The photophysical properties of low symmetry phthalocyanines in conjunction with quantum dots
- Authors: D'Souza, Sarah
- Date: 2011
- Subjects: Phthalocyanines , Photochemistry , Zinc , Quantum dots , Spectrum analysis , Nanoparticles
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4331 , http://hdl.handle.net/10962/d1004992 , Phthalocyanines , Photochemistry , Zinc , Quantum dots , Spectrum analysis , Nanoparticles
- Description: he synthesis, extensive spectroscopic characterization and photophysical studies of low symmetry zinc phthalocyanine have been conducted. Comparisons have been made taking into consideration the influence of the solvent properties as well as substituent type and position. Photosensitizing properties of the zinc phthalocyanine derivatives in the presence of thiol capped CdTe quantum dots (QDs) were compared. The QDs were used as energy transfer donors and to facilitate with energy transfer through Förster resonance energy transfer (FRET) from the QDs to the MPcs. The linkage of unsymmetrically substituted 4-monoaminophenoxy zinc phthalocyanine (ZnAPPc) to CdTe quantum dots capped with mercaptopropionic acid (MPA), L-cysteine (L-cys) or thioglycolic acid (TGA) has been achieved using the coupling agents ethyl-N3 dimethylaminopropyl)carbodiimide (EDC) and N-hydroxy succinimide (NHS), which facilitate formation of an amide bond to form the QD-ZnAPPc-linked complex. The formation of the amide bond was confirmed using UV-Vis, Raman and IR spectroscopies, as well as AFM (atomic force microscopy). Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnAPPc in both the linked (QDZnAPPc-linked) and mixed (QD:ZnAPPc-mixed) conjugates for MPA only. The linked L-cys and TGA complexes (QD-ZnAPPc-linked) gave the largest FRET efficiencies hence showing the advantages of covalent linking. Fluorescence quantum yields of QDs were decreased in QD:ZnAPPc-mixed and QD:ZnAPPc-linked. High triplet state quantum yields were obtained for the linked QD-phthalocyanine derivatives (ZnAPPc)and monoaminozinc phthalocyanine (ZnAPc) compared to when ZnAPPc and ZnAPc were mixed with MPA QDs without a chemical bond.
- Full Text:
- Date Issued: 2011
- Authors: D'Souza, Sarah
- Date: 2011
- Subjects: Phthalocyanines , Photochemistry , Zinc , Quantum dots , Spectrum analysis , Nanoparticles
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4331 , http://hdl.handle.net/10962/d1004992 , Phthalocyanines , Photochemistry , Zinc , Quantum dots , Spectrum analysis , Nanoparticles
- Description: he synthesis, extensive spectroscopic characterization and photophysical studies of low symmetry zinc phthalocyanine have been conducted. Comparisons have been made taking into consideration the influence of the solvent properties as well as substituent type and position. Photosensitizing properties of the zinc phthalocyanine derivatives in the presence of thiol capped CdTe quantum dots (QDs) were compared. The QDs were used as energy transfer donors and to facilitate with energy transfer through Förster resonance energy transfer (FRET) from the QDs to the MPcs. The linkage of unsymmetrically substituted 4-monoaminophenoxy zinc phthalocyanine (ZnAPPc) to CdTe quantum dots capped with mercaptopropionic acid (MPA), L-cysteine (L-cys) or thioglycolic acid (TGA) has been achieved using the coupling agents ethyl-N3 dimethylaminopropyl)carbodiimide (EDC) and N-hydroxy succinimide (NHS), which facilitate formation of an amide bond to form the QD-ZnAPPc-linked complex. The formation of the amide bond was confirmed using UV-Vis, Raman and IR spectroscopies, as well as AFM (atomic force microscopy). Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnAPPc in both the linked (QDZnAPPc-linked) and mixed (QD:ZnAPPc-mixed) conjugates for MPA only. The linked L-cys and TGA complexes (QD-ZnAPPc-linked) gave the largest FRET efficiencies hence showing the advantages of covalent linking. Fluorescence quantum yields of QDs were decreased in QD:ZnAPPc-mixed and QD:ZnAPPc-linked. High triplet state quantum yields were obtained for the linked QD-phthalocyanine derivatives (ZnAPPc)and monoaminozinc phthalocyanine (ZnAPc) compared to when ZnAPPc and ZnAPc were mixed with MPA QDs without a chemical bond.
- Full Text:
- Date Issued: 2011
Photophysical and photoelectrochemical properties of water soluble metallophthalocyanines
- Authors: Masilela, Nkosiphile
- Date: 2010
- Subjects: Phthalocyanines , Electrochemistry , Photoelectrochemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4330 , http://hdl.handle.net/10962/d1004991 , Phthalocyanines , Electrochemistry , Photoelectrochemistry
- Description: This work presents the synthesis, characterization, photophysicochemical and photoelectrochemical properties of anionic octa-caboxylated (MOCPcs), tetra-sulfonated (MTSPcs) and quaternized cationic (Q(T-2-Py)MPcs) water soluble aluminium, gallium, silicon, titanium and zinc phthalocynines. The peripherally tetra-substituted cationic (Q(T-2-Py)MPcs) and anionic (MTSPcs) were found to be aggregated in aqueous media, yet the octa-carboxylated (MOCPcs) counterparts were monomeric in solution. Cremophor EL (CEL) was used as a disaggregating agent, all the aggregated complexes disaggregated partially or completely in the presence of CEL. The photophysicochemical properties of aggregated complexes were investigated both in the presence of CEL and in aqueous media of pH 11 alone. Low triplet, singlet oxygen and fluorescence quantum yield were obtained in aqueous media (especially for the aggregated complexes) but a high improvement was achieved upon addition of CEL. The gallium complexes ((OH)GaOCPc and (OH)GaTSPc) showed good photophysicochemical properties with higher triplet and singlet oxygen quantum yields. For photoelectrochemistry the (MPcs) dyes were adsorbed to nanoporous ZnO, electrodeposited in the presence of eosin Y as structure directing agent (SDA) on FTO substrates by refluxing or soaking the films in a solution containing the dye of interest such that a full surface coverage was achieved. Quaternized cationic (Q(T-2-Py)MPc) and tetrasulfonated (MTSPcs) phthalocyanines formed strong aggregates when deposited on the surface of FTO/ZnO substrate leading. High external (IPCE) and internal (APCE) quantum efficiencies of up to 50.6% and 96.7% were achieved for the OTiOCPc complex. There was a lower overall cell efficiency for quaternized and tetrasulfonated metallophthalocyanines because of the strong aggregates when they were on the surface of the electrodes. Among the studied materials, OTiOCPc gave the highest overall cell efficiency of phthalocyanine electrodeposited on ZnO of so far = 0.48%.
- Full Text:
- Date Issued: 2010
- Authors: Masilela, Nkosiphile
- Date: 2010
- Subjects: Phthalocyanines , Electrochemistry , Photoelectrochemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4330 , http://hdl.handle.net/10962/d1004991 , Phthalocyanines , Electrochemistry , Photoelectrochemistry
- Description: This work presents the synthesis, characterization, photophysicochemical and photoelectrochemical properties of anionic octa-caboxylated (MOCPcs), tetra-sulfonated (MTSPcs) and quaternized cationic (Q(T-2-Py)MPcs) water soluble aluminium, gallium, silicon, titanium and zinc phthalocynines. The peripherally tetra-substituted cationic (Q(T-2-Py)MPcs) and anionic (MTSPcs) were found to be aggregated in aqueous media, yet the octa-carboxylated (MOCPcs) counterparts were monomeric in solution. Cremophor EL (CEL) was used as a disaggregating agent, all the aggregated complexes disaggregated partially or completely in the presence of CEL. The photophysicochemical properties of aggregated complexes were investigated both in the presence of CEL and in aqueous media of pH 11 alone. Low triplet, singlet oxygen and fluorescence quantum yield were obtained in aqueous media (especially for the aggregated complexes) but a high improvement was achieved upon addition of CEL. The gallium complexes ((OH)GaOCPc and (OH)GaTSPc) showed good photophysicochemical properties with higher triplet and singlet oxygen quantum yields. For photoelectrochemistry the (MPcs) dyes were adsorbed to nanoporous ZnO, electrodeposited in the presence of eosin Y as structure directing agent (SDA) on FTO substrates by refluxing or soaking the films in a solution containing the dye of interest such that a full surface coverage was achieved. Quaternized cationic (Q(T-2-Py)MPc) and tetrasulfonated (MTSPcs) phthalocyanines formed strong aggregates when deposited on the surface of FTO/ZnO substrate leading. High external (IPCE) and internal (APCE) quantum efficiencies of up to 50.6% and 96.7% were achieved for the OTiOCPc complex. There was a lower overall cell efficiency for quaternized and tetrasulfonated metallophthalocyanines because of the strong aggregates when they were on the surface of the electrodes. Among the studied materials, OTiOCPc gave the highest overall cell efficiency of phthalocyanine electrodeposited on ZnO of so far = 0.48%.
- Full Text:
- Date Issued: 2010
Photophysical studies of zinc and indium tetraaminophthalocyanines in the presence of CdTe quantum dots
- Authors: Britton, Jonathan
- Date: 2010
- Subjects: Indium , Zinc , Quantum dots , Phthalocyanines , Photochemotherapy , Nonlinear optics , Nanocrystals
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4332 , http://hdl.handle.net/10962/d1004993 , Indium , Zinc , Quantum dots , Phthalocyanines , Photochemotherapy , Nonlinear optics , Nanocrystals
- Description: CdTe QDs capped with mercaptopropionic acid (MPA) and thioglycolic acid (TGA) were covalently linked to zinc and indium tetraaminophthalocyanines (TAPcs) using N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) as the coupling agents. The results presented give evidence in favour of formation of an amide bond between the MTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and the mixture of QDs and ZnTAPc (without chemical linking) showed Förster resonance energy transfer (FRET), though the linked showed less FRET, whereas the QD interactions with InTAPc yielded no evidence of FRET. Both MTAPcs quenched the QDs emission, with quenching constants of the order of 103–104M−1, binding constants of the order of 108-1010M-1 and the number of binding sites for the MTAPc upon the QD being 2. High energy transfer efficiencies were obtained (in some cases as high as 93%), due to the low donor to acceptor distances. Lastly, both MTAPc were shown to be poor optical limiters because their imaginary third-order susceptibility (Im[χ(3)]) was of the order of 10-17-10-16 (optimal range is 10-9-10-11), the hyperpolarizability (γ) of the order of 10-37-10-36 (optimal range is 10-29-10-34) and the k values were above one but below ten.
