Adsorption of 4-nitrophenol onto Amberlite® IRA-900 modified with metallophthalocyanines
- Marais, Eloïse A, Nyokong, Tebello
- Authors: Marais, Eloïse A , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268576 , vital:54211 , xlink:href="https://doi.org/10.1016/j.jhazmat.2007.06.096"
- Description: The adsorption of 4-nitrophenol using commercially available Amberlite® IRA-900 modified with metal phthalocyanines (MPc) was investigated. The metallophthalocyanines immobilised onto the surface of Amberlite® IRA-900 include Fe (FePcS4), Co (CoPcS4) and Ni (NiPcS4) tetrasulphophthalocyanines, and differently sulphonated phthalocyanine mixtures of Fe (FePcSmix), Co (CoPcSmix) and Ni (NiPcSmix). Adsorption rates were fastest for the modified adsorbents at a loading of 1 × 10−3 g MPc/g Amberlite, at pH 9. The highest amount of 4-NP removal was obtained on FePcSmix modified Amberlite® IRA-900 with Qt = 42.9 mmol g−1 and adsorption efficiency of 86%. The recovery efficiency of 4-NP within 150 min was 76%. Using the Langmuir–Hinshelwood kinetic model, the complexes showed an order of 4-nitrophenol adsorption to be as follows: CoPcSmix > NiPcS4 > NiPcSmix > FePcS4 > FePcSmix > CoPcS4. The MPc modified Amberlite® IRA-900 was used repeatedly, following removal of 4-NP by nitric acid, without any significant loss of activity.
- Full Text:
- Date Issued: 2008
- Authors: Marais, Eloïse A , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268576 , vital:54211 , xlink:href="https://doi.org/10.1016/j.jhazmat.2007.06.096"
- Description: The adsorption of 4-nitrophenol using commercially available Amberlite® IRA-900 modified with metal phthalocyanines (MPc) was investigated. The metallophthalocyanines immobilised onto the surface of Amberlite® IRA-900 include Fe (FePcS4), Co (CoPcS4) and Ni (NiPcS4) tetrasulphophthalocyanines, and differently sulphonated phthalocyanine mixtures of Fe (FePcSmix), Co (CoPcSmix) and Ni (NiPcSmix). Adsorption rates were fastest for the modified adsorbents at a loading of 1 × 10−3 g MPc/g Amberlite, at pH 9. The highest amount of 4-NP removal was obtained on FePcSmix modified Amberlite® IRA-900 with Qt = 42.9 mmol g−1 and adsorption efficiency of 86%. The recovery efficiency of 4-NP within 150 min was 76%. Using the Langmuir–Hinshelwood kinetic model, the complexes showed an order of 4-nitrophenol adsorption to be as follows: CoPcSmix > NiPcS4 > NiPcSmix > FePcS4 > FePcSmix > CoPcS4. The MPc modified Amberlite® IRA-900 was used repeatedly, following removal of 4-NP by nitric acid, without any significant loss of activity.
- Full Text:
- Date Issued: 2008
Electro-catalyzed oxidation of reduced glutathione and 2-mercaptoethanol by cobalt phthalocyanine-containing screen printed graphite electrodes
- Sehlotho, Nthapo, Griveau, Sophie, Ruillé, Nadine, Boujtita, Mohammed, Nyokong, Tebello, Bedioui, Fethi
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Ruillé, Nadine , Boujtita, Mohammed , Nyokong, Tebello , Bedioui, Fethi
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265935 , vital:53902 , xlink:href="https://doi.org/10.1016/j.msec.2007.10.054"
- Description: Electro-catalytic behavior of screen printed graphite electrodes modified with cobalt phthalocyanine (CoPc) towards the oxidation of reduced glutathione (GSH) and 2-mercaptoethanol (2-ME) is reported. We find, by using cyclic voltammetry, that the oxidation of 2-ME occurs at 0.2 V vs Ag/AgCl and − 0.3 vs Ag/AgCl V at pH = 7 and pH = 13, respectively and that of GSH occurs at 0.4 V vs Ag/AgCl and 0.0 V vs Ag/AgCl at pH = 7 and 13, respectively. The electro-catalytic activity depends on the method of electrode modification and the amount of catalyst incorporated in the ink used to fabricate the SPCEs. The highest activity was obtained with electrodes prepared with 2.5% (w:w) of CoPc.
- Full Text:
- Date Issued: 2008
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Ruillé, Nadine , Boujtita, Mohammed , Nyokong, Tebello , Bedioui, Fethi
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265935 , vital:53902 , xlink:href="https://doi.org/10.1016/j.msec.2007.10.054"
- Description: Electro-catalytic behavior of screen printed graphite electrodes modified with cobalt phthalocyanine (CoPc) towards the oxidation of reduced glutathione (GSH) and 2-mercaptoethanol (2-ME) is reported. We find, by using cyclic voltammetry, that the oxidation of 2-ME occurs at 0.2 V vs Ag/AgCl and − 0.3 vs Ag/AgCl V at pH = 7 and pH = 13, respectively and that of GSH occurs at 0.4 V vs Ag/AgCl and 0.0 V vs Ag/AgCl at pH = 7 and 13, respectively. The electro-catalytic activity depends on the method of electrode modification and the amount of catalyst incorporated in the ink used to fabricate the SPCEs. The highest activity was obtained with electrodes prepared with 2.5% (w:w) of CoPc.
