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The Influence of the Linker Geometry in Bis(3-hydroxy-N-methyl-pyridin-2-one) Ligands on Solution-Phase Uranyl Affinity

Description: Seven water-soluble, tetradentate bis(3-hydroxy-N-methyl-pyridin-2-one) (bis-Me-3,2-HOPO) ligands were synthesized that vary only in linker geometry and rigidity. Solution phase thermodynamic measurements were conducted between pH 1.6 and pH 9.0 to determine the effects of these variations on proton and uranyl cation affinity. Proton affinity decreases by introduction of the solubilizing triethylene glycol group as compared to un-substituted reference ligands. Uranyl affinity was found to follow no discernable trends with incremental geometric modification. The butyl-linked 4Li-Me-3,2-HOPO ligand exhibited the highest uranyl affinity, consistent with prior in vivo decorporation results. Of the rigidly-linked ligands, the o-phenylene linker imparted the best uranyl affinity to the bis-Me-3,2-HOPO ligand platform.
Date: August 12, 2010
Creator: Szigethy, Geza & Raymond, Kenneth
Partner: UNT Libraries Government Documents Department

Cleaning Products and Air Fresheners: Emissions and ResultingConcentrations of Glycol Ethers and Terpenoids

Description: Experiments were conducted to quantify emissions and concentrations of glycol ethers and terpenoids from cleaning product and air freshener use in a 50-m{sup 3} room ventilated at {approx}0.5 h{sup -1}. Five cleaning products were applied full-strength (FS); three were additionally used in dilute solution. FS application of pine-oil cleaner (POC) yielded 1-h concentrations of 10-1300 {micro}g m{sup -3} for individual terpenoids, including {alpha}-terpinene (90-120), d-limonene (1000-1100), terpinolene (900-1300), and {alpha}-terpineol (260-700). One-hour concentrations of 2-butoxyethanol and/or dlimonene were 300-6000 {micro}g m{sup -3} after FS use of other products. During FS application including rinsing with sponge and wiping with towels, fractional emissions (mass volatilized/dispensed) of 2-butoxyethanol and d-limonene were 50-100% with towels retained, {approx}25-50% when towels were removed after cleaning. Lower fractions (2-11%) resulted from dilute use. Fractional emissions of terpenes from FS use of POC were {approx}35-70% with towels retained, 20-50% with towels removed. During floor cleaning with dilute solution of POC, 7-12% of dispensed terpenes were emitted. Terpene alcohols were emitted at lower fractions: 7-30% (FS, towels retained), 2-9% (FS, towels removed), and 2-5% (dilute). During air-freshener use, d-limonene, dihydromyrcenol, linalool, linalyl acetate, and {beta}-citronellol were emitted at 35-180 mg d{sup -1} over three days while air concentrations averaged 30-160 {micro}g m{sup -3}.
Date: August 1, 2005
Creator: Singer, Brett C.; Destaillat, Hugo; Hodgson, Alfred T. & Nazaroff,William W.
Partner: UNT Libraries Government Documents Department

Preparation of Size-tunable, Highly Monodisperse PVP-Protected Pt-nanoparticles by Seed-mediated Growth

Description: We demonstrate a preparative method which produces highly-monodisperse Pt-nanoparticles of tunable size without the external addition of seed particles. Hexachloroplatinic acid is dosed slowly to an ethylene glycol solution at 120 C and reduced in the presence of a stabilizing polymer poly-N-vinylpyrollidone (PVP). Slow addition of the Pt-salt first will first lead to the formation of nuclei (seeds) which then grow further to produce larger particles of any desired size between 3 and 8nm. The amount of added hexachloroplatinic acid precursor controls the size of the final nanoparticle product. TEM was used to determine size and morphology and to confirm the crystalline nature of the nanoparticles. Good reproducibility of the technique was demonstrated. Above 7nm, the particle shape and morphology changes suddenly indicating a change in the deposition selectivity of the Pt-precursor from (100) towards (111) crystal faces and breaking up of larger particles into smaller entities.
Date: April 2, 2008
Creator: Koebel, Matthias Michael; Jones, Louis C. & Somorjai, Gabor A.
Partner: UNT Libraries Government Documents Department

Efficient on-site degradation of high concentration of spent deicing fluids: A laboratory study. Final report