- Full Text:
- Date Issued: 2010
- Authors: Britton, Jonathan
- Date: 2010
- Subjects: Indium , Zinc , Quantum dots , Phthalocyanines , Photochemotherapy , Nonlinear optics , Nanocrystals
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4332 , http://hdl.handle.net/10962/d1004993 , Indium , Zinc , Quantum dots , Phthalocyanines , Photochemotherapy , Nonlinear optics , Nanocrystals
- Description: CdTe QDs capped with mercaptopropionic acid (MPA) and thioglycolic acid (TGA) were covalently linked to zinc and indium tetraaminophthalocyanines (TAPcs) using N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) as the coupling agents. The results presented give evidence in favour of formation of an amide bond between the MTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and the mixture of QDs and ZnTAPc (without chemical linking) showed Förster resonance energy transfer (FRET), though the linked showed less FRET, whereas the QD interactions with InTAPc yielded no evidence of FRET. Both MTAPcs quenched the QDs emission, with quenching constants of the order of 103–104M−1, binding constants of the order of 108-1010M-1 and the number of binding sites for the MTAPc upon the QD being 2. High energy transfer efficiencies were obtained (in some cases as high as 93%), due to the low donor to acceptor distances. Lastly, both MTAPc were shown to be poor optical limiters because their imaginary third-order susceptibility (Im[χ(3)]) was of the order of 10-17-10-16 (optimal range is 10-9-10-11), the hyperpolarizability (γ) of the order of 10-37-10-36 (optimal range is 10-29-10-34) and the k values were above one but below ten.
- Full Text:
- Date Issued: 2010
Photophysiochemical studies of d¹⁰ metallophthalocyanines and their interaction with nanoparticles
- Chidawanyika, Wadzanai Janet Upenyu
- Authors: Chidawanyika, Wadzanai Janet Upenyu
- Date: 2010
- Subjects: Nanoparticles Phthalocyanines Photochemistry Electrochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4335 , http://hdl.handle.net/10962/d1004996
- Description: The syntheses, extensive spectroscopic characterization, photophysical and photochemical studies have been conducted for a variation of d10 metallophthaloycanines (MPcs). Comparisons have been made taking into consideration the nfluence of the central metal ion, solvent properties, substituent type and position. Coordination to heavy central metals i.e. Hg gives enhanced triplet state properties. Low symmetry metallophthalocyanine complexes were similarly haracterized and the influence of nteractions with nanoparticles on their photophysical and photochemical properties determined. The MPcs have been linked and adsorbed or mixed with nanoparticles i.e. hemically functionalized single-walled carbon nanotubes SWCNT) and mercaptocarboxylic acid capped CdTe quantum dots (QDs) and changes in the spectra accounted for with respect to the proposed conjugate structures. Distinct differences ccur for linked and adsorbed or mixed conjugates in the bsorption, infrared (IR) and Raman spectra and for thermal ravimetric decay profiles, suggesting successful formation f covalent bonds (linked) and point to structurally ifferent materials. SWCNT quench MPc fluorescence by a photoinduced electron transfer mediated process to give low fluorescence quantum yields. The QDs were used as energy transfer donors and facilitate energy transfer, through Förster resonance energy transfer (FRET) from the QDs to the MPcs. Improved FRET efficiencies were found for linked MPc-QD conjugates relative to the mixed species. Photophysicochemical properties of MPcs were, in general, improved as a result of interactions with nanoparticles.
- Full Text:
- Date Issued: 2010
- Authors: Chidawanyika, Wadzanai Janet Upenyu
- Date: 2010
- Subjects: Nanoparticles Phthalocyanines Photochemistry Electrochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4335 , http://hdl.handle.net/10962/d1004996
- Description: The syntheses, extensive spectroscopic characterization, photophysical and photochemical studies have been conducted for a variation of d10 metallophthaloycanines (MPcs). Comparisons have been made taking into consideration the nfluence of the central metal ion, solvent properties, substituent type and position. Coordination to heavy central metals i.e. Hg gives enhanced triplet state properties. Low symmetry metallophthalocyanine complexes were similarly haracterized and the influence of nteractions with nanoparticles on their photophysical and photochemical properties determined. The MPcs have been linked and adsorbed or mixed with nanoparticles i.e. hemically functionalized single-walled carbon nanotubes SWCNT) and mercaptocarboxylic acid capped CdTe quantum dots (QDs) and changes in the spectra accounted for with respect to the proposed conjugate structures. Distinct differences ccur for linked and adsorbed or mixed conjugates in the bsorption, infrared (IR) and Raman spectra and for thermal ravimetric decay profiles, suggesting successful formation f covalent bonds (linked) and point to structurally ifferent materials. SWCNT quench MPc fluorescence by a photoinduced electron transfer mediated process to give low fluorescence quantum yields. The QDs were used as energy transfer donors and facilitate energy transfer, through Förster resonance energy transfer (FRET) from the QDs to the MPcs. Improved FRET efficiencies were found for linked MPc-QD conjugates relative to the mixed species. Photophysicochemical properties of MPcs were, in general, improved as a result of interactions with nanoparticles.
- Full Text:
- Date Issued: 2010
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
Photophysical and photochemical behaviour of metallophthalocyanines effect of nanoparticles and molecules of biological importance
- Authors: Idowu, Mopelola Abidemi
- Date: 2009
- Subjects: Electrochemistry Phthalocyanines Nanoparticles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4329 , http://hdl.handle.net/10962/d1004990
- Description: Syntheses, spectral, photophysical and photochemical studies of some neutral, anionic and cationic metallophthalocyanine derivatives are presented. The effects of central metal ions, solvents, aggregation, surfactant, nanoparticles and bovine serum albumin on the photophysical and photochemical behaviour are investigated. Mercaptocarboxylic acid stabilized CdTe quantum dots (QDs) were used as energy donors to anionic water-soluble MPcs through Förster resonance energy transfer (FRET). Energy transfer (ET) from the QDs to the MPcs occurred upon photoexcitation of the QDs. An enhancement in efficiency of ET with the nature of the cappings on the QDs was observed with few occurrences of a non-Förster type ET. QDs were found to improve the photophysicochemical behaviour of the MPcs, with the possibility of indirect production of singlet oxygen (Φ[subscript Δ]) via FRET mechanism. Interaction of the QDs with cationic water-souble MPcs produced ion-pair complexes resulting in aggregates due to strong electronic coupling. The stoichiometry of the reaction and association constants are evaluated by the continuous variation method. Improved photophysicochemical behaviour with no spectral alterations was observed in MPcs in the presence of magnetic fluid. Complexes showed high triplet quantum yields with corresponding long lifetimes and high photostability. Elucidation of the results of the interaction of bovine serum albumin (BSA) with MPcs or QDs is presented. Increased efficiency of Φ[subscript Δ] generation of MPcs in the presence of BSA coupled with large binding constants, suggesting strong interaction of the MPcs with BSA was observed. Enhanced emission intensity of QDs when linked to or in a mixture with BSA due to radiationless recombination at the surface vacancies was also observed. The study revealed positive deviation from Stern-Volmer relationship suggesting the occurrence of static and dynamic mechanisms of quenching together. Fluorescence quenching of the MPcs by benzoquinone, analysed by Stern-Volmer relationship is also presented; the results were employed in determining fluorescence lifetimes of the complexes. Photoelectrochemical characteristics of MPc-sensitized electrodeposited ZnO thin films were studied; ZnOCPc / ZnO films have been improved to an incident photon-to-currentconversion (IPCE) value of 31.1 % with an absorbed photon-to-current conversion (APCE) of 59.6 %. The best obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films. Fluorescent-magnetic nanocomposite with excellent photophysical properties which can be exploited for combined photodynamic and hyperthermia therapies is also presented.
- Full Text:
- Date Issued: 2009
- Authors: Idowu, Mopelola Abidemi
- Date: 2009
- Subjects: Electrochemistry Phthalocyanines Nanoparticles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4329 , http://hdl.handle.net/10962/d1004990
- Description: Syntheses, spectral, photophysical and photochemical studies of some neutral, anionic and cationic metallophthalocyanine derivatives are presented. The effects of central metal ions, solvents, aggregation, surfactant, nanoparticles and bovine serum albumin on the photophysical and photochemical behaviour are investigated. Mercaptocarboxylic acid stabilized CdTe quantum dots (QDs) were used as energy donors to anionic water-soluble MPcs through Förster resonance energy transfer (FRET). Energy transfer (ET) from the QDs to the MPcs occurred upon photoexcitation of the QDs. An enhancement in efficiency of ET with the nature of the cappings on the QDs was observed with few occurrences of a non-Förster type ET. QDs were found to improve the photophysicochemical behaviour of the MPcs, with the possibility of indirect production of singlet oxygen (Φ[subscript Δ]) via FRET mechanism. Interaction of the QDs with cationic water-souble MPcs produced ion-pair complexes resulting in aggregates due to strong electronic coupling. The stoichiometry of the reaction and association constants are evaluated by the continuous variation method. Improved photophysicochemical behaviour with no spectral alterations was observed in MPcs in the presence of magnetic fluid. Complexes showed high triplet quantum yields with corresponding long lifetimes and high photostability. Elucidation of the results of the interaction of bovine serum albumin (BSA) with MPcs or QDs is presented. Increased efficiency of Φ[subscript Δ] generation of MPcs in the presence of BSA coupled with large binding constants, suggesting strong interaction of the MPcs with BSA was observed. Enhanced emission intensity of QDs when linked to or in a mixture with BSA due to radiationless recombination at the surface vacancies was also observed. The study revealed positive deviation from Stern-Volmer relationship suggesting the occurrence of static and dynamic mechanisms of quenching together. Fluorescence quenching of the MPcs by benzoquinone, analysed by Stern-Volmer relationship is also presented; the results were employed in determining fluorescence lifetimes of the complexes. Photoelectrochemical characteristics of MPc-sensitized electrodeposited ZnO thin films were studied; ZnOCPc / ZnO films have been improved to an incident photon-to-currentconversion (IPCE) value of 31.1 % with an absorbed photon-to-current conversion (APCE) of 59.6 %. The best obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films. Fluorescent-magnetic nanocomposite with excellent photophysical properties which can be exploited for combined photodynamic and hyperthermia therapies is also presented.