- Full Text:
- Date Issued: 2008
Electrocatalytic and photosensitizing behavior of metallophthalocyanine complexes
- Authors: Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265908 , vital:53899 , xlink:href="https://doi.org/10.1142/S1088424608000388"
- Description: Electrocatalytic or photosensitizing (photocatalytic) properties of metallophthalocyanine (MPc) complexes are dependent on the central metal. Electrocatalytic behavior is observed for electroactive central metals such as Co, Mn and Fe, whereas photosensitizing behavior is observed for diamagnetic metals such as Al, Zn and Si. In the presence of nanoparticles such as quantum dots, the photosensitizing behavior of MPc complexes is improved. Carbon nanotubes enhance the electrocatalytic behavior of MPc complexes.
- Full Text:
- Date Issued: 2008
- Authors: Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265908 , vital:53899 , xlink:href="https://doi.org/10.1142/S1088424608000388"
- Description: Electrocatalytic or photosensitizing (photocatalytic) properties of metallophthalocyanine (MPc) complexes are dependent on the central metal. Electrocatalytic behavior is observed for electroactive central metals such as Co, Mn and Fe, whereas photosensitizing behavior is observed for diamagnetic metals such as Al, Zn and Si. In the presence of nanoparticles such as quantum dots, the photosensitizing behavior of MPc complexes is improved. Carbon nanotubes enhance the electrocatalytic behavior of MPc complexes.
- Full Text:
- Date Issued: 2008
Electrocatalytic detection of amitrole on the multi-walled carbon nanotube–iron (II) tetra-aminophthalocyanine platform
- Siswana, Msimelelo P, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Siswana, Msimelelo P , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265924 , vital:53901 , xlink:href="https://doi.org/10.3390/s8085096"
- Description: It is shown that iron(II) tetra-aminophthalocyanine complex electropolymerized onto a multi-walled carbon nanotube-modified basal plane pyrolytic graphite electrode greatly enhanced the electrocatalytic detetion of amitrole (a toxic herbicide), resulting in a very low detection limit (0.5 nM) and excellent sensitivity of 8.80±0.44 μA/nM, compared to any known work reported so far. The electrocatalytic detection of amitrole at this electrode occurred at less positive potential (~0.3 V vs Ag|ACl) and also revealed a typical coupled chemical reaction. The mechanism for this response is proposed. The electrode gave satisfactory selectivity to amitrole in the presence of other potential interfering pesticides in aqueous solutions.
- Full Text:
- Date Issued: 2008
- Authors: Siswana, Msimelelo P , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265924 , vital:53901 , xlink:href="https://doi.org/10.3390/s8085096"
- Description: It is shown that iron(II) tetra-aminophthalocyanine complex electropolymerized onto a multi-walled carbon nanotube-modified basal plane pyrolytic graphite electrode greatly enhanced the electrocatalytic detetion of amitrole (a toxic herbicide), resulting in a very low detection limit (0.5 nM) and excellent sensitivity of 8.80±0.44 μA/nM, compared to any known work reported so far. The electrocatalytic detection of amitrole at this electrode occurred at less positive potential (~0.3 V vs Ag|ACl) and also revealed a typical coupled chemical reaction. The mechanism for this response is proposed. The electrode gave satisfactory selectivity to amitrole in the presence of other potential interfering pesticides in aqueous solutions.
- Full Text:
- Date Issued: 2008
Electrochemical and electrocatalytic properties of α-substituted manganese and titanium phthalocyanines
- Nombona, Nolwazi, Tau, Prudence, Sehlotho, Nthapo, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Tau, Prudence , Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268587 , vital:54212 , xlink:href="https://doi.org/10.1016/j.electacta.2007.11.046"
- Description: This work reports on the synthesis of manganese and titanium phthalocyanine complexes that are tetra-substituted at four non-peripheral positions with amino ligands. The complexes are investigated for the first time for their electrochemical properties using cyclic voltammetry, rotating disc electrode voltammetry and spectroelectrochemistry. Electropolymerisation on a glassy carbon electrode was performed with ease and the modified electrodes were investigated for electrocatalysis of nitrite oxidation. Nitrite oxidation to nitrate is confirmed from the transfer of a total of two electrons.
- Full Text:
- Date Issued: 2008
- Authors: Nombona, Nolwazi , Tau, Prudence , Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268587 , vital:54212 , xlink:href="https://doi.org/10.1016/j.electacta.2007.11.046"
- Description: This work reports on the synthesis of manganese and titanium phthalocyanine complexes that are tetra-substituted at four non-peripheral positions with amino ligands. The complexes are investigated for the first time for their electrochemical properties using cyclic voltammetry, rotating disc electrode voltammetry and spectroelectrochemistry. Electropolymerisation on a glassy carbon electrode was performed with ease and the modified electrodes were investigated for electrocatalysis of nitrite oxidation. Nitrite oxidation to nitrate is confirmed from the transfer of a total of two electrons.
