Digital Commons Network^™

Evaluation Of Adsorption Effects On Measurements Of Ammonia, Acetic Acid, And Methanol, Robert J. Yokelson, Ted J. Christian, Isaac T. Bertschi, Wei M. Hao

Chemistry and Biochemistry Faculty Publications

[1] We examined how adsorption and desorption of gases from inlets and a cell could affect the accuracy of closed-cell FTIR measurements of carbon dioxide (CO₂), carbon monoxide (CO), methane (CH₄), nitric oxide (NO), nitrogen dioxide (NO₂), methanol (CH₃OH), acetic acid (CH₃COOH), and ammonia (NH₃). When standards were delivered to the cell through a stainless steel inlet, temporarily reduced transmission was observed for CH₃OH and NH₃. However, a halocarbon wax coated inlet (normally used on the system) had excellent transmission (comparable to room temperature …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix, Spencer M. Steinberg, David W. Emerson, Gary Cerefice

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. During the first year of this program we have examined the potential of Fullerene Containing Carbon compounds (FCC) developed by KRI, and natural organic matter (NOM) as sorbents for iodine released during the reprocessing of nuclear fuel. This work involved the development of bench-scale testing of the FCC and NOM material in a simulated process off-gas environment.

During the first two quarters of this program we explored various analytical methods available for measurement of iodine, iodide, and iodate. …

Pyridoxamine Traps Intermediates In Lipid Peroxidation Reactions In Vivo: Evidence On The Role Of Lipids In Chemical Modification Of Protein And Development Of Diabetic Complications, Thomas O. Metz, Nathan L. Alderson, Mark E. Chachich, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

Maillard or browning reactions between reducing sugars and protein lead to formation of advanced glycation end products (AGEs) and are thought to contribute to the pathogenesis of diabetic complications. AGE inhibitors such as aminoguanidine and pyridoxamine (PM) inhibit both the formation of AGEs and development of complications in animal models of diabetes. PM also inhibits the chemical modification of protein by advanced lipoxidation end products (ALEs) during lipid peroxidation reactions in vitro. We show here that several PM adducts, formed in incubations of PM with linoleate and arachidonate in vitro, are also excreted in the urine of PM-treated animals. The …

Electrochemical Preparation Of Chitosan/Hydroxyapatite Composite Coatings On Titanium Substrates, Jody G. Redepenning, Guhanand Venkataraman, Jun Chen, Nathan Stafford

Jody Redepenning Publications

Composite coatings containing brushite (CaHPO₄ • 2H₂O) and chitosan were prepared by electrochemical deposition. The brushite/chitosan composites were converted to hydroxyapatite/chitosan composites in aqueous solutions of sodium hydroxide. The coatings ranged from 1 to 15% chitosan by weight. Qualitative assessment of the coatings showed adhesion signifi cantly improved over that observed for electrodeposited coatings of pure HA.

Hygroscopic Growth Of Ammonium Sulfate/Dicarboxylic Acids, Matthew E. Wise, Jason D. Surratt, Daniel B. Curtis, John E. Shilling, Margaret A. Tolbert

CUP Faculty Research

Recent studies have shown that tropospheric sulfate aerosols commonly contain 50% by mass organic species. The influence of these organics on the chemical and physical properties of sulfate aerosols is not fully established. We have measured the water activity of pure dicarboxylic acids and eutonic mixtures of ammonium sulfate/dicarboxylic acids at 25°C and have calculated van't Hoff factors for each individual system. We have also used the vapor pressure data to determine the hygroscopic growth curves for pure dicarboxylic acids and eutonic mixtures and provide power law fits to the data. For the systems studied we find that the presence …

Magnetic Storage Device Using Induced Magnetic Reversal Of A Cobalt Element Array, Hanning Chen, Scott L. Whittenburg

Chemistry and Biochemistry Faculty Publications

The effects of the applied field, cell size, and cutting area on the ‘‘seed’’ induced magnetic reversal of a cobalt element array have been studied by a stochastic dynamic micromagnetics code using the Laudau–Lifshitz–Gilbert equation. Three magnetic reversal mechanisms under different magnitudes of the applied field have been investigated by examining the energy profiles. To minimize the effect of the thermal fluctuations on the switching time, an applied field with magnitude around 0.7 or 0.8 T and an element array with cutting area less than 10 nm X 10 nm are required. By using the smaller cellsize, the switching time …

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

Chemistry & Biochemistry Newsletter: 2002-2015

Inside:

