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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

Recent advances in tandem reductive processes

Hartley, Benjamin C. January 2009 (has links)
The research presented herein is concerned with the exploration of tandem processes initiated by the conjugate reduction of Michael acceptors, encompassing the asymmetric reductive Dieckmann reaction and the two-carbon homologation of aldehydes by two complementary methodologies. Chapter 1 introduces the area of transition metal catalysed tandem reductive processes as a tool for carbon-carbon bond formation. An extensive discussion of this methodology is included and recent advances in the area are highlighted. Chapter 2 discusses the initial study into the asymmetric reductive Dieckmann condensation. 3,3’-Disubstituted 4-oxopyrrolidines were synthesised in up to 93% ee using both molybdenum and copper catalysis. Chapter 3 describes the novel molybdenum-catalysed two-carbon homologation of aldehydes by the reduction of alkylidene Meldrum’s acid derivatives. No over reduction to the corresponding alcohol is observed, as the aldehyde functionality remains protected until hydrolysis. Chapter 4 discusses the mild, expeditious amine promoted reduction of cyclic malonates to β-substituted propionaldehydes. The synthetic utility of the methodology is demonstrated by the synthesis of γ-substituted propylamines in a one-pot hydrosilylation/reductive amination process. Chapter 5 describes the synthesis and characterisation for the compounds discussed in chapters 2, 3 and 4.
12

Four-Dimensional Non-Reductive Homogeneous Manifolds with Neutral Metrics

Renner, Andrew 01 May 2004 (has links)
A method due to É. Cartan was used to algebraically classify the possible four-dimensional manifolds that allow a (2, 2)-signature metric with a transitive group action which acts by isometries. These manifolds are classified according to the Lie algebra of the group action. There are six possibilities: four non-parameterized Lie algebras, one discretely parameterized family, and one family parameterized by R.
13

Affine Embeddings of Homogeneous Spaces

I.V. Arzhantsev, D.A. Timashev, Andreas.Cap@esi.ac.at 29 August 2000 (has links)
No description available.
14

On Polynomial Automorphisms of Affine Spaces

Vladimir L. Popov, popov@ppc.msk.ru 18 September 2000 (has links)
No description available.
15

Isolation and Ecology of Bacterial Populations Involved in Reductive Dechlorination of Chlorinated Solvents

Sung, Youlboong 20 July 2005 (has links)
The findings of this study demonstrate that Dehalococcoides species are intimately involved in complete reductive detoxification of chlorinated ethenes and are widely distributed in anoxic sediments and aquifers, including non-contaminated (pristine) environments. Careful examination of enrichment culture dechlorination kinetics, 16S rRNA gene based analyses, and reductive dehalogenase gene targeted PCR approaches revealed that complete reductive dechlorination is carried out by multiple dechlorinators. Two new dechlorinating species were isolated from contaminated and non-contaminated site materials. The first new isolate, designated strain SZ, was isolated from PCE-to-ethene dechlorinating microcosms established with creek sediment. 16S rRNA gene sequence of the strain SZ indicates that the new isolate is affiliated with the genus Geobacter most closely related to G. thiogenes. Strain SZ is capable of stepwise dechlorination of PCE to cis-DCE, while the closest relatives were not able to dechlorinate PCE or TCE. Dechlorination of PCE or TCE by strain SZ was supported by acetate, hydrogen or pyruvate as electron donor. Chloroethene-dechlorinating populations have been shown to have distinct electron donor requirements. However, none of previously described chlorinated ethene degrading population can use both, acetate and hydrogen, as electron donors. PCE dechlorination by strain SZ uses both acetate and hydrogen as electron donors suggesting that the ability to versatile electron donor utilization may increase the efficiency of bioremediation approaches. Importantly, strain SZ reduced two environmental priority pollutants, PCE and U(VI) concomitantly and detected from both bio-stimulated chloroethene and uranium contaminated sites, strongly suggesting that strain SZ play a important roles in in-situ bioremediation of chloroethene and U(VI) contaminated sites. The second, a new Dehalococcoides species designated strain GT, was isolated from contaminated site materials. Strain GT uses trichloroethene (TCE), cis-DCE, 1,1-dichloroethene (1,1-DCE), and the human carcinogen vinyl chloride (VC) as growth supporting electron acceptors producing products ethene and inorganic chloride. The new isolate shares common traits of Dehalococcoides such as ampicillin resistance, strict hydrogen-dependent metabolism, and a low hydrogen consumption threshold concentration. Culture-dependent and independent, 16S rRNA gene and reductive dehalogenase gene targeted PCR approaches suggested culture purity.
16

