Chemistry Commons^™

Preparations Of Spherical Polymeric Particles From Tanzanian Cashew Nut Shell Liquid By Suspension Polymerization, L L Mkayula, Y M M Makame, T H Matechi

Tanzania Journal of Science

Spherical Polymeric Particles (SPP) have been prepared from Tanzanian Cashew Nut Shell Liquid (CNSL) by suspension polymerization technique involving either step-growth or chain- growth polymerization mechanisms. The sizes of the SPP, which ranged from 0.1 to 2.0 mm were strongly influenced by the amounts of stabilizers in polymerization recipes used. The particles showed variable surface areas, indicative of the presence of pores in some of the preparations and the highest surface area recorded was about 260 m2g-1. The particles were found to exhibit Langmuir-type adsorption isotherms with saturation capacity of about 9.0 and 44.2 mg/g for Na+ and Ca2+, respectively. …

Physical And Chemical Characteristics Of Water In Selected Locations In Lake Victoria, Tanzania, M A Kishe

Tanzania Journal of Science

A study conducted during the period of March/April 2002 aimed at measuring physical and chemical parameters in Tanzanian portion of Lake Victoria. Temperature and conductivity values were homogeneous among and within the study stations. Levels of dissolved oxygen (DO) ranged from 4 - 9 mgl-1 and there was significant difference between stations (P < 0.05). Water transparency was poor (< 2 m secchi depth) and differed from one sampling station to another. Ammonium nitrogen (NH4+-N), with few exceptions, showed the highest concentrations both at the bottom and near-surface followed by total phosphates (TP), nitrate nitrogen (NO2+NO3--N), nitrite nitrogen (NO2--N) and Soluble Reactive Silicon (SRSi). Concentrations of NH4+-N, TP and SRSi were high at bottom waters and the reverse was true for NO2+NO3--N and NO2--N. Differences in nutrients and physical water parameters among sampling stations were statistically significant (P < 0.05). However, temperature and nutrient levels at studied areas were higher than that of 50 years ago and the trend reversed for DO and transparency. This indicates that Lake Victoria is receiving organic materials from the catchment area leading to the decline of water quality. Long-term efforts for rehabilitation, conservation and sustainable management of the lake are suggested.

Evaluation Of Fluorapatite As A Waste-Form Material: First Quarter Report (2004-05), October 1 - December 31, 2004, Dennis W. Lindle, Oliver Hemmers

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 …

Elemental And Isotopic Compositions Of Organic Carbon And Nitrogen Of Recently Deposited Organic Matter In Empakai Crater And Its Implication For Climatic Changes In Northern Tanzania, A N N Muzuka

Tanzania Journal of Science

A 29 cm long core recovered from a water depth of 5 m in a small closed lake located in the Empakai crater northern Tanzania, is used to document the contents of organic carbon and nitrogen, stable isotopes composition of organic carbon and nitrogen, and C/N ratios and to infer climatic changes from these data. The δ 13C and δ15N values for this core, which averages - 16.5±2.1l and 11.0±5.6l respectively, show a general downcore decrease below 5 cm. However, within this general trend, two peaks enriched in 13C are observable at about 8 cm and 13 cm. The peak …

Cofactor Fingerprinting With Std Nmr To Characterize Proteins Of Unknown Function: Identification Of A Rare Ccmp Cofactor Preference, Huili Yao, Daniel Sem

Chemistry Faculty Research and Publications

Proteomics efforts have created a need for better strategies to functionally categorize newly discovered proteins. To this end, we have employed saturation transfer difference NMR with pools of closely related cofactors, to determine cofactor preferences. This approach works well for dehydrogenases and has also been applied to cyclic nucleotide‐binding proteins. In the latter application, a protein (radial spoke protein‐2, RSP2) that plays a central role in forming the radial spoke of Chlamydomonas reinhardtii flagella was shown to bind cCMP. cCMP‐binding proteins are rare, although previous reports of their presence in sperm and flagella suggest that cCMP may have a more …

