Photophysical characterization of dysprosium, erbium and lutetium phthalocyanines tetrasubstituted with phenoxy groups at non-peripheral positions
- Zugle, Ruphino, Litwinski, Christian, Nyokong, Tebello
- Authors: Zugle, Ruphino , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247561 , vital:51595 , xlink:href="https://doi.org/10.1016/j.poly.2011.03.030"
- Description: Dysprosium bis-phthalocyanine and monomeric phthalocyanines of erbium and lutetium with non-peripheral phenoxy substituents have been synthesized using two different preparative routes. Photophysical studies on these phthalocyanines revealed that the triplet states of dysprosium and erbium are not populated while the monomeric phthalocyanine complex of lutetium is populated with a quantum yield of 0.83 and a lifetime of 25 μs in DMSO. It was further found that the phthalocyanine complex of lutetium was capable of photochemical generation of singlet state molecular oxygen with yield of 0.71 in THF, thus a promising photosensitizer. However, the three phthalocyanine molecules have very low fluorescence quantum yields of less than 0.01.
- Full Text:
- Date Issued: 2011
- Authors: Zugle, Ruphino , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247561 , vital:51595 , xlink:href="https://doi.org/10.1016/j.poly.2011.03.030"
- Description: Dysprosium bis-phthalocyanine and monomeric phthalocyanines of erbium and lutetium with non-peripheral phenoxy substituents have been synthesized using two different preparative routes. Photophysical studies on these phthalocyanines revealed that the triplet states of dysprosium and erbium are not populated while the monomeric phthalocyanine complex of lutetium is populated with a quantum yield of 0.83 and a lifetime of 25 μs in DMSO. It was further found that the phthalocyanine complex of lutetium was capable of photochemical generation of singlet state molecular oxygen with yield of 0.71 in THF, thus a promising photosensitizer. However, the three phthalocyanine molecules have very low fluorescence quantum yields of less than 0.01.
- Full Text:
- Date Issued: 2011
Photophysical and photochemical behavior of electrospun fibers of a polyurethane polymer chemically linked to lutetium carboxyphenoxy phthalocyanine
- Zugle, Ruhpino, Litwinski, Christian, Torto, Nelson, Nyokong, Tebello
- Authors: Zugle, Ruhpino , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248428 , vital:51685 , xlink:href="https://doi.org/10.1039/C1NJ20126C"
- Description: A phthalocyanine complex of lutetium substituted with four peripherally substituted 4-carboxyphenoxy groups was synthesized using cyclotetramerisation reaction. Its structure was elucidated using conventional spectroscopic methods and elemental analysis. The spectral behavior of the complex was studied in DMF solution and in a solid polyurethane fiber matrix. The UV-Visible spectrum showed a red shift in its Q-band maximum absorption within the fiber as compared to that in solution. The triplet quantum yield in DMF was determined to be 0.51 with a lifetime of 2.7 μs and a singlet oxygen quantum yield of 0.33 with a lifetime of 19.85 μs in the same solvent. The functionalized phthalocyanine fiber could be a promising fabric material for applications such as self-disinfecting in wound dressing. A method based on the conversion of ADMA was used to estimate the singlet oxygen quantum yield of the Pc in the hybrid fiber. An estimated singlet oxygen quantum yield value of 0.11 in aqueous medium was obtained. The fluorescence quantum yield of the Pc was found to be 0.01 with a lifetime of 3.20 ns in DMF.
- Full Text:
- Date Issued: 2011
- Authors: Zugle, Ruhpino , Litwinski, Christian , Torto, Nelson , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248428 , vital:51685 , xlink:href="https://doi.org/10.1039/C1NJ20126C"
- Description: A phthalocyanine complex of lutetium substituted with four peripherally substituted 4-carboxyphenoxy groups was synthesized using cyclotetramerisation reaction. Its structure was elucidated using conventional spectroscopic methods and elemental analysis. The spectral behavior of the complex was studied in DMF solution and in a solid polyurethane fiber matrix. The UV-Visible spectrum showed a red shift in its Q-band maximum absorption within the fiber as compared to that in solution. The triplet quantum yield in DMF was determined to be 0.51 with a lifetime of 2.7 μs and a singlet oxygen quantum yield of 0.33 with a lifetime of 19.85 μs in the same solvent. The functionalized phthalocyanine fiber could be a promising fabric material for applications such as self-disinfecting in wound dressing. A method based on the conversion of ADMA was used to estimate the singlet oxygen quantum yield of the Pc in the hybrid fiber. An estimated singlet oxygen quantum yield value of 0.11 in aqueous medium was obtained. The fluorescence quantum yield of the Pc was found to be 0.01 with a lifetime of 3.20 ns in DMF.