- 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
Synthesis and photophysical properties of antimony and lead phthalocyanines
- Modibane, Kwena Desmond, Guest
- Authors: Modibane, Kwena Desmond , Guest
- Date: 2009 , 2009-02-27
- Subjects: Phthalocyanines , Photochemistry , Antimony compounds , Lead compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4370 , http://hdl.handle.net/10962/d1005035 , Phthalocyanines , Photochemistry , Antimony compounds , Lead compounds
- Description: This work hereby presents the synthesis, spectroscopic and photophysical properties of newly synthesized lead (PbPc) and antimony (SbPc) phthalocyanines. The complexes are either unsubstituted or substituted at the peripheral and non-peripheral positions with phenoxy, 4-t-butylphenoxy and 4-benzyloxyphenoxy groups. The photophysical properties of these complexes were studied in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform as solvents. The fluorescence spectra for PbPc complexes were different to that of the excitation spectra due to demetallation upon excitation. On the other hand, the excitation spectra of oxidized antimony (Sb(V)Pc) derivatives were found to be similar to absorption spectra. High triplet quantum yields for PbPc and SbPc complexes ranging from 0.70 to 0.86, low triplet lifetimes (20–60 μs in DMSO, while they were <10 μs in the rest of the solvents) and low fluorescence quantum yields were observed and is attributed to the presence of heavy atoms (Pb and Sb ions). The nonlinear optical properties of PbPc complexes were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.8 W/cm2. The photodegradation studies of the PbPc and SbPc complexes synthesized showed that then are stable.
- Full Text:
- Date Issued: 2009
- Authors: Modibane, Kwena Desmond , Guest
- Date: 2009 , 2009-02-27
- Subjects: Phthalocyanines , Photochemistry , Antimony compounds , Lead compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4370 , http://hdl.handle.net/10962/d1005035 , Phthalocyanines , Photochemistry , Antimony compounds , Lead compounds
- Description: This work hereby presents the synthesis, spectroscopic and photophysical properties of newly synthesized lead (PbPc) and antimony (SbPc) phthalocyanines. The complexes are either unsubstituted or substituted at the peripheral and non-peripheral positions with phenoxy, 4-t-butylphenoxy and 4-benzyloxyphenoxy groups. The photophysical properties of these complexes were studied in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform as solvents. The fluorescence spectra for PbPc complexes were different to that of the excitation spectra due to demetallation upon excitation. On the other hand, the excitation spectra of oxidized antimony (Sb(V)Pc) derivatives were found to be similar to absorption spectra. High triplet quantum yields for PbPc and SbPc complexes ranging from 0.70 to 0.86, low triplet lifetimes (20–60 μs in DMSO, while they were <10 μs in the rest of the solvents) and low fluorescence quantum yields were observed and is attributed to the presence of heavy atoms (Pb and Sb ions). The nonlinear optical properties of PbPc complexes were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.8 W/cm2. The photodegradation studies of the PbPc and SbPc complexes synthesized showed that then are stable.
- Full Text:
- Date Issued: 2009
Removal and photocatalysis of 4-Nitrophenol using metallophthalocyanines
- Authors: Marais, Eloïse Ann
- Date: 2008
- Subjects: Photocatalysis , Catalysis , Electrochemistry , Nitrophenols , Phthalocyanines
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4343 , http://hdl.handle.net/10962/d1005005 , Photocatalysis , Catalysis , Electrochemistry , Nitrophenols , Phthalocyanines
- Description: Photodegradation of 4-nitrophenol (4-Np) in the presence of water-soluble zinc phthalocyanines and water-insoluble metallophthalocyanines is reported. The water-soluble phthalocyanines employed include zinc tetrasulphophthalocyanine (ZnPcS[subscript 4]), zinc octacarboxyphthalocyanine (ZnPc(COOH)[subscript 8]) and a sulphonated ZnPc containing a mixture of differently sulphonated derivatives (ZnPcS[subscript mix]), while the water-insoluble phthalocyanines used include unsubstituted magnesium (MgPc), zinc (ZnPc) and chloroaluminium (ClAlPc) phthalocyanine complexes and the ring-substituted zinc tetranitro (ZnPc(NO[subscript 2])[subscript 4]), zinc tetraamino (ZnPc(NH[subscript 2])[subscript 4]), zinc hexadecafluoro (ZnPcF[subscript 16]) and zinc hexadecachloro (ZnPcCl[subscript 16]) phthalocyanines. The most effective water-soluble photocatalyst is ZnPcS[subscript mix] in terms of the high quantum yield obtained for 4-Np degradation (Φ[subscript 4-Np]) as well as its photostability. While ZnPc(COOH)[subscript 8] has the highest Φ[subscript 4-Np] value relative to the other water-soluble complexes, it degrades readily during photocatalysis. The Φ[subscript 4-Np] values were closely related to the singlet oxygen quantum yields Φ[subscript Δ] and hence aggregation. The rate constants for the reaction with 4-Np were kr = 0.67 x 10[superscript 6] mol[superscript -1] dm[superscript 3] s[superscript -1] for ZnPcS[subscript mix] and 7.7 x 10[superscript 6] mol[superscript -1] dm[superscript 3] s[superscript -1] for ZnPc(COOH)[subscript 8]. ClAlPc is the most effective photocatalyst relative to the other heterogeneous photocatalysts for the phototransformation of 4-Np, with 89 ± 8.4 % degradation of 4-Np achieved after 100 min. The least effective catalysts were ZnPcCl[subscript 16] and MgPc. The final products of the photocatalysis of 4-Np in the presence of the homogeneous photocatalysts include 4-nitrocatechol and hydroquinone, while degradation of 4-Np in the presence of the heterogeneous photocatalysts resulted in fumaric acid and 4-nitrocatechol. ClAlPc was employed for the heterogeneous photocatalysis of the non-systemic insecticide, methyl paraoxon. Complete degradation of the pesticide was confirmed by the disappearance of the HPLC trace for methyl paraoxon after 100 min of irradiation with visible light. The removal of 4-Np from an aqueous medium using commercially available Amberlite[superscript ®] IRA-900 modified with metal phthalocyanines was also investigated. The metallophthalocyanines immobilised onto the surface of Amberlite[superscript ®] IRA-900 include Fe (FePcS[subscript 4]), Co (CoPcS[subscript 4]) and Ni (NiPcS[subscript 4]) tetrasulphophthalocyanines, and differently sulphonated phthalocyanine mixtures of Fe (FePcS[subscript mix]), Co (CoPcS[subscript mix]) and Ni (NiPcS[subscript mix]). Adsorption rates were fastest for the modified adsorbents at pH 9. Using the Langmuir-Hinshelwood kinetic model, the complexes showed the following order of 4-Np adsorption: CoPcS[subscript mix] > NiPcS[subscript 4] > NiPcS[subscript mix] > FePcS[subscript 4] > FePcS[subscript mix] > CoPcS[subscript 4]. The adsorbents were regenerated using dilute HNO[subscript 3], with 76 % (7.6 x 10[superscript -5] mol) of 4-Np recovered within 150 min.
- Full Text:
- Date Issued: 2008
- Authors: Marais, Eloïse Ann
- Date: 2008
- Subjects: Photocatalysis , Catalysis , Electrochemistry , Nitrophenols , Phthalocyanines
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4343 , http://hdl.handle.net/10962/d1005005 , Photocatalysis , Catalysis , Electrochemistry , Nitrophenols , Phthalocyanines
- Description: Photodegradation of 4-nitrophenol (4-Np) in the presence of water-soluble zinc phthalocyanines and water-insoluble metallophthalocyanines is reported. The water-soluble phthalocyanines employed include zinc tetrasulphophthalocyanine (ZnPcS[subscript 4]), zinc octacarboxyphthalocyanine (ZnPc(COOH)[subscript 8]) and a sulphonated ZnPc containing a mixture of differently sulphonated derivatives (ZnPcS[subscript mix]), while the water-insoluble phthalocyanines used include unsubstituted magnesium (MgPc), zinc (ZnPc) and chloroaluminium (ClAlPc) phthalocyanine complexes and the ring-substituted zinc tetranitro (ZnPc(NO[subscript 2])[subscript 4]), zinc tetraamino (ZnPc(NH[subscript 2])[subscript 4]), zinc hexadecafluoro (ZnPcF[subscript 16]) and zinc hexadecachloro (ZnPcCl[subscript 16]) phthalocyanines. The most effective water-soluble photocatalyst is ZnPcS[subscript mix] in terms of the high quantum yield obtained for 4-Np degradation (Φ[subscript 4-Np]) as well as its photostability. While ZnPc(COOH)[subscript 8] has the highest Φ[subscript 4-Np] value relative to the other water-soluble complexes, it degrades readily during photocatalysis. The Φ[subscript 4-Np] values were closely related to the singlet oxygen quantum yields Φ[subscript Δ] and hence aggregation. The rate constants for the reaction with 4-Np were kr = 0.67 x 10[superscript 6] mol[superscript -1] dm[superscript 3] s[superscript -1] for ZnPcS[subscript mix] and 7.7 x 10[superscript 6] mol[superscript -1] dm[superscript 3] s[superscript -1] for ZnPc(COOH)[subscript 8]. ClAlPc is the most effective photocatalyst relative to the other heterogeneous photocatalysts for the phototransformation of 4-Np, with 89 ± 8.4 % degradation of 4-Np achieved after 100 min. The least effective catalysts were ZnPcCl[subscript 16] and MgPc. The final products of the photocatalysis of 4-Np in the presence of the homogeneous photocatalysts include 4-nitrocatechol and hydroquinone, while degradation of 4-Np in the presence of the heterogeneous photocatalysts resulted in fumaric acid and 4-nitrocatechol. ClAlPc was employed for the heterogeneous photocatalysis of the non-systemic insecticide, methyl paraoxon. Complete degradation of the pesticide was confirmed by the disappearance of the HPLC trace for methyl paraoxon after 100 min of irradiation with visible light. The removal of 4-Np from an aqueous medium using commercially available Amberlite[superscript ®] IRA-900 modified with metal phthalocyanines was also investigated. The metallophthalocyanines immobilised onto the surface of Amberlite[superscript ®] IRA-900 include Fe (FePcS[subscript 4]), Co (CoPcS[subscript 4]) and Ni (NiPcS[subscript 4]) tetrasulphophthalocyanines, and differently sulphonated phthalocyanine mixtures of Fe (FePcS[subscript mix]), Co (CoPcS[subscript mix]) and Ni (NiPcS[subscript mix]). Adsorption rates were fastest for the modified adsorbents at pH 9. Using the Langmuir-Hinshelwood kinetic model, the complexes showed the following order of 4-Np adsorption: CoPcS[subscript mix] > NiPcS[subscript 4] > NiPcS[subscript mix] > FePcS[subscript 4] > FePcS[subscript mix] > CoPcS[subscript 4]. The adsorbents were regenerated using dilute HNO[subscript 3], with 76 % (7.6 x 10[superscript -5] mol) of 4-Np recovered within 150 min.