Description: The on-site treatment of antifreeze compounds and aircraft deicing fluids (ethylene glycol and propylene glycol) will reduce disposal costs, decrease environmental impact, minimize the potential for additional spills/contamination and meet the goals of pollution prevention by reducing the amount of hazardous materials generated. The authors have identified bacteria that can degrade 1-10% glycol waste at room temperatures of ca. 23C. A second subculture was isolated that could degrade glycol waste at ca. 4C.
Date: October 1, 1997
Creator: Strong, J.M. & Waltz, M.
Partner: UNT Libraries Government Documents Department

High Activity catalysts for Polyols Production From C-6 Sugars

Description: Over the course of this project, many significant discoveries have been made in the process for the conversion of sorbitol to value added products. The object was developing a process for the production of propylene glycol (PG), ethylene glycol (EG), and glycerol from sorbitol.
Date: May 6, 2003
Creator: Werpy, Todd; Zacher, Alan; Frye, John; Peterson, Keith; Neuenschwander, Gary; Alderson, Eric et al.
Partner: UNT Libraries Government Documents Department

Remarks on ConstitutiveModeling of Nanofluids

Description: Nanofluids are made by adding nanoscale particles in low volumetric fractions to a fluid in order to enhance or improve their rheological, mechanical, optical, and thermal properties. The base fluid can be any liquid such as oil, water, ethylene glycol, or conventional fluid mixtures. Limited available studies on nanofluid viscosity have been reported [1-19]. In most of these studies, the behavior of the viscosity and the shear stress of nanofluids have been interpreted using the widely used empirical model developed by Casson [20].
Date: January 1, 2012
Creator: Massoudi, Mehrdad & Phuoc, Tran X.
Partner: UNT Libraries Government Documents Department

Seedless Polyol Synthesis and CO Oxidation Activity of Monodisperse (111) and (100)-Oriented Rhodium Nanocrystals in Sub-10 nm Sizes

Description: Monodisperse sub-10 nm (6.5 nm) sized Rh nanocrystals with (111) and (100) surface structures were synthesized by a seedless polyol reduction in ethylene glycol, with poly(vinylpyrrolidone) as a capping ligand. When using [Rh(Ac){sub 2}]{sub 2} as the metal precursor, (111)-oriented Rh nanopolyhedra containing 76% (111)-twined hexagons (in 2D projection) were obtained; whereas, when employing RhCl{sub 3} as the metal precursor in the presence of alkylammonium bromide, such as tetramethylammonium bromide and trimethyl(tetradecyl)ammonium bromide, (100)-oriented Rh nanocubes were obtained with 85% selectivity. The {l_brace}100{r_brace} faces of the Rh nanocrystals are stabilized by chemically adsorbed Br{sup -} ions from alkylammonium bromides, which led to (100)-oriented nanocubes. Monolayer films of the (111)-oriented Rh nanopolyhedra and (100)-oriented Rh nanocubes were deposited on silicon wafers in a Langmuir-Blodgett trough to make model 2D nanoarray catalysts. These nanocatalysts were active for CO oxidation by O{sub 2}, and the turnover frequency was independent of nanoparticle shape, consistent with that previously observed for Rh(111) and Rh(100) single crystals.
Date: March 15, 2010
Creator: Zhang, Yawen; Grass, Michael E.; Huang, Wenyu & Somorjai, Gabor A.
Partner: UNT Libraries Government Documents Department


Description: Reaction of optically pure (+) and (-) 7{beta},8{alpha}-dihydroxy-9{alpha},10{alpha}-epoxy-7,8,9.10-tetrahydrobenzo[a]pyrene with DNA in vitro yielded diastereomeric covalent adducts with the exocyclic amino groups of deoxyguanosine and deoxyadenosine. The ratio of two deoxyguanosine diastereomers derived by reacting the (+) and (-) hydrocarbons with native calf thymus and double stranded 0X174 DNA was 20:1 while reaction of the enantiomers with heat denatured calf thymus and single stranded 0X174 DNA resulted in a ratio near 1:1. In contrast, deoxyaadenosine diastereomer pairs were approximately 1:1 in all cases studied. The (+) and (-) enantiomers of the benzo[a]pyrene diol epoxide, therefore, interact asymmetrically with the guanine binding sites of double stranded but not single stranded polydeoxynucleotides. In contrast, reaction of the enantiomers with adenine is not stereoselective.
Date: July 1, 1978
Creator: Meehan, T. & Straub, K.
Partner: UNT Libraries Government Documents Department