- Full Text:
- Date Issued: 2011
Optimizing the electrocatalytic activity of surface confined Co macrocyclics for the electrooxidation of thiocyanate at pH 4
- Tshangana, Charmaine, Pavez, Jorge, Gulppi, Miguel A, De Mattos, Ivanildo Luiz, Arratia-Perez, Ramiro, Linares-Flores, Cristian, Paez, Maritza, Nyokong, Tebello, Zagal, Jos H
- Authors: Tshangana, Charmaine , Pavez, Jorge , Gulppi, Miguel A , De Mattos, Ivanildo Luiz , Arratia-Perez, Ramiro , Linares-Flores, Cristian , Paez, Maritza , Nyokong, Tebello , Zagal, Jos H
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247726 , vital:51612 , xlink:href="https://doi.org/10.1002/elan.201000599"
- Description: We have studied the trends in catalytic activity of several Co macrocyclics confined on the surface graphite electrodes for the oxidation of thiocyanate. A plot of log i (at constant E) versus the formal potential of the catalyst gives a volcano correlation, indicating that the Co(II/I) redox potential needs to be tuned, in order to achieve maximum reactivity. Graphite electrodes modified with Co phthalocyanine at pH 4 exhibit linear amperometric response for thiocyanate concentration in the range 10−7 and 10−3 M. Theoretical calculations show that electrocatalytic activity (as log i at constant E) plotted versus the energy of the LUMO of the Co complex also gives a volcano correlation.
- Full Text:
- Date Issued: 2011
- Authors: Tshangana, Charmaine , Pavez, Jorge , Gulppi, Miguel A , De Mattos, Ivanildo Luiz , Arratia-Perez, Ramiro , Linares-Flores, Cristian , Paez, Maritza , Nyokong, Tebello , Zagal, Jos H
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247726 , vital:51612 , xlink:href="https://doi.org/10.1002/elan.201000599"
- Description: We have studied the trends in catalytic activity of several Co macrocyclics confined on the surface graphite electrodes for the oxidation of thiocyanate. A plot of log i (at constant E) versus the formal potential of the catalyst gives a volcano correlation, indicating that the Co(II/I) redox potential needs to be tuned, in order to achieve maximum reactivity. Graphite electrodes modified with Co phthalocyanine at pH 4 exhibit linear amperometric response for thiocyanate concentration in the range 10−7 and 10−3 M. Theoretical calculations show that electrocatalytic activity (as log i at constant E) plotted versus the energy of the LUMO of the Co complex also gives a volcano correlation.
- Full Text:
- Date Issued: 2011
Temperature activated ionic conductivity in gallium and indium phthalocyanines
- San, Sait Eren, Okutan, Mustafa, Nyokong, Tebello, Durmus, Mahmut, Ozturk, Birol
- Authors: San, Sait Eren , Okutan, Mustafa , Nyokong, Tebello , Durmus, Mahmut , Ozturk, Birol
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247686 , vital:51607 , xlink:href="https://doi.org/10.1016/j.poly.2010.12.047"
- Description: The effects of introducing gallium and indium metals into phthalocyanine molecules were investigated via temperature and frequency dependent dielectric spectroscopy. The dielectric properties of Ga(III) and In(III) phthalocyanine pellets were measured at frequencies from 1 kHz to 1 MHz in the temperature range 300–530 K. The temperature dependence of the real part of the dielectric constant suggested that these compounds exhibit semiconductor behavior. The activation energy values were calculated from the Arrhenius plots at different frequencies. A distinct transition in these plots indicated the activation of ionic conductivity at higher temperatures.
- Full Text:
- Date Issued: 2011
- Authors: San, Sait Eren , Okutan, Mustafa , Nyokong, Tebello , Durmus, Mahmut , Ozturk, Birol
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247686 , vital:51607 , xlink:href="https://doi.org/10.1016/j.poly.2010.12.047"
- Description: The effects of introducing gallium and indium metals into phthalocyanine molecules were investigated via temperature and frequency dependent dielectric spectroscopy. The dielectric properties of Ga(III) and In(III) phthalocyanine pellets were measured at frequencies from 1 kHz to 1 MHz in the temperature range 300–530 K. The temperature dependence of the real part of the dielectric constant suggested that these compounds exhibit semiconductor behavior. The activation energy values were calculated from the Arrhenius plots at different frequencies. A distinct transition in these plots indicated the activation of ionic conductivity at higher temperatures.
- Full Text:
- Date Issued: 2011
Cyclic voltammetry and spectroelectrochemistry of a novel manganese phthalocyanine substituted with hexynyl groups
- Quinton, Damien, Antunes, Edith M, Griveau, Sophie, Nyokong, Tebello, Bedioui, Fethi
- Authors: Quinton, Damien , Antunes, Edith M , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248450 , vital:51687 , xlink:href="https://doi.org/10.1016/j.inoche.2010.11.029"
- Description: We report here on the synthesis of a new manganese phthalocyanine complex, namely Mn tetrakis(5-hexyn-oxy) phthalocyanine (3), specifically designed to possess an alkyne moiety for its potential use in controlled immobilization on electrodes via the so called “click” chemistry reaction. The electrochemical activity of complex 3 was investigated by cyclic voltammetry and the nature of the observed redox couples was elucidated by spectroelectrochemistry. This work has also shown that the reduction of Mn(III)Pc complex to Mn(II)Pc is accompanied by the formation of MnPc μ-oxo species. Further reduction results in the formation of Mn(II)Pc(− 3) rather than Mn(I)Pc(− 2).
- Full Text:
- Date Issued: 2011
- Authors: Quinton, Damien , Antunes, Edith M , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248450 , vital:51687 , xlink:href="https://doi.org/10.1016/j.inoche.2010.11.029"
- Description: We report here on the synthesis of a new manganese phthalocyanine complex, namely Mn tetrakis(5-hexyn-oxy) phthalocyanine (3), specifically designed to possess an alkyne moiety for its potential use in controlled immobilization on electrodes via the so called “click” chemistry reaction. The electrochemical activity of complex 3 was investigated by cyclic voltammetry and the nature of the observed redox couples was elucidated by spectroelectrochemistry. This work has also shown that the reduction of Mn(III)Pc complex to Mn(II)Pc is accompanied by the formation of MnPc μ-oxo species. Further reduction results in the formation of Mn(II)Pc(− 3) rather than Mn(I)Pc(− 2).