- Full Text:
- Date Issued: 2008
Electrochemical Characterization of Self-Assembled Monolayer of a Novel Manganese Tetrabenzylthio-Substituted Phthalocyanine and Its Use in Nitrite Oxidation
- Matemadombo, Fungisai, Griveau, Sophie, Bedioui, Fethi, Nyokong, Tebello
- Authors: Matemadombo, Fungisai , Griveau, Sophie , Bedioui, Fethi , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265950 , vital:53903 , xlink:href="https://doi.org/10.1002/elan.200804269"
- Description: Manganese phthalocyanine MnPc(SPh)4 has been synthesized and used to form self assembled monolayers on gold electrodes. The well packed SAM monolayer was characterized by analyzing the blocking of a number of Faradic processes by cyclic voltammetry, evaluating the electrical characteristics of the modified electrode by electrochemical impedance and imaging the modified surface by electrochemical scanning microscopy. Finally, MnPc(SPh)4-SAM modified electrode displayed an electrocatalytic behavior toward the oxidation of nitrite.
- Full Text:
- Date Issued: 2008
- Authors: Matemadombo, Fungisai , Griveau, Sophie , Bedioui, Fethi , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265950 , vital:53903 , xlink:href="https://doi.org/10.1002/elan.200804269"
- Description: Manganese phthalocyanine MnPc(SPh)4 has been synthesized and used to form self assembled monolayers on gold electrodes. The well packed SAM monolayer was characterized by analyzing the blocking of a number of Faradic processes by cyclic voltammetry, evaluating the electrical characteristics of the modified electrode by electrochemical impedance and imaging the modified surface by electrochemical scanning microscopy. Finally, MnPc(SPh)4-SAM modified electrode displayed an electrocatalytic behavior toward the oxidation of nitrite.
- Full Text:
- Date Issued: 2008
Electrooxidation of hydrazine catalyzed by noncovalently functionalized single-walled carbon nanotubes with CoPc
- Geraldo, Daniela A, Togo, Chamunorwa A, Limson, Janice L, Nyokong, Tebello
- Authors: Geraldo, Daniela A , Togo, Chamunorwa A , Limson, Janice L , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265963 , vital:53904 , xlink:href="https://doi.org/10.1016/j.electacta.2008.05.083"
- Description: We report on the electrooxidation of hydrazine catalyzed by single-walled carbon nanotube (SWCNT) functionalized with cobalt phthalocyanine (CoPc) which shows that the presence of the single-walled carbon nanotubes enhances the catalytic activity of the CoPc itself without any change in the reaction mechanism. A synergistic effect, in terms of reactivity when the new nanocomposite material was adsorbed on the GC electrode, was observed. The obtained hybrid electrodes were tested under hydrodynamic conditions, showing two different oxidation processes, which suggest the presence of two different types of active sites on the electrode surface catalyzing the reaction. Electrochemical impedance spectroscopy (EIS) analyses in the presence of [Fe(CN)6]3−/4− as a redox probe revealed that the GC/SWCNT + CoPc showed much lower electron-resistance (Ret) confirming the synergistic effect of the composite mentioned above. Atomic force microscopy (AFM) images showed the clear differences in surface roughness for each film, confirming the different compositions of the hybrid electrodes used in this study.
- Full Text:
- Date Issued: 2008
- Authors: Geraldo, Daniela A , Togo, Chamunorwa A , Limson, Janice L , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265963 , vital:53904 , xlink:href="https://doi.org/10.1016/j.electacta.2008.05.083"
- Description: We report on the electrooxidation of hydrazine catalyzed by single-walled carbon nanotube (SWCNT) functionalized with cobalt phthalocyanine (CoPc) which shows that the presence of the single-walled carbon nanotubes enhances the catalytic activity of the CoPc itself without any change in the reaction mechanism. A synergistic effect, in terms of reactivity when the new nanocomposite material was adsorbed on the GC electrode, was observed. The obtained hybrid electrodes were tested under hydrodynamic conditions, showing two different oxidation processes, which suggest the presence of two different types of active sites on the electrode surface catalyzing the reaction. Electrochemical impedance spectroscopy (EIS) analyses in the presence of [Fe(CN)6]3−/4− as a redox probe revealed that the GC/SWCNT + CoPc showed much lower electron-resistance (Ret) confirming the synergistic effect of the composite mentioned above. Atomic force microscopy (AFM) images showed the clear differences in surface roughness for each film, confirming the different compositions of the hybrid electrodes used in this study.
- Full Text:
- Date Issued: 2008
Energy transfer in zinc porphyrin–phthalocyanine heterotrimer and heterononamer studied by fluorescence resonance energy transfer (FRET)
- Durmus, Mahmut, Chen, Jiyao Y, Zhao, Zhixin X, Nyokong, Tebello
- Authors: Durmus, Mahmut , Chen, Jiyao Y , Zhao, Zhixin X , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268599 , vital:54213 , xlink:href="https://doi.org/10.1016/j.saa.2007.07.010"
- Description: Two or eight zinc triphenyl porphyrins were conjugated with Zn-phthalocyanine or H2-phthalocyanine to form ZnPc–(ZnTPP)2, ZnPc–(ZnTPP)8, H2Pc–(ZnTPP)2 and H2Pc–(ZnTPP)8. Energy transfers from the porphyrin moiety to phthalocyanine part were quantitatively studied with the modality of fluorescence resonance energy transfer (FRET). By measuring the fluorescence increment from the phthalocyanine moiety and the decrease from porphyrin part under selective excitation at the B band of the porphyrin part in those conjugated compounds and their equimolar mixture of compositions, energy transfer efficiencies were estimated to be 90% for H2Pc–(ZnTPP)8 and ZnPc–(ZnTPP)8, and 60%, 30% for ZnPc–(ZnTPP)2 and H2Pc–(ZnTPP)2, respectively.