Application of emulsified substrate to remediate TCE-contaminated groundwater

Chen, Yi-ming 16 August 2010 (has links)
Trichloroethene (TCE) and tetrachloroethene (PCE) are among the most commonly detected groundwater contaminants, and are often difficult to remediate due to their presence as dense non-aqueous phase liquids (DNAPLs) in the subsurface. The objective of this study was to assess the potential of using a passive in situ carbon/hydrogen releasing barrier system to bioremediate TCE-contaminated groundwater. The slow carbon/hydrogen releasing material would cause the aerobic cometabolism and reductive dechlorination of TCE in aquifer. The carbon/hydrogen releasing materials would release carbon when contacts with groundwater and release hydrogen after the anaerobic biodegradation of released carbon, thus cause the reductive dechlorination of TCE. Results from the microcosm study indicate that the addition of emulsified substrate, cane molasses, Simple GreenTM (a biodegradable surfactant), or lecithin would enhance the biodegradation rate of TCE under anaerobic conditions. However, addition of multivitamin would increase the bacterial population in the media but would not be able to enhance the TCE degradation rate. Results show that a significant pH drop was observed due to the production of organic acids after the aerobic biodegradation process of cane molasses and lecithin. This also caused the inhibition of microbial growth in microcosms. Results reveal that higher TCE removal efficiency was observed in microcosms with Simple GreenTM addition followed by the addition of cane molasses, lecithin, multivitamin, emulsified substrate, groundwater (without substrate addition). Results from the microcosm study indicate that the addition of emulsified substrate would enhance the biodegradation rate of TCE under anaerobic conditions. However, appearance of high nitrate concentration would inhibit the TCE degradation process due to the occurrence of denitrification. Compared with nitrate, high sulfate concentration would not have significant impact on the reductive dechlorination of TCE. Results reveal that higher TCE removal efficiency was observed in microcosms with emulsified substrate addition followed by the addition of high sulfate concentration, high nitriate concentration, groundwater (without substrate addition). Results from the gene analysis show that phenol monooxygenase, toluene monooxygenase, and toluene dioxygenase were observed in the microcosms with lecithin, cane molasses, Simple GreenTM, and emulsified substrate. This indicates that the addition of substrates would induce the potential of TCE-degrading enzyme. Addition of emulsified substrate and emulsified substrate in nitrate or sulfate-rich media would stimulate Dehalococcoides sp. to induce tceA, bvcA, and vcrA, enzymes for TCE reductive dechlorination.
17

Identification of active agents for tetrachloroethylene degradation in Portland cement slurry containing ferrous iron

Ko, Sae Bom 16 August 2006 (has links)
Fe(II)-based degradative solidification/stabilization (Fe(II)-DS/S) technology is the modification of conventional solidification/stabilization (S/S). Inorganic pollutants are immobilized by Fe(II)-DS/S while organic pollutants are destroyed. Experimental studies were conducted to identify the active agents for Tetrachloroethylene (PCE) degradation as well as the conditions that enhance the formation of the active agents in the Fe(II)-DS/S system. PCE was chosen as a model chlorinated aliphatic hydrocarbon in this study. First, the conditions that lead to maximizing production of the active agents were identified by measuring the ability of various chemical mixtures to degrade PCE. Results showed that Fe(II), Fe(III), Ca, and Cl were the the important elements that affect degradation activity. Elemental compositions of the mixtures and the conditions affecting solid formation might be the important factors in determining how active solids are formed. Second, instrumental analyses (XRD, SEM, SEM-EDS) were used to identify minerals in chemical mixtures that have high activities. Results indicate that active agents for PCE degradation in Portland cement slurries and in cement extracts might be one of several AFm phases. However, systems without cement did not form the same solids as those with cement or cement extract. Ferrous hydroxide was identified as a major solid phase formed in systems without cement. Finally, the effect of using different types of ordinary Portland cement (OPC) on PCE degradation rate during Fe(II)-DS/S was examined and the solids were examined by instrumental analyses (XRD, SEM, SEM-EDS). Four different OPC (Txi, Lehigh, Quikrete, and Capitol) showed different PCE degradation behaviors. Pseudo first-order kinetics was observed for Capitol and Txi OPC and second-order kinetics was observed for Quikrete. In the case of Lehigh cement, pseudo first-order kinetics was observed in cement slurry and second-order kinetics in cement extract. Calcium aluminum hydroxide hydrates dominated solids made with Txi, Quikrete, and Lehigh cements and Friedel’s salt was the major phase found in solids made with Capitol cements. Fe tended to be associated with hexagonal thin plate particles, which were supposed to be a LDH.
18

Reductive Dehalogenation of Gas-phase Trichloroethylene using Heterogeneous Catalytic and Electrochemical Methods

Ju, Xiumin January 2005 (has links)
REDUCTIVE DEHALOGENATION OF GAS-PHASE TRICHLOROETHYLENE USING HETEROGENEOUS CATALYTIC AND ELECTROCHEMICAL METHODSXiumin Ju, Ph.D.The University of Arizona, 2005Director: Dr. Robert G. ArnoldThe first part of this work investigates catalytic hydrodechlorination (HDC) of gas-phase trichloroethylene (TCE) using 0.5 wt.% Pt/g-Al2O3 and 0.0025 wt.% Pt/SiO2 in packed-bed reactors. TCE was efficiently transformed on the platinum surface using H2 as reducing agent. The main products of the reaction were ethane and chloroethane. In the case of Pt/Al2O3, more than 94% TCE conversion efficiency was maintained for over 700 hours of operation at 100ºC at a residence time of 0.37 seconds. At 22ºC, severe catalyst deactivation was observed. Catalyst deactivation was attributed to coking and chlorine poisoning. A series of treatments including (i) hydrogen gas addition at high temperature (oxygen free) to remove chlorine and (ii) oxygen addition at 500ºC to remove coke were attempted to regenerate the deactivated catalyst. Only hydrogen treatment partially restored catalyst activity. When using Pt/SiO2, catalyst deactivation was severe even at 100ºC, probably due to low surface area of Pt and the silica support. Adding KOH to the packed Pt/SiO2 catalyst during (otherwise) normal operation slowed catalyst deactivation. Adding O2 to the influent improved catalyst activity and slowed deactivation.The second part of this research involves the destruction of gas-phase TCE using an electrochemical reactor similar in design of a polymer electrolyte membrane (PEM) fuel cell. With a proton-conducting membrane in the middle, the anode and cathode comprised of carbon cloth and carbon-black-supported Pt were hotpressed together to form a membrane electrode assembly (MEA). TCE contaminated gas streams were fed to the cathode side of the fuel cell, where TCE was reduced to ethane and hydrochloric acid. The results suggest that TCE reduction occurs via a catalytic reaction with atomic hydrogen that is reformed on the cathode's surface rather than an electrochemical reduction via direct electron transfer. Substantial conversion of TCE was obtained, even in the presence of molecular oxygen in the cathode chamber. The process was modeled successfully by conceptualizing the cathode chamber as a plug flow reactor with a continuous source of H2(g) emanating from the boundary.
19

SYNTHETIC EFFORTS TOWARD FUMONISIN via AMINO ACID SCHIFF BASE METHODOLOGY

Kim, Shang U January 2009 (has links)
Synthetic efforts toward fumonisin analog were described. These are accomplished via amino acid Schiff base methodology. These efforts can be divided three major phases. First, tandem reductive alkylation with DIBAL/TRIBAL and different types of organo-lithium or Grignard nucleophiles provided threo-amino alcohol with excellent stereoselecitivites (2-27:1). The reductive alkylation utilized most hydrocarbon nucleophiles, e.g. alkyl-, vinyl-, alkenyl-, phenyl-, and dienyl-, and afforded high selectivites unless donor solvents (e.g. THF and Et2O) were used. Second, syntheses of the protected threo-γ-amino-β-hydroxy aldehydes and their stereoselectivities were introduced. The reductive alkylated threo-amino allyl alcohol was transformed via Brown’s hydroboration/oxidation protocol with 9-BBN, followed by TEMPO oxidation to give the resultant aldehydes in reasonable yields. Then, TBDPS and Schiff base protected aldehyde was coupled with phenyl- and decyl Grignard reagents to obtain predominant 3,5-anti-diols (ca. 80:20 anti:syn), characterized by ¹³C NMR analysis of Rychnovsky’s 1,3-acetonide groups. Products can be useful analogues for fumonisin and 5-hydroxy-sphingosine due to their structural similarity. Third stage involved the synthesis of C₁₁-C₂₀ fragment analog of fumonisin. Chiral auxiliaries (e.g. Evans and Myers) were administrated for stereoselective methylation, Sharpless asymmetric dihydroxylation in the presence of (DHQ)2PHAL catalyst was performed to form 1,2- syn-diols, and the manipulation of protection/deprotection and Finklestein reaction furnished C₁₁-C₂₀ fragment analog of fumonisin.
20

Surface Reductive Capacity of Carbon Nanomaterials after Various Heating and Aging Processes

Lee, Chunghoon 2011 August 1900 (has links)
Understanding the toxicity of carbon nanomaterials, such as carbon nanotubes and graphenes, is important for the development of nanotechnology. Studies have shown that surface redox capability is an important factor for toxicity of carbon nanomaterials. We have measured the surface reductive capacity for a number of carbon nanomaterials in previous studies, but the effects of various engineering processes on surface redox capability have not been investigated until this study. In this study, commercially available carbon black, carbon nanotubes, standard reference materials, fullerenes, graphenes and acetylene soot generated in the lab were used. The carbon nanomaterials were subjected to heating at various temperatures in various atmospheres up to 500 ˚C, and soaking in water at room temperature under various atmospheres, and weathering in the powder form at room temperature under various atmospheres. The redox capability of the carbon nanomaterials was quantified in terms of the reductive capacity towards Fe3+ ions (RCFI). The RCFI values of the asreceived nanomaterials and that of the nanomaterials after various treatments were compared. The carbon nanomaterials were also characterized using x-ray photoelectron spectroscopy (XPS), for understanding the surface chemistry mechanisms of RCFI and the effects of various treatments. In general, heating induced a significant increase in RCFI, regardless of the atmosphere under which the nanomaterials were heated. On the other hand, aging in O2- containing atmospheres brought about significant decrease in RCFI, either in water suspension or in the powder form. Water vapor enhanced the aging effect of O2. CO2 was found to affect the RCFI and the aging of carbon nanomaterials. The extent of RCFI change due to heating or aging was dependent on the type of material. According to the XPS results, the RCFI of some carbon nanomaterials such as carbon black may be correlated with the C-O surface functional groups. However, the definitive correlation between the oxygen-containing surface functional group and RCFI for all carbon nanomaterials couldn’t be determined by the XPS result. This indicates that the RCFI changes of carbon nanomaterials after treatments mainly derived from the factors such as the active sites of edges other than the oxygen-containing surface functional group changes as other studies show. This suggests that the RCFI measurement cannot be replaced by XPS analysis. The effects of heating and aging on RCFI, and more generally the surface redox capability of carbon nanomaterials, reveals that various engineering and environmental processes may significantly change the toxicity of carbon nanomaterials. The findings of this study suggest that it is important to take into account the effects of engineering and environmental processes when assessing the toxicity of carbon nanomaterials.

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