- Full Text:
- Date Issued: 2011
Photocatalytic transformation of chlorophenols under homogeneous and heterogeneous conditions using palladium octadodecylthio phthalocyanine
- Ogunbayo, Taofeek B, Nyokong, Tebello
- Authors: Ogunbayo, Taofeek B , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246816 , vital:51516 , xlink:href="https://doi.org/10.1016/j.molcata.2011.09.003"
- Description: Homogeneous and heterogeneous photosensitized transformations of 4-chlorophenol (4-CP) and pentachlorophenol (PCP) using palladium octadodecylthiophthalocyanine (PdODPc) were investigated. Under heterogeneous conditions, the photosensitizer was supported on functionalized single walled carbon nanotubes (SWCNTs). Homogeneous photosensitization proved to be more effective than the heterogeneous reaction in terms of percentage of transformation achieved. The kinetics of heterogeneous catalysis proved that ads-PdODPc–SWCNT–COOH (where SWCNT has been functionalized with COOH groups) was reusable for 4-CP while its activity degenerated when reused for PCP. Singlet oxygen was confirmed as playing an active role in the reactions.
- Full Text:
- Date Issued: 2011
- Authors: Ogunbayo, Taofeek B , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246816 , vital:51516 , xlink:href="https://doi.org/10.1016/j.molcata.2011.09.003"
- Description: Homogeneous and heterogeneous photosensitized transformations of 4-chlorophenol (4-CP) and pentachlorophenol (PCP) using palladium octadodecylthiophthalocyanine (PdODPc) were investigated. Under heterogeneous conditions, the photosensitizer was supported on functionalized single walled carbon nanotubes (SWCNTs). Homogeneous photosensitization proved to be more effective than the heterogeneous reaction in terms of percentage of transformation achieved. The kinetics of heterogeneous catalysis proved that ads-PdODPc–SWCNT–COOH (where SWCNT has been functionalized with COOH groups) was reusable for 4-CP while its activity degenerated when reused for PCP. Singlet oxygen was confirmed as playing an active role in the reactions.
- Full Text:
- Date Issued: 2011
Investigation of homogeneous photosensitized oxidation activities of palladium and platinum octasubstituted phthalocyanines
- Ogunbayo, Taofeek B, Antunes, Edith M, Nyokong, Tebello
- Authors: Ogunbayo, Taofeek B , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248394 , vital:51682 , xlink:href="https://doi.org/10.1016/j.molcata.2010.11.008"
- Description: Photosensitized oxidation of 4-nitrophenol was studied in organic solutions with seven octasubstituted thio and aryloxy palladium and platinum phthalocyanines acting as photosensitizers. Kinetic studies conducted also showed that the complexes have different singlet oxygen quenching constants with direct implication on the quantum yield of photodegradation of 4-nitrophenol (Φ4-NP). Palladium analogues gave better results than the platinum analogues in terms of Φ4-NP with palladium-(dodecylthio)phthalocyanine giving the highest yield of 1.8 × 10−3. Gas chromatography (GC) and liquid chromatography connected to a mass spectrometer (LC–MS) were used to confirm the photodegradation products which were hydroquinone and 1,4-benzoquinone.
- Full Text:
- Date Issued: 2011
- Authors: Ogunbayo, Taofeek B , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248394 , vital:51682 , xlink:href="https://doi.org/10.1016/j.molcata.2010.11.008"
- Description: Photosensitized oxidation of 4-nitrophenol was studied in organic solutions with seven octasubstituted thio and aryloxy palladium and platinum phthalocyanines acting as photosensitizers. Kinetic studies conducted also showed that the complexes have different singlet oxygen quenching constants with direct implication on the quantum yield of photodegradation of 4-nitrophenol (Φ4-NP). Palladium analogues gave better results than the platinum analogues in terms of Φ4-NP with palladium-(dodecylthio)phthalocyanine giving the highest yield of 1.8 × 10−3. Gas chromatography (GC) and liquid chromatography connected to a mass spectrometer (LC–MS) were used to confirm the photodegradation products which were hydroquinone and 1,4-benzoquinone.
- Full Text:
- Date Issued: 2011
Phototransformation of 4-nitrophenol using Pd phthalocyanines supported on single walled carbon nanotubes
- Ogunbayo, Taofeek B, Nyokong, Tebello
- Authors: Ogunbayo, Taofeek B , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247800 , vital:51619 , xlink:href="https://doi.org/10.1016/j.molcata.2011.01.016"
- Description: Adsorption of palladium phthalocyanines complexes on single walled carbon nanotubes was carried out. The resulting composites were employed as catalysts for heterogeneous photocatalytic oxidation of 4-nitrophenol (4-NP) in aqueous media. Singlet oxygen was found to be involved in the phototransformation of 4-NP. Gas chromatographic separation gave hydroquinone and benzoquinone as the phototransformation products. Langmuir–Hinshelwood (L–H) model was employed to evaluate the adsorption and desorption equilibria of the reactants and the products. 2,3,9,10,16,17,23,24-octakis(dodecylthiophthalocyaninato) palladium(II) and 1,4,8,11,15,18,22,25-octakis(dodecylthio phthalocyaninato) palladium, containing the longest alkyl chain gave the best performances.