- Full Text:
- Date Issued: 2008
Synthesis, photochemical and photophysical properties of gallium and indium phthalocyanine derivatives
- Authors: Chauke, Vongani Portia
- Date: 2008
- Subjects: Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4375 , http://hdl.handle.net/10962/d1005040 , Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Description: The syntheses of octasubstituted and unsusbstitituted Gallium(III) chloride and indium(III) chloride phthalocyanines (GaPc and InPc), their photophysical, photochemical and nonlinear optical parameters are hereby presented. The photocatalytic oxidation of 1-hexene using the synthesized GaPc and InPc complexes as well as electrochemical characterization is also presented in this thesis. Fluorescence quantum yields do not vary much among the four Ga complexes, except for complex 21c; therefore it was concluded that the effect of substituents is not significant among them. Solvents however, had an effect on the results. Lower Φ[subscript F] values were obtained in low viscosity solvents like toluene, relative to highly viscous solvents, such as DMSO. The triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. Photodegradation and singlet oxygen quantum yields have also been reported. There was no clear correlation between the latter parameters. It was however established that the four gallium MPcs were stable, within the allowed stability range for phthalocyanines. High quantum yields of triplet state (Φ[subscript T] ranging from 0.70 to 0.91 in dimethysulfoxide, DMSO) and singlet oxygen generation (Φ[subscript greek capital letter delta], ranging from 0.61 to 0.79 in DMSO) were obtained. Short triplet lifetimes 50 to 60 μs were obtained in DMSO). Calculated non-linear parameters of these complexes are compared with those of the corresponding GaPc derivatives and tetrasubstituted GaPc and InPc complexes. The optical limiting threshold intensity (I[subscript lim]) values for the InPc and GaPc derivatives were calculated and compared with those of corresponding tetrasubstituted InPc and GaPc complexes. The octasubstituted were found to be better optical limiters. Photocatalytic oxidation of 1-hexene by GaPc (21a-c) and InPc (22a-c) derivatives is also presented. The photocatalytic oxidation products for 1-hexene were 1,2- epoxyhexane and 1-hexen-3-ol. The % conversion values of 1-hexene and % selectivity of 1,2-epoxyhexane were generally higher for InPc derivatives. Even though InPc derivatives showed better photocatalytic results than GaPc derivatives, the former were less stable relative to the latter. Both type I and type II mechanism were implicated in the photocatalysis mechanism.
- Full Text:
- Date Issued: 2008
- Authors: Chauke, Vongani Portia
- Date: 2008
- Subjects: Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4375 , http://hdl.handle.net/10962/d1005040 , Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Description: The syntheses of octasubstituted and unsusbstitituted Gallium(III) chloride and indium(III) chloride phthalocyanines (GaPc and InPc), their photophysical, photochemical and nonlinear optical parameters are hereby presented. The photocatalytic oxidation of 1-hexene using the synthesized GaPc and InPc complexes as well as electrochemical characterization is also presented in this thesis. Fluorescence quantum yields do not vary much among the four Ga complexes, except for complex 21c; therefore it was concluded that the effect of substituents is not significant among them. Solvents however, had an effect on the results. Lower Φ[subscript F] values were obtained in low viscosity solvents like toluene, relative to highly viscous solvents, such as DMSO. The triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. Photodegradation and singlet oxygen quantum yields have also been reported. There was no clear correlation between the latter parameters. It was however established that the four gallium MPcs were stable, within the allowed stability range for phthalocyanines. High quantum yields of triplet state (Φ[subscript T] ranging from 0.70 to 0.91 in dimethysulfoxide, DMSO) and singlet oxygen generation (Φ[subscript greek capital letter delta], ranging from 0.61 to 0.79 in DMSO) were obtained. Short triplet lifetimes 50 to 60 μs were obtained in DMSO). Calculated non-linear parameters of these complexes are compared with those of the corresponding GaPc derivatives and tetrasubstituted GaPc and InPc complexes. The optical limiting threshold intensity (I[subscript lim]) values for the InPc and GaPc derivatives were calculated and compared with those of corresponding tetrasubstituted InPc and GaPc complexes. The octasubstituted were found to be better optical limiters. Photocatalytic oxidation of 1-hexene by GaPc (21a-c) and InPc (22a-c) derivatives is also presented. The photocatalytic oxidation products for 1-hexene were 1,2- epoxyhexane and 1-hexen-3-ol. The % conversion values of 1-hexene and % selectivity of 1,2-epoxyhexane were generally higher for InPc derivatives. Even though InPc derivatives showed better photocatalytic results than GaPc derivatives, the former were less stable relative to the latter. Both type I and type II mechanism were implicated in the photocatalysis mechanism.
- Full Text:
- Date Issued: 2008
Synthesis, photophysics and electrochemical study of tin macrocycles
- Authors: Khene, Mielie Samson
- Date: 2008
- Subjects: Electrochemistry , Photochemistry , Phthalocyanines , Macrocyclic compounds , Spectrum analysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4376 , http://hdl.handle.net/10962/d1005041 , Electrochemistry , Photochemistry , Phthalocyanines , Macrocyclic compounds , Spectrum analysis
- Description: Three non-peripherally substituted tin(IV) macrocylic compounds, octahexylphthalocyaninato dichlorotin(IV) (35a), octahexyltetrabenzo-5,10,15-triazaporphyrinato dichlorotin(IV) (35b) and octadecylphthalocyaninato dichlorotin(IV) (35c) were synthesized and their photophysical and electrochemical behaviour studied. Complex (35b), containing a CH group in place of one of the aza nitrogen atom of the phthalocyanine core, shows a split Q band due to its lower symmetry. The triplet state quantum yields were found to be lower than would be expected on the basis of the heavy atom effect of tin as the central metal for phthalocyanine derivatives (35a and 35c). In contrast, (35b) shows a triplet quantum yield ΦT = 0.78. The triplet state lifetimes were solvent dependent, and were higher in THF than in toluene. Cyclic voltammetry and spectroelectrochemistry of the complexes revealed only ring based redox processes. This thesis also reports on the microwave syntheses of tetrasulphonated tin phthalocyanine and tetrasulphonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (< 1:8) of 4-sulfophthalic acid to urea. Both complexes are aggregated in aqueous media, but can be partly or fully disaggregated by the addition of Triton X-100. The SnTSTBC complex has lower triplet life times and yields, while binding constant and quenching (of bovine serum albumin) constant are lower for SnTSTBC, compared to SnTSPc. Finally Non-peripherally (α) tetra- (40) and octa-(38a) substituted dodecyl-mercapto tin(IV) phthalocyanines where synthesized and the electrochemical behavior studied. Cyclic voltammetry and spectroelectrochemistry show ring-based reductions for (38a) and (40); the former shows two ring oxidations, while the latter shows only one ring based oxidation. The adsorption kinetics of (38a) and (40) on a gold electrode have been investigated by electrochemical impedance spectroscopy (EIS). The equilibrium constant (K) for the adsorption and the Gibbs free energy ΔG(ads) of the self-assembled monolayer (SAMs) were evaluated based on the Frumkin isotherm. The interaction factor between adsorbate –adsorbate molecules is also discussed.
- Full Text:
- Date Issued: 2008
- Authors: Khene, Mielie Samson
- Date: 2008
- Subjects: Electrochemistry , Photochemistry , Phthalocyanines , Macrocyclic compounds , Spectrum analysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4376 , http://hdl.handle.net/10962/d1005041 , Electrochemistry , Photochemistry , Phthalocyanines , Macrocyclic compounds , Spectrum analysis
- Description: Three non-peripherally substituted tin(IV) macrocylic compounds, octahexylphthalocyaninato dichlorotin(IV) (35a), octahexyltetrabenzo-5,10,15-triazaporphyrinato dichlorotin(IV) (35b) and octadecylphthalocyaninato dichlorotin(IV) (35c) were synthesized and their photophysical and electrochemical behaviour studied. Complex (35b), containing a CH group in place of one of the aza nitrogen atom of the phthalocyanine core, shows a split Q band due to its lower symmetry. The triplet state quantum yields were found to be lower than would be expected on the basis of the heavy atom effect of tin as the central metal for phthalocyanine derivatives (35a and 35c). In contrast, (35b) shows a triplet quantum yield ΦT = 0.78. The triplet state lifetimes were solvent dependent, and were higher in THF than in toluene. Cyclic voltammetry and spectroelectrochemistry of the complexes revealed only ring based redox processes. This thesis also reports on the microwave syntheses of tetrasulphonated tin phthalocyanine and tetrasulphonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (< 1:8) of 4-sulfophthalic acid to urea. Both complexes are aggregated in aqueous media, but can be partly or fully disaggregated by the addition of Triton X-100. The SnTSTBC complex has lower triplet life times and yields, while binding constant and quenching (of bovine serum albumin) constant are lower for SnTSTBC, compared to SnTSPc. Finally Non-peripherally (α) tetra- (40) and octa-(38a) substituted dodecyl-mercapto tin(IV) phthalocyanines where synthesized and the electrochemical behavior studied. Cyclic voltammetry and spectroelectrochemistry show ring-based reductions for (38a) and (40); the former shows two ring oxidations, while the latter shows only one ring based oxidation. The adsorption kinetics of (38a) and (40) on a gold electrode have been investigated by electrochemical impedance spectroscopy (EIS). The equilibrium constant (K) for the adsorption and the Gibbs free energy ΔG(ads) of the self-assembled monolayer (SAMs) were evaluated based on the Frumkin isotherm. The interaction factor between adsorbate –adsorbate molecules is also discussed.