Benzo[a]Pyrene Diol Epoxide Perturbation of Cell Cycle Kinetics of Synchronized Mouse Liver Epithelial Cells

Description: A cell cycle synchronization system is described for the analysis of the perturbation of cell cycle kinetics and the cycle-phase specificity of chemicals and other agents. We used the system to study the effects of ({+-})r-7, t-8-dihydroxy-t-9, 10-oxy-7,8,9,10-tetrahydrobenzo[a]pyrene (BaP diol epoxide) upon the cell cycle of mouse liver epithelial cells(NMuLi). BaP diol epoxide(0.6 uM) was added to replated cultures of NMuLi cells that had been synchronized in various stages of the cell cycle by centrifugal elutriation. DNA histograms were obtained by flow cytometry as a function of time after replating. The data were analyzed by a computer modeling routine and reduced to a few graphs illustrating the 'net effects' of the BaP diol epoxide relative to controls. BaP diol epoxide slowed S-phase traversal in all samples relative to their respective control. Traversal through G{sub 2}M was also slowed by at least 50%. BaP diol epoxide had no apparent effect upon G{sub 1} traversal by cycling cells, but delayed the recruitment of quiescent G{sub 0} cells by about 2 hrs. The methods described constitute a powerful new approach for probing the cell cycle effects of a wide variety of agents. The present system appears to be extremely sensitive and capable of characterizing the action of agents on each phase of the cell cycle. The methods are automatable and would allow for the assay and possible differential characterization of mutagens and carcinogens.
Date: July 1, 1980
Creator: Pearlman, A.L.; Navsky, B.N. & Bartholomew, J.C
Partner: UNT Libraries Government Documents Department


Description: Ever-stringent environmental constraints dictate that future coal cleaning technologies be compatible with micron-size particles. This research program seeks to develop an advanced coal cleaning technology uniquely suited to micron-size particles, i.e., aqueous biphase extraction. The partitioning behaviors of silica in the polyethylene glycol (PEG)/dextran (Dex) and dextran/Triton X-100 (TX100) systems have been investigated, and the effects of sodium dodecylsulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) on solid partition have been studied. In both biphase systems, silica particles stayed in the top PEG-rich phase at low pH. With increase in pH, the particles moved from the top phase to the interface, then to the bottom phase. At very high pH, the solids preferred the top phase again. These trends are attributable to variations in the polymer/solid and nonionic surfactant/solid interactions. Addition of ionic surfactants into these two systems introduces a weakly charged environment, since ionic surfactants concentrate into one phase, either the top phase or the bottom phase. Therefore, coulombic forces also play a key role in the partition of silica particles because electrostatic attractive or repulsive forces are produced between the solid surface and the ionic-surfactant-concentrated phase. For the PEG/dextran system in the presence of SDS, SiO{sub 2} preferred the bottom dextran-rich phase above its pH{sub PZC}. However, addition of DTAB moved the oxide particles from the top phase to the interface, and then to the bottom phase, with increase in pH. These different behaviors are attributable to the fact that SDS and DTAB concentrated into the opposite phase of the PEG/dextran system. On the other hand, in the dextran/Triton X-100 system, both ionic surfactants concentrated in the top surfactant-rich phase and formed mixed micelles with TX100. Therefore, addition of the anionic surfactant, SDS, moved the silica particles from top phase to the interface or bottom phase. On the other hand, ...
Date: June 30, 2001
Creator: Osseo-Asare, K. & Zeng, X.
Partner: UNT Libraries Government Documents Department