- Full Text:
- Date Issued: 2011
- Authors: Ogunbayo, Taofeek B , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247800 , vital:51619 , xlink:href="https://doi.org/10.1016/j.molcata.2011.01.016"
- Description: Adsorption of palladium phthalocyanines complexes on single walled carbon nanotubes was carried out. The resulting composites were employed as catalysts for heterogeneous photocatalytic oxidation of 4-nitrophenol (4-NP) in aqueous media. Singlet oxygen was found to be involved in the phototransformation of 4-NP. Gas chromatographic separation gave hydroquinone and benzoquinone as the phototransformation products. Langmuir–Hinshelwood (L–H) model was employed to evaluate the adsorption and desorption equilibria of the reactants and the products. 2,3,9,10,16,17,23,24-octakis(dodecylthiophthalocyaninato) palladium(II) and 1,4,8,11,15,18,22,25-octakis(dodecylthio phthalocyaninato) palladium, containing the longest alkyl chain gave the best performances.
- Full Text:
- Date Issued: 2011
Distinguished women in Chemistry Award (PACN)
- Authors: Nyokong, Tebello
- Date: 2011
- Identifier: vital:7223 , http://hdl.handle.net/10962/d1005901
- Description: Distinguished Women in Chemistry Award as part of the Pan Africa Chemistry Network (PACN) and Royal Society of Chemistry (RSC) International Year of Chemistry Celebration of the 100th Anniversary of Marie Curie’s Nobel Award in Chemistry.
- Full Text: false
- Date Issued: 2011
- Authors: Nyokong, Tebello
- Date: 2011
- Identifier: vital:7223 , http://hdl.handle.net/10962/d1005901
- Description: Distinguished Women in Chemistry Award as part of the Pan Africa Chemistry Network (PACN) and Royal Society of Chemistry (RSC) International Year of Chemistry Celebration of the 100th Anniversary of Marie Curie’s Nobel Award in Chemistry.
- Full Text: false
- Date Issued: 2011
Graduation ceremony photographs
- Authors: Nyokong, Tebello
- Date: 2010-2012
- Type: still image
- Identifier: vital:7232 , http://hdl.handle.net/10962/d1006503
- Description: Photographs taken of Prof Tebello Nyokong's students during different graduation ceremonies 2010 - 2012.
- Full Text:
- Date Issued: 2010-2012
- Authors: Nyokong, Tebello
- Date: 2010-2012
- Type: still image
- Identifier: vital:7232 , http://hdl.handle.net/10962/d1006503
- Description: Photographs taken of Prof Tebello Nyokong's students during different graduation ceremonies 2010 - 2012.
- Full Text:
- Date Issued: 2010-2012
Synthesis and photophysical studies of phthalocyanine–gold nanoparticle conjugates
- Nombona, Nolwazi, Antunes, Edith M, Litwinski, Christian, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Antunes, Edith M , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248438 , vital:51686 , xlink:href="https://doi.org/10.1039/C1DT11151E"
- Description: This work reports on the synthesis, characterization and photophysical studies of phthalocyanine–gold nanoparticle conjugates. The phthalocyanine complexes are: tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyanine (3), 2,9,17,23-tetrakis-[(1, 6-hexanedithiol) phthalocyaninato]zinc(II) (8) and [8,15,22-tris-(naptho)-2(amidoethanethiol) phthalocyanato] zinc(II)(10). The gold nanoparticles were characterized using transmission electron microscopy, X-ray diffraction, atomic force microscopy and UV-vis spectroscopy where the size was confirmed to be ∼5 nm. The phthalocyanine Au nanoparticle conjugates showed lower fluorescence quantum yield values with similar fluorescence lifetimes compared to the free phthalocyanines. The Au nanoparticle conjugates of 3 and 10 also showed higher triplet quantum yields of 0.69 to 0.71, respectively. A lower triplet quantum yield was obtained for the conjugate compared to free phthalocyanine for complex 8. The triplet lifetimes ranged from 70 to 92 μs for the conjugates and from 110 to 304 μs for unbound Pc complexes.
- Full Text:
- Date Issued: 2011
- Authors: Nombona, Nolwazi , Antunes, Edith M , Litwinski, Christian , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248438 , vital:51686 , xlink:href="https://doi.org/10.1039/C1DT11151E"
- Description: This work reports on the synthesis, characterization and photophysical studies of phthalocyanine–gold nanoparticle conjugates. The phthalocyanine complexes are: tris-(5-trifluoromethyl-2-mercaptopyridine)-2-(carboxy)phthalocyanine (3), 2,9,17,23-tetrakis-[(1, 6-hexanedithiol) phthalocyaninato]zinc(II) (8) and [8,15,22-tris-(naptho)-2(amidoethanethiol) phthalocyanato] zinc(II)(10). The gold nanoparticles were characterized using transmission electron microscopy, X-ray diffraction, atomic force microscopy and UV-vis spectroscopy where the size was confirmed to be ∼5 nm. The phthalocyanine Au nanoparticle conjugates showed lower fluorescence quantum yield values with similar fluorescence lifetimes compared to the free phthalocyanines. The Au nanoparticle conjugates of 3 and 10 also showed higher triplet quantum yields of 0.69 to 0.71, respectively. A lower triplet quantum yield was obtained for the conjugate compared to free phthalocyanine for complex 8. The triplet lifetimes ranged from 70 to 92 μs for the conjugates and from 110 to 304 μs for unbound Pc complexes.