Inelastic Electron Tunneling Via Molecular Vibrations In Single-Molecule Transistors, L H. Yu, Z K. Keane, Jacob W. Ciszek, L Cheng, M P. Stewart, J M. Tour, D Natelson

Chemistry: Faculty Publications and Other Works

In single-molecule transistors, we observe inelastic cotunneling features that correspond energetically to vibrational excitations of the molecule, as determined by Raman and infrared spectroscopy. This is a form of inelastic electron tunneling spectroscopy of single molecules, with the transistor geometry allowing in situ tuning of the electronic states via a gate electrode. The vibrational features shift and change shape as the electronic levels are tuned near resonance, indicating significant modification of the vibrational states. When the molecule contains an unpaired electron, we also observe vibrational satellite features around the Kondo resonance.

Kinetics And Mechanism Of The Catalysis Of The Decomposition Of Hydrogen Peroxide By Schiff Base Complexes Of Copper(Ii)., Timothy Kum Beng

Electronic Theses and Dissertations

Spectroscopic studies have been used to describe the mechanism of the decomposition of hydrogen peroxide by solutions of a dimeric Cu(II) complex of a dissymetric Schiff base, [CuSALAD]₂.H₂O, and imidazole or methyl substituted imidazoles, B, which form monomeric CuSALAD.B₂ complexes, in aqueous ethanol solvent. Freezing point depression and vapor pressure lowering studies were carried out to confirm the dimeric nature of the [CuSALAD]₂.H₂O complex that had been previously reported. The stoichiometry of the [CuSALAD]₂.H₂O-imidazole equilibrium was extensively studied pointing to a 1:4 stoichiometry. The CuSALAD.B₂ adducts …

Gas-Phase Chemical Characteristics Of Asian Emission Plumes Observed During Itct 2k2 Over The Eastern North Pacific Ocean, J. B. Nowak, D. D. Parrish, J. A. Neuman, J. S. Holloway, O. R. Cooper, T. B. Ryerson, Jr K. Nicks, F. Flocke, J. M. Roberts, E. Atlas, J. A. De Gouw, Stephen G. Donnelly Ph.D., E. Dunlea, G. Hübler, L. G. Huey, S. Schauffler, D. J. Tanner, C. Warneke, F. C. Fehsenfeld

Chemistry Faculty Publications

The gas-phase chemical characteristics of emission plumes transported from Asia across the Pacific Ocean observed during the Intercontinental Transport and Chemical Transformation experiment in 2002 (ITCT 2K2) are described. Plumes measured in the troposphere from an aircraft were separated from the background air in data analysis using 1-s measurements of carbon monoxide (CO), total reactive nitrogen (NOy), and other gasphase species along with back trajectory analysis. On the basis of these measurements, Asian transport plumes with CO mixing ratios greater than 150 ppbv were observed on seven flights. Correlations between 1-s observations of CO, ozone (O3), and NOy are used …

Changes In The Photochemical Environment Of The Temperate North Pacific Troposphere In Response To Increased Asian Emissions, D. D. Parrish, E. J. Dunlea, E. L. Atlas, S. Schauffler, Stephen G. Donnelly Ph.D., V. Stroud, A. H. Goldstein, D. B. Millet, M. Mckay, D. A. Jaffe, H. U. Price, P. G. Hess, F. Flocke, J. M. Roberts

Chemistry Faculty Publications

Measurements during the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) field study characterized the springtime, eastern Pacific ozone distribution at two ground sites, from the National Oceanic and Atmospheric Administration WP-3D aircraft, and from a light aircraft operated by the University of Washington. D. Jaffe and colleagues compared the 2002 ozone distribution with measurements made in the region over the two previous decades and show that average ozone levels over the eastern midlatitude Pacific have systematically increased by ∼10 ppbv in the last two decades. Here we provide substantial evidence that a marked change in the photochemical environment in …