Description: Ever-stringent environmental constraints dictate that future coal cleaning technologies be compatible with micron-size particles. This research program seeks to develop an advanced coal cleaning technology uniquely suited to micron-size particles, i.e., aqueous biphase extraction. The partitioning behaviors of hematite in the dextran (Dex)/Triton X-100 (TX100) and polyethylene glycol (PEG)/dextran systems were investigated and the effects of some ionic surfactants on solid partition were studied. In both biphase systems, the particles stayed in the bottom dextran-rich phase under all pH conditions. This behavior is attributable to the fact that the hydrophilic oxide particles prefer the more hydrophilic bottom phase. Also, the strong favorable interaction between dextran and ferric oxide facilitates the dispersion of the solids in the polysaccharide-rich phase. In the Dex/TX100 system, addition of sodium dodecylsulfate (SDS) or potassium oleate had no effect on the solid partition; on the other hand, addition of dodecyltrimethylammonium bromide (DTAB) transferred the particles to the top phase or interface at high pH values. In the PEG/Dex system, the preferred location of hematite remained the bottom phase in the presence of either SDS or DTAB. The effects of anionic surfactants on the partition behavior are attributable to the fact that they are not able to replace the strongly adsorbed polysaccharide layer on the ferric oxide surface. The results with the cationic surfactant are due to electrostatic interaction between the cationic surfactant and the charged surface of the solid particles. The difference in solids partitioning in the two systems is the result of the different distribution of DTAB in these systems. In the Dex/TX100 system, DTAB prefers the top surfactant-rich phase, while it concentrates in the bottom phase in the PEG/dextran system.
Date: June 30, 2001
Creator: Osseo-Asare, K. & Zeng, X.
Partner: UNT Libraries Government Documents Department


Description: Mixed-conducting membranes have the ability to conduct oxygen with perfect selectivity at elevated temperatures, which makes them an extremely attractive alternative for oxygen separation and membrane reactor applications. The ability to reliably fabricate these membranes in thin or thick films would enable solid-state divisional limitations to be minimized, thus providing higher oxygen flux. Based on that motivation, the overall objective for this project is to develop and demonstrate a strategy for the fabrication of supported Wick film ceramic mixed conducting membranes, and improve the understanding of the fundamental issues associated with reliable fabrication of these membranes. The project has focused on the mixed-conducting ceramic composition SrCo{sub 0.5}FeO{sub x} because of its superior permeability and stability in reducing atmospheres. The fabrication strategy employed involves the deposition of SrCo{sub 0.5}FeO{sub x} thick films onto porous supports of the same composition. In the second year of this project, we completed characterization of the sintering and phase behavior of the porous SrCo{sub 0.5}FeO{sub x} supports, leading to a standard support fabrication methodology. Using a doctor blade method, pastes made from aerosol-derived SrCo{sub 0.5}FeO{sub x} powder dispersed with polyethylene glycol were applied to the supports, and the sintering behavior of the thick film membranes was examined in air and nitrogen atmospheres. It has been demonstrated that the desired crystalline phase content can be produced in the membranes, and that the material in the membrane layer can be highly densified without densifying the underlying support. However, considerable cracking and opening of the film occurred when films densified to a high extent. The addition of MgO into the SrCo{sub 0.5}FeO{sub x} supports was shown to inhibit support sintering so that temperatures up to 1300 C, where significant liquid formation occurs, could be used for film sintering. This successfully reduced cracking, however the films retained open porosity. The ...
Date: June 30, 2000
Creator: Ward, Timothy L.
Partner: UNT Libraries Government Documents Department

Formation of PS-b-PEO/Silica Films with Flat or Curved Multi-Bilayer Mesostructures of Large-Characteristic Length Scales Prepared by Solvent Evaporation-Induced Self-Assembly

Description: Diblock/silica films with multi-bilayer vesicular mesostructures of large characteristic length scales were synthesized through evaporation-induced self-assembly of PS-b-PEO. The present system is believed to be the first to yield diblock/silica films with multi-bilayer vesicular mesostructures through solvent evaporation-induced self-assembly (EISA). The ready formation in the present system is argued to be the polydispersity of polymer chains.
Date: November 22, 2000
Partner: UNT Libraries Government Documents Department

1995 Toxic chemical release inventory: Emergency Planning and Community Right-to-Know Act of 1986, Section 313

Description: Section 313 of the Emergency Planning and Community Right-To-Know Act (EPCRA) requires the annual submittal of toxic chemical release information to the U.S. Environmental Protection Agency.Executive Order 12856, `Federal Compliance With Right-to-Know Laws and Pollution Prevention Requirements` extends the requirements of EPCRA to all Federal agencies. The following document is the August 1996 submittal of the Hanford Site Toxic Chemical Release Inventory report. Included is a Form R for ethylene glycol, the sole chemical used in excess of the established regulatory thresholds at the Hanford Site by the U.S. Department of Energy, Richland Operations Office and its contractors during Calendar Year 1995.
Date: August 1, 1996
Creator: Mincey, S.L.
Partner: UNT Libraries Government Documents Department

Interaction of polymer with clays.