Page 2 New Graduate Students in Chemistry/Biochemistry

Page 3 and 4 New Faculty

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

Page 6 Recent Faculty Publications

Extensive Regional Atmospheric Hydrocarbon Pollution In The Southwestern United States, Lambert A. Doezema

Chemistry and Biochemistry Faculty Works

Light alkane hydrocarbons are present in major quantities in the near-surface atmosphere of Texas, Oklahoma, and Kansas during both autumn and spring seasons. In spring 2002, maximum mixing ratios of ethane [34 parts per 109 by volume (ppbv)], propane (20 ppbv), and n-butane (13 ppbv) were observed in north-central Texas. The elevated alkane mixing ratios are attributed to emissions from the oil and natural gas industry. Measured alkyl nitrate mixing ratios were comparable to urban smog values, indicating active photochemistry in the presence of nitrogen oxides, and therefore with abundant formation of tropospheric ozone. We estimate that 4-6 teragrams of …

Direct Determination Of Kinetic Rates From Single-Molecule Photon Arrival Trajectories Using Hidden Markov Models, Michael Andrec, Ronald M. Levy, David Talaga

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

The kinetic rates of single-molecule photon trajectories were determined using hidden Markov model (HMM). The data from single-molecule experiments were in the form of photon trajectories consisting of arrival times and wavelength information on individual photons. HMM was used as an alternative to higher-order correlation function analysis for the detection of conformational memory.

Distributions Of Trace Gases And Aerosols During The Dry Biomass Burning Season In Southern Africa, Parikhit Sinha, Peter V. Hobbs, Robert J. Yokelson, Donald R. Blake, Song Gao, Thomas W. Kirschsetter

Chemistry and Biochemistry Faculty Publications

[1] Vertical profiles in the lower troposphere of temperature, relative humidity, sulfur dioxide (SO₂), ozone (O₃), condensation nuclei (CN), and carbon monoxide (CO), and horizontal distributions of twenty gaseous and particulate species, are presented for five regions of southern Africa during the dry biomass burning season of 2000. The regions are the semiarid savannas of northeast South Africa and northern Botswana, the savanna-forest mosaic of coastal Mozambique, the humid savanna of southern Zambia, and the desert of western Namibia. The highest average concentrations of carbon dioxide (CO₂), CO, methane (CH₄), O_{3 …}

Structural Requirements For Expression Of Factor Va Activity, Michael Kalafatis, Daniel O. Beck, Kenneth G. Mann

Chemistry Faculty Publications

Thrombin activated factor Va (factor VIIa, residues 1-709 and 1546-2196) has an apparent dissociation constant (Kd,app) for factor Xa within prothrombinase of approximately 0.5 nM. A protease (NN) purified from the venom of the snake Naja nigricollis nigricollis, cleaves human factor V at Asp697, Asp1509, and Asp1514 to produce a molecule (factor VNN) that is composed of a Mr 100,000 heavy chain (amino acid residues 1-696) and a Mr 80,000 light chain (amino acid residues 1509/1514-2196). Factor VNN, has a Kd,app for factor Xa of 4 nm and reduced clotting activity. Cleavage of factor VIIa by NN at Asp697 results …

Why Should Students Do Research?, Bruce R. Branchini

Convocation Addresses

No abstract provided.

Phase Changes In Internally Mixed Maleic Acid/Ammonium Sulfate Aerosols, Sarah D. Brooks, Rebecca M. Garland, Matthew E. Wise, Anthony J. Prenni, Melinda Cushing, Erika Hewitt, Margaret A. Tolbert

CUP Faculty Research

A temperature controlled flow tube system equipped with Fourier transform infrared (FTIR) detection of particle phase and relative humidity was used to measure the deliquescence and efflorescence of ammonium sulfate, maleic acid, and internally mixed maleic acid/ammonium sulfate particles. Our results indicate that maleic acid aerosols begin to take up water starting at a low relative humidity, ∼20%, and continue the constant uptake of water until the final deliquescence relative humidity (DRH), 89%, is reached. Internally mixed particles containing maleic acid and ammonium sulfate were found to deliquesce at a lower relative humidity (RH) than either of the pure species. …

Spectroscopic Examination Of The Catalytic Decomposition Of Hydrogen Peroxide By A Copper (Ii) Complex Of A Dissymmetric Schiff Base And An Imidazole Derivative., John D. Davis Jr.

