Enantioselective transformations using tetrol as a chiral mediator
- Authors: Dorfling, Sasha-Lee
- Date: 2015
- Subjects: Enantioselective catalysis , Trichothecenes , Catalysts , Titanium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10445 , http://hdl.handle.net/10948/d1021195
- Description: (+)-(2R,3R)-1,1,4,4-Tetraphenylbutane-1,2,3,4-tetraol (TETROL) and its derivatives were reacted with varying molar ratios of titanium isopropoxide (2:1, 1:1 and 1:2 tetraol:titanium isopropoxide) in an attempt to prepare potential titanium-based tetraol catalysts for enantioselective transformations. In each case, infrared and HNMR spectra suggested that the product was formed. We tentatively proposed that the structure of the catalyst was a spiro-type, but we could not determine conclusively what its exact structure was, despite using numerous techniques at our disposal (molecular modelling calculations, H NMR and IR spectroscopy, thermal analyses, powder diffraction, and single crystal X-ray diffraction). The catalyst and derivatives thereof were able to act catalytically for the enantioselective additions of diethylzinc compounds to aldehydes. The effects of temperature and solvent were investigated, and toluene and -78 °C were selected as optimal from the results obtained. (The reaction could, however, not be maintained at this low temperature for extended periods due to the fact that we did not have, at our disposal, the correct equipment. Each 16 h reaction was thus allowed to reach room temperature in each case.) The selectivity for the product 1-phenylpropan-1-ol (when benzaldehyde was the starting aldehyde) varied depending on the nature of the aryl substituents of the titanium-based catalyst. Using 0.2 molar equivalents of the chiral titanates, the highest selectivity was 42 percent (e.e.), but only when excess Ti(O-i-Pr)4 had been added to the reaction mixture. This was achieved with the tetra(ortho-methoxyphenyl)-TETROLate derivative. TETROL and its derivatives were also successful in metal-free catalysis where higher conversions and selectivities were observed, compared to when these were complexed to titanium. The highest selectivity was 70 percent (e.e.), achieved with the tetra(ortho-methylphenyl)TETROL derivative.
- Full Text:
- Date Issued: 2015
- Authors: Dorfling, Sasha-Lee
- Date: 2015
- Subjects: Enantioselective catalysis , Trichothecenes , Catalysts , Titanium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10445 , http://hdl.handle.net/10948/d1021195
- Description: (+)-(2R,3R)-1,1,4,4-Tetraphenylbutane-1,2,3,4-tetraol (TETROL) and its derivatives were reacted with varying molar ratios of titanium isopropoxide (2:1, 1:1 and 1:2 tetraol:titanium isopropoxide) in an attempt to prepare potential titanium-based tetraol catalysts for enantioselective transformations. In each case, infrared and HNMR spectra suggested that the product was formed. We tentatively proposed that the structure of the catalyst was a spiro-type, but we could not determine conclusively what its exact structure was, despite using numerous techniques at our disposal (molecular modelling calculations, H NMR and IR spectroscopy, thermal analyses, powder diffraction, and single crystal X-ray diffraction). The catalyst and derivatives thereof were able to act catalytically for the enantioselective additions of diethylzinc compounds to aldehydes. The effects of temperature and solvent were investigated, and toluene and -78 °C were selected as optimal from the results obtained. (The reaction could, however, not be maintained at this low temperature for extended periods due to the fact that we did not have, at our disposal, the correct equipment. Each 16 h reaction was thus allowed to reach room temperature in each case.) The selectivity for the product 1-phenylpropan-1-ol (when benzaldehyde was the starting aldehyde) varied depending on the nature of the aryl substituents of the titanium-based catalyst. Using 0.2 molar equivalents of the chiral titanates, the highest selectivity was 42 percent (e.e.), but only when excess Ti(O-i-Pr)4 had been added to the reaction mixture. This was achieved with the tetra(ortho-methoxyphenyl)-TETROLate derivative. TETROL and its derivatives were also successful in metal-free catalysis where higher conversions and selectivities were observed, compared to when these were complexed to titanium. The highest selectivity was 70 percent (e.e.), achieved with the tetra(ortho-methylphenyl)TETROL derivative.