Description: Normally synthetic well defined monodisperse discotic laponite clays are known to form a gel phase at mass concentrations as low as a few percent in distilled water. Hydrosoluble polymer polyethylene oxide was added to this intriguing clay system, it was observed that it either prevents gelation or slows it down extremely depending on the polymer weight, concentration or the laponite concentration. Small Angle Neutron scattering (SANS) was used to study these systems because only by isotopic labelling can the structure of the adsorbed polymer layers be determined. The contrast variation technique is specifically used to determine separately the different partial structure factors of the clay and polymer. In this way the signal of the adsorbed chains is separated from the signal of the free chains.
Date: July 2, 1999
Creator: Auvray, L. & Lal, J.
Partner: UNT Libraries Government Documents Department

Recovery of propylene glycol from dilute aqueous solutions by reversible chemical complexation with organoboronates

Description: Extractants consisting of an ion-pair of Aliquat 336 with phenylboronate or 3-nitrophenylboronate were prepared in various diluents (2-ethylhexanol, toluene, o-xylene or diisobutylketone). In batch experiments propyleneglycol (1,2-PD) was effectively extracted even at low concentrations. Heterogeneous complexation constants {beta}{sub 11} calculated at 25 C were 45-120 (mol/1){sup {minus}1} in 2-ethylhexanol, 34.8 (mol/l){sup {minus}1} in toluene, 37.6 (mol/l){sup {minus}1} in o-xylene and 14.4 (mol/l){sup {minus}1} in diisobutylketone. In 2-ethythexanol, there was no significant effect of extractant concentration on the complexation constant. Equilibrium water concentration in the extractants was 8-12 wt %, decreasing with 1,2-PD uptake. Nearly all extractant/diluent systems exhibited overloading (more than stoichiometric uptake of 1,2-PD). Evidence for aggregation of the ion-pair extractant in organic phase was found from water solubilization studies (molar solubilization ratios up to 10) and {sup 1}H NMR spectroscopy studies. Solubilization of 1,2-PD within hydrophilic aggregate interiors may explain the observed overloading. The complexation constant decreased with increasing temperature, but not enough to make back extraction after a temperature change attractive. Back extraction may be achieved after acidification with carbon dioxide to convert the organoboronate anion to the corresponding organoboronic acid. Up to 80% of the extracted 1,2-PD was backextracted in a batch extraction using C0{sub 2}. The extractant could then be regenerated by stripping carbon dioxide from solution at temperatures exceeding 110 C. However, at these temperatures the extractant appears to undergo a transformation in which color changes and extraction capacity is reduced to about 60% of original value.
Date: May 1, 1995
Creator: Broekhuis, R.R.; Lynn, S. & King, C.J.
Partner: UNT Libraries Government Documents Department

Materials compatibility and lubricants research on CFC-refrigerant substitute: Miscibility of lubricants with refrigerants. Quarterly report, 6 February 1992--31 March 1992

Description: During this reporting period, modifications were made to the experimental apparatus in preparation for performing the experiments required in this project. In addition, new procedures for charging the lubricant and refrigerant into the cells for high temperature tests have been adopted. All of the refrigerants (10 different types) and lubricants (seven different types) have been ordered from the manufacturers. To date, the data obtained includes that for R-134a and four lubricants, namely, two esters and two polypropylene glycols (PAGs). Methods for quantifying immiscibility based on observation by different lab workers have been developed.
Date: April 1, 1992
Creator: Pate, M. B.; Zoz, S. & Berkenbosch, L.
Partner: UNT Libraries Government Documents Department

Effects of diesel fuel combustion-modifier additives on In-cylinder soot formation in a heavy-duty Dl diesel engine.

