Chemistry Commons^™

Petrology And Lithogeochemistry Of The Mineralized Tanzanite-Grossular Bearings Rocks In The Merelani-Lelatema Area, Northeastern Tanzania, Ep Malisa

Tanzania Journal of Science

The Merelani-Lelatema area, which is occupied by late Proterozoic metasedimentary rocks, lies along the Lelatema fault zone. The rocks are mainly pelitic and semi-pelitic gneisses, psammitic gneisses, hydrothermally altered rocks, crystalline dolostones, pegmatites and quartz veins. The occurrence of gem-quality tanzanite and grossular has been found to occur mainly in boudinaged pegmatitic veins and hydrothermal fracture fillings. These fracture fillings occur in brecciated and hydrothermally altered graphite-bearing gneiss in a mineral association containing glass-clear quartz, diopside, zoisite, graphite and calcite. The psammitic gneisses are more siliceous and enriched in feldspars. They are grouped into graphite-kyanite gneiss with thin interlayers of …

Synthesis Of Some Cis-4,4-Dimethyl-2-Isopropenylcyclopentane Derivatives As Potential Intermediates Towards The Protoilludane Skeleton, Sjm Mdachi

Tanzania Journal of Science

The three gem-dimethyl-substituted cyclopentane derivatives 1-(2-propionyl)-4,4-dimethyl-2-isopropenylcyclopentane, 2-isopropenyl-4,4-dimethylcyclopentanecarboxyaldehyde and 1-hydroxy- methyl-2-isopropenyl-4,4-dimethylcyclopentane have been synthesized employing a thermally induced ene reaction as a key step. Each of the three compounds has been obtained predominantly as the cis isomer. The successful synthesis of these compounds affords opportunities for their further ellaboration towards sesquiterpenes of the protoilludane skeleton.

Solvent And Primary Deuterium Isotope Effects Show That Lactate Ch And Oh Bond Cleavages Are Concerted In Y254f Flavocytochrome B2, Consistent With A Hydride Transfer Mechanism, Pablo Sobrado, Paul F. Fitzpatrick

Chemistry Faculty Research & Creative Works

Yeast flavocytochrome b2 catalyzes the oxidation of lactate to pyruvate; because of the wealth of structural and mechanistic information available, this enzyme has served as the model for the family of flavoproteins catalyzing oxidation of α-hydroxy acids. Primary deuterium and solvent isotope effects have now been used to analyze the effects of mutating the active site residue Tyr254 to phenylalanine. Both the Vmax and the V/Klactate values decrease about 40-fold in the mutant enzyme. The primary deuterium isotope effects on the Vmax and the V/K lactate values increase to 5.0, equivalent to the intrinsic isotope effect for the wild-type enzyme. …

Macrocyclic Antibiotics As Separation Agents, Daniel W. Armstrong

Chemistry Faculty Research & Creative Works

Macrocyclic antibiotics having ring structures with at least 10 members act as separation agents in crystallization, precipitation, filtration, electrophoresis, and chromatography. The macrocyclic antibiotics include ansamacrolides, macrolides, macrocyclic peptides, polyenes and derivatives thereof. The process has been found to be especially advantageous for separation of optical isomers by electrophoresis and chromatography.

Self-Aligned Mechanical Attachment Of Carbon Nanotubes To Silicon Dioxide Structures By Selective Silicon Dioxide Chemical-Vapor Deposition, Jed D. Whittaker, Ghaleb A. Husseini, Matthew A. Linford, Robert C. Davis, Markus Brink

Faculty Publications

A self-aligned thin-film deposition technique was developed to mechanically attach carbon nanotubes to surfaces for the fabrication of structurally robust nanotube-based nanomechanical devices. Single-walled carbon nanotubes were grown by thermal chemical-vapor deposition (CVD) across 150-nm-wide SiO2 trenches. The nanotubes were mechanically attached to the trench tops by selective silicon tetraacetate-based SiO2 CVD. No film was deposited on the nanotubes where they were suspended across the trenches.