- Full Text:
- Date Issued: 2008
- Authors: Durmus, Mahmut , Chen, Jiyao Y , Zhao, Zhixin X , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268599 , vital:54213 , xlink:href="https://doi.org/10.1016/j.saa.2007.07.010"
- Description: Two or eight zinc triphenyl porphyrins were conjugated with Zn-phthalocyanine or H2-phthalocyanine to form ZnPc–(ZnTPP)2, ZnPc–(ZnTPP)8, H2Pc–(ZnTPP)2 and H2Pc–(ZnTPP)8. Energy transfers from the porphyrin moiety to phthalocyanine part were quantitatively studied with the modality of fluorescence resonance energy transfer (FRET). By measuring the fluorescence increment from the phthalocyanine moiety and the decrease from porphyrin part under selective excitation at the B band of the porphyrin part in those conjugated compounds and their equimolar mixture of compositions, energy transfer efficiencies were estimated to be 90% for H2Pc–(ZnTPP)8 and ZnPc–(ZnTPP)8, and 60%, 30% for ZnPc–(ZnTPP)2 and H2Pc–(ZnTPP)2, respectively.
- Full Text:
- Date Issued: 2008
Interaction of water-soluble thiol capped CdTe quantum dots and bovine serum albumin
- Idowu, Mopelola, Lamprecht, Emmanuel, Nyokong, Tebello
- Authors: Idowu, Mopelola , Lamprecht, Emmanuel , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265974 , vital:53906 , xlink:href="https://doi.org/10.1016/j.jphotochem.2008.02.008"
- Description: Luminescent water-soluble CdTe quantum dots (QDs) capped with different thiol carboxylic acids were synthesized in aqueous medium and then cross linked to bovine serum albumin (BSA) with 1-ethyl3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC). Enhancement of fluorescence emission intensity occurred for QDs in the presence of bovine serum albumin (BSA, mixed or linked) signifying inhibition of non-radiative recombination of the surface vacancies. Fluorescence studies reveal a positive deviation behaviour suggesting the occurrence of static and dynamic mechanisms of quenching together which was accounted for by the modified Stern–Volmer equation.
- Full Text:
- Date Issued: 2008
- Authors: Idowu, Mopelola , Lamprecht, Emmanuel , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265974 , vital:53906 , xlink:href="https://doi.org/10.1016/j.jphotochem.2008.02.008"
- Description: Luminescent water-soluble CdTe quantum dots (QDs) capped with different thiol carboxylic acids were synthesized in aqueous medium and then cross linked to bovine serum albumin (BSA) with 1-ethyl3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC). Enhancement of fluorescence emission intensity occurred for QDs in the presence of bovine serum albumin (BSA, mixed or linked) signifying inhibition of non-radiative recombination of the surface vacancies. Fluorescence studies reveal a positive deviation behaviour suggesting the occurrence of static and dynamic mechanisms of quenching together which was accounted for by the modified Stern–Volmer equation.
- Full Text:
- Date Issued: 2008
Photocatalytic oxidation of 1-hexene using GaPc and InPc octasubstituted derivatives
- Chauke, Vongani, Nyokong, Tebello
- Authors: Chauke, Vongani , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268611 , vital:54214 , xlink:href="https://doi.org/10.1016/j.molcata.2008.04.003"
- Description: Photocatalytic oxidation of 1-hexene by GaPc (1a–1c) and InPc (2a–2c) derivatives (Pc = phthalocyanine) is hereby presented. The derivatives studied are Pc octasubstituted with phenoxy (a), 4-tert-butylphenoxy (b) or benzyloxyphenoxy (c) at the peripheral positions. 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 , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268611 , vital:54214 , xlink:href="https://doi.org/10.1016/j.molcata.2008.04.003"
- Description: Photocatalytic oxidation of 1-hexene by GaPc (1a–1c) and InPc (2a–2c) derivatives (Pc = phthalocyanine) is hereby presented. The derivatives studied are Pc octasubstituted with phenoxy (a), 4-tert-butylphenoxy (b) or benzyloxyphenoxy (c) at the peripheral positions. 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
Photocatalytic transformation of 4-nitrophenol in aqueous media using suspended, water-insoluble metallophthalocyanine complexes
- Marais, Eloïse A, Antunes, Edith M, Nyokong, Tebello
- Authors: Marais, Eloïse A , Antunes, Edith M , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265986 , vital:53907 , xlink:href="https://doi.org/10.1080/00958970802146056"
- Description: Unsubstituted magnesium (MgPc), zinc (ZnPc) and chloroaluminium (ClAlPc) phthalocyanine complexes and the ring substituted zinc tetranitro (ZnPc(NO2)4), zinc tetraamino (ZnPc(NH2)4), zinc hexadecafluoro (ZnPcF16) and zinc hexadecachloro (ZnPcCl16), phthalocyanine complexes are employed as photocatalysts for the heterogeneous transformation of 4-nitrophenol (4-Np) to fumaric acid and 4-nitrocatechol. ClAlPc is the best catalyst, with 89 ± 8% degradation of 4-Np after 100 min. The least effective catalysts were ZnPcCl16 and MgPc.