- Full Text:
- Date Issued: 2008
Catalytic activities of metallophthalocyanines towards detection and transformation of pollutants
- Authors: Agboola, Bolade Oyeyinka
- Date: 2007
- Subjects: Phthalocyanines Electrochemistry Pollutants -- Biodegradation Pollutants -- Measurement
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4427 , http://hdl.handle.net/10962/d1006922
- Description: Syntheses, spectral, electrochemical and spectroelectrochemical studies of new thiol-derivatised MPc complexes were satisfactorily carried out. For the first time, spectroelectrochemistry gave evidence for the formation of Ni²⁺/Ni⁺ process in a NiPc complex. Significant insights as to the nature of Fe⁺Pc and Ni⁺Pc spectra were obtained. Transformations of chlorophenols using chemical and photochemical methods are presented. For cobalt tetrasulphophthalocyanine catalysed oxidation of chlorophenols using hydrogen peroxide as the oxidant, types of oxidation products formed depended on the solvent conditions. Photolysis of aqueous solutions of chlorophenols in the presence of immobilised non-transition metal phthalocyanine photosensitisers onto Amerlite® was carried out. For the first time, MPcS[subscript mix] complexes were immobilised on Amberlite® for use in heterogeneous photocatalysis. Photolysis of the chlorophenols resulted mainly in the formation of chlorobenzoquinone derivatives. The generation of singlet oxygen (¹O₂) by these immobilised MPc photosensitisers was found to play a major role in their photoactivities. Modifications of gold electrodes with the newly synthesised thiol-derivatised MPc complexes via electropolymerisation and SAM techniques are presented. Cyclic voltammetry, impedance spectroscopy (NiPcs only) and spectroelectrochemical techniques (NiPcs only) confirmed that the complexes formed films on gold electrodes. Stable and well packed SAM films as evidenced by the voltammetric characterisation were obtained. For the first time, optimisation of the time for SAM formation based on CV technique was studied. First example of a formation of MnPc-SAM was achieved. Catalytic activities of the NiPc towards chlorophenol depended on the nature of the NiPc in the polymer films and also anti-fouling ability of the films depended on polymer film thickness. The FeTBMPc polymer modified gold electrode showed the best catalytic activity in terms of peak potential, E[subscript p] when compared to reported work in literature for nitrate electrooxidation. Cyclic voltammetry and spectroscopy studies showed that the CoPcs, FePcs and NiPcs catalysed nitrite oxidation involve 2 electrons in total while that of McPcs involve 1 electron. Better catalytic performance towards sulphite electrooxidation were obtained for the CoPcs, FePcs and MnPcs which have metal based redox processes within the range of the sulphite electrooxidation peak while the NiPcs which did not show metal based oxidation reaction performed less.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade Oyeyinka
- Date: 2007
- Subjects: Phthalocyanines Electrochemistry Pollutants -- Biodegradation Pollutants -- Measurement
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4427 , http://hdl.handle.net/10962/d1006922
- Description: Syntheses, spectral, electrochemical and spectroelectrochemical studies of new thiol-derivatised MPc complexes were satisfactorily carried out. For the first time, spectroelectrochemistry gave evidence for the formation of Ni²⁺/Ni⁺ process in a NiPc complex. Significant insights as to the nature of Fe⁺Pc and Ni⁺Pc spectra were obtained. Transformations of chlorophenols using chemical and photochemical methods are presented. For cobalt tetrasulphophthalocyanine catalysed oxidation of chlorophenols using hydrogen peroxide as the oxidant, types of oxidation products formed depended on the solvent conditions. Photolysis of aqueous solutions of chlorophenols in the presence of immobilised non-transition metal phthalocyanine photosensitisers onto Amerlite® was carried out. For the first time, MPcS[subscript mix] complexes were immobilised on Amberlite® for use in heterogeneous photocatalysis. Photolysis of the chlorophenols resulted mainly in the formation of chlorobenzoquinone derivatives. The generation of singlet oxygen (¹O₂) by these immobilised MPc photosensitisers was found to play a major role in their photoactivities. Modifications of gold electrodes with the newly synthesised thiol-derivatised MPc complexes via electropolymerisation and SAM techniques are presented. Cyclic voltammetry, impedance spectroscopy (NiPcs only) and spectroelectrochemical techniques (NiPcs only) confirmed that the complexes formed films on gold electrodes. Stable and well packed SAM films as evidenced by the voltammetric characterisation were obtained. For the first time, optimisation of the time for SAM formation based on CV technique was studied. First example of a formation of MnPc-SAM was achieved. Catalytic activities of the NiPc towards chlorophenol depended on the nature of the NiPc in the polymer films and also anti-fouling ability of the films depended on polymer film thickness. The FeTBMPc polymer modified gold electrode showed the best catalytic activity in terms of peak potential, E[subscript p] when compared to reported work in literature for nitrate electrooxidation. Cyclic voltammetry and spectroscopy studies showed that the CoPcs, FePcs and NiPcs catalysed nitrite oxidation involve 2 electrons in total while that of McPcs involve 1 electron. Better catalytic performance towards sulphite electrooxidation were obtained for the CoPcs, FePcs and MnPcs which have metal based redox processes within the range of the sulphite electrooxidation peak while the NiPcs which did not show metal based oxidation reaction performed less.
- Full Text:
- Date Issued: 2007
Phthalocyanines : photochemical, electrochemical and biomimetic catalytic behaviour
- Authors: Sehlotho, Nthapo
- Date: 2007
- Subjects: Phthalocyanines Photochemistry Electrochemistry Biomimetics Oxidation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4336 , http://hdl.handle.net/10962/d1004997
- Description: This thesis explored use of metallophthalocyanines as electrocatalysts towards thiol and thiocyanate oxidation, nitrosothiol decomposition and reduction of oxygen, as well as biomimetic and photo-catalysts of cyclohexene oxidation. 2-mercaptoethanol (2-ME), L-cysteine (CYS) and reduced glutathione (GSH) thiols were oxidized on cobalt tetra ethoxythiophene and cobalt tetra phenoxy pyrrole phthalocyanine modified glassy carbon electrodes, whose catalytic activity was found to depend on pH, film thickness and method of electrode modification. Oxidation of thiocyanate (SCN-), CYS and 2-ME was catalyzed by a selfassembled monolayer of cobalt tetraethoxythiophene Thiocyanate oxidation occurred via two electron transfer, whereas that of CYS and 2-ME required 1 electron. The oxidations of SCN- and 2-ME were catalyzed by ring based processes, while CYS was catalyzed by both Co[superscript III]/Co[superscript II] process and ring-based processes. Oxidation of GSH and 2-ME was conducted on screen printed graphite electrodes modified with cobalt phthalocyanine. Activity depended on method of electrode modification and CoPc % composition. Decomposition of Snitrosoglutathione occurred in the presence of copper ions and NaBH[subscript 4]. Reduced and oxidized glutathione were detected as products using cobalt phthalocyanine adsorbed on an ordinary pyrolytic graphite electrode. Reduction of oxygen was electro-catalyzed by adsorbed manganese phthalocyanine complexes on glassy carbon electrodes. FePc, FePc(Cl)[subscript 16], CoPc and CoPc substituted with phenoxypyrrole and ethoxythiophene ligands were also used as electro-catalysts. Oxygen reduction occurred via two electron transfer in acidic and neutral media forming hydrogen peroxide, while water was formed in basic media via four electron transfer. Cyclohexene oxidation using tert-butylhydroperoxide or chloroperoxy benzoic acid as oxidants in the presence of FePc, FePc(Cl)[subscript 16] and CoPc formed cyclohexene oxide, 2-cyclohexen-1-ol, 2- cyclohexen-1-one and adipic acid. Product selectivity depended on the nature of catalyst and oxidant. The FePc(Cl)[subscript 16] catalyst was transformed into a µ-oxo dimer during the oxidation process while M[superscript III]Pc intermediates were formed with Co[superscript II]Pc and Fe[superscript II]Pc catalysts. Cyclohexene photooxidation catalyzed by zinc phthalocyanine using either red or white light formed 2-cyclohexen-1-one, 2-cyclohexen-1-ol, transcyclohexane diol, cyclohexene oxide and cyclohexene hydroperoxide via singlet oxygen and radical mechanisms. Product yields depended on the light wavelength and intensity, solvent, irradiation time and the rate of photodegradation of the catalyst.
- Full Text:
- Date Issued: 2007
- Authors: Sehlotho, Nthapo
- Date: 2007
- Subjects: Phthalocyanines Photochemistry Electrochemistry Biomimetics Oxidation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4336 , http://hdl.handle.net/10962/d1004997
- Description: This thesis explored use of metallophthalocyanines as electrocatalysts towards thiol and thiocyanate oxidation, nitrosothiol decomposition and reduction of oxygen, as well as biomimetic and photo-catalysts of cyclohexene oxidation. 2-mercaptoethanol (2-ME), L-cysteine (CYS) and reduced glutathione (GSH) thiols were oxidized on cobalt tetra ethoxythiophene and cobalt tetra phenoxy pyrrole phthalocyanine modified glassy carbon electrodes, whose catalytic activity was found to depend on pH, film thickness and method of electrode modification. Oxidation of thiocyanate (SCN-), CYS and 2-ME was catalyzed by a selfassembled monolayer of cobalt tetraethoxythiophene Thiocyanate oxidation occurred via two electron transfer, whereas that of CYS and 2-ME required 1 electron. The oxidations of SCN- and 2-ME were catalyzed by ring based processes, while CYS was catalyzed by both Co[superscript III]/Co[superscript II] process and ring-based processes. Oxidation of GSH and 2-ME was conducted on screen printed graphite electrodes modified with cobalt phthalocyanine. Activity depended on method of electrode modification and CoPc % composition. Decomposition of Snitrosoglutathione occurred in the presence of copper ions and NaBH[subscript 4]. Reduced and oxidized glutathione were detected as products using cobalt phthalocyanine adsorbed on an ordinary pyrolytic graphite electrode. Reduction of oxygen was electro-catalyzed by adsorbed manganese phthalocyanine complexes on glassy carbon electrodes. FePc, FePc(Cl)[subscript 16], CoPc and CoPc substituted with phenoxypyrrole and ethoxythiophene ligands were also used as electro-catalysts. Oxygen reduction occurred via two electron transfer in acidic and neutral media forming hydrogen peroxide, while water was formed in basic media via four electron transfer. Cyclohexene oxidation using tert-butylhydroperoxide or chloroperoxy benzoic acid as oxidants in the presence of FePc, FePc(Cl)[subscript 16] and CoPc formed cyclohexene oxide, 2-cyclohexen-1-ol, 2- cyclohexen-1-one and adipic acid. Product selectivity depended on the nature of catalyst and oxidant. The FePc(Cl)[subscript 16] catalyst was transformed into a µ-oxo dimer during the oxidation process while M[superscript III]Pc intermediates were formed with Co[superscript II]Pc and Fe[superscript II]Pc catalysts. Cyclohexene photooxidation catalyzed by zinc phthalocyanine using either red or white light formed 2-cyclohexen-1-one, 2-cyclohexen-1-ol, transcyclohexane diol, cyclohexene oxide and cyclohexene hydroperoxide via singlet oxygen and radical mechanisms. Product yields depended on the light wavelength and intensity, solvent, irradiation time and the rate of photodegradation of the catalyst.