Seasonal Variation And Ecosystem Dependence Of Emission Factors For Selected Trace Gases And Pm2.5 For Southern African Savanna Fires, S. Korontzi, Darold E. Ward, Ronald A. Susott, Robert J. Yokelson, C. O. Justice, Peter V. Hobbs, E.A. H. Smithwick, Wei Min Hao

Chemistry and Biochemistry Faculty Publications

[1] In this paper we present the first early dry season (early June-early August) emission factor measurements for carbon dioxide (CO₂), carbon monoxide (CO), methane (CH₄), nonmethane hydrocarbons (NMHC), and particulates with a diameter less than 2.5 μm (PM_2.5) for southern African grassland and woodland fires. Seasonal emission factors for grassland fires correlate linearly with the proportion of green grass, used as a surrogate for the fuel moisture content, and are higher for products of incomplete combustion in the early part of the dry season compared with later in the dry season. Models of …

Dual Stage Microvalue And Method Of Use, Marc J. Madou, Sylvia Daunert

Chemistry Faculty Patents

A micro-machined drug delivery device and method of use for the delivery of labile drugs is disclosed. A micro-machined sensing device and method of use is also disclosed. A micro-machined drug delivery and sensing device and method of use is additionally disclosed. All three devices are intended to be inserted into a patient's body. The drug delivery devices allow for the mixing of drug components prior to the release of the mixture into the patient's body where the mixture is labile. The micro-machined sensing device is suitable for monitoring the concentration of a specific chemical in a patient's body fluids …

Investigation Of Nanodispersion In Polystyrene-Montmorillonite Nanocomposites By Solid State Nmr, Serge Bourbigot, David L. Vanderhart, Jeffery W. Gilman Sr., Walid Awad, Rick D. Davis, Alexander B. Morgan, Charles A. Wilkie

Chemistry Faculty Research and Publications

Nanocomposites result from combinations of materials with vastly different properties in the nanometer scale. These materials exhibit many unique properties such as improved thermal stability, reduced flammability, and improved mechanical properties. Many of the properties associated with polymer–clay nanocomposites are a function of the extent of exfoliation of the individual clay sheets or the quality of the nanodispersion. This work demonstrates that solid-state NMR can be used to characterize, quantitatively, the nanodispersion of variously modified montmorillonite (MMT) clays in polystyrene (PS) matrices. The direct influence of the paramagnetic Fe3, embedded in the aluminosilicate layers of MMT, on polymer protons within …

Comprehensive Laboratory Measurements Of Biomass-Burning Emissions: 1. Emissions From Indonesian, African, And Other Fuels, Ted J. Christian, B. Kleiss, Robert J. Yokelson, R. Holzinger, P. J. Crutzen, Wei Min Hao, B. H. Saharjo, Darold E. Ward

Chemistry and Biochemistry Faculty Publications

[1] Trace gas and particle emissions were measured from 47 laboratory fires burning 16 regionally to globally significant fuel types. Instrumentation included the following: open-path Fourier transform infrared spectroscopy; proton transfer reaction mass spectrometry; filter sampling with subsequent analysis of particles with diameter <2.5 μm for organic and elemental carbon and other elements; and canister sampling with subsequent analysis by gas chromatography (GC)/flame ionization detector, GC/electron capture detector, and GC/mass spectrometry. The emissions of 26 compounds are reported by fuel type. The results include the first detailed measurements of the emissions from Indonesian fuels. Carbon dioxide, CO, CH₄, NH₃, HCN, methanol, and acetic acid were the seven most abundant emissions (in order) from burning Indonesian peat. Acetol (hydroxyacetone) was a major, previously unobserved emission from burning rice straw (21–34 g/kg). The emission factors for our simulated African fires are consistent with field data for African fires for compounds measured in both …

Identification Of Tyr413 As An Active Site Residue In The Flavoprotein Tryptophan 2-Monooxygenase And Analysis Of Its Contribution To Catalysis, Pablo Sobrado, Paul F. Fitzpatrick

Chemistry Faculty Research & Creative Works

The flavoenzyme tryptophan 2-monooxygenase catalyzes the oxidation of tryptophan to indole acetamide, carbon dioxide, and water. The enzyme is a homologue of L-amino acid oxidase. In the structure of L-amino acid oxidase complexed with aminobenzoate, Tyr372 hydrogen bonds with the carboxylate of the inhibitor in the active site. All 10 conserved tyrosine residues in tryptophan 2-monooxygenase were mutated to phenylalanine; steady state kinetic characterization of the purified proteins identified Tyr413 as the residue homologous to Tyr372 of L-amino acid oxidase. Y413F and Y413A tryptophan 2-monooxygenase were characterized more completely with tryptophan as the substrate to probe the contribution of this …