- Full Text:
- Date Issued: 2008
- Authors: Marais, Eloïse A , Antunes, Edith M , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265986 , vital:53907 , xlink:href="https://doi.org/10.1080/00958970802146056"
- Description: Unsubstituted magnesium (MgPc), zinc (ZnPc) and chloroaluminium (ClAlPc) phthalocyanine complexes and the ring substituted zinc tetranitro (ZnPc(NO2)4), zinc tetraamino (ZnPc(NH2)4), zinc hexadecafluoro (ZnPcF16) and zinc hexadecachloro (ZnPcCl16), phthalocyanine complexes are employed as photocatalysts for the heterogeneous transformation of 4-nitrophenol (4-Np) to fumaric acid and 4-nitrocatechol. ClAlPc is the best catalyst, with 89 ± 8% degradation of 4-Np after 100 min. The least effective catalysts were ZnPcCl16 and MgPc.
- Full Text:
- Date Issued: 2008
Photoinduced energy transfer between water-soluble CdTe quantum dots and aluminium tetrasulfonated phthalocyanine
- Idowu, Mopelola, Chen, Ji-Yao, Nyokong, Tebello
- Authors: Idowu, Mopelola , Chen, Ji-Yao , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268564 , vital:54210 , xlink:href="https://doi.org/10.1039/B707808K"
- Description: Thiol stabilized CdTe quantum dots (QDs) synthesized in aqueous phase were used as energy donors to aluminium tetrasulfonated phthalocyanine (AlTSPc) through fluorescence resonance energy transfer (FRET). Energy transfer occurred from the QDs to AlTSPc upon photoexcitation of the QDs. An enhancement in efficiency of energy transfer with the nature of the carboxylic thiol stabilizers on the QDs was observed. The results showed that for enhanced FRET to occur, the donor–acceptor distance has to be lower than the critical distance. The quenching constant K as well as the binding constant kb values were calculated suggesting strong interaction of the QDs with the AlTSPc. Study of the photophysics of AlTSPc in the presence of the QDs revealed a high triplet state yield, hence the possibility of using QDs in combination with phthalocyanines as photosensitizers in photodynamic therapy. The triplet state lifetimes of AlTSPc in the presence of the QDs were calculated and the lifetime in the presence of CdTe capped with 3-mercaptopropionic acid (MPA) was found to be the longest. MPA capped QD in a mixture with AlTSPc resulted in long triplet lifetime and high triplet yield of the latter, and high energy transfer efficiency, hence was found to be most suitable as a potential candidate for photodynamic therapy of cancer studies.
- Full Text:
- Date Issued: 2008
- Authors: Idowu, Mopelola , Chen, Ji-Yao , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268564 , vital:54210 , xlink:href="https://doi.org/10.1039/B707808K"
- Description: Thiol stabilized CdTe quantum dots (QDs) synthesized in aqueous phase were used as energy donors to aluminium tetrasulfonated phthalocyanine (AlTSPc) through fluorescence resonance energy transfer (FRET). Energy transfer occurred from the QDs to AlTSPc upon photoexcitation of the QDs. An enhancement in efficiency of energy transfer with the nature of the carboxylic thiol stabilizers on the QDs was observed. The results showed that for enhanced FRET to occur, the donor–acceptor distance has to be lower than the critical distance. The quenching constant K as well as the binding constant kb values were calculated suggesting strong interaction of the QDs with the AlTSPc. Study of the photophysics of AlTSPc in the presence of the QDs revealed a high triplet state yield, hence the possibility of using QDs in combination with phthalocyanines as photosensitizers in photodynamic therapy. The triplet state lifetimes of AlTSPc in the presence of the QDs were calculated and the lifetime in the presence of CdTe capped with 3-mercaptopropionic acid (MPA) was found to be the longest. MPA capped QD in a mixture with AlTSPc resulted in long triplet lifetime and high triplet yield of the latter, and high energy transfer efficiency, hence was found to be most suitable as a potential candidate for photodynamic therapy of cancer studies.
- Full Text:
- Date Issued: 2008
Photophysical and photochemical properties of tetrasulfonated silicon and germanium phthalocyanine in aqueous and non-aqueous media
- Idowu, Mopolela, Nyokong, Tebello
- Authors: Idowu, Mopolela , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268624 , vital:54215 , xlink:href="https://doi.org/10.1016/j.jphotochem.2008.01.004"
- Description: The photophysical and photochemical properties of tetrasulfonated silicon and germanium phthalocyanine (SiPcS4 and GePcS4) in aqueous solution (phosphate-buffered saline (PBS) solution, pH 7.4) (in the presence and absence of cremophore EL (CEL)) and in dimethylsulphoxide (DMSO) were studied. The complexes have intense absorption in the visible/near-IR region though they highly aggregate in aqueous solution with a dimerization constant of ∼2 × 104 dm3 mol−1. The fluorescence excitation spectra however have only one band suggesting that only the monomer fluoresces. Both the quantum yields of the triplet state (ΦT) and the triplet lifetimes (τT) were found to be higher in DMSO compared to in aqueous solution. Aggregation is hindered by addition of cremophore EL in aqueous solution and this induced disaggregation caused an increased ΦT and τT probably due to the reduced interaction of the phthalocyanines with the aqueous medium in the presence of CEL.