- Full Text:
- Date Issued: 2011
Photophysical behaviour of asymmetrically substituted metal free, Mg and Zn phthalocyanines in the presence of folic acid
- Nombona, Nolwazi, Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247705 , vital:51608 , xlink:href="https://doi.org/10.1016/j.poly.2010.11.033"
- Description: This work reports on the synthesis, characterisation and photophysical properties of new asymmetric metal free, magnesium and zinc phthalocyanines containing a mono carboxylic acid group for possible linking to biological molecules via an amide bond. Successful synthesis of the phthalocyanines was achieved through the statistical condensation method. The phthalocyanines were mixed with folic acid and their photophysical properties were examined. The triplet quantum yield values for all the complexes in DMSO were between 0.49 and 0.74 and in the presence of folic acid they were between 0.37 and 0.63. The lifetimes were generally good ranging from 70 to 290 μs in the absence or presence of folic acid.
- Full Text:
- Date Issued: 2011
- Authors: Nombona, Nolwazi , Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247705 , vital:51608 , xlink:href="https://doi.org/10.1016/j.poly.2010.11.033"
- Description: This work reports on the synthesis, characterisation and photophysical properties of new asymmetric metal free, magnesium and zinc phthalocyanines containing a mono carboxylic acid group for possible linking to biological molecules via an amide bond. Successful synthesis of the phthalocyanines was achieved through the statistical condensation method. The phthalocyanines were mixed with folic acid and their photophysical properties were examined. The triplet quantum yield values for all the complexes in DMSO were between 0.49 and 0.74 and in the presence of folic acid they were between 0.37 and 0.63. The lifetimes were generally good ranging from 70 to 290 μs in the absence or presence of folic acid.
- Full Text:
- Date Issued: 2011
Electrochemical, microscopic and spectroscopic characterization of benzene diamine functionalized single walled carbon nanotube-cobalt (II) tetracarboxy-phthalocyanine conjugates
- Mugadza, Tawanda, Nyokong, Tebello
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247859 , vital:51624 , xlink:href="https://doi.org/10.1016/j.jcis.2010.10.057"
- Description: In this paper we report on the synthesis and characterization of 1,4-benzene diamine (BDA) functionalized single walled carbon nanotubes linked to cobalt (II) tetracarboxy-phthalocyanine. The characterization of the conjugate was through UV–vis, FTIR and X-ray diffraction (XRD) spectroscopies and by transmission electron microscope (TEM) and electrochemical methods. The conjugate is used for the electrochemical characterization of diuron. The catalytic rate constant for diuron was 4.4 × 103 M−1 s−1 and the apparent electron transfer rate constant was 18.5 × 10−6 cm s−1. The linear dynamic range was 1.0 × 10−5–2.0 × 10−4 M, with a sensitivity of ∼0.42 A mol−1L cm−2 and a limit of detection of 0.18 μM using the 3δ notation.
- Full Text:
- Date Issued: 2011
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247859 , vital:51624 , xlink:href="https://doi.org/10.1016/j.jcis.2010.10.057"
- Description: In this paper we report on the synthesis and characterization of 1,4-benzene diamine (BDA) functionalized single walled carbon nanotubes linked to cobalt (II) tetracarboxy-phthalocyanine. The characterization of the conjugate was through UV–vis, FTIR and X-ray diffraction (XRD) spectroscopies and by transmission electron microscope (TEM) and electrochemical methods. The conjugate is used for the electrochemical characterization of diuron. The catalytic rate constant for diuron was 4.4 × 103 M−1 s−1 and the apparent electron transfer rate constant was 18.5 × 10−6 cm s−1. The linear dynamic range was 1.0 × 10−5–2.0 × 10−4 M, with a sensitivity of ∼0.42 A mol−1L cm−2 and a limit of detection of 0.18 μM using the 3δ notation.
- Full Text:
- Date Issued: 2011
Synthesis and electrocatalytic behavior of cobalt (II)-tris (benzyl-mercapto)-monoaminophthalocyanine–single walled carbon nanotube nanorods
- Mugadza, Tawanda, Nyokong, Tebello
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247882 , vital:51626 , xlink:href="https://doi.org/10.1016/j.electacta.2010.11.016"
- Description: In this paper we report on synthesis and electrocatalytic behavior of cobalt (II)-tris(benzyl-mercapto)-monoaminophthalocyanine–single walled carbon nanotube nanorods towards the oxidation of amitrole. SWCNTs that were terminally functionalized with carboxylic acid groups were chemically linked to cobalt (II)-tris(benzyl-mercapto) monoaminophthalocyanine (CoMAPc) via an amide bond to form nanorods. UV–vis, FTIR, TEM, Raman and XRD spectroscopies were used in characterization of the nanorods (CoMAPc–SWCNT-linked), while cyclic voltammetry and chronoamperometry were used during the characterization of amitrole on the modified glassy carbon electrode. The linear dynamic range for the amitrole was from 1.0 × 10−6 M to 1.2 × 10−4 M, with a sensitivity of 6.76 A mol−1 L cm−2. The estimated limit of detection for amitrole was 0.10 μM, using the 3δ criterion. The catalytic rate constant was found to be 1.09 × 105 M−1 s−1.