Analysis Of The Role Of The Active Site Residue Arg98 In The Flavoprotein Tryptophan 2-Monooxygenase, A Member Of The L-Amino Oxidase Family, Pablo Sobrado, Paul F. Fitzpatrick

Chemistry Faculty Research & Creative Works

The flavoprotein tryptophan 2-monooxygenase catalyzes the oxidative decarboxylation of tryptophan to indole acetamide. We have previously identified tryptophan 2-monooxygenase as a homologue of L-amino acid oxidase [Sobrado, P., and Fitzpatrick, P. F. (2002) Arch. Biochem. Biophys. 402, 24-30]. On the basis of the sequence comparisons of the different LAAO family members, Arg98 of tryptophan 2-monooxygenase can be identified as an active site residue which interacts with the carboxylate of the amino acid substrate. The catalytic properties of R98K and R98A tryptophan 2-monooxygenase have been characterized to evaluate the role of this residue. Mutation of Arg98 to lysine decreases the first-order …

Targeting Methanopterin Biosynthesis To Inhibit Methanogenesis, Razvan Dumitru, Hector Palencia, Scott D. Schroeder, Bree A. Demontigny, James M. Takacs, Madeline E. Rasche, Jess L. Miner, Stephen W. Ragsdale

James M. Takacs Publications

This paper describes the design, synthesis, and successful employment of inhibitors of 4-( β -D-ribofuranosyl) aminobenzene-5’-phosphate (RFA-P) synthase, which catalyzes the first committed step in the biosynthesis of methanopterin, to specifically halt the growth of methane-producing microbes. RFA-P synthase catalyzes the first step in the synthesis of tetrahydromethanopterin, a key cofactor required for methane formation and for one-carbon transformations in methanogens. A number of inhibitors, which are N-substituted derivatives of p-aminobenzoic acid (pABA), have been synthesized and their inhibition constants with RFA-P synthase have been determined. Based on comparisons of the inhibition constants among various inhibitors, we propose that the …

Development And Optimization Of Hplc-Icpms For The Determination Of Iodine Speciation In Groundwater, Yun Qiu

All-Inclusive List of Electronic Theses and Dissertations

High performance liquid chromatography has been coupled with online inductively coupled plasma mass spectrometry detection for the determination of iodine speciation in drinking and groundwaters. Using ion exchange chromatography, the method is applied to quantify the concentrations of iodine species in groundwaters. The HPLC-UV detection was used first to examine the separation efficiency of the HPLC method. The limit of quantification was obtained for the HPLC-UV analysis. Direct ICPMS analysis of iodine species has been validated and optimized using an HC03"/C03 2 - aqueous solvent. HPLC was then interfaced to the ICPMS T-shape connection to allow online addition of internal …

A Comparative Study Of Photomultiplier Tubes And Charge Coupled Devices In Glow Discharge-Optical Emission Spectrometry, Robert James Broadwater

Masters Theses

This Masters Thesis compared two glow discharge-optical emission spectrometers designed around two different types of detectors: the photomultiplier tube (PMT) and the charge-coupled device (CCD). The two instruments compared were the LECO SA2000 (PMT-based) and the LECO GDS500a (CCD-based). Detection limit, dynamic range, precision, accuracy, and drift were determined to compare the detection systems between 165 and 450nm.

The PMT-based system outperformed the CCD-based system in all five of the categories studied based on the initial protocol. However, it was shown that improvements could be made in four of the five categories studied by exploiting the CCDs ability to monitor …

Evaluation Of 2,2'-Bipyridylpyridinetricarbonylrhenium (I) Triflate Complex As A Luminescent Probe For The Study Of Macromolecular Solution Dynamics, Richard Allen Allston

Seton Hall University Dissertations and Theses (ETDs)

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Capillary Electrophoretic Separations Of Metal Ions, Elena Hofman

Masters Theses

Transition-metal (Zn(II), Co(II), Ni(II) and Cu(II)) ion separation was studied using 8-hydroxyquinoline-5-sulfonic acid and 2-methyl-8-hydroxyquinoline ligands with surfactants (cationic and anionic) by capillary electrophoresis under a variety of conditions (like pH, ionic strength, voltage and ion, ligand and surfactant amounts) and has debuted a clear separation mechanism. With cationic surfactants, ligands compete with capillary surface silanols for the metal ions; with anionic surfactants, ligands, silanols and micelles compete.