- Full Text:
- Date Issued: 2008
- Authors: Idowu, Mopolela , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268624 , vital:54215 , xlink:href="https://doi.org/10.1016/j.jphotochem.2008.01.004"
- Description: The photophysical and photochemical properties of tetrasulfonated silicon and germanium phthalocyanine (SiPcS4 and GePcS4) in aqueous solution (phosphate-buffered saline (PBS) solution, pH 7.4) (in the presence and absence of cremophore EL (CEL)) and in dimethylsulphoxide (DMSO) were studied. The complexes have intense absorption in the visible/near-IR region though they highly aggregate in aqueous solution with a dimerization constant of ∼2 × 104 dm3 mol−1. The fluorescence excitation spectra however have only one band suggesting that only the monomer fluoresces. Both the quantum yields of the triplet state (ΦT) and the triplet lifetimes (τT) were found to be higher in DMSO compared to in aqueous solution. Aggregation is hindered by addition of cremophore EL in aqueous solution and this induced disaggregation caused an increased ΦT and τT probably due to the reduced interaction of the phthalocyanines with the aqueous medium in the presence of CEL.
- Full Text:
- Date Issued: 2008
Photophysicochemical and Fluorescence quenching studies of benzyloxyphenoxy substituted zinc phthalocyanines
- Durmuş, Mahmut, Nyokong, Tebello
- Authors: Durmuş, Mahmut , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6570 , http://hdl.handle.net/10962/d1004133
- Description: Photochemical and photophysical measurements were conducted on peripheral and non-peripheral tetrakis- and octakis(4-benzyloxyphenoxy)-substituted zinc phthalocyanines (1, 2 and 3). General trends are described for photodegradation, and fluorescence quantum yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds in dimethylsulphoxide (DMSO) and toluene. The fluorescence of the complexes is quenched by benzoquinone (BQ), and fluorescence quenching properties are investigated in DMSO and toluene. The effects of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (1, 2 and 3) are also reported. Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications.
- Full Text:
- Date Issued: 2008
- Authors: Durmuş, Mahmut , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6570 , http://hdl.handle.net/10962/d1004133
- Description: Photochemical and photophysical measurements were conducted on peripheral and non-peripheral tetrakis- and octakis(4-benzyloxyphenoxy)-substituted zinc phthalocyanines (1, 2 and 3). General trends are described for photodegradation, and fluorescence quantum yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds in dimethylsulphoxide (DMSO) and toluene. The fluorescence of the complexes is quenched by benzoquinone (BQ), and fluorescence quenching properties are investigated in DMSO and toluene. The effects of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (1, 2 and 3) are also reported. Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications.
- Full Text:
- Date Issued: 2008
Photosensitizing properties of octacarboxy metallophthalocyanines in aqueous medium and their interaction with bovine serum albumin
- Idowu, Mopelola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264552 , vital:53744 , xlink:href="https://doi.org/10.1016/j.jphotochem.2008.09.003"
- Description: Photosensitizing properties of aluminium, silicon, zinc and germanium octacarboxy phthalocyanines ((OH)AlOCPc, (OH)2SiOCPc, ZnOCPc and (OH)2GeOCPc) were studied in aqueous medium and in the presence of bovine serum albumin (BSA). Triplet quantum yields increased with increasing atomic number of the central metals of the metallophthalocyanine. The efficiency of singlet oxygen generation via energy transfer from the excited triplet state of the octacarboxy metallophthalocyanines (MOCPcs) to ground state oxygen increased markedly in the presence of BSA. The triplet state lifetimes of the MOCPc complexes in the presence of BSA were found to be longer than in the absence of BSA, ranging from 110 to 580 μs. These complexes bind readily to BSA. Stern–Volmer quenching constant KSV as well as the binding constant kb values were calculated. The probable mechanism of quenching of BSA fluorescence by the MOCPc complexes is by static quenching.
- Full Text:
- Date Issued: 2008
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264552 , vital:53744 , xlink:href="https://doi.org/10.1016/j.jphotochem.2008.09.003"
- Description: Photosensitizing properties of aluminium, silicon, zinc and germanium octacarboxy phthalocyanines ((OH)AlOCPc, (OH)2SiOCPc, ZnOCPc and (OH)2GeOCPc) were studied in aqueous medium and in the presence of bovine serum albumin (BSA). Triplet quantum yields increased with increasing atomic number of the central metals of the metallophthalocyanine. The efficiency of singlet oxygen generation via energy transfer from the excited triplet state of the octacarboxy metallophthalocyanines (MOCPcs) to ground state oxygen increased markedly in the presence of BSA. The triplet state lifetimes of the MOCPc complexes in the presence of BSA were found to be longer than in the absence of BSA, ranging from 110 to 580 μs. These complexes bind readily to BSA. Stern–Volmer quenching constant KSV as well as the binding constant kb values were calculated. The probable mechanism of quenching of BSA fluorescence by the MOCPc complexes is by static quenching.