- Full Text:
- Date Issued: 2007
Study of metallophthalocyanines attached onto pre-modified gold surfaces
- Authors: Mashazi, Philani Nkosinathi
- Date: 2007
- Subjects: Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Glucose -- Measurement
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4361 , http://hdl.handle.net/10962/d1005026 , Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Glucose -- Measurement
- Description: Tetra-carboxy acid chloride phthalocyanine complexes of cobalt, iron and manganese were synthesized and characterized using spectroscopic and electrochemical techniques. These complexes were fabricated as thin films on gold electrode following a covalent immobilization and self-assembling methods. Surface electrochemical and spectroscopic characterization showed that these complexes are surface-confined species. The characterization using spectroscopic and electrochemical methods confirmed the formation of thiol and MPc SAMs on gold electrode. The electrocatalytic behaviour of the SAM modified gold electrodes was studied for the detection of L-cysteine and hydrogen peroxide. The limits of detection (LoD) for Lcysteine were of the orders of 10[superscript -7] mol.L[superscript -1] for all the MPc complexes studied and the LoD for hydrogen peroxide at cobalt phthalocyanine modified gold electrode was of the orders of 10[superscript -7]mol.L[superscript -1] for both electrocatalytic oxidation and reduction. The modification process for gold electrodes was reproducible and showed good stability, if stored in pH 4 phosphate buffer solutions and can be used over a long period of time. The cobalt phthalocyanine modified gold electrode was also investigated for the fabrication of glucose oxidase (GOx)-based biosensor and as an electron mediator between the enzyme and gold electrode. The behaviour of the enzyme modified gold electrode towards the detection of glucose was studied and the results gave a limit of detection of the orders of 10[superscript -6] mol.L[superscript -1] with low binding constant (4.8 mM) of enzyme (GOx) to substrate (glucose) referred to as Michaelis-Menten constant. The practical applications, i.e. the real sample analysis and interference studies, for the enzyme modified gold electrodes were investigated. These studies showed that the enzyme electrode is valuable and can be used for glucose detection.
- Full Text:
- Date Issued: 2007
- Authors: Mashazi, Philani Nkosinathi
- Date: 2007
- Subjects: Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Glucose -- Measurement
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4361 , http://hdl.handle.net/10962/d1005026 , Phthalocyanines , Electrochemistry , Electrodes, Enzyme , Glucose -- Measurement
- Description: Tetra-carboxy acid chloride phthalocyanine complexes of cobalt, iron and manganese were synthesized and characterized using spectroscopic and electrochemical techniques. These complexes were fabricated as thin films on gold electrode following a covalent immobilization and self-assembling methods. Surface electrochemical and spectroscopic characterization showed that these complexes are surface-confined species. The characterization using spectroscopic and electrochemical methods confirmed the formation of thiol and MPc SAMs on gold electrode. The electrocatalytic behaviour of the SAM modified gold electrodes was studied for the detection of L-cysteine and hydrogen peroxide. The limits of detection (LoD) for Lcysteine were of the orders of 10[superscript -7] mol.L[superscript -1] for all the MPc complexes studied and the LoD for hydrogen peroxide at cobalt phthalocyanine modified gold electrode was of the orders of 10[superscript -7]mol.L[superscript -1] for both electrocatalytic oxidation and reduction. The modification process for gold electrodes was reproducible and showed good stability, if stored in pH 4 phosphate buffer solutions and can be used over a long period of time. The cobalt phthalocyanine modified gold electrode was also investigated for the fabrication of glucose oxidase (GOx)-based biosensor and as an electron mediator between the enzyme and gold electrode. The behaviour of the enzyme modified gold electrode towards the detection of glucose was studied and the results gave a limit of detection of the orders of 10[superscript -6] mol.L[superscript -1] with low binding constant (4.8 mM) of enzyme (GOx) to substrate (glucose) referred to as Michaelis-Menten constant. The practical applications, i.e. the real sample analysis and interference studies, for the enzyme modified gold electrodes were investigated. These studies showed that the enzyme electrode is valuable and can be used for glucose detection.
- Full Text:
- Date Issued: 2007
Study of titanium, tantalum and chromium catalysts for use in industrial transformations
- Authors: Tau, Prudence Lerato
- Date: 2007
- Subjects: Titanium Tantalum Phthalocyanines Electrochemistry Photochemotherapy Chromium Spectrum analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4363 , http://hdl.handle.net/10962/d1005028
- Description: PART A The syntheses, spectroscopic and electrochemical characterisation of a series of titanium and tantalum phthalocyanine complexes are reported. The complexes are unsubstituted and substituted at either the peripheral or non-peripheral positions with sulphonates, aryloxy, arylthio or amino groups. The complexes mostly exhibit Qbands in the near-infrared region as well as interesting properties in different solvents. The interaction of differently sulphonated titanium and tantalum phthalocyanine complexes with methyl viologen (MV[superscript 2+]), and hence the stoichiometry and association constants are evaluated. Detailed photophysicochemical properties of the complexes were investigated and are for the first time presented with fluorescence lifetimes easily obtained from fluorescence quenching studies. The transformation of 1-hexene photocatalysed by aryloxy- and arylthio-appended complexes is also presented for the first time. The electrochemical properties of the complexes are unknown and are thus presented. Cyclic (CV) and square wave (SWV) voltammetries, chronocoulometry and spectroelectrochemistry are employed in the study of the complexes. Two oneelectron reductions and a simultaneous 4-electron reduction are observed for the unsubstituted Cl[subscript 3]TaPc. Reduction occurs first at the metal followed by ring-based processes. The tetra- and octa-substituted derivatives however exhibit peculiar electrochemical behaviour where a multi-electron transfer process occurs for complexes bearing certain substituents. For all complexes, the first two reductions are metal-based followed by ring-based processes. A comparative study of the electrocatalytic activities of the complexes towards the oxidation of nitrite is also investigated. The complexes are immobilised onto a glassy carbon electrode either by drop-dry or electropolymerisation methods. All the modified electrodes exhibit improved electrocatalytic oxidation of nitrite than the unmodified electrodes by a twoelectron mechanism producing nitrate ions. Catalytic currents are enhanced and nitrite overpotential reduced to ~ 0.60 V. Kinetic parameters are determined for all complexes and a mechanism is proposed. PART B: The syntheses and electrochemical characterisation of chromium and titanium complexes for the selective trimerisation of ethylene to 1-hexene are presented. The synthesis of the chromium complex requires simple steps while tedious steps are used for the air-sensitive titanium complex. The spectroscopic interaction of the chromium complex with the co-catalyst methylaluminoxane is investigated. The complexes are characterised by electrochemical methods such as cyclic voltammetry and spectroelectrochemistry.
- Full Text:
- Date Issued: 2007
- Authors: Tau, Prudence Lerato
- Date: 2007
- Subjects: Titanium Tantalum Phthalocyanines Electrochemistry Photochemotherapy Chromium Spectrum analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4363 , http://hdl.handle.net/10962/d1005028
- Description: PART A The syntheses, spectroscopic and electrochemical characterisation of a series of titanium and tantalum phthalocyanine complexes are reported. The complexes are unsubstituted and substituted at either the peripheral or non-peripheral positions with sulphonates, aryloxy, arylthio or amino groups. The complexes mostly exhibit Qbands in the near-infrared region as well as interesting properties in different solvents. The interaction of differently sulphonated titanium and tantalum phthalocyanine complexes with methyl viologen (MV[superscript 2+]), and hence the stoichiometry and association constants are evaluated. Detailed photophysicochemical properties of the complexes were investigated and are for the first time presented with fluorescence lifetimes easily obtained from fluorescence quenching studies. The transformation of 1-hexene photocatalysed by aryloxy- and arylthio-appended complexes is also presented for the first time. The electrochemical properties of the complexes are unknown and are thus presented. Cyclic (CV) and square wave (SWV) voltammetries, chronocoulometry and spectroelectrochemistry are employed in the study of the complexes. Two oneelectron reductions and a simultaneous 4-electron reduction are observed for the unsubstituted Cl[subscript 3]TaPc. Reduction occurs first at the metal followed by ring-based processes. The tetra- and octa-substituted derivatives however exhibit peculiar electrochemical behaviour where a multi-electron transfer process occurs for complexes bearing certain substituents. For all complexes, the first two reductions are metal-based followed by ring-based processes. A comparative study of the electrocatalytic activities of the complexes towards the oxidation of nitrite is also investigated. The complexes are immobilised onto a glassy carbon electrode either by drop-dry or electropolymerisation methods. All the modified electrodes exhibit improved electrocatalytic oxidation of nitrite than the unmodified electrodes by a twoelectron mechanism producing nitrate ions. Catalytic currents are enhanced and nitrite overpotential reduced to ~ 0.60 V. Kinetic parameters are determined for all complexes and a mechanism is proposed. PART B: The syntheses and electrochemical characterisation of chromium and titanium complexes for the selective trimerisation of ethylene to 1-hexene are presented. The synthesis of the chromium complex requires simple steps while tedious steps are used for the air-sensitive titanium complex. The spectroscopic interaction of the chromium complex with the co-catalyst methylaluminoxane is investigated. The complexes are characterised by electrochemical methods such as cyclic voltammetry and spectroelectrochemistry.
- Full Text:
- Date Issued: 2007
Substituted phthalocyanines development and self-assembled monolayer sensor studies
- Authors: Matemadombo, Fungisai
- Date: 2006
- Subjects: Phthalocyanines , Monomolecular films , Electrochemistry , Spectrum analysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4364 , http://hdl.handle.net/10962/d1005029 , Phthalocyanines , Monomolecular films , Electrochemistry , Spectrum analysis
- Description: Zinc, cobalt and iron phenylthio substituted phthalocyanines have been synthesized and characterized. Cyclic and square wave voltammetry in dimethylformamide containing tetrabutylammonium perchlorate revealed five and six redox processes respectively for the cobalt and iron phenylthio substituted phthalocyanines. These complexes are easier to reduce compared to the corresponding unsubstituted MPc and to butylthio substituted derivatives. Spectroelectrochemistry (in dimethylformamide containing tetrabutylammonium perchlorate) was employed to assign the cyclic voltammetry peaks, and gave spectra characteristic of Fe(I)Pc for reduction of iron phenylthio substituted phthalocyanine and Co(I)Pc for the reduction of cobalt phenylthio substituted phthalocyanine. The spectrum of the former is particularly of importance since such species have not received much attention in literature. Cobalt and iron phenylthio substituted phthalocyanines have been deposited on Au electrode surfaces through the self assembled monolayer (SAM) technique. The so formed layers were studied using voltammetric techniques. These SAMs blocked a number of Faradic processes and electrocatalyzed the oxidation of L-cysteine. Amine substituted cobalt phthalocyanine (CoTAPc) was deposited on gold surfaces by using an interconnecting SAM of mercaptopropionic acid or dithiobis(N-succinimidyl propionate) through the creation of an amide. Reductive and oxidative desorption of the SAMs limit the useful potential window. The SAM-CoTAPc layers show electrocatalytic activities towards oxygen reduction through the Co(I) central metal ion. Both SAMs were highly stable and hence will be interesting tools for further research in surface modification and sensor development.