Multiscale Simulations Of Tropospheric Chemistry In The Eastern Pacific And On The U.S. West Coast During Spring 2002, Youhua Tang, Gregory R. Carmichael, Larry W. Horowitz, Itsushi Uno, Jung Hun Woo, David G. Streets, Donald Dabdub, Gakuji Kurata, Adrian Sandu, James Allan, Elliot Atlas, Frank Flocke, Lewis Gregory Huey, Roger O. Jakoubek, Dylan B. Millet, Patricia K. Quinn, James M. Roberts, Douglas R. Worsnop, Allen Goldstein, Stephen G. Donnelly Ph.D., Sue Schauffler, Verity Stroud, Kristen Johnson, Melody A. Avery, Hanwant B. Singh, Eric C. Apel

Chemistry Faculty Publications

Regional modeling analysis for the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) experiment over the eastern Pacific and U.S. West Coast is performed using a multiscale modeling system, including the regional tracer model Chemical Weather Forecasting System (CFORS), the Sulfur Transport and Emissions Model 2003 (STEM-2K3) regional chemical transport model, and an off-line coupling with the Model of Ozone and Related Chemical Tracers (MOZART) global chemical transport model. CO regional tracers calculated online in the CFORS model are used to identify aircraft measurement periods with Asian influences. Asian-influenced air masses measured by the National Oceanic and Atmospheric Administration (NOAA) …

Chemical Composition Of Air Masses Transported From Asia To The U.S. West Coast During Itct 2k2: Fossil Fuel Combustion Versus Biomass-Burning Signatures, J. A. De Gouw, O. R. Cooper, C. Warneke, P. K. Hudson, F. C. Fehsenfeld, J. S. Holloway, G. Hübler, Jr K. Nicks, J. B. Nowak, D. D. Parrish, T. B. Ryerson, E. L. Atlas, Stephen G. Donnelly Ph.D., S. M. Schauffler, V. Stroud, K. Johnson, G. R. Carmichael, D. G. Streets

Chemistry Faculty Publications

As part of the Intercontinental Transport and Chemical Transformation experiment in 2002 (ITCT 2K2), a National Oceanic and Atmospheric Administration (NOAA) WP-3D research aircraft was used to study the long-range transport of Asian air masses toward the west coast of North America. During research flights on 5 and 17 May, strong enhancements of carbon monoxide (CO) and other species were observed in air masses that had been transported from Asia. The hydrocarbon composition of the air masses indicated that the highest CO levels were related to fossil fuel use. During the flights on 5 and 17 May and other days, …

Chemical Analyses In Support Of Yucca Mountain Studies, Jeanette Daniels, Klaus J. Stetzenbach, Drew Coleman, Amy J. Smiecinski, Raymond E. Keeler

Publications (YM)

The objective of this task “Chemical Analyses in Support of Yucca Mountain Studies” is to provide the Department of Energy (DOE) with data and reports from comprehensive chemical analyses of waters sampled from the wells of the Nye County Early Warning Drilling Program (NCEWDP), the Inyo County’s Drilling Program, and the Nye county Tracer Test. In addition, this task will be used to provide other laboratory support needs as they arise within the Yucca Mountain Project. This support is provided by the Harry Reid Center for Environmental Studies (HRC) at University of Nevada, Las Vegas (UNLV), which is part of …

Sm2Nairo6, A Monoclinically Distorted Double Perovskite, Samuel J. Mugavero Iii, Irina V. Puzdrjakova, Mark D. Smith, Hans-Conrad Zur Loye

Faculty Publications

Single crystals of the lanthanide-containing iridate, disamarium sodium iridium hexaoxide, Sm₂NaIrO₆, were prepared via high-temperature flux growth and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P2₁/n and is a double perovskite, consisting of a 1:1 ordered rock-salt-type lattice of corner-shared NaO₆ and IrO₆ distorted octahedra. Samarium occupies the eightfold coordination site generated by the connectivity of the octahedra.