- Full Text:
- Date Issued: 2008
Spontaneous charge transfer between zinc tetramethyl-tetra-2, 3-pyridinoporphyrazine and CdTe and ZnS quantum dots
- Moeno, Sharon, Idowu, Mopelola, Nyokong, Tebello
- Authors: Moeno, Sharon , Idowu, Mopelola , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265997 , vital:53908 , xlink:href="https://doi.org/10.1016/j.ica.2008.02.048"
- Description: Zinc tetramethyl-tetra-2,3-pyridinoporphyrazine (ZnTmtppa(-2)) gets reduced to the ZnTmtppa(-3) species on interaction with CdTe QDs capped with 2-mercaptoethanol (2-ME) or thioglycolic acid (TGA) and ZnS QDs capped with 2-ME. The interaction occurs without photolysis. The fluorescence of the QDs is quenched by ZnTmtppa resulting in large quenching constants. Binding of ZnTmtppa to QDs occurs with two molecules of the former binding to the latter.
- Full Text:
- Date Issued: 2008
- Authors: Moeno, Sharon , Idowu, Mopelola , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265997 , vital:53908 , xlink:href="https://doi.org/10.1016/j.ica.2008.02.048"
- Description: Zinc tetramethyl-tetra-2,3-pyridinoporphyrazine (ZnTmtppa(-2)) gets reduced to the ZnTmtppa(-3) species on interaction with CdTe QDs capped with 2-mercaptoethanol (2-ME) or thioglycolic acid (TGA) and ZnS QDs capped with 2-ME. The interaction occurs without photolysis. The fluorescence of the QDs is quenched by ZnTmtppa resulting in large quenching constants. Binding of ZnTmtppa to QDs occurs with two molecules of the former binding to the latter.
- Full Text:
- Date Issued: 2008
Synthesis and electrochemical characterisation of a near infrared absorbing oxo vanadium (IV) octapentylthio-phthalocyanine
- Mbambisa, Gcineka, Nyokong, Tebello
- Authors: Mbambisa, Gcineka , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/266008 , vital:53909 , xlink:href="https://doi.org/10.1016/j.poly.2008.06.004"
- Description: The synthesis of an α-substituted phthalocyanine oxo vanadium(IV) 1,4,8,11,15,18,22,25-octapentathiophthalocyanine (4) which absorbs at 850 nm in dichloromethane is reported. The complex is purple in colour and becomes green on reduction. The cyclic and square wave voltammetries of the complex show five redox couples. The spectroelectrochemical data showed only ring based processes. The ring reduced species is observed at wavelengths greater than 680 nm rather than the usual 500–600 nm range typical of ring reduced phthalocyanine complexes.
- Full Text:
- Date Issued: 2008
- Authors: Mbambisa, Gcineka , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/266008 , vital:53909 , xlink:href="https://doi.org/10.1016/j.poly.2008.06.004"
- Description: The synthesis of an α-substituted phthalocyanine oxo vanadium(IV) 1,4,8,11,15,18,22,25-octapentathiophthalocyanine (4) which absorbs at 850 nm in dichloromethane is reported. The complex is purple in colour and becomes green on reduction. The cyclic and square wave voltammetries of the complex show five redox couples. The spectroelectrochemical data showed only ring based processes. The ring reduced species is observed at wavelengths greater than 680 nm rather than the usual 500–600 nm range typical of ring reduced phthalocyanine complexes.
- Full Text:
- Date Issued: 2008
Synthesis and photophysical properties of lead phthalocyanines
- Modibane, D.K., Nyokong, Tebello
- Authors: Modibane, D.K. , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268636 , vital:54216 , xlink:href="https://doi.org/10.1016/j.poly.2007.12.004"
- Description: This work reports on the synthesis and photophysical parameters of tetra-and octa-substituted new lead phthalocyanines. The complexes synthesized are: 1,4-(tetraphenoxyphthalocyaninato)lead (7a), 1,4-(tetra-tert-butylphenoxyphthalocyaninato)lead (7b), 2,3-(tetraphenoxyphthalocyaninato)lead (8a), 2,3-(tetra-tert-butylphenoxyphthalocyaninato)lead (8b), 2,3-octaphenoxyphthalocyaninatolead (9a) 2,3-[octakis(4-t-butylphenoxyphthalocyaninato)]lead (9b). Photophysical properties were studied for these complexes in a dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform. The fluorescence spectra were different from excitation spectra due to demetallation upon excitation. High triplet quantum yields ranging from 0.70 to 0.88 (in DMSO, DMF and toluene) and low triplet lifetimes (20–50 μs in DMSO, and more than 10 μs in the rest of the solvents) were observed due to the presence of heavy atom.
- Full Text:
- Date Issued: 2008
- Authors: Modibane, D.K. , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268636 , vital:54216 , xlink:href="https://doi.org/10.1016/j.poly.2007.12.004"
- Description: This work reports on the synthesis and photophysical parameters of tetra-and octa-substituted new lead phthalocyanines. The complexes synthesized are: 1,4-(tetraphenoxyphthalocyaninato)lead (7a), 1,4-(tetra-tert-butylphenoxyphthalocyaninato)lead (7b), 2,3-(tetraphenoxyphthalocyaninato)lead (8a), 2,3-(tetra-tert-butylphenoxyphthalocyaninato)lead (8b), 2,3-octaphenoxyphthalocyaninatolead (9a) 2,3-[octakis(4-t-butylphenoxyphthalocyaninato)]lead (9b). Photophysical properties were studied for these complexes in a dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform. The fluorescence spectra were different from excitation spectra due to demetallation upon excitation. High triplet quantum yields ranging from 0.70 to 0.88 (in DMSO, DMF and toluene) and low triplet lifetimes (20–50 μs in DMSO, and more than 10 μs in the rest of the solvents) were observed due to the presence of heavy atom.
- Full Text:
- Date Issued: 2008
Synthesis and solvent effects on the photophysicochemical properties of novel cadmium phenoxy phthalocyanines
- Chidawanyika, Wadzanai J U, Antunes, Edith M, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Antunes, Edith M , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268649 , vital:54217 , xlink:href="https://doi.org/10.1016/j.jphotochem.2007.09.020"
- Description: The syntheses of novel cadmium phenoxy complexes; tetrakis{1,(4)-tert-butylphenoxyphthalocyaninato}cadmium(II) (5a), tetrakis{1,(4)-phenoxyphthalocyaninato}cadmium(II) (5b), tetrakis{2,(3)-tert-butylphenoxyphthalocyaninato}cadmium(II) (6a) and tetrakis{2,(3)-phenoxyphthalocyaninato}cadmium(II) (6b) are presented herein. The spectroscopic and photophysicochemical properties have also been carried out and discussed together with the influence of various organic solvents on these properties. Spectroscopic properties, i.e. ground state electronic absorption and fluorescence spectra have been found to vary as a function of substituent position on the phthalocyanine macrocycle, i.e. α-substitution versus β-substitution. The photophysical parameters are reported as well as the photodegradation and singlet oxygen quantum yields, where the complexes were found to exhibit good photostability with the production of appreciable amounts of singlet oxygen.
- Full Text:
- Date Issued: 2008
- Authors: Chidawanyika, Wadzanai J U , Antunes, Edith M , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268649 , vital:54217 , xlink:href="https://doi.org/10.1016/j.jphotochem.2007.09.020"
- Description: The syntheses of novel cadmium phenoxy complexes; tetrakis{1,(4)-tert-butylphenoxyphthalocyaninato}cadmium(II) (5a), tetrakis{1,(4)-phenoxyphthalocyaninato}cadmium(II) (5b), tetrakis{2,(3)-tert-butylphenoxyphthalocyaninato}cadmium(II) (6a) and tetrakis{2,(3)-phenoxyphthalocyaninato}cadmium(II) (6b) are presented herein. The spectroscopic and photophysicochemical properties have also been carried out and discussed together with the influence of various organic solvents on these properties. Spectroscopic properties, i.e. ground state electronic absorption and fluorescence spectra have been found to vary as a function of substituent position on the phthalocyanine macrocycle, i.e. α-substitution versus β-substitution. The photophysical parameters are reported as well as the photodegradation and singlet oxygen quantum yields, where the complexes were found to exhibit good photostability with the production of appreciable amounts of singlet oxygen.
- Full Text:
- Date Issued: 2008
Synthesis, electrochemical characterization of tetra-and octa-substituted dodecyl-mercapto tin phthalocyanines in solution and as self-assembled monolayers
- Khene, Samson M, Geraldo, Daniela A, Togo, Chamunorwa A, Limson, Janice L, Nyokong, Tebello
- Authors: Khene, Samson M , Geraldo, Daniela A , Togo, Chamunorwa A , Limson, Janice L , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264541 , vital:53743 , xlink:href="https://doi.org/10.1016/j.electacta.2008.08.018"
- Description: Non-peripherally (α) tetra- (9) and octa-(7) substituted dodecyl-mercapto tin(IV) phthalocyanines were synthesized and their electrochemical behavior studied. Cyclic voltammetry and spectroelectrochemistry show ring-based reductions for 7 and 9, the former shows two ring oxidations, while the latter shows only one ring-based oxidation. The adsorption kinetics of (7) and (9) on gold electrode were investigated by electrochemical impedance spectroscopy (EIS). The equilibrium constant (K) for the adsorption and the Gibbs free energy (ΔGads) of the SAMs were evaluated based on the Frumkin isotherm.
- Full Text:
- Date Issued: 2008
- Authors: Khene, Samson M , Geraldo, Daniela A , Togo, Chamunorwa A , Limson, Janice L , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264541 , vital:53743 , xlink:href="https://doi.org/10.1016/j.electacta.2008.08.018"
- Description: Non-peripherally (α) tetra- (9) and octa-(7) substituted dodecyl-mercapto tin(IV) phthalocyanines were synthesized and their electrochemical behavior studied. Cyclic voltammetry and spectroelectrochemistry show ring-based reductions for 7 and 9, the former shows two ring oxidations, while the latter shows only one ring-based oxidation. The adsorption kinetics of (7) and (9) on gold electrode were investigated by electrochemical impedance spectroscopy (EIS). The equilibrium constant (K) for the adsorption and the Gibbs free energy (ΔGads) of the SAMs were evaluated based on the Frumkin isotherm.
- Full Text:
- Date Issued: 2008