electrical & Computer Engineering Faculty Publications

The nucleation and growth of indium on a vicinal Si (100) - (2×1) surface at high temperature by femtosecond pulsed laser deposition was investigated by in situ reflection high energy electron diffraction (RHEED). RHEED intensity relaxation was observed for the first ∼2 ML during the growth of In (4×3) by step flow. From the temperature dependence of the rate of relaxation, an activation energy of 1.4±0.2 eV of surface diffusion was determined. The results indicate that indium small clusters diffused to terrace step edges with a diffusion frequency constant of (1.0±0.1) × 10¹¹ s^-1. The RHEED specular …

Oligo(Vinylidene Fluoride) Langmuir-Blodgett Films Studied By Spectroscopic, Rafal Korlacki, J. Travis Johnston, Jihee Kim, Stephen Ducharme, Daniel W. Thompson, Vladimir M. Fridkin, Zhongxin Ge, James M. Takacs

Stephen Ducharme Publications

Thin films of amphiphilic vinylidene fluoride oligomers prepared by Langmuir–Blodgett deposition on silicone substrates were investigated by comparing experimental and theoretical mid-infrared (IR) spectra. The experimental spectra were obtained using infrared spectroscopic ellipsometry. Theoretical spectra were calculated using density functional theory. Excellent correspondence of major IR bands in both data sets shows that the molecular backbone is oriented with the long axis normal to the substrate plane. This is in contrast to poly vinylidene fluoride[1] LB films, in which the polymer chains are parallel to the substrate.

University Of Nevada, Las Vegas Transmutation Research Program Annual Progress Report Academic Year 2007-2008, Anthony Hechanova, Rebecca Paulson

Transmutation Research Program Reports (TRP)

It is my pleasure to present the UNLV Transmutation Research Program’s seventh annual report that highlights the academic year 2007-2008. Supporting this document are the many technical reports and theses that have been generated over the past seven years.

In the seventh year of our program, we continued to see growth in the Radiochemistry Ph.D. program with a total of 20 students in the fourth year of the program (we anticipated twelve in the program proposal). Since our inception, the program has sponsored to their conclusion 48 M.S. and 6 Ph.D. degrees. The program supported 53 graduate students, 11 undergraduates, …

Separation Of Technetium From Uranium And Waste Form Synthesis, Kenneth Czerwinski

Waste Forms Campaign (TRP)

In this project, systematic investigations on the Tc-Zr binary metal system will be evaluated for the first time. The synthesis of metallic Tc as well as its alloys with Zr will be evaluated. In order to provide valuable data to AFC R&D, the thermodynamic equilibrium phases, as well as their performance under repository conditions, will be examined.

The research objectives of this project are as follows:

• Evaluate anion exchange methods for achieving the separation of Tc from U.

• Synthesize metallic Tc from the separated product.

• Synthesize and characterize Tc alloys.

• Investigate Tc-corrosion and Tc-leaching of binary …

Dissolution, Reactor, And Environmental Behavior Of Zro2-Mgo Inert Fuel Matrix, Kenneth Czerwinski

Fuels Campaign (TRP)

This project will examine inert fuels containing ZrO₂ and MgO as the inert matrix. Ceramics with this inert matrix, Ce, U and eventually Pu will be synthesized and examined. While the Advanced Fuel Cycle Initiative focus is on inert fuels with Pu as the fissile component, this task will perform initial laboratory experiments with Ce and U. The initial work with Ce will be performed early in the project with results used as a basis for U studies. Reactor physics calculations will be used to examine suitable quantities of burnable poisons from the candidate elements Gd, Er, or Hf. …

Impact Of The Synthesis Process On Structure Properties For Afci Fuel Candidates, Kenneth Czerwinski

Fuels Campaign (TRP)

The research objectives are:

• To explore a low-temperature fluoride route to synthesize actinide nitrides. • To characterize actinide nitrides structurally and thermally.

• To use high resolution TEM techniques to explore the microstructure of the radioactive samples.

Solution-Based Synthesis Of Nitride Fuels, Kenneth Czerwinski, Tyler A. Sullens

Fuels Campaign (TRP)

One of the original synthetic routes devised for the synthesis of U (III)N involved the entire reaction taking place in liquid ammonia. Several experimental reactions were conducted in an attempt to synthesize the UI₃(NH₃)_x and U(NH₂)₃(NH₃)_x precursors of U(III) N. Each attempt involved cleaning of the uranium metal to remove the oxide coating of the metal reagent with 3 washes of concentrated nitric acid, each followed by a rinse with liquid ammonia. Success of this cleaning procedure was varied, with a majority of cleaned metal oxidizing rapidly once …

Gnep Quarterly Input – Unlv July 1 Through September 30, 2007, Harry Reid Center For Environmental Studies. Nuclear Science And Technology Division

Transmutation Research Program Reports (TRP)

Quarterly report highlighting research projects, activities and objectives of the Transmutation Research Program at the Nuclear Science & Technology Division, Harry Reid Research Center.

The University of Nevada, Las Vegas supports the Global Nuclear Energy Partnership (GNEP) 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.

A Novel Empirical Free Energy Function That Explains And Predicts Protein–Protein Binding Affinities, Joseph Audie, Suzanne Scarlata

Chemistry & Physics Faculty Publications

A free energy function can be defined as a mathematical expression that relates macroscopic free energy changes to microscopic or molecular properties. Free energy functions can be used to explain and predict the affinity of a ligand for a protein and to score and discriminate between native and non-native binding modes. However, there is a natural tension between developing a function fast enough to solve the scoring problem but rigorous enough to explain and predict binding affinities. Here, we present a novel, physics-based free energy function that is computationally inexpensive, yet explanatory and predictive. The function results from a derivation …