An empirical parameter, K_e, (electrophoretic-mobilities based) rationalizing the separation was proposed, experimentally analyzed and supported; it provides a silanol group per cm² value of the capillary surface, an equilibrium …

Synthesis Of Adenosine Derivatives As Transcription Initiators And Preparation Of 5 ' Fluorescein- And Biotin-Labeled Rna Through One-Step In Vitro Transcription, Faqing Huang, Guocan Wang, Tricia Coleman, Na Li

Faculty Publications

Expanding our previous finding of an adenosine-initiated transcription system, we now demonstrate that either the 5' site or the N6 site of adenosine nucleotides can be modified extensively without abolishing their ability to initiate transcription under the T7 phi2.5 promoter. Two series of amino derivatives of adenosine nucleotides were synthesized. Fluorescein and biotin groups were coupled to AMP derivatives through linkers of different sizes and hydrophobicities. Both fluorescein- and biotin-conjugated (at either the 5' or N6 site) adenosine nucleotides can act as efficient transcription initiators, producing fluorescein- and biotin-labeled RNA at the specific 5' end by a one-step transcription procedure, …

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

Transmutation Research Program Reports (TRP)

Quarterly report highlighting research projects 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 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.

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quaterly Report September-December 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. …

Inside Unlv, Gian Galassi, Katrina Hudak, Carol C. Harter, Eric Sandgren, Tom Hagge

Inside UNLV

No abstract provided.

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics-Task V: Fourth Quarterly Report 09/01/2003-11/30/2003, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

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

Preparation And Characterization Of Y-Type Carbon Nanotubes By Using Anodized Alumina Oxide (Aao) Template, Jing Zhang, Quan-Yong Gao, Yong Yang

Journal of Electrochemistry

In this work, potential-modulation method was used in two-step anodization process to make an AAO template with Y-type nanochannels. Then Y-type carbon nanotubes with controlled length and branch angle were prepared in the template based on chemical vapor decomposion (CVD) method with Co particles as catalyst and C₂H₂ as carbon source. The Y-type nanotube branches exhibit the angle distribution ranging from 20° to 120°. The results demonstrated that the oxidation potential should be responsible for the angles and length of the branches. Short pulse and high oxidation potential will result in the short and dense nanotube branches.

Study On The Gas Generation In Different Charging Voltage During Formation Process In Polymer Lithium-Ion Battery, Li Huang, Ming-Gang Jin, Hui-Qun Cai, Ming-Sen Zheng, Quan-Feng Dong, Jin-Kua You, Zu-Geng Lin

Journal of Electrochemistry

The gases of polymer lithium-ion battery (PLI) generated under different voltages during the first charging process were examined by means of gas chromatography (GC), and the mechanism of the gas generation was discussed. The electrolyte used in batteries was 1 mol/L LiPF₆-EC～DMC～EMC=1∶1∶1(in volume). The results showed that when the charging voltage is less than 2.5 V,  the main component of generated gases are H₂ and CO₂, and when the charging voltage is 2.5 V, EC begins to decompose. Due to the decomposition of EC, the main generated gas is C₂H₄ when the …

Electrochemical And In-Situ Scanning Tunneling Microscopy Studies On The Sb Underpotential Deposition On Cu Single Crystal Electrodes, Ji-Hong Wu, Jia-Wei Yan, Jing Tang, Wen-Yun Hu, Bing-Wei Mao

Journal of Electrochemistry

We report electrochemical and in-situ STM studies on Sb UPD onto Cu(111) and Cu(100) electrode surfaces in HClO₄ and H₂SO₄ solutions. The results indicate that the electrode surface structure as well as anion can considerably influence Sb UPD. Sb UPD on Cu(100) forms open adlayer structures, which is accompanied by surface alloying due to the more open structure of the (100) surface, On Cu(111), a more compact Sb adlayer is formed instead. Anion adsorption influences the dynamics as well as the adlayer structure of Sb UPD. Owing to the strong adsorption of SO₄^2-, …

Application Of Hydrogen-Storage Alloy Electrode In Electrochemical Reduction Of Glucose, Hui Chen, You-Gen Tang, Zheng Tang

Journal of Electrochemistry

Electrolysis of glucose was performed at constant potential using hydrogen-storage alloy as catalytic reduction electrode. It was found that the superficial treatment and activation of hydrogen-storage alloy powder had obvious effects on improving the current efficiency of sorbitol. Under the optimums, current efficiency of sorbitol by electrolyzing glucose was over 94%. The yield of sorbitol was over 80%, the lifespan of electrode was tested and analyzed, the ways of regeneration were discussed.