- Full Text:
- Date Issued: 2011
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247882 , vital:51626 , xlink:href="https://doi.org/10.1016/j.electacta.2010.11.016"
- Description: In this paper we report on synthesis and electrocatalytic behavior of cobalt (II)-tris(benzyl-mercapto)-monoaminophthalocyanine–single walled carbon nanotube nanorods towards the oxidation of amitrole. SWCNTs that were terminally functionalized with carboxylic acid groups were chemically linked to cobalt (II)-tris(benzyl-mercapto) monoaminophthalocyanine (CoMAPc) via an amide bond to form nanorods. UV–vis, FTIR, TEM, Raman and XRD spectroscopies were used in characterization of the nanorods (CoMAPc–SWCNT-linked), while cyclic voltammetry and chronoamperometry were used during the characterization of amitrole on the modified glassy carbon electrode. The linear dynamic range for the amitrole was from 1.0 × 10−6 M to 1.2 × 10−4 M, with a sensitivity of 6.76 A mol−1 L cm−2. The estimated limit of detection for amitrole was 0.10 μM, using the 3δ criterion. The catalytic rate constant was found to be 1.09 × 105 M−1 s−1.
- Full Text:
- Date Issued: 2011
Synthesis, characterization and application of monocarboxy-phthalocyanine-single walled carbon nanotube conjugates in electrocatalysis
- Mugadza, Tawanda, Nyokong, Tebello
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247399 , vital:51577 , xlink:href="https://doi.org/10.1016/j.poly.2011.04.020"
- Description: In this paper we report on the synthesis, characterization and use of monocarboxy-phthalocyanine-single walled carbon nanotube conjugates in the electrocatalysis of amitrole and diuron. UV–Vis, FTIR and XRD spectroscopies were used in the characterization of cobalt(II)-tris(benzyl-mercapto)-mono(carboxyphenoxy)-phthalocyanine conjugates (CoMCPc–PA-SWCNT(linked)), while AFM was used to show changes in surface morphologies of the modified electrodes. Cyclic voltammetry and chronoamperometry were used for the electrocatalytic oxidation of amitrole and diuron on the modified glassy carbon electrode. The catalytic rate constants for amitrole and diuron were found to be 1.83 × 106 and 1.99 × 106 M−1 s−1, respectively. The linear range for both was 1.0 × 10−5–2.0 × 10−4 M, with sensitivities of 5.10 and 3.70 A mol−1 L cm−2 for amitrole and diuron, respectively. The limits of detection were estimated to be 0.14 and 0.20 μM for amitrole and diuron, respectively, using the 3δ notation.
- Full Text:
- Date Issued: 2011
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247399 , vital:51577 , xlink:href="https://doi.org/10.1016/j.poly.2011.04.020"
- Description: In this paper we report on the synthesis, characterization and use of monocarboxy-phthalocyanine-single walled carbon nanotube conjugates in the electrocatalysis of amitrole and diuron. UV–Vis, FTIR and XRD spectroscopies were used in the characterization of cobalt(II)-tris(benzyl-mercapto)-mono(carboxyphenoxy)-phthalocyanine conjugates (CoMCPc–PA-SWCNT(linked)), while AFM was used to show changes in surface morphologies of the modified electrodes. Cyclic voltammetry and chronoamperometry were used for the electrocatalytic oxidation of amitrole and diuron on the modified glassy carbon electrode. The catalytic rate constants for amitrole and diuron were found to be 1.83 × 106 and 1.99 × 106 M−1 s−1, respectively. The linear range for both was 1.0 × 10−5–2.0 × 10−4 M, with sensitivities of 5.10 and 3.70 A mol−1 L cm−2 for amitrole and diuron, respectively. The limits of detection were estimated to be 0.14 and 0.20 μM for amitrole and diuron, respectively, using the 3δ notation.
- Full Text:
- Date Issued: 2011
Synthesis and photophysical properties of a novel zinc photosensitizer and its gold nanoparticle conjugate
- Moeno, Sharon, Antunes, Edith M, Nyokong, Tebello
- Authors: Moeno, Sharon , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247100 , vital:51546 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.07.007"
- Description: The peripherally tetra substituted zinc phthalocyanine with 1,6-hexanedithiol as substituent (THdTZnPc, 3) was synthesized and is reported for the first time in this work. The potential of this zinc complex as a suitable photosensitizer for use in photodynamic therapy was determined through the investigation of the photophysical and photochemical properties. In this work complex 3 is attached to gold nanoparticles through the terminal thiol groups of the phthalocyanine resulting in a 3-AuNP conjugate whose photophysicochemical properties are investigated. Fluorescence lifetimes were determined using time correlated single photon counting and they show an increase in the abundance of the monomeric species (τ2) for the Pc in the 3-AuNP conjugate: ∼1 and 0.71 (with respective lifetimes 2.69 ns and 2.86 ns) compared to the free complex 3 with abundances of 0.12 and 0.13 (with respective lifetimes 3.36 ns and 3.28 ns) in DMSO and DMF, respectively.