- Full Text:
- Date Issued: 2006
- Authors: Matemadombo, Fungisai
- Date: 2006
- Subjects: Phthalocyanines , Monomolecular films , Electrochemistry , Spectrum analysis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4364 , http://hdl.handle.net/10962/d1005029 , Phthalocyanines , Monomolecular films , Electrochemistry , Spectrum analysis
- Description: Zinc, cobalt and iron phenylthio substituted phthalocyanines have been synthesized and characterized. Cyclic and square wave voltammetry in dimethylformamide containing tetrabutylammonium perchlorate revealed five and six redox processes respectively for the cobalt and iron phenylthio substituted phthalocyanines. These complexes are easier to reduce compared to the corresponding unsubstituted MPc and to butylthio substituted derivatives. Spectroelectrochemistry (in dimethylformamide containing tetrabutylammonium perchlorate) was employed to assign the cyclic voltammetry peaks, and gave spectra characteristic of Fe(I)Pc for reduction of iron phenylthio substituted phthalocyanine and Co(I)Pc for the reduction of cobalt phenylthio substituted phthalocyanine. The spectrum of the former is particularly of importance since such species have not received much attention in literature. Cobalt and iron phenylthio substituted phthalocyanines have been deposited on Au electrode surfaces through the self assembled monolayer (SAM) technique. The so formed layers were studied using voltammetric techniques. These SAMs blocked a number of Faradic processes and electrocatalyzed the oxidation of L-cysteine. Amine substituted cobalt phthalocyanine (CoTAPc) was deposited on gold surfaces by using an interconnecting SAM of mercaptopropionic acid or dithiobis(N-succinimidyl propionate) through the creation of an amide. Reductive and oxidative desorption of the SAMs limit the useful potential window. The SAM-CoTAPc layers show electrocatalytic activities towards oxygen reduction through the Co(I) central metal ion. Both SAMs were highly stable and hence will be interesting tools for further research in surface modification and sensor development.
- Full Text:
- Date Issued: 2006
Photophysical and photochemical studies of non-transition metal phthalocyanine derivatives
- Ogunsipe, Abimbola Olukayode
- Authors: Ogunsipe, Abimbola Olukayode
- Date: 2005
- Subjects: Photochemotherapy Phthalocyanines Spectrum analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4445 , http://hdl.handle.net/10962/d1007721
- Description: A detailed photophysicochemical study of some non-transition metal (AI, Zn, Si, Ge, and Sn) metallophthalocyanine (MPc) derivatives is presented. The effects of substituents, central metal ions and solvents on the photophysical and photochemical properties are investigated and rationalized accordingly. The presence of peripheral substituents on the macrocycle enhances the yield of the triplet state. Near infra-red absorptions of the solvents reveal that solvents which absorb around 1100 nm and around 1270 nm, quench the triplet state of the MPc derivative and singlet oxygen, respectively. Although water has a high singlet oxygen quenching effect, the singlet oxygen quantum yield (Φ∆) value for sulphonated zinc phthalocyanine in water is still reasonably high at 0.48, which may provide an explanation for the efficient photosensitization by this molecule in photodynamic studies. The lowering of Φ∆ following protonation of the MPc macrocycle is attributed to the lowering of triplet energy to the level where energy transfer to ground state oxygen is no longer favourable. MPc inclusion complexes with cyclodextrins showed larger Φ∆ values when compared to the complexes before inclusion. Job's plots show that 2:1 and 4:1 (CD:MPc) complexes may be formed. Fluorescence quenching by electron donors and acceptors were analysed by StemVolmer relationship and the results used in determining fluorescence lifetimes of the complexes. Qualitative and quantitative interpretations of the interaction of sulphonated MPcs with bovine serum albumin (BSA) are provided in this thesis. 1:1 adducts were formed with BSA, but the binding feasibilities varied markedly. Spectral, photophysical and photochemical properties of the complexes are altered in the presence of BSA.
- Full Text:
- Date Issued: 2005
- Authors: Ogunsipe, Abimbola Olukayode
- Date: 2005
- Subjects: Photochemotherapy Phthalocyanines Spectrum analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4445 , http://hdl.handle.net/10962/d1007721
- Description: A detailed photophysicochemical study of some non-transition metal (AI, Zn, Si, Ge, and Sn) metallophthalocyanine (MPc) derivatives is presented. The effects of substituents, central metal ions and solvents on the photophysical and photochemical properties are investigated and rationalized accordingly. The presence of peripheral substituents on the macrocycle enhances the yield of the triplet state. Near infra-red absorptions of the solvents reveal that solvents which absorb around 1100 nm and around 1270 nm, quench the triplet state of the MPc derivative and singlet oxygen, respectively. Although water has a high singlet oxygen quenching effect, the singlet oxygen quantum yield (Φ∆) value for sulphonated zinc phthalocyanine in water is still reasonably high at 0.48, which may provide an explanation for the efficient photosensitization by this molecule in photodynamic studies. The lowering of Φ∆ following protonation of the MPc macrocycle is attributed to the lowering of triplet energy to the level where energy transfer to ground state oxygen is no longer favourable. MPc inclusion complexes with cyclodextrins showed larger Φ∆ values when compared to the complexes before inclusion. Job's plots show that 2:1 and 4:1 (CD:MPc) complexes may be formed. Fluorescence quenching by electron donors and acceptors were analysed by StemVolmer relationship and the results used in determining fluorescence lifetimes of the complexes. Qualitative and quantitative interpretations of the interaction of sulphonated MPcs with bovine serum albumin (BSA) are provided in this thesis. 1:1 adducts were formed with BSA, but the binding feasibilities varied markedly. Spectral, photophysical and photochemical properties of the complexes are altered in the presence of BSA.
- Full Text:
- Date Issued: 2005
Synthesis and electrocatalytic properties of polymerizable metallophthalocyanines
- Authors: Obirai, Joseph Chinye
- Date: 2005
- Subjects: Phthalocyanines Electrochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4447 , http://hdl.handle.net/10962/d1007733
- Description: The syntheses, spectral and electrochemical characterization of new family electropolymerizable pyrrole, thiophene and mercaptopyrimidin substituted metallophthalocyanine (MPc) complexes are described. Tetraamino substituted chromium and manganese phthalocyanine complexes were also synthesized and characterized. The spectral and electrochemical results are comparable to literature reports. The complexes formed stable films when deposited on electrode surfaces. The MPc films were formed by electropolymerization, drop-dry method and self-assembling. Nickel hydroxide-like electrodes were formed by electrotransformation of nickel-tetra-4- (pyrrol-1-yl)phenoxy phthalocyanine polymer films to the corresponding PcNi-O-NiPc modified electrodes in alkaline solution. The thiophene, mercaptopyrimidine functionalized MPcs and amino group containing complexes formed good self-assembled monolayers (SAMs) on gold electrode. The electrode modification processes were reproducible. The conductivities of the electrode were dependent on the surface concentrations of the complexes as a function of electropolymerization scan numbers. The electrodes showed good catalytic responses toward L-cysteine, nitrite, nitric oxide (NO), glycine, phenol and its derivative and oxygen. The results also suggest that the presence of thio groups on the ring substituents lowers the oxidation potential of Lcysteine more compared to literature values. The stability of the amperometric responses toward the various analytes is used to diagnose the applicability of the materials for electroanalytical purposes. The limits of detection for L-cysteine, nitrite, NO and glycine were in the range of ~10⁻⁷ to 10⁻⁵ mol dm⁻³.
- Full Text:
- Date Issued: 2005
- Authors: Obirai, Joseph Chinye
- Date: 2005
- Subjects: Phthalocyanines Electrochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4447 , http://hdl.handle.net/10962/d1007733
- Description: The syntheses, spectral and electrochemical characterization of new family electropolymerizable pyrrole, thiophene and mercaptopyrimidin substituted metallophthalocyanine (MPc) complexes are described. Tetraamino substituted chromium and manganese phthalocyanine complexes were also synthesized and characterized. The spectral and electrochemical results are comparable to literature reports. The complexes formed stable films when deposited on electrode surfaces. The MPc films were formed by electropolymerization, drop-dry method and self-assembling. Nickel hydroxide-like electrodes were formed by electrotransformation of nickel-tetra-4- (pyrrol-1-yl)phenoxy phthalocyanine polymer films to the corresponding PcNi-O-NiPc modified electrodes in alkaline solution. The thiophene, mercaptopyrimidine functionalized MPcs and amino group containing complexes formed good self-assembled monolayers (SAMs) on gold electrode. The electrode modification processes were reproducible. The conductivities of the electrode were dependent on the surface concentrations of the complexes as a function of electropolymerization scan numbers. The electrodes showed good catalytic responses toward L-cysteine, nitrite, nitric oxide (NO), glycine, phenol and its derivative and oxygen. The results also suggest that the presence of thio groups on the ring substituents lowers the oxidation potential of Lcysteine more compared to literature values. The stability of the amperometric responses toward the various analytes is used to diagnose the applicability of the materials for electroanalytical purposes. The limits of detection for L-cysteine, nitrite, NO and glycine were in the range of ~10⁻⁷ to 10⁻⁵ mol dm⁻³.