Anchoring The Potential Energy Surface Of The Cyclic Water Trimer, Julie A. Andersen, Kelly Crager, Lisa Fedoroff, Gregory S. Tschumper

Chemistry Faculty Research & Creative Works

Six cyclic stationary points on the water trimer potential energy surface have been fully optimized at the MP2 level with the aug-cc-pVQZ basis set. In agreement with previous work, harmonic vibrational frequencies indicate that two structures are minima, three are transition states connecting minima on the surface while the remaining stationary point is a higher-order saddle point. The 1-and n-particle limits of the electronic energies of each of these six structures were estimated by systematically varying both the basis sets and theoretical methods. The former limit was approached with the cc-pVXZ and aug-cc-pVXZ families of basis sets (X=2-7) while MP2, …

Parallel Writing On Zirconium Nitride Thin Films By Local Oxidation Nanolithography, N. Farkas, J. R. Comer, G. Zhang, Edward A. Evans, R. D. Ramsier, S. Wight, J. A. Dagata

Chemical, Biomolecular, and Corrosion Engineering Faculty Research

Parallel pattern transfer of submicrometer-scale oxide features onto zirconium nitride thin films is reported. The oxidation reaction was verified by Auger microprobe analysis and secondary ion mass spectrometry. Oxide features of similar to70 nm in height can be formed and selectively etched in a dilute aqueous hydrogen fluoride solution. This provides an interesting route to potential new applications for high-melting point, biocompatible surfaces that possess small feature sizes with controlled geometries. (C) 2004 American Institute of Physics.

Manganese Oxide Thin Films Prepared By Nonaqueous Sol-Gel Processing: Preferential Formation Of Birnessite, Stanton Ching, Steven M. Hughes, Timothy P. Gray, Eric J. Welch

Chemistry Faculty Publications

High quality manganese oxide thin films with smooth surfaces and even thicknesses have been prepared with a nonaqueous sol–gel process involving reduction of tetraethylammonium permanganate in methanol. Spin-coated films have been cast onto soft glass, quartz, and Ni foil substrates, with two coats being applied for optimum crystallization. The addition of alkali metal cations as dopants results in exclusive formation of the layered birnessite phase. By contrast, analogous reactions in bulk sol–gel reactions yield birnessite, tunneled, and spinel phases depending on the dopant cation. XRD patterns confirm the formation of well-crystallized birnessite. SEM images of Li-, Na-, and K–birnessite reveal …

The Characterization Of Nanosized Nickel-Zinc Ferrites Synthesized Within Reverse Micelles Of Ctab/1-Hexanol/Water Microemulsion, Vuk Uskoković, Miha Drofenik, Irena Ban

Pharmacy Faculty Articles and Research

Stoichiometric nanocrystalline nickel–zinc ferrites were synthesized by a reverse micelle method following a multi-microemulsion approach. Different pH values were chosen for the alkali precipitating reaction during the synthesis of different powders. Synthesized, as-dried and subsequently calcined powders were characterized in terms of their magnetic properties. XRD analyses and specific-surface area measurements were used to determine the average particle sizes of the synthesized samples. DCS and TGA measurements were performed to reveal the phase transitions within the samples at elevated temperatures, whereas TEM was used to view and record the microstructure of the nanosized ferrite samples. A possible mechanism of the …

Toward The Design Of Mr Agents For Imaging Β-Cell Function, Mark Woods, Shanrong Zhang, A. Dean Sherry

Chemistry Faculty Publications and Presentations

The chemistry of Gd3+-based MRI agents has advanced considerably during the past decade toward agents with higher relaxivity and agents that respond to physiology and / or metabolism. This review describes various approaches that have been taken toward the development of responsive contrast agents and discusses the importance of fast water exchange for advancement of targeted Gd3+-based agents with higher sensitivity. The recent discovery of Eu3+ complexes having extraordinarily slow water exchange has opened a new avenue in contrast agent design based upon the chemical exchange saturation transfer (CEST) mechanism. These new paramagnetic complexes called PARACEST agents offer new possibilities …

Mössbauer Spectral Study Of The Magnetocaloric Femnp₁₋ₓasₓ Compounds, Raphäel P. Hermann, Ojied Tegus, Ekkehard H. Brück, K. H. J. Buschow, Frank R. De Boer, Gary J. Long, Fernande Grandjean