- Full Text:
- Date Issued: 2015
Preparation of photocatalytic TiO₂ nanoparticles immobilized on carbon nanofibres for water purification
- Authors: Nyamukamba, Pardon
- Date: 2011
- Subjects: Water -- Purification , Titanium alloys -- Industrial applications , Titanium , Nanoparticles , Drinking water -- Purification , Drinking water -- Contamination
- Language: English
- Type: Thesis , Masters , MSc (Chemistry)
- Identifier: vital:11330 , http://hdl.handle.net/10353/367 , Water -- Purification , Titanium alloys -- Industrial applications , Titanium , Nanoparticles , Drinking water -- Purification , Drinking water -- Contamination
- Description: Titanium dioxide nanoparticles were prepared using the sol-gel process. The effect of temperature and precursor concentration on particle size was investigated. The optimum conditions were then used to prepare carbon and nitrogen doped titanium dioxide (TiO2) nanoparticles. Doping was done to reduce band gap of the nanoparticles in order to utilize visible light in the photocatalytic degradation of organic compounds. A significant shift of the absorption edge to a longer wavelength (lower energy) from 420 nm to 456 nm and 420 nm to 428 nm was observed for the carbon doped and nitrogen doped TiO2 respectively. In this study, the prepared TiO2 photocatalyst was immobilized on carbon nanofibres to allow isolation and reuse of catalyst. The photocatalytic activity of the catalyst was tested using methyl orange as a model pollutant and was based on the decolourization of the dye as it was degraded. The doped TiO2 exhibited higher photocatalytic activity than the undoped TiO2. The materials prepared were characterized by XRD, TEM, SEM, FT-IR, DSC and TGA while the doped TiO2 was characterized by XPS, ESR and Raman Spectroscopy.
- Full Text:
- Date Issued: 2011
- Authors: Nyamukamba, Pardon
- Date: 2011
- Subjects: Water -- Purification , Titanium alloys -- Industrial applications , Titanium , Nanoparticles , Drinking water -- Purification , Drinking water -- Contamination
- Language: English
- Type: Thesis , Masters , MSc (Chemistry)
- Identifier: vital:11330 , http://hdl.handle.net/10353/367 , Water -- Purification , Titanium alloys -- Industrial applications , Titanium , Nanoparticles , Drinking water -- Purification , Drinking water -- Contamination
- Description: Titanium dioxide nanoparticles were prepared using the sol-gel process. The effect of temperature and precursor concentration on particle size was investigated. The optimum conditions were then used to prepare carbon and nitrogen doped titanium dioxide (TiO2) nanoparticles. Doping was done to reduce band gap of the nanoparticles in order to utilize visible light in the photocatalytic degradation of organic compounds. A significant shift of the absorption edge to a longer wavelength (lower energy) from 420 nm to 456 nm and 420 nm to 428 nm was observed for the carbon doped and nitrogen doped TiO2 respectively. In this study, the prepared TiO2 photocatalyst was immobilized on carbon nanofibres to allow isolation and reuse of catalyst. The photocatalytic activity of the catalyst was tested using methyl orange as a model pollutant and was based on the decolourization of the dye as it was degraded. The doped TiO2 exhibited higher photocatalytic activity than the undoped TiO2. The materials prepared were characterized by XRD, TEM, SEM, FT-IR, DSC and TGA while the doped TiO2 was characterized by XPS, ESR and Raman Spectroscopy.