- Full Text:
- Date Issued: 2005
Synthesis, photochemical and photophysical properties of phthalocyanine derivatives
- Authors: Maqanda, Weziwe Theorine
- Date: 2005 , 2013-06-18
- Subjects: Photochemotherapy , Phthalocyanines , Zinc , Magnesium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4436 , http://hdl.handle.net/10962/d1007472 , Photochemotherapy , Phthalocyanines , Zinc , Magnesium
- Description: Substituted zinc and magnesium phthalocyanine and porphyrazine derivatives were synthesized according to the reported procedures. The magnesium and zinc phthalocyanine and porphyrazine derivatives were synthesized by ring enlargement of subphthalocyanine and statistical condensation of the two phthalonitrile derivatives. Characterization of the complexes involved the use of infrared spectroscopy, nuclear magnetic resonance spectroscopy, ultraviolet and visible spectroscopy, and Maldi-TOF spectroscopy (for selected compounds) and elemental analysis. Photochemical and photophysical properties of the complexes in non-aqueous solution was then investigated. Photobleaching quantum yields are in order of 10⁻⁵ indicating their relative photostability. Complexes containing more electron-donating substituents were more easily oxidized. For complexes 66 and 69 (as these complexes have the same number of substituents but differ in the metal center) photobleaching quantum yield for the ZincPc complex 69 was slightly less than that of the MgPc complex 66. Singlet oxygen quantum yields of the various complexes in DMSO using diphenylisobenzofuran (DPBF) as a quencher in organic solvents were determined. Singlet oxygen quantum yields of the complexes range from 0.23 to 0.67. High values of Φ[subscript]Δ ZnPc complexes was observed compared to the corresponding MgPc, complexes. This was evidenced by complexes 66 and 69 with Φ[subscript]Δ values of Φ[subscript]Δ = 0.26 and 0.40, respectively. Varying number of phenoxy substituents, complex 71 gave significantly large value of Φ[subscript]Δ compared to 70 (that is, the presence of more electron-donating substituted group, gave higher singlet oxygen quantum yields (0 .67 and 0.25 for 71 and 70 repectively). The triplet quantum yields and triplet lifetimes were determined by laser flash photolysis for selected compounds. The triplet quantum yields increase as the number of substituents increases e.g 68 > 67 > 66. Comparing porphyrazine complexes (63, 64 and 65), 63 with benzene attached to the ring, has higher triplet state lifetime (420 μs) compared to 64 and 65 containing long alkyl chain and tertbutyl substituents, 350 and 360 μs,respectively). The observed Φ[subscript]f values for 68 and 63 were quiet suprising, since low values are observed compared to the rest of the complexes (e.g 0.03 and 0.02 respectively). Although these values seem so low, they are sufficient for fluorescence imaging applications. The Φ[subscript]f values for the complexes under study are within the range reported for complexes currently used for PDT. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2005
- Authors: Maqanda, Weziwe Theorine
- Date: 2005 , 2013-06-18
- Subjects: Photochemotherapy , Phthalocyanines , Zinc , Magnesium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4436 , http://hdl.handle.net/10962/d1007472 , Photochemotherapy , Phthalocyanines , Zinc , Magnesium
- Description: Substituted zinc and magnesium phthalocyanine and porphyrazine derivatives were synthesized according to the reported procedures. The magnesium and zinc phthalocyanine and porphyrazine derivatives were synthesized by ring enlargement of subphthalocyanine and statistical condensation of the two phthalonitrile derivatives. Characterization of the complexes involved the use of infrared spectroscopy, nuclear magnetic resonance spectroscopy, ultraviolet and visible spectroscopy, and Maldi-TOF spectroscopy (for selected compounds) and elemental analysis. Photochemical and photophysical properties of the complexes in non-aqueous solution was then investigated. Photobleaching quantum yields are in order of 10⁻⁵ indicating their relative photostability. Complexes containing more electron-donating substituents were more easily oxidized. For complexes 66 and 69 (as these complexes have the same number of substituents but differ in the metal center) photobleaching quantum yield for the ZincPc complex 69 was slightly less than that of the MgPc complex 66. Singlet oxygen quantum yields of the various complexes in DMSO using diphenylisobenzofuran (DPBF) as a quencher in organic solvents were determined. Singlet oxygen quantum yields of the complexes range from 0.23 to 0.67. High values of Φ[subscript]Δ ZnPc complexes was observed compared to the corresponding MgPc, complexes. This was evidenced by complexes 66 and 69 with Φ[subscript]Δ values of Φ[subscript]Δ = 0.26 and 0.40, respectively. Varying number of phenoxy substituents, complex 71 gave significantly large value of Φ[subscript]Δ compared to 70 (that is, the presence of more electron-donating substituted group, gave higher singlet oxygen quantum yields (0 .67 and 0.25 for 71 and 70 repectively). The triplet quantum yields and triplet lifetimes were determined by laser flash photolysis for selected compounds. The triplet quantum yields increase as the number of substituents increases e.g 68 > 67 > 66. Comparing porphyrazine complexes (63, 64 and 65), 63 with benzene attached to the ring, has higher triplet state lifetime (420 μs) compared to 64 and 65 containing long alkyl chain and tertbutyl substituents, 350 and 360 μs,respectively). The observed Φ[subscript]f values for 68 and 63 were quiet suprising, since low values are observed compared to the rest of the complexes (e.g 0.03 and 0.02 respectively). Although these values seem so low, they are sufficient for fluorescence imaging applications. The Φ[subscript]f values for the complexes under study are within the range reported for complexes currently used for PDT. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2005
Metal interactions with neural substrates and their role in neurodegeneration
- Authors: Lack, Barbara Anne
- Date: 2003
- Subjects: Nervous system -- Degeneration Neurotoxicology Chemical reactions Metals -- Physiological effect Melatonin -- Physiological effect
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4391 , http://hdl.handle.net/10962/d1005709
- Description: "Life" may be characterized as a controlled stationary flow equilibrium, maintained by energy consuming chemical reactions. The physiological functioning of these life systems include at least 28 of the elements isolated on the periodic table thus far, most of which are metals. However, as with Paracelsus Principle: "The dose makes the poison", there exists a definite link between metal levels, essential and toxic, and the onset of neurodegenerative diseases. The economic costs of brain dysfunction are enormous, but this pales in comparison to the staggering emotional toll on the victims themselves and their families. In an attempt to improve the understanding of the causes of neurodegeneration, this study focuses on one potential aspect: the possible link between metals and neurotransmitter homeostasis utilising a variety of electronanalytical techniques. Adsorptive cathodic stripping voltammetry was employed to investigate the binding affinities and complex formation of melatonin and its precursor serotonin with calcium, potassium, sodium, lithium and aluminium. The results showed that all the metals studied formed complexes with both pineal indoleamines. However, the stability and affmity of the ligands toward the various metals varied greatly. The study suggests a further role for melatonin, that of metalloregulator and possible metal detoxifier in the brain, the in vivo studies which followed will further substantiate this notion. This research additionally focused on the cholinergic system, in particular acetylcholine complex formation studies with mercury, lead, cadmium, copper and zinc using the adsorptive cathodic stripping voltammetry method. The formation and characterisation of a solid mercury-acetylcholine complex lent further strength to the in situ electrochemical complex formation observed. The results showed the preference of acetylcholine for environmentally toxic heavy metals (such as Cd²⁺) over those divalent cations that occur naturally in the body. The possible metalloregulatory role melatonin played in the three brain regIOns: cerebellum, cortex and corpus striatum of male Wistar rats was studied as an in vivo extension of the earlier in vitro studies. Anodic stripping voltammetry was employed to detect metal levels present. The results showed that daily injections of melatonin was responsible for significantly decreasing copper(I), cadmium(II) and lead(II) levels in various regions of the rat brain of those animals that had undergone a pinealectomy in comparison to the saline injected group having undergone the same treatment. Histological and electrochemical stripping techniques were applied to investigate the implications of high A1³⁺ levels in the brain regions, particularly the hippocampus. Melatonin showed signs of promise in indirect symptom alleviation and by significantly decreasing A1³⁺ levels in rats that had been dosed with melatonin prior to A1³⁺ treatments in comparison with the control groups. Finally a preliminary study outlining a method for the production of a calcium selective microelectrode was undertaken. Further work is still needed to optimise the microelectrode production as well as its possible applications. However, whilst the overall conclusions of this entire multidisciplinary study may indeed only be in effect one piece of a very large puzzle on neurodegenerative diseases, this piece will no doubt serve as a building block for further ideas and work in this field.
- Full Text:
- Date Issued: 2003
- Authors: Lack, Barbara Anne
- Date: 2003
- Subjects: Nervous system -- Degeneration Neurotoxicology Chemical reactions Metals -- Physiological effect Melatonin -- Physiological effect
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4391 , http://hdl.handle.net/10962/d1005709
- Description: "Life" may be characterized as a controlled stationary flow equilibrium, maintained by energy consuming chemical reactions. The physiological functioning of these life systems include at least 28 of the elements isolated on the periodic table thus far, most of which are metals. However, as with Paracelsus Principle: "The dose makes the poison", there exists a definite link between metal levels, essential and toxic, and the onset of neurodegenerative diseases. The economic costs of brain dysfunction are enormous, but this pales in comparison to the staggering emotional toll on the victims themselves and their families. In an attempt to improve the understanding of the causes of neurodegeneration, this study focuses on one potential aspect: the possible link between metals and neurotransmitter homeostasis utilising a variety of electronanalytical techniques. Adsorptive cathodic stripping voltammetry was employed to investigate the binding affinities and complex formation of melatonin and its precursor serotonin with calcium, potassium, sodium, lithium and aluminium. The results showed that all the metals studied formed complexes with both pineal indoleamines. However, the stability and affmity of the ligands toward the various metals varied greatly. The study suggests a further role for melatonin, that of metalloregulator and possible metal detoxifier in the brain, the in vivo studies which followed will further substantiate this notion. This research additionally focused on the cholinergic system, in particular acetylcholine complex formation studies with mercury, lead, cadmium, copper and zinc using the adsorptive cathodic stripping voltammetry method. The formation and characterisation of a solid mercury-acetylcholine complex lent further strength to the in situ electrochemical complex formation observed. The results showed the preference of acetylcholine for environmentally toxic heavy metals (such as Cd²⁺) over those divalent cations that occur naturally in the body. The possible metalloregulatory role melatonin played in the three brain regIOns: cerebellum, cortex and corpus striatum of male Wistar rats was studied as an in vivo extension of the earlier in vitro studies. Anodic stripping voltammetry was employed to detect metal levels present. The results showed that daily injections of melatonin was responsible for significantly decreasing copper(I), cadmium(II) and lead(II) levels in various regions of the rat brain of those animals that had undergone a pinealectomy in comparison to the saline injected group having undergone the same treatment. Histological and electrochemical stripping techniques were applied to investigate the implications of high A1³⁺ levels in the brain regions, particularly the hippocampus. Melatonin showed signs of promise in indirect symptom alleviation and by significantly decreasing A1³⁺ levels in rats that had been dosed with melatonin prior to A1³⁺ treatments in comparison with the control groups. Finally a preliminary study outlining a method for the production of a calcium selective microelectrode was undertaken. Further work is still needed to optimise the microelectrode production as well as its possible applications. However, whilst the overall conclusions of this entire multidisciplinary study may indeed only be in effect one piece of a very large puzzle on neurodegenerative diseases, this piece will no doubt serve as a building block for further ideas and work in this field.
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- Date Issued: 2003