Electronic Theses and Dissertations

Previous studies involving copper (II) complexed with a dissymmetric Schiff base and imidazole derivatives had identified catalase activity of these complexes towards H₂O₂. Reactions such as this are of great interest due to the important role of copper-based complexes in biological systems. Our research has been conducted to add to the base of knowledge regarding the efforts of other researchers to investigate copper complexes that exhibit similar reactivity as copper-based proteins towards dioxygen. The copper complex chosen for this study contained a tri-dentate Schiff base adduct which, when complexed with an imidazole derivative, limited the manner …

Investigation Of The Relationship Between Particulate Bound Mercury And Properties Of Fly Ash In A Full-Scale 100 Mwe Pulverized Coal Combustion Boiler, Sen Li

Masters Theses & Specialist Projects

There is an increasing concern over mercury emissions from coal-fired boilers. Coal-fired power generation accounts for approximately 33% of total mercury emission in the United States. Once it is emitted into the atmosphere and deposited on land or water, mercury can transform into methylmercury, an organic form. Mercury can then enter the food chain, which poses a potential threat to human health and the environment. To study the relationship between particulate bound mercury and fly ash properties, fly ash samples were collected from the mechanical hopper (MHP) and the electrostatic precipitator (ESP) of a 100 MWe pulverized coal-fired boiler and …

Receptor Activation Regulates Cortical, But Not Vesicular Localization Of Ndp Kinase, Betty C. Gallagher, Kimberly A.P. Mitchell, Gabor Szabo, Angela De S. Otero

Faculty Publications and Presentations

We used immunofluorescence techniques to determine the localization of nucleoside diphosphate (NDP) kinase in NIH-3T3 fibroblasts. We found that cytoplasmic NDP kinase can be separated into two populations according to subcellular localization and response to extracellular stimuli. Specifically, within minutes of stimulation of resting fibroblasts with serum, growth factors or bombesin, a portion of NDP kinase becomes associated with membrane ruffles and lamellipodia. Another pool of NDP kinase accumulates independently of stimulation around intracellular vesicles. Transfection of cells with activated Rac mimics, whereas expression of dominant negative Rac inhibits, the effects of extracellular stimulation on the translocation of NDP kinase …

Photofragmentation Dynamics Of Core-Excited Water By Anion-Yield Spectroscopy, Wayne C. Stolte, M. M. Sant'anna, Gunnar Ohrwall, Maria Novella Piancastelli, I. Dominguez-Lopez, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Partial-anion and- cation yields from H₂O are presented for photon energies near the oxygen K edge. The O^- yield exhibits a feature above threshold attributed to doubly excited states, in contrast to the H^- and cation yields, which are nearly featureless above threshold. Additionally, the lack of the OH^- fragment indicates radiative decay and provides a negligible amount of anion formation.

A Multicentered Approach To Integrated Qm/Qm Calculations. Applications To Multiply Hydrogen Bonded Systems, Brian W. Hopkins, Gregory S. Tschumper

Chemistry Faculty Research & Creative Works

A multicentered integrated QM/QM technique has been developed. By separating high-level calculations in distinct regions of molecules, the multicentered approach supplants a single large high-level calculation with several smaller calculations. Due to the step polynomial scaling of traditional ab initio quantum chemical methods, this separation significantly enhances the computational efficiency of QM/QM methods. The straightforward implementation of this multicentered approach is illustrated with several large poly-alcohols that form hydrogen bonds with water. The largest alcohol-water complex contains 81 atoms. For properly selected model systems, this multicentered approach introduces essentially no error in the dissociation energies of these complexes relative to …

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 …

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 …

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 …

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, …

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 …

Evaluating The Effects Of Enhanced Processivity And Metal Ions On Translesion Dna Replication Catalyzed By The Bacteriophage T4 Dna Polymerase, Edmunds Z. Reineks, Anthony J. Berdis

Chemistry Faculty Publications

The fidelity of DNA replication is achieved in a multiplicative process encompassing nucleobase selection and insertion, removal of misinserted nucleotides by exonuclease activity, and enzyme dissociation from primer/templates that are misaligned due to mispairing. In this study, we have evaluated the effect of altering these kinetic processes on the dynamics of translesion DNA replication using the bacteriophage T4 replication apparatus as a model system. The effect of enhancing the processivity of the T4 DNA polymerase, gp43, on translesion DNA replication was evaluated using a defined in vitro assay system. While the T4 replicase (gp43 in complex with gp45) can perform …

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. …