Description: Based on a phenomenological model of diesel combustion and pollutant-formation processes, a number of fuel additives that could potentially reduce in-cylinder soot formation by altering combustion chemistry have been identified. These fuel additives, or ''combustion modifiers'', included ethanol and ethylene glycol dimethyl ether, polyethylene glycol dinitrate (a cetane improver), succinimide (a dispersant), as well as nitromethane and another nitro-compound mixture. To better understand the chemical and physical mechanisms by which these combustion modifiers may affect soot formation in diesel engines, in-cylinder soot and diffusion flame lift-off were measured, using an optically-accessible, heavy-duty, direct-injection diesel engine. A line-of-sight laser extinction diagnostic was employed to measure the relative soot concentration within the diesel jets (''jetsoot'') as well as the rates of deposition of soot on the piston bowl-rim (''wall-soot''). An OH chemiluminescence imaging technique was utilized to measure the lift-off lengths of the diesel diffusion flames so that fresh oxygen entrainment rates could be compared among the fuels. Measurements were obtained at two operating conditions, using blends of a base commercial diesel fuel with various combinations of the fuel additives. The ethanol additive, at 10% by mass, reduced jet-soot by up to 15%, and reduced wall-soot by 30-40%. The other fuel additives also affected in-cylinder soot, but unlike the ethanol blends, changes in in-cylinder soot could be attributed solely to differences in the ignition delay. No statistically-significant differences in the diesel flame lift-off lengths were observed among any of the fuel additive formulations at the operating conditions examined in this study. Accordingly, the observed differences in in-cylinder soot among the fuel formulations cannot be attributed to differences in fresh oxygen entrainment upstream of the soot-formation zones after ignition.
Date: July 1, 2005
Creator: Musculus, Mark P. (Sandia National Laboratories, Livermore, CA) & Dietz, Jeff (The Lubrizol Corp.)
Partner: UNT Libraries Government Documents Department

Analysis of metals in solution using electrospray ionization mass spectrometry

Description: Electrospray ionization-mass spectrometry (ES-MS) has gained most of its recent attention because of the ability to produce multiply charged ions from very large biomolecules making them amenable to analysis by most modern mass spectrometers. However, ES-MS is equally well suited for compounds of low or moderate molecular weight that are difficult to volatilize intact by others methods. Moreover, the early work of Fenn and co-workers (1,2) and recent reports by Kebarle and co-workers (3,4) attest to the applicability of ES-MS to the study of the gas-phase chemistry of multiply solvated or coordinated metal ions. The utility of ES-MS for the analysis of metals in solution derives in part from the facility with which the metal ions are solvated by or form complexes with the ES solvent or other reagents added to the solvent. Solvation and complexation can be a hindrance, however, in the analytical application of ES-MS to the analysis of metals in solution, especially solutions of metals in water. The data presented here demonstrate that many of the problems in the ES-MS analysis of metals can be overcome by complexing the metals with crown ethers and/or extracting the metals from water into an organic phase using crown ethers. 5 refs., 4 figs.
Date: January 1, 1991
Creator: Van Berkel, G.J.; McLuckey, S.A. & Glish, G.L.
Partner: UNT Libraries Government Documents Department

Sorption of organic gases in residential bedrooms andbathrooms

Description: Experiments were conducted to characterize organic gas sorption in residential bedrooms (n=4), bathrooms (n=2), and a furnished test chamber. Rooms were studied ''as-is'' with material surfaces and furnishings unaltered. Surface materials were characterized and areas quantified. Experiments included rapid volatilization of a volatile organic compound (VOC) mixture with the room closed and sealed for a 5-h Adsorb phase, followed by 30-min Flush and 2-h closed-room Desorb phases. The mixture included n-alkanes, aromatics, glycol ethers, 2-ethyl-1-hexanol, dichlorobenzene, and organophosphorus compounds. Measured gas-phase concentrations were fit to three variations of a mathematical model that considers sorption occurring at one surface sink and one potential embedded sink. The 2-parameter sink model tracked measurements for most compounds, but improved fits were obtained for some VOCs with a 3-parameter sink-diffusion or a 4-parameter two-sink model. Sorptive partitioning and initial adsorption rates increased with decreasing vapor pressure within each chemical class.
Date: January 5, 2005
Creator: Singer, B.C.; Hodgson, A.T.; Hotchi, T.; Ming, K.Y.; Sextro,R.G.; Wood, E.E. et al.
Partner: UNT Libraries Government Documents Department