- Full Text:
- Date Issued: 2011
- Authors: Moeno, Sharon , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247100 , vital:51546 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.07.007"
- Description: The peripherally tetra substituted zinc phthalocyanine with 1,6-hexanedithiol as substituent (THdTZnPc, 3) was synthesized and is reported for the first time in this work. The potential of this zinc complex as a suitable photosensitizer for use in photodynamic therapy was determined through the investigation of the photophysical and photochemical properties. In this work complex 3 is attached to gold nanoparticles through the terminal thiol groups of the phthalocyanine resulting in a 3-AuNP conjugate whose photophysicochemical properties are investigated. Fluorescence lifetimes were determined using time correlated single photon counting and they show an increase in the abundance of the monomeric species (τ2) for the Pc in the 3-AuNP conjugate: ∼1 and 0.71 (with respective lifetimes 2.69 ns and 2.86 ns) compared to the free complex 3 with abundances of 0.12 and 0.13 (with respective lifetimes 3.36 ns and 3.28 ns) in DMSO and DMF, respectively.
- Full Text:
- Date Issued: 2011
The determination of the photosensitizing properties of mercapto substituted phthalocyanine derivatives in the presence of quantum dots capped with mercaptopropionic acid
- Moeno, Sharon, Antunes, Edith M, Nyokong, Tebello
- Authors: Moeno, Sharon , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247870 , vital:51625 , xlink:href="https://doi.org/10.1016/j.jphotochem.2010.12.009"
- Description: This work reports on the synthesis of several novel water soluble metallophthalocyanines containing Zn2+, In3+, Ga3+ or Si4+ as central metal ions and tetra substituted with mercaptoacetic acid and mercaptopropionic acid. The complexes were characterized using infra red, nuclear magnetic resonance and mass spectroscopies as well as elemental analysis. All the complexes are water soluble but the majority are highly aggregated in water and organic solvents. The complex containing Zn as a central metal and mercaptopropionic acid as a substituent was not aggregated allowing for the determination of photophysical parameters. This complex had triplet state quantum yield of 0.61 in DMF and 0.88 in DMSO while the fluorescence quantum yield was 0.13 in DMSO. The determination of photophysical properties of the complex containing Zn as a central metal and mercaptopropionic acid were carried out in the presence of mercaptopropionic acid capped CdTe quantum dots. There is an increase in triplet state quantum yield from 0.88 (for the phthalocyanine alone) to 0.94 (in the presence of CdTe quantum dots) in DMSO.
- Full Text:
- Date Issued: 2011
- Authors: Moeno, Sharon , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247870 , vital:51625 , xlink:href="https://doi.org/10.1016/j.jphotochem.2010.12.009"
- Description: This work reports on the synthesis of several novel water soluble metallophthalocyanines containing Zn2+, In3+, Ga3+ or Si4+ as central metal ions and tetra substituted with mercaptoacetic acid and mercaptopropionic acid. The complexes were characterized using infra red, nuclear magnetic resonance and mass spectroscopies as well as elemental analysis. All the complexes are water soluble but the majority are highly aggregated in water and organic solvents. The complex containing Zn as a central metal and mercaptopropionic acid as a substituent was not aggregated allowing for the determination of photophysical parameters. This complex had triplet state quantum yield of 0.61 in DMF and 0.88 in DMSO while the fluorescence quantum yield was 0.13 in DMSO. The determination of photophysical properties of the complex containing Zn as a central metal and mercaptopropionic acid were carried out in the presence of mercaptopropionic acid capped CdTe quantum dots. There is an increase in triplet state quantum yield from 0.88 (for the phthalocyanine alone) to 0.94 (in the presence of CdTe quantum dots) in DMSO.
- Full Text:
- Date Issued: 2011
Selective adsorption of PVP on the surface of silver nanoparticles
- Mdluli, Phumlani S, Sosibo, Ndabenhle M, Mashazi, Philani N, Nyokong, Tebello, Tshikhudo, Robert T, Skepu, Amanda, van der Lingen, Elma
- Authors: Mdluli, Phumlani S , Sosibo, Ndabenhle M , Mashazi, Philani N , Nyokong, Tebello , Tshikhudo, Robert T , Skepu, Amanda , van der Lingen, Elma
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247143 , vital:51550 , xlink:href="https://doi.org/10.1016/j.molstruc.2011.07.049"
- Description: The use of surfactants to affect the shape evolution of silver nanoparticles is explored. This allows one to fine-tune the morphological evolution and the optical properties of the metal nanoparticles. Polyvinyl pyrrolidone (PVP) has been used as a surfactant to control the growth of silver nanoparticles at room temperature. In this paper, molecular dynamics simulations were performed to understand regio-selective adsorption of PVP that leads to the preferential growth of silver nanoparticles in dimethylformamide (DMF). The interaction energies between PVP and Ag(1 1 0), Ag(1 0 0) and Ag(1 1 1) crystal planes were calculated and in addition the length density profile of the surfactant on silver surfaces was also examined. Importantly, it has been demonstrated that the length distribution profiles analysis obtained from the molecular dynamics study fully explained the adsorption of PVP on the surface of silver nanoparticles through the carbonyl group of the PVP ring. The application of molecular dynamics simulation technique is important in understanding the evolution of silver nanoparticles and is vital in choosing the right surfactants.