The Study Of Green Corrosion Inhibitors For Mild Steel 907 In Natural Seawater Environment, Ping Gong, Min Du, Qing-Zhang Wang, Zhen-Jun Mu

Journal of Electrochemistry

Nine green compounds, including calcium gluconate, zinc gluconate, zinc sulfate, garlic, ACUSOL 445N, OS-15, APG, OCTA and STPP were selected according to the methods of molecule design and function groups prune. The functions of combined corrosion inhibitors mixed by the compounds mentioned above for mild steel in seawater were studied in this work using the methods of polarization curve and weight-loss.The best weight ratio and distinct synergistic effect of calcium gluconate, zinc sulfate and OCTA were studied by Latin experiment. The afgereffects of the best weight ratio corrosoin inhibitor were studied by subsection experiment. In this way, a kind of …

Preparation And Properties Of The Composite Microporous Pvdf-Hfp/Sio2 Based Polymer Electrolytes, Bao-Wen Zhang, Lu Qi, Hui Hen, Xiao-Hui Zhu, Li-Yan Liu, Yun-Xiang Ci

Journal of Electrochemistry

Microporous PVDF-HFP/SiO₂ film were prepared using a solvent/nonsolvent method-phase inversion method and the volatile plasticizers DMC, DEC or PC. The conductivity of the films increased pore volume measured by a nonsolvent uptake method. The conductivity of 1.86×10^-3 S⋅m^-1 were obtained using the liquid electrolyte LiPF₆(1 M) in EC/DMC (1:1).

Optimizing Catalyst Layer Composition Of Pemfc By Orthogonal Method, Ming-Hua Wang, Xin-Jian Zhu, Guang-Yi Cao, Sheng Sui, Qing-Chun Yu, Ming-Ruo Hu, Zheng-Yu Fan

Journal of Electrochemistry

The optimal composition of catalyst layer in a PEMFC electrode was studied through orthogonal method. It was showed that the performance of hydrophilic electrodes, in which there is no PTFE in the catalyst layer, were more favorable than that of hydrophobic electrodes. According to this condition, the power density of PEMFC attained 0.37 w·cm^-2 when the Nafion loading was 1.4 mg·cm^-2, and the Pt loading was 0.4 mg·cm^-2 in the catalyst layer, using H₂ as fuel and air as oxidant both at atmospheric pressure. Additionally, the results showed that increasing Pt loading in Pt/C catalyst …

The Study On Carbon Nanotube-Loaded Pt Catalysts For Proton Exchange Membrane Fuel Cells, Hong Zhu, Feng-Juan Ge, Xiao-Hong Kang, Yu-Guo Yang, Yun-Hua Xu

Journal of Electrochemistry

Carbon nanotube-supported-platinum (Pt/CNTs) and carbon-supported-platinum (Pt/C) catalysts were synthesized by in-situ chemical reduction. They were analyzed using TEM and XRD, then made into electrodes to be part of assemable PEMFC for the performence tests. The resulted show that Pt clusters in both catalysts are of small particle size (about 4nm), and Pt/CNTs exhibits a higher catalytic activity than Pt/C.

Effect Of Dspp Al2O3 On Electrical Properties Of Polymer Electrolyte, Hai-Fen Xie, Xiao-Xiang Sun, Yi-Pin Wang, Guang-Yuan Li

Journal of Electrochemistry

The PEO-NaSCN polymer solid electrolytes by adding dispersed second phase particles (DSPP) of Al₂O₃ were studied. The characteristics of solid electrolytes and conductivity values are dependent on DSPP Al₂O₃ sizes and its contents. It was found that when the Al₂O₃ sizes are less than 1 μm, which is a criticle size, the sample conductivities were larger than those of the pure PEO-NaSCN samples and when the Al₂O₃ sizes are larger than 1 μm then the sample conductivities are less then those of the pure samples. The maximum conductivity …