Chemistry Faculty Research & Creative Works

The magnetic phase transitions in the FeMnP_1-xAs_x compounds with x= 0.25, 0.35, 0.45, 0.50, and 0.55, have been studied by iron-57 Mössbauer spectroscopy. The ferromagnetic and antiferromagnetic spectra have been analyzed with a model that takes into account the random distribution of the P and As near-neighbor anions of a given iron site. This distribution is a binomial distribution of the contributions to the spectra of each iron with n As near neighbors. A magnetostriction model has been used to characterize the temperature induced paramagnetic to ferromagnetic first-order phase transition and order parameters, η_F=2.6, 2.3, …

Synthesis And Characterization Of A Recombinant Thrombin Inhibitor, Joel Lwande

Masters Theses

The final step of the blood coagulation cascade is catalyzed by thrombin, a serine protease. Like most enzyme activities, thrombin activity encounters inhibition from both direct and indirect inhibitors. A new thrombin inhibitor peptide named theromin was recently isolated from the leech Theromyzon tessulatum, and it is the most potent thrombin inhibitor isolated to date. Theromin is made up of 67 amino acid residues, out of which 16 are cysteines engaged in 8-disulfide bridges.

We synthesized the theromin gene and expressed the protein in Eschericia coli. We purified the recombinant protein and carried out thrombin inhibition assays that …

The Electrochemical Separation Of Curium And Americium: Quaterly Report August-December 2004, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This research report outlines the current status and progress associated with the electrochemical separation of Curium and Americium. The following pages outline the progress on our project to date. We have been actively performing research on this project for three months and are currently on schedule in terms of the proposed timelines.

The initial focus of the project involved setting up the laboratories for the studies outlined in the grant proposal. The instrumentation needed included an electrochemical work station that will perform the bulk of the electrochemical studies. This instrument will complement the electrochemical instrumentation in Dr. Hatchett’s laboratory and …

Dissolution, Reactor, And Environmental Behavior Of Zro2-Mgo Inert Fuel Matrix: Quarterly Report, October 2004 To December 2004, Earl Wolfram, Thomas Hartmann, Kenneth Czerwinski

Fuels Campaign (TRP)

This project will examine inert matrix fuels containing ZrO₂ and MgO as the inert matrix, with the relative amount of MgO varied from 30% to 70% in ZrO₂. Reactor physics calculations will be used to examine suitable quantities of burnable poisons from the candidate elements Gd, Er, or Hf with reactor grade Pu providing the fissile component, with up to 10% of ²³⁹Pu. Ceramics will be synthesized and characterized based on the reactor physics results. The solubility the fuel ceramics, in reactor conditions, reprocessing conditions, and repository conditions, will be investigated in a manner to provide …

Analysis Of Benzo(A)Pyrene-Induced Gene Expression Changes In Fisher 344 Rat Liver By Affymetrix Microarray And Quantitative Real-Time Pcr, Alhaji Umar N’Jai

Dissertations

No abstract provided.

A Tga/Ftir And Mass Spectral Study On The Thermal Degradation Of Bisphenol A Polycarbonate, Bok Nam Jang, Charles A. Wilkie

Chemistry Faculty Research and Publications

The thermal degradation of polycarbonate under nitrogen was studied using TGA/FTIR, GC/MS and LC/MS as a function of mass loss. The gases evolved during degradation were inspected by in situ FTIR and then the evolved products were collected and analysed using FTIR, GC–MS and LC–MS. The structures of the evolved products are assigned on the basis of FTIR and GC/MS results. The main thermal degradation pathways follow chain scission of the isopropylidene linkage, and hydrolysis/alcoholysis and rearrangement of carbonate linkages. In the case of chain scission, it was proposed that methyl scission of isopropylidene occurs first, according to the bond …

Electrochemical Behaviours Of Hemoglobin-Ddab-Modified Powder Microelectrode And The Application Of The Powder Microelectrode In Determination Of Nitric Oxide, Zhi-Mou Guo, Huan Liu, Jian Chen, Wen-Ting Zhang

Journal of Electrochemistry

The electrochemical behaviours of DDAB-Hb-PME were studied in this paper. The (apparent) surface concentration of Hb was enhanced greatly by using the powder microelectrode (technique). NO reacts with Hb and absorbs on the surface of the modified carbon powder. Therefore, the output of the electrode was enhanced greatly by employing PME with higher reaction surface (area). The sensitivity of DDAB-Hb-PME is 3.1 mA/μmol·L^-1·cm², which is much larger than the values obtained with the traditional electrodes. The detection limit is 9 nmol·L^-1 and the linear response range is 9～100 nmol·L^-1.

Improvement And Its Mechanism Of Storage Performance Of Ni-Mh Battery, Xiao-Feng Li, Li-Ping Ma, Yu-Wan Lou, Feng Li, Bao-Jia Xia

Journal of Electrochemistry

The storage performance of nickel-metal-hydride (Ni-MH) battery was studied by using galvanostatic charge-discharge and cyclic voltammetry. The experimental results indicated that CoOOH could not be completely restored after its being thoroughly reduced at lower potential, which might weaken electric conduction network in the positive electrode and result in fading of electrochemical properties of Ni-MH battery. Addition of nickel powder as a conductive agent into the positive electrode was beneficial to the capacity recovery after storage.

Effect Of Fe3+ Dopen Of Titanium Dioxide Film On Absorption Spectra And Photo Catalysis, Mei-Qun Xiao, Jia-Nian Shen, Moucheng Li, Peng-Fei Wu, Dong Liu, Yu-Juan Zhang

Journal of Electrochemistry

Photo-catalytic titanium dioxide film in nano crystalline has been prepared by electrochemical oxidation process and adding different amount of ferric ion into the electrolyte during the anodic oxidation.The effects of Fe³⁺ dopen on absorption spectra and photo-catalytic of the titanium dioxide films have been studied. It shows that the Fe³⁺ dopen caused the red shife of the absorption edge for the incoming light and exhibited the improved photocatalytic reactivity.

Preparation And Electrochemical Magnesium Insertion Behaviors Of Mgv2O6, Hua-Tang Yuan, Li-Fang Jiao, Jian-Sheng Cao, Xiu-Sheng Liu, Ming Zhao, Yong-Mei Wang

Journal of Electrochemistry

MgV₂O₆ was synthesized by conventional solid-state reaction from MgO and V₂O₅ as starting materials. X-Ray diffraction analysis showed that the prepared sample belongs to the monoclinic structure. Electrochemical magnesium insertion from aprotic electrolytes such as organomagnesium halides into this host was found possible and exhibited charge/discharge circulation.

LicoXNi1-XO2 Cathode Materials Prepared By Electrolysis Of Co And Ni, Jin-Ping Wei, Xin Sun, Xiao-Yu Wang, Xi-Kui Bian, Jin-Ling Zhai, Yan-Jie Yan-Jie

Journal of Electrochemistry

A new electrolytic method was developed to prepare LiCo_xNi_1-xO₂ as a cathode material of lithium-ion battery. Contrary to the traditional method, electrolytic method is a potential method with simple process to industrialization and no pollution. Metal cobalt and nickel were electrolysed in parallel to prepare the precursor of Co_xNi_{1- x}(OH)₂.Different compositional precursors could be conveniently prepared by changing electrolytic current. The LiCo_0.3Ni_0.7O₂ cathode prepared by this method was found favorable charge-discharge and cycle properties. For the LiCo_0.3Ni_0.7O₂ cathode material, …

Anodic Dissolution Of Aluminum In Koh-Ethanol Solutions, Hai-Bo Shao, Jian-Ming Wang, Xiao-Yan Wang, Yi Zheng, Jian-Qing Zhang

Journal of Electrochemistry

The feasibility of employing aluminum in KOH ethanol solution as a battery anode system was discussed. Weight loss measurement showed that the corrosion rate of Al is low enough to be used in sealed batteries. Through the measurements done by anodic polarization, EIS and galvanostatic discharge, it was found that Al is electrochemical active in a wide potential range in this system, and its discharge mechanism is similar to that of Al in aqueous solution. The discharge potential increased rapidly after a period of time, which might be caused by the discharge products depositing on the electrode surface.