- Full Text:
- Date Issued: 2011
- Authors: Mdluli, Phumlani S , Sosibo, Ndabenhle M , Mashazi, Philani N , Nyokong, Tebello , Tshikhudo, Robert T , Skepu, Amanda , van der Lingen, Elma
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247143 , vital:51550 , xlink:href="https://doi.org/10.1016/j.molstruc.2011.07.049"
- Description: The use of surfactants to affect the shape evolution of silver nanoparticles is explored. This allows one to fine-tune the morphological evolution and the optical properties of the metal nanoparticles. Polyvinyl pyrrolidone (PVP) has been used as a surfactant to control the growth of silver nanoparticles at room temperature. In this paper, molecular dynamics simulations were performed to understand regio-selective adsorption of PVP that leads to the preferential growth of silver nanoparticles in dimethylformamide (DMF). The interaction energies between PVP and Ag(1 1 0), Ag(1 0 0) and Ag(1 1 1) crystal planes were calculated and in addition the length density profile of the surfactant on silver surfaces was also examined. Importantly, it has been demonstrated that the length distribution profiles analysis obtained from the molecular dynamics study fully explained the adsorption of PVP on the surface of silver nanoparticles through the carbonyl group of the PVP ring. The application of molecular dynamics simulation technique is important in understanding the evolution of silver nanoparticles and is vital in choosing the right surfactants.
- Full Text:
- Date Issued: 2011
Conjugates of low-symmetry Ge, Sn and Ti carboxy phthalocyanines with glutathione caped gold nanoparticles
- Masilela, Nkosiphile, Nyokong, Tebello
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247003 , vital:51536 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.08.009"
- Description: This work reports on conjugation of low symmetry Ge (GeMCPc), Ti (TiMCPc) and Sn (SnMCPc) carboxy phthalocyanines with glutathione capped gold nanoparticles (GSH-AuNPs). The photophysical behaviour of the novel phthalocyanines–GSH-AuNPs conjugate was investigated and compared to the monocarboxy Pcs and to the mixture of Pc with GSH-AuNPs without a chemical bond. Blue shifting of Q band of the phthalocyanines was observed on linking to GSH-AuNPs. An improvement in triplet lifetimes was obtained for all the MPcs–GSH-AuNPs-linked conjugates compared to the MPcs alone. The highest triplet quantum yield of 0.75 and the longest triplet lifetime of 130 μs were obtained for the GeMCPc–GSH-AuNPs-linked conjugate. Fluorescence quantum yields and lifetimes were low for the conjugates due to quenching by the nanoparticles.
- Full Text:
- Date Issued: 2011
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247003 , vital:51536 , xlink:href="https://doi.org/10.1016/j.jphotochem.2011.08.009"
- Description: This work reports on conjugation of low symmetry Ge (GeMCPc), Ti (TiMCPc) and Sn (SnMCPc) carboxy phthalocyanines with glutathione capped gold nanoparticles (GSH-AuNPs). The photophysical behaviour of the novel phthalocyanines–GSH-AuNPs conjugate was investigated and compared to the monocarboxy Pcs and to the mixture of Pc with GSH-AuNPs without a chemical bond. Blue shifting of Q band of the phthalocyanines was observed on linking to GSH-AuNPs. An improvement in triplet lifetimes was obtained for all the MPcs–GSH-AuNPs-linked conjugates compared to the MPcs alone. The highest triplet quantum yield of 0.75 and the longest triplet lifetime of 130 μs were obtained for the GeMCPc–GSH-AuNPs-linked conjugate. Fluorescence quantum yields and lifetimes were low for the conjugates due to quenching by the nanoparticles.
- Full Text:
- Date Issued: 2011
The synthesis and fluorescence behaviour of new unsymmetrically mono-functionalized carboxy Ge, Ti and Sn phthalocynines
- Masilela, Nkosiphile, Nyokong, Tebello
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246977 , vital:51534 , xlink:href="https://doi.org/10.1016/j.dyepig.2011.03.026"
- Description: This work reports on the synthesis and fluorescence behaviour of novel unsymmetrically substituted monocarboxy germanium ((OH)2GeMCPc, 3), titanium (OTiMCPc 4) and tin ((ac)2SnMCPc, 5) phthalocyanines. The fluorescence quantum yields ranged from 0.09 to 0.14. The fluorescence lifetimes were found to be higher for the complex with higher fluorescence quantum yield value. Higher fluorescence quantum yields and lifetimes were obtained for the (ac)2SnMCPc complex (5), followed by OTiMCPc complex (4), and the lowest fluorescence quantum yield and lifetime were observed for (OH)2GeMCPc (3).
- Full Text:
- Date Issued: 2011
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246977 , vital:51534 , xlink:href="https://doi.org/10.1016/j.dyepig.2011.03.026"
- Description: This work reports on the synthesis and fluorescence behaviour of novel unsymmetrically substituted monocarboxy germanium ((OH)2GeMCPc, 3), titanium (OTiMCPc 4) and tin ((ac)2SnMCPc, 5) phthalocyanines. The fluorescence quantum yields ranged from 0.09 to 0.14. The fluorescence lifetimes were found to be higher for the complex with higher fluorescence quantum yield value. Higher fluorescence quantum yields and lifetimes were obtained for the (ac)2SnMCPc complex (5), followed by OTiMCPc complex (4), and the lowest fluorescence quantum yield and lifetime were observed for (OH)2GeMCPc (3).
- Full Text:
- Date Issued: 2011