- Full Text:
- Date Issued: 2011
Electrochemical studies of titanium, manganese and cobalt phthalocyanines
- Authors: Nombona, Nolwazi
- Date: 2009
- Subjects: Titanium , Manganese , Cobalt , Phthalocyanines , Electrochemistry , Electrodes , Self-assembly (Chemistry)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4312 , http://hdl.handle.net/10962/d1004970 , Titanium , Manganese , Cobalt , Phthalocyanines , Electrochemistry , Electrodes , Self-assembly (Chemistry)
- Description: Syntheses, spectral, electrochemical and spectroelectrochemical studies of phenylthio and amino derivatised metallophthalocyanines complexes are reported. The complexes are immobilized onto a gold macro disk, gold ultramicroelectrode and gold coated fiber electrodes via self assembly with phenylthio MPc derivatives or onto a glassy carbon electrode via electropolymerisation with amino MPc derivatives. For the first time MPc SAMs were formed on gold coated fiber. The electrocatalytic behavior of the modified electrodes was studied for the detection of nitrite and L-cysteine, all modified electrodes showed improved electrocatalytic oxidation compared to the unmodified electrode. The MPc complexes catalyzed nitrite oxidation via a two-electron mechanism producing nitrate. Cobalt tetraaminophthalocyanine showed the best catalytic activity for nitrite oxidation in terms of overpotential lowering compared to other complexes and thus was used for nitrite detection in a food sample, the nitrite concentration was determined to be 59.13 ppm, well within the limit for cured meat products. Electrocatalytic oxidation of L-cysteine on SAM modified gold coated fiber was reported for the first time. The gold coated fiber and ultamicro cylinder electrode were less stable towards the electro-oxidation of cysteine compared to its oxidation on the gold disk. The gold disk electrode gave better catalytic performance in terms of stability and reduction of overpotential. The phenylthio cobalt phthalocyanine derivative gave the best catalytic activity for L-cysteine oxidation in terms of overpotential lowering compared to other phenylthio derivatized MPc complexes. The amount of L-cysteine in human urine was 2.4 mM, well within the urinary L-cysteine excretion range for a healthy human being.
- Full Text:
- Date Issued: 2009
- Authors: Nombona, Nolwazi
- Date: 2009
- Subjects: Titanium , Manganese , Cobalt , Phthalocyanines , Electrochemistry , Electrodes , Self-assembly (Chemistry)
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4312 , http://hdl.handle.net/10962/d1004970 , Titanium , Manganese , Cobalt , Phthalocyanines , Electrochemistry , Electrodes , Self-assembly (Chemistry)
- Description: Syntheses, spectral, electrochemical and spectroelectrochemical studies of phenylthio and amino derivatised metallophthalocyanines complexes are reported. The complexes are immobilized onto a gold macro disk, gold ultramicroelectrode and gold coated fiber electrodes via self assembly with phenylthio MPc derivatives or onto a glassy carbon electrode via electropolymerisation with amino MPc derivatives. For the first time MPc SAMs were formed on gold coated fiber. The electrocatalytic behavior of the modified electrodes was studied for the detection of nitrite and L-cysteine, all modified electrodes showed improved electrocatalytic oxidation compared to the unmodified electrode. The MPc complexes catalyzed nitrite oxidation via a two-electron mechanism producing nitrate. Cobalt tetraaminophthalocyanine showed the best catalytic activity for nitrite oxidation in terms of overpotential lowering compared to other complexes and thus was used for nitrite detection in a food sample, the nitrite concentration was determined to be 59.13 ppm, well within the limit for cured meat products. Electrocatalytic oxidation of L-cysteine on SAM modified gold coated fiber was reported for the first time. The gold coated fiber and ultamicro cylinder electrode were less stable towards the electro-oxidation of cysteine compared to its oxidation on the gold disk. The gold disk electrode gave better catalytic performance in terms of stability and reduction of overpotential. The phenylthio cobalt phthalocyanine derivative gave the best catalytic activity for L-cysteine oxidation in terms of overpotential lowering compared to other phenylthio derivatized MPc complexes. The amount of L-cysteine in human urine was 2.4 mM, well within the urinary L-cysteine excretion range for a healthy human being.
- Full Text:
- Date Issued: 2009
Synthesis and electrochemistry of octapentylthio phthalocyanine complexes of manganese, titanium and vanadium
- Authors: Mbambisa, Gcineka
- Date: 2009
- Subjects: Electrochemistry , Phthalocyanines -- Synthesis , Manganese , Titanium , Vanadium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4368 , http://hdl.handle.net/10962/d1005033 , Electrochemistry , Phthalocyanines -- Synthesis , Manganese , Titanium , Vanadium
- Description: Synthesis of new thio derivatised Pcs with manganese, titanium and vanadium as a central metal is reported. The complexes synthesised were characterised using spectroscopic and electrochemical means. The complexes displayed interesting spectroscopic properties with absorption of the Q band being observed in the near infrared region. These complexes have unusual colours for MPc complexes, with purple or red colour being observed in solution. Interesting electrochemical properties were observed, with rare observation of the MnIV/MnIII redox couple. There was observation of oxidation peaks for the pentylthio derivatised Pc with titanium as the central metal; this is unusual since for reported thio derivatives based on TiPc, no oxidation was observed. The vanadium based Pc showed an interesting spectrum for the first ring based reduction. The absorption spectrum obtained for the 1st reduction of the vanadium complex using spectroelectrochemistry would normally indicate a metal based process but comparing with literature it was concluded that it is a ring based reduction process. Generally all the MPc complexes formed a well ordered stable monolayer on the gold electrode. Electrocatalytic studies using L-cysteine revealed that the SAM based on manganese (III) octapentylthio phthalocyanine (AcOMnOPTPc) was the most effective since it catalyses L-cysteine at much lower oxidation potentials and it is also much more stable.
- Full Text:
- Date Issued: 2009
- Authors: Mbambisa, Gcineka
- Date: 2009
- Subjects: Electrochemistry , Phthalocyanines -- Synthesis , Manganese , Titanium , Vanadium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4368 , http://hdl.handle.net/10962/d1005033 , Electrochemistry , Phthalocyanines -- Synthesis , Manganese , Titanium , Vanadium
- Description: Synthesis of new thio derivatised Pcs with manganese, titanium and vanadium as a central metal is reported. The complexes synthesised were characterised using spectroscopic and electrochemical means. The complexes displayed interesting spectroscopic properties with absorption of the Q band being observed in the near infrared region. These complexes have unusual colours for MPc complexes, with purple or red colour being observed in solution. Interesting electrochemical properties were observed, with rare observation of the MnIV/MnIII redox couple. There was observation of oxidation peaks for the pentylthio derivatised Pc with titanium as the central metal; this is unusual since for reported thio derivatives based on TiPc, no oxidation was observed. The vanadium based Pc showed an interesting spectrum for the first ring based reduction. The absorption spectrum obtained for the 1st reduction of the vanadium complex using spectroelectrochemistry would normally indicate a metal based process but comparing with literature it was concluded that it is a ring based reduction process. Generally all the MPc complexes formed a well ordered stable monolayer on the gold electrode. Electrocatalytic studies using L-cysteine revealed that the SAM based on manganese (III) octapentylthio phthalocyanine (AcOMnOPTPc) was the most effective since it catalyses L-cysteine at much lower oxidation potentials and it is also much more stable.
- Full Text:
- Date Issued: 2009
The genesis of ilmenite-rich heavy mineral deposits in the Bothaville/Delmas area, and an economic analysis of titanium, with particular reference to the Dwarsfontein deposit, Delmas district
- Authors: Brennan, Michael Brendan
- Date: 1991
- Subjects: Heavy minerals -- South Africa -- Transvaal , Titanium , Geology -- South Africa -- Transvaal
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4949 , http://hdl.handle.net/10962/d1005561 , Heavy minerals -- South Africa -- Transvaal , Titanium , Geology -- South Africa -- Transvaal
- Description: A number of ilmenite-rich heavy mineral deposits occur along the northern margin of the intracratonic Karoo basin, and are hosted by the fluvio-deltaic Middle Ecca Group. Coastal reworking of delta front sands within a regressive, microtidal shoreline may be considered as a depositional model for the development of the heavy mineral deposits. An economic analysis of titanium suggests long term positive demand, and sustained high prices for this commodity. An evaluation of the Dwarsfontein ilmenite-rich heavy mineral deposit, using available data, indicates how important it is for deposits of this type to be situated close to an upgrading plant or export harbour.
- Full Text:
- Date Issued: 1991
- Authors: Brennan, Michael Brendan
- Date: 1991
- Subjects: Heavy minerals -- South Africa -- Transvaal , Titanium , Geology -- South Africa -- Transvaal
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4949 , http://hdl.handle.net/10962/d1005561 , Heavy minerals -- South Africa -- Transvaal , Titanium , Geology -- South Africa -- Transvaal
- Description: A number of ilmenite-rich heavy mineral deposits occur along the northern margin of the intracratonic Karoo basin, and are hosted by the fluvio-deltaic Middle Ecca Group. Coastal reworking of delta front sands within a regressive, microtidal shoreline may be considered as a depositional model for the development of the heavy mineral deposits. An economic analysis of titanium suggests long term positive demand, and sustained high prices for this commodity. An evaluation of the Dwarsfontein ilmenite-rich heavy mineral deposit, using available data, indicates how important it is for deposits of this type to be situated close to an upgrading plant or export harbour.
- Full Text:
- Date Issued: 1991
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