Iron perchlorophthalocyanine and tetrasulfophthalocyanine catalyzed oxidation of cyclohexane using hydrogen peroxide, chloroperoxybenzoic acid and tert-butylhydroperoxide as oxidants
- Grootboom, Natasha, Nyokong, Tebello
- Authors: Grootboom, Natasha , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289606 , vital:56653 , xlink:href="https://doi.org/10.1016/S1381-1169(01)00404-6"
- Description: Polychlorophthalocyanine (Cl16PcFeII) and tetrasulfophthalocyanine ([FeIITSPc]4−) complexes of iron are employed as catalysts for the oxidation of cyclohexane using tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (m-CPBA) and hydrogen peroxide as oxidants. Catalysis using the Cl16PcFeII was performed in a dimethylformamide:dichloromethane (3:7) solvent mixture. For the [FeIITSPc]4−catalyst, a water:methanol (1:9) mixture was employed. The products of the catalysis are cyclohexanone, cyclohexanol and cyclohexanediol. The relative yields of the products depended on oxidant and the catalyst. TBHP was found to be the best oxidant since minimal destruction of the catalyst and higher selectivity in the products were observed when this oxidant was employed. The mechanism of the oxidation of cyclohexane in the presence of the Cl16PcFeII and [FeIITSPc]4− involves the oxidation of these catalysts, forming an Fe(III) phthalocyanine species as an intermediate. Higher yields were observed when [FeTSPc]4− was employed as a catalyst, which is more soluble than the perchlorinated iron phthalocyanine catalyst.
- Full Text:
- Date Issued: 2002
- Authors: Grootboom, Natasha , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289606 , vital:56653 , xlink:href="https://doi.org/10.1016/S1381-1169(01)00404-6"
- Description: Polychlorophthalocyanine (Cl16PcFeII) and tetrasulfophthalocyanine ([FeIITSPc]4−) complexes of iron are employed as catalysts for the oxidation of cyclohexane using tert-butyl hydroperoxide (TBHP), m-chloroperoxybenzoic acid (m-CPBA) and hydrogen peroxide as oxidants. Catalysis using the Cl16PcFeII was performed in a dimethylformamide:dichloromethane (3:7) solvent mixture. For the [FeIITSPc]4−catalyst, a water:methanol (1:9) mixture was employed. The products of the catalysis are cyclohexanone, cyclohexanol and cyclohexanediol. The relative yields of the products depended on oxidant and the catalyst. TBHP was found to be the best oxidant since minimal destruction of the catalyst and higher selectivity in the products were observed when this oxidant was employed. The mechanism of the oxidation of cyclohexane in the presence of the Cl16PcFeII and [FeIITSPc]4− involves the oxidation of these catalysts, forming an Fe(III) phthalocyanine species as an intermediate. Higher yields were observed when [FeTSPc]4− was employed as a catalyst, which is more soluble than the perchlorinated iron phthalocyanine catalyst.
- Full Text:
- Date Issued: 2002
Electrooxidation of cresols on carbon electrodes modified with phthalocyaninato and octabutoxyphthalocyaninato cobalt (II) complexes
- Grootboom, Natasha, Nyokong, Tebello
- Authors: Grootboom, Natasha , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293207 , vital:57065 , xlink:href="https://doi.org/10.1016/S0003-2670(00)01351-9"
- Description: Glassy carbon electrodes (GCE) modified with cobalt(II) phthalocyanine (CoPc-GCE) and cobalt(II) octabutoxyphthalocyanine (CoOBuPc-GCE) were employed for the electrochemical analysis of ortho-, meta-, and para-cresols. The oxidation potential of p-cresol was shifted towards less positive values to a larger extent, when compared to m- and o-cresols, on CoOBuPc-GCE. However, the GCE was less stable when modified with CoOBuPc than with CoPc. This is explained using the possible differences in the orientation of the adsorbed phthalocyanine molecules on the electrode. Bulk electrolysis of p-cresol at anodic potentials (1.0 V versus Ag|AgCl) on carbon electrodes modified with CoPc resulted in the formation of radicals which coupled to form trimeric products. On unmodified carbon electrodes, coupling of the radicals resulted in dimeric products following bulk electrolysis. The products formed following bulk electrolysis were characterized by liquid chromatography coupled with mass spectrometry.
- Full Text:
- Date Issued: 2001
- Authors: Grootboom, Natasha , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293207 , vital:57065 , xlink:href="https://doi.org/10.1016/S0003-2670(00)01351-9"
- Description: Glassy carbon electrodes (GCE) modified with cobalt(II) phthalocyanine (CoPc-GCE) and cobalt(II) octabutoxyphthalocyanine (CoOBuPc-GCE) were employed for the electrochemical analysis of ortho-, meta-, and para-cresols. The oxidation potential of p-cresol was shifted towards less positive values to a larger extent, when compared to m- and o-cresols, on CoOBuPc-GCE. However, the GCE was less stable when modified with CoOBuPc than with CoPc. This is explained using the possible differences in the orientation of the adsorbed phthalocyanine molecules on the electrode. Bulk electrolysis of p-cresol at anodic potentials (1.0 V versus Ag|AgCl) on carbon electrodes modified with CoPc resulted in the formation of radicals which coupled to form trimeric products. On unmodified carbon electrodes, coupling of the radicals resulted in dimeric products following bulk electrolysis. The products formed following bulk electrolysis were characterized by liquid chromatography coupled with mass spectrometry.
- Full Text:
- Date Issued: 2001
Co (ii) Tetraphenyltetraphenanthroporphyrin@ MWCNTs
- Gu, Tingting, Tao, Jaiyu, Zhu, Weihua, Mack, John, Soy, Rodah C, Nyokong, Tebello, Xu, Haijin, Li, Minzhi, Liang, Xu
- Authors: Gu, Tingting , Tao, Jaiyu , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Xu, Haijin , Li, Minzhi , Liang, Xu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234580 , vital:50210 , xlink:href="https://doi.org/10.1039/C9NJ01707K"
- Description: Herein, a cobalt(II)tetraphenyltetraphenanthroporphyrin (Co(II)TPTPP) with phenanthrene-fused pyrrole rings was synthesized and characterized. Moreover, a detailed analysis of its optical and redox properties was carried out by comparing the results obtained via optical spectroscopy and electrochemistry with the trends predicted via a series of DFT and TD-DFT calculations. The electrochemistry results demonstrated that the π-expanded Co(II)TPTPP interacted strongly with multiwall carbon nanotubes (MWCNTs), which were finally immobilized on carbon nanotubes via noncovalent interactions and further deposited on glassy carbon. This strong immobilization via π–π stacking between Co(II)TPTPP and MWCNTs leads to significantly stable electrochemically catalyzed hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), which provides a new insight into the understanding electron transfer channels.
- Full Text:
- Date Issued: 2019
- Authors: Gu, Tingting , Tao, Jaiyu , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Xu, Haijin , Li, Minzhi , Liang, Xu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234580 , vital:50210 , xlink:href="https://doi.org/10.1039/C9NJ01707K"
- Description: Herein, a cobalt(II)tetraphenyltetraphenanthroporphyrin (Co(II)TPTPP) with phenanthrene-fused pyrrole rings was synthesized and characterized. Moreover, a detailed analysis of its optical and redox properties was carried out by comparing the results obtained via optical spectroscopy and electrochemistry with the trends predicted via a series of DFT and TD-DFT calculations. The electrochemistry results demonstrated that the π-expanded Co(II)TPTPP interacted strongly with multiwall carbon nanotubes (MWCNTs), which were finally immobilized on carbon nanotubes via noncovalent interactions and further deposited on glassy carbon. This strong immobilization via π–π stacking between Co(II)TPTPP and MWCNTs leads to significantly stable electrochemically catalyzed hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), which provides a new insight into the understanding electron transfer channels.
- Full Text:
- Date Issued: 2019
Platinum nanoparticles supported on carbon nanodots as anode catalysts for direct alcohol fuel cells
- Gwebu, Sandile Surprise, Nomngongo, Philiswa Nosizo, Mashazi, Philani Nkosinathi, Maxakato, Nobanathi Wendy, Nyokong, Tebello
- Authors: Gwebu, Sandile Surprise , Nomngongo, Philiswa Nosizo , Mashazi, Philani Nkosinathi , Maxakato, Nobanathi Wendy , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233118 , vital:50058 , xlink:href="https://doi.org/10.20964/2017.07.09"
- Description: Carbon nanodots (CNDs) were successfully synthesized employing a cheap and green method using oats as a starting material. The Pt/CNDs electrocatalyst was synthesized using carbon nanodots as a reductant and support material without adjusting the pH of the solution. The synthesized materials were characterized using Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller Nitrogen adsorption (BET), X-ray photoelectron spectroscopy (XPS), Transmission electron microscopy (TEM), X-ray diffractometry (XRD) and Inductively coupled plasma optical emission spectroscopy (ICP-OES). The FTIR results proved that the synthesized carbon nanodots contain carboxylic acid functional groups which facilitate the attachment of Pt nanoparticles. The BET surface area for carbon nanodots was found to be 312.5 m2 g -1 two times higher than that of commercial carbon. XPS results revealed the composition of the materials and the oxidation states of Pt in Pt/CNDs electrocatalyst. TEM images proved that the materials were of the nanoscale. XRD peaks proved that the carbon nanodots were amorphous and Pt (111) was present in the Pt/CNDs electrocatalyst. ICPOES determined the platinum concentration in Pt/CNDs electrocatalyst to be 8.12%. The electrochemical oxidation of methanol and ethanol were studied by cyclic voltammetry (CV) and chronoamperometry (CA). Cyclic voltammetry results showed that the Pt/CNDs electrocatalyst prepared by this method exhibit superior performance for methanol and ethanol electro-oxidation at room temperature.
- Full Text:
- Date Issued: 2017
Platinum nanoparticles supported on carbon nanodots as anode catalysts for direct alcohol fuel cells
- Authors: Gwebu, Sandile Surprise , Nomngongo, Philiswa Nosizo , Mashazi, Philani Nkosinathi , Maxakato, Nobanathi Wendy , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233118 , vital:50058 , xlink:href="https://doi.org/10.20964/2017.07.09"
- Description: Carbon nanodots (CNDs) were successfully synthesized employing a cheap and green method using oats as a starting material. The Pt/CNDs electrocatalyst was synthesized using carbon nanodots as a reductant and support material without adjusting the pH of the solution. The synthesized materials were characterized using Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller Nitrogen adsorption (BET), X-ray photoelectron spectroscopy (XPS), Transmission electron microscopy (TEM), X-ray diffractometry (XRD) and Inductively coupled plasma optical emission spectroscopy (ICP-OES). The FTIR results proved that the synthesized carbon nanodots contain carboxylic acid functional groups which facilitate the attachment of Pt nanoparticles. The BET surface area for carbon nanodots was found to be 312.5 m2 g -1 two times higher than that of commercial carbon. XPS results revealed the composition of the materials and the oxidation states of Pt in Pt/CNDs electrocatalyst. TEM images proved that the materials were of the nanoscale. XRD peaks proved that the carbon nanodots were amorphous and Pt (111) was present in the Pt/CNDs electrocatalyst. ICPOES determined the platinum concentration in Pt/CNDs electrocatalyst to be 8.12%. The electrochemical oxidation of methanol and ethanol were studied by cyclic voltammetry (CV) and chronoamperometry (CA). Cyclic voltammetry results showed that the Pt/CNDs electrocatalyst prepared by this method exhibit superior performance for methanol and ethanol electro-oxidation at room temperature.
- Full Text:
- Date Issued: 2017
Optical Limiting Properties of 3, 5-Dithienylenevinylene BODIPY Dyes at 532 nm
- Harris, Jessica, Gai, Lizhi, Kubheka, Gugu, Mack, John, Nyokong, Tebello, Shen, Zhen
- Authors: Harris, Jessica , Gai, Lizhi , Kubheka, Gugu , Mack, John , Nyokong, Tebello , Shen, Zhen
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189274 , vital:44833 , xlink:href="https://doi.org/10.1002/chem.201702503"
- Description: The optical limiting properties of a series of near infrared absorbing 3,5-dithienylenevinylene BODIPY (borondipyrromethene) dyes (1–3) that contain donor and acceptor moieties in their p-conjugation systems were studied by using the z-scan technique at 532 nm in the nanosecond pulse range. A strong reverse saturable absorption response was observed when the compounds are embedded into poly(bisphenol carbonate A) polymer thin films, which demonstrates that BODIPY dyes with this type of structure are suitable for use in optical limiting applications.
- Full Text:
- Date Issued: 2017
- Authors: Harris, Jessica , Gai, Lizhi , Kubheka, Gugu , Mack, John , Nyokong, Tebello , Shen, Zhen
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189274 , vital:44833 , xlink:href="https://doi.org/10.1002/chem.201702503"
- Description: The optical limiting properties of a series of near infrared absorbing 3,5-dithienylenevinylene BODIPY (borondipyrromethene) dyes (1–3) that contain donor and acceptor moieties in their p-conjugation systems were studied by using the z-scan technique at 532 nm in the nanosecond pulse range. A strong reverse saturable absorption response was observed when the compounds are embedded into poly(bisphenol carbonate A) polymer thin films, which demonstrates that BODIPY dyes with this type of structure are suitable for use in optical limiting applications.
- Full Text:
- Date Issued: 2017
Effects of redox mediators on the catalytic activity of iron porphyrins towards oxygen reduction in acidic media
- He, Qinggang, Wu, Gang, Liu, Ke, Khene, Samson M, Li, Qing, Mugadza, Tawanda, Deunf, Elise, Nyokong, Tebello, Chen, Shaowei W
- Authors: He, Qinggang , Wu, Gang , Liu, Ke , Khene, Samson M , Li, Qing , Mugadza, Tawanda , Deunf, Elise , Nyokong, Tebello , Chen, Shaowei W
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241472 , vital:50942 , xlink:href="https://doi.org/10.1002/celc.201402054"
- Description: The effects of different redox mediators on the oxygen reduction reaction (ORR) catalyzed by an iron porphyrin complex, iron(III) meso-tetra(N-methyl-4-pyridyl)porphine chloride [FeIIITMPyP], in 0.1 M triflic acid were investigated by cyclic voltammetry (CV) and spectroelectrochemistry in conjunction with density functional theory (DFT) calculations. The formal potentials of the FeIIITMPyP catalyst and the redox mediators, as well as the half-wave potentials for the ORR, were determined by CV in the absence and presence of oxygen in acidic solutions. UV/Vis spectroscopic and spectroelectrochemical studies confirmed that only the 2,2′-azino-bis(3-ethylbenzothiazioline-6-sulfonic acid)diammonium salt (C18H24N6O6S4) showed effective interactions with FeIIITMPyP during the ORR. DFT calculations suggested strong interaction between FeIIITMPyP and the C18H24N6O6S4 redox mediator. The redox mediator caused lengthening of the dioxygen iron bond, which thus suggested easier dioxygen reduction. Consistent results were observed in electrochemical impedance spectroscopic measurements for which the electron-transfer kinetics were also evaluated.
- Full Text:
- Date Issued: 2014
- Authors: He, Qinggang , Wu, Gang , Liu, Ke , Khene, Samson M , Li, Qing , Mugadza, Tawanda , Deunf, Elise , Nyokong, Tebello , Chen, Shaowei W
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241472 , vital:50942 , xlink:href="https://doi.org/10.1002/celc.201402054"
- Description: The effects of different redox mediators on the oxygen reduction reaction (ORR) catalyzed by an iron porphyrin complex, iron(III) meso-tetra(N-methyl-4-pyridyl)porphine chloride [FeIIITMPyP], in 0.1 M triflic acid were investigated by cyclic voltammetry (CV) and spectroelectrochemistry in conjunction with density functional theory (DFT) calculations. The formal potentials of the FeIIITMPyP catalyst and the redox mediators, as well as the half-wave potentials for the ORR, were determined by CV in the absence and presence of oxygen in acidic solutions. UV/Vis spectroscopic and spectroelectrochemical studies confirmed that only the 2,2′-azino-bis(3-ethylbenzothiazioline-6-sulfonic acid)diammonium salt (C18H24N6O6S4) showed effective interactions with FeIIITMPyP during the ORR. DFT calculations suggested strong interaction between FeIIITMPyP and the C18H24N6O6S4 redox mediator. The redox mediator caused lengthening of the dioxygen iron bond, which thus suggested easier dioxygen reduction. Consistent results were observed in electrochemical impedance spectroscopic measurements for which the electron-transfer kinetics were also evaluated.
- Full Text:
- Date Issued: 2014
Effects of Redox Mediators on the Catalytic Activity of Iron Porphyrins towards Oxygen Reduction in Acidic Media
- He, Qinggang, Wu, Gang, Liu, Ke, Khene, M Samson, Li, Qing, Mugadza, Tawanda, Deunf, Elise, Nyokong, Tebello, Chen, Shaowei W
- Authors: He, Qinggang , Wu, Gang , Liu, Ke , Khene, M Samson , Li, Qing , Mugadza, Tawanda , Deunf, Elise , Nyokong, Tebello , Chen, Shaowei W
- Language: English
- Type: Article
- Identifier: vital:7291 , http://hdl.handle.net/10962/d1020354
- Description: The effects of different redox mediators on the oxygen reduction reaction (ORR) catalyzed by an iron porphyrin complex, iron(III) meso-tetra(N-methyl-4-pyridyl)porphine chloride [FeIIITMPyP], in 0.1 M triflic acid were investigated by cyclic voltammetry (CV) and spectroelectrochemistry in conjunction with density functional theory (DFT) calculations. The formal potentials of the FeIIITMPyP catalyst and the redox mediators, as well as the half-wave potentials for the ORR, were determined by CV in the absence and presence of oxygen in acidic solutions. UV/Vis spectroscopic and spectroelectrochemical studies confirmed that only the 2,2′-azino-bis(3-ethylbenzothiazioline-6-sulfonic acid)diammonium salt (C18H24N6O6S4) showed effective interactions with FeIIITMPyP during the ORR. DFT calculations suggested strong interaction between FeIIITMPyP and the C18H24N6O6S4 redox mediator. The redox mediator caused lengthening of the dioxygen iron bond, which thus suggested easier dioxygen reduction. Consistent results were observed in electrochemical impedance spectroscopic measurements for which the electron-transfer kinetics were also evaluated. , Original publication is available at http://dx.doi.org/10.1002/celc.201402054
- Full Text: false
- Authors: He, Qinggang , Wu, Gang , Liu, Ke , Khene, M Samson , Li, Qing , Mugadza, Tawanda , Deunf, Elise , Nyokong, Tebello , Chen, Shaowei W
- Language: English
- Type: Article
- Identifier: vital:7291 , http://hdl.handle.net/10962/d1020354
- Description: The effects of different redox mediators on the oxygen reduction reaction (ORR) catalyzed by an iron porphyrin complex, iron(III) meso-tetra(N-methyl-4-pyridyl)porphine chloride [FeIIITMPyP], in 0.1 M triflic acid were investigated by cyclic voltammetry (CV) and spectroelectrochemistry in conjunction with density functional theory (DFT) calculations. The formal potentials of the FeIIITMPyP catalyst and the redox mediators, as well as the half-wave potentials for the ORR, were determined by CV in the absence and presence of oxygen in acidic solutions. UV/Vis spectroscopic and spectroelectrochemical studies confirmed that only the 2,2′-azino-bis(3-ethylbenzothiazioline-6-sulfonic acid)diammonium salt (C18H24N6O6S4) showed effective interactions with FeIIITMPyP during the ORR. DFT calculations suggested strong interaction between FeIIITMPyP and the C18H24N6O6S4 redox mediator. The redox mediator caused lengthening of the dioxygen iron bond, which thus suggested easier dioxygen reduction. Consistent results were observed in electrochemical impedance spectroscopic measurements for which the electron-transfer kinetics were also evaluated. , Original publication is available at http://dx.doi.org/10.1002/celc.201402054
- Full Text: false
Molecular catalysis of the oxygen reduction reaction by iron porphyrin catalysts tethered into Nafion layers
- He, Qinggang, Mugadza, Tawanda, Kang, Xiongwu, Zhu, Xiaobing, Chen, Shaowei, Kerr, John, Nyokong, Tebello
- Authors: He, Qinggang , Mugadza, Tawanda , Kang, Xiongwu , Zhu, Xiaobing , Chen, Shaowei , Kerr, John , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243168 , vital:51123 , xlink:href="https://doi.org/10.1016/j.jpowsour.2012.05.043"
- Description: This study was motivated by the need for improved understanding of the kinetics and transport phenomena in a homogeneous catalyst system for the oxygen reduction reaction (ORR). Direct interaction between the sulfonic groups of Nafion and an Fe(III) meso-tetra(N-methyl-4-pyridyl) porphine chloride (Fe(III)TMPyP) compound was observed using FTIR and in situ UV–Vis spectroelectrochemical characterizations. A positive shift of the half wave potential value (E1/2) for ORR on the iron porphyrin catalyst (Fe(III)TMPyP) was observed upon addition of a specific quantity of Nafion ionomer on a glassy carbon working electrode, indicating not only a faster charge transfer rate but also the role of protonation in the oxygen reduction reaction (ORR) process. A membrane electrode assembly (MEA) was made as a sandwich of a Pt-coated anode, a Nafion® 212 membrane, and a Fe(III)TMPyP + Nafion ionomer-coated cathode. This three-dimensional catalysis system has been demonstrated to be working in a H2/O2 proton exchange membrane (PEM) fuel cell test.
- Full Text:
- Date Issued: 2012
- Authors: He, Qinggang , Mugadza, Tawanda , Kang, Xiongwu , Zhu, Xiaobing , Chen, Shaowei , Kerr, John , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243168 , vital:51123 , xlink:href="https://doi.org/10.1016/j.jpowsour.2012.05.043"
- Description: This study was motivated by the need for improved understanding of the kinetics and transport phenomena in a homogeneous catalyst system for the oxygen reduction reaction (ORR). Direct interaction between the sulfonic groups of Nafion and an Fe(III) meso-tetra(N-methyl-4-pyridyl) porphine chloride (Fe(III)TMPyP) compound was observed using FTIR and in situ UV–Vis spectroelectrochemical characterizations. A positive shift of the half wave potential value (E1/2) for ORR on the iron porphyrin catalyst (Fe(III)TMPyP) was observed upon addition of a specific quantity of Nafion ionomer on a glassy carbon working electrode, indicating not only a faster charge transfer rate but also the role of protonation in the oxygen reduction reaction (ORR) process. A membrane electrode assembly (MEA) was made as a sandwich of a Pt-coated anode, a Nafion® 212 membrane, and a Fe(III)TMPyP + Nafion ionomer-coated cathode. This three-dimensional catalysis system has been demonstrated to be working in a H2/O2 proton exchange membrane (PEM) fuel cell test.
- Full Text:
- Date Issued: 2012
Excited state dynamics of zinc and aluminum phthalocyanine carboxylates
- Idowu, Mopelola, Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271228 , vital:54523 , xlink:href="https://doi.org/10.1016/j.saa.2007.01.025"
- Description: Photophysical parameters for zinc and aluminium tetracarboxylphthalocyanines (ZnTCPc and AlTCPc, respectively) and their octacarboxy substituted counterparts (ZnOCPc and AlOCPc) were studied. Data for the fluorescence quenching of the complexes by benzoquinone (BQ) were treated using the Stern–Volmer analysis, and the quenching was found to follow a diffusion-controlled (dynamic) bimolecular mechanism. Theoretical values of bimolecular rate constant for complex-BQ interactions were determined using the Stokes–Einstein–Smoluchowski model; and the values, together with the Stern–Volmer quenching constants were used in calculating the fluorescence lifetimes of the complexes. The thermodynamics of the MPc-BQ interaction, in terms of solvent reorientation energy is also discussed.
- Full Text:
- Date Issued: 2007
- Authors: Idowu, Mopelola , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271228 , vital:54523 , xlink:href="https://doi.org/10.1016/j.saa.2007.01.025"
- Description: Photophysical parameters for zinc and aluminium tetracarboxylphthalocyanines (ZnTCPc and AlTCPc, respectively) and their octacarboxy substituted counterparts (ZnOCPc and AlOCPc) were studied. Data for the fluorescence quenching of the complexes by benzoquinone (BQ) were treated using the Stern–Volmer analysis, and the quenching was found to follow a diffusion-controlled (dynamic) bimolecular mechanism. Theoretical values of bimolecular rate constant for complex-BQ interactions were determined using the Stokes–Einstein–Smoluchowski model; and the values, together with the Stern–Volmer quenching constants were used in calculating the fluorescence lifetimes of the complexes. The thermodynamics of the MPc-BQ interaction, in terms of solvent reorientation energy is also discussed.
- Full Text:
- Date Issued: 2007
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
Photophysical and photochemical properties of zinc and aluminum phthalocyanines in the presence of magnetic fluid
- Idowu, Mopelola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281298 , vital:55710 , xlink:href="https://doi.org/10.1016/j.jphotochem.2006.12.013"
- Description: The effect of magnetic fluid (MF) on the photophysical and photochemical parameters of zinc and aluminum phthalocyanines are reported. The complexes studied are zinc (II) phthalocyanine (ZnPc), chloroaluminum phthalocyanine ((Cl)AlPc) and tetrasulfonated aluminum phthalocyanine ((Cl)AlTSPc). The parameters are studied in dimethylsulfoxide (DMSO) for all complexes and also in aqueous media for (Cl)AlTSPc. The triplet lifetimes for (Cl)AlTSPc and ZnPc decreased while the triplet quantum yields increased in the presence of MF. For (Cl)AlPc, the triplet lifetimes were found to increase with decrease in laser energy while there was photoreduction to the Pc−3 species. Singlet oxygen and photodegradation quantum yields decreased in the presence of MF, suggesting quenching.
- Full Text:
- Date Issued: 2007
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281298 , vital:55710 , xlink:href="https://doi.org/10.1016/j.jphotochem.2006.12.013"
- Description: The effect of magnetic fluid (MF) on the photophysical and photochemical parameters of zinc and aluminum phthalocyanines are reported. The complexes studied are zinc (II) phthalocyanine (ZnPc), chloroaluminum phthalocyanine ((Cl)AlPc) and tetrasulfonated aluminum phthalocyanine ((Cl)AlTSPc). The parameters are studied in dimethylsulfoxide (DMSO) for all complexes and also in aqueous media for (Cl)AlTSPc. The triplet lifetimes for (Cl)AlTSPc and ZnPc decreased while the triplet quantum yields increased in the presence of MF. For (Cl)AlPc, the triplet lifetimes were found to increase with decrease in laser energy while there was photoreduction to the Pc−3 species. Singlet oxygen and photodegradation quantum yields decreased in the presence of MF, suggesting quenching.
- Full Text:
- Date Issued: 2007
Photoelectrochemical characterization of electrodeposited ZnO thin films sensitized by octacarboxymetallophthalocyanine derivatives
- Idowu, Mopelola, Loewenstein, Thomas, Hastall, Andreas, Nyokong, Tebello, Schlettwein, Derck
- Authors: Idowu, Mopelola , Loewenstein, Thomas , Hastall, Andreas , Nyokong, Tebello , Schlettwein, Derck
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262655 , vital:53541 , xlink:href="https://doi.org/10.1142/S1088424610001854"
- Description: Hybrid thin films of crystalline zinc oxide (ZnO) modified by different octacarboxymetallophthalocyanines (MOCPc) were prepared by the readsorption method. Homogeneously blue or green thin films were formed. The photoelectrochemical characteristics of the electrodes were studied by time-resolved photocurrent measurements. Zinc(II) 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine (ZnOCPc) showed considerably large quantum efficiency in sensitization of ZnO, one of the highest quantum efficiencies obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films.
- Full Text:
- Date Issued: 2010
- Authors: Idowu, Mopelola , Loewenstein, Thomas , Hastall, Andreas , Nyokong, Tebello , Schlettwein, Derck
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262655 , vital:53541 , xlink:href="https://doi.org/10.1142/S1088424610001854"
- Description: Hybrid thin films of crystalline zinc oxide (ZnO) modified by different octacarboxymetallophthalocyanines (MOCPc) were prepared by the readsorption method. Homogeneously blue or green thin films were formed. The photoelectrochemical characteristics of the electrodes were studied by time-resolved photocurrent measurements. Zinc(II) 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine (ZnOCPc) showed considerably large quantum efficiency in sensitization of ZnO, one of the highest quantum efficiencies obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films.
- Full Text:
- Date Issued: 2010
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
Photophysicochemical and fluorescence quenching studies of tetra-and octa-carboxy substituted silicon and germanium phthalocyanines
- Idowu, Mopelola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263500 , vital:53633 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.02.002"
- Description: Spectral, photophysical and photochemical properties of tetra- and octa-carboxy substituted metallophthalocyanines containing silicon and germanium as central metals ((OH)2GeTCPc, (OH)2SiTCPc, (OH)2GeOCPc and (OH)2SiOCPc) have been studied in dimethylsulfoxide (DMSO) and the trends in triplet, fluorescence, singlet oxygen quantum yields and triplet lifetimes are described for these compounds. The GePc derivatives exhibited high triplet quantum yields (ΦT = 0.79 for (OH)2GeOCPc and 0.82 for (OH)2GeTCPc compared to ΦT = 0.66 for (OH)2SiTCPc and 0.48 for (OH)2SiOCPc) due to the spin–orbit coupling induced by Ge(IV). The triplet lifetimes were higher for MOCPc (τT = 760 μs for (OH)2SiOCPc and 480 μs for (OH)2GeOCPc compared to τT = 210 μs for (OH)2SiTCPc and 260 μs for (OH)2GeTCPc). The fluorescent states of the metallophthalocyanine (MPc) complexes were effectively quenched by benzoquinone (BQ) and the quenching course was found to follow a diffusion-controlled (dynamic) bimolecular mechanism. Theoretical values of bimolecular rate constant for the interaction of the complexes with BQ were determined using the Stokes–Einstein–Smoluchowski model, and values together with the Stern–Volmer quenching constants were used in calculating the fluorescence lifetimes of the complexes.
- Full Text:
- Date Issued: 2009
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263500 , vital:53633 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.02.002"
- Description: Spectral, photophysical and photochemical properties of tetra- and octa-carboxy substituted metallophthalocyanines containing silicon and germanium as central metals ((OH)2GeTCPc, (OH)2SiTCPc, (OH)2GeOCPc and (OH)2SiOCPc) have been studied in dimethylsulfoxide (DMSO) and the trends in triplet, fluorescence, singlet oxygen quantum yields and triplet lifetimes are described for these compounds. The GePc derivatives exhibited high triplet quantum yields (ΦT = 0.79 for (OH)2GeOCPc and 0.82 for (OH)2GeTCPc compared to ΦT = 0.66 for (OH)2SiTCPc and 0.48 for (OH)2SiOCPc) due to the spin–orbit coupling induced by Ge(IV). The triplet lifetimes were higher for MOCPc (τT = 760 μs for (OH)2SiOCPc and 480 μs for (OH)2GeOCPc compared to τT = 210 μs for (OH)2SiTCPc and 260 μs for (OH)2GeTCPc). The fluorescent states of the metallophthalocyanine (MPc) complexes were effectively quenched by benzoquinone (BQ) and the quenching course was found to follow a diffusion-controlled (dynamic) bimolecular mechanism. Theoretical values of bimolecular rate constant for the interaction of the complexes with BQ were determined using the Stokes–Einstein–Smoluchowski model, and values together with the Stern–Volmer quenching constants were used in calculating the fluorescence lifetimes of the complexes.
- Full Text:
- Date Issued: 2009
Interaction of water-soluble CdTe quantum dots with octacarboxy metallophthalocyanines
- Idowu, Mopelola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264197 , vital:53708 , xlink:href="https://doi.org/10.1016/j.jlumin.2008.11.005"
- Description: Water-soluble CdTe quantum dots capped with L-cysteine (QD-CYS) were found to improve the photophysical and photochemical properties of octacarboxy metallophthalocyanine (MOCPc, M=Zn(II), Al(III)(OH), Ge(IV)(OH)2 and Si(IV)(OH)2) complexes. Increased diffusional interactions between the molecules and the ground-state molecular oxygen were established resulting from the increase in the triplet-state quantum yield and lifetimes of the MOCPcs in the presence of QD-CYS. Energy transfer occurred from QD-CYS to the MOCPcs upon excitation of QD-CYS. It was found that an efficient energy transfer process, which is not directly related to the amount of spectral overlap between the donor (QD-CYS) and the acceptor (MOCPc) can occur. Singlet oxygen via fluorescence resonance energy transfer (FRET) mechanism was produced in the QD-MPc mixture.
- Full Text:
- Date Issued: 2009
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264197 , vital:53708 , xlink:href="https://doi.org/10.1016/j.jlumin.2008.11.005"
- Description: Water-soluble CdTe quantum dots capped with L-cysteine (QD-CYS) were found to improve the photophysical and photochemical properties of octacarboxy metallophthalocyanine (MOCPc, M=Zn(II), Al(III)(OH), Ge(IV)(OH)2 and Si(IV)(OH)2) complexes. Increased diffusional interactions between the molecules and the ground-state molecular oxygen were established resulting from the increase in the triplet-state quantum yield and lifetimes of the MOCPcs in the presence of QD-CYS. Energy transfer occurred from QD-CYS to the MOCPcs upon excitation of QD-CYS. It was found that an efficient energy transfer process, which is not directly related to the amount of spectral overlap between the donor (QD-CYS) and the acceptor (MOCPc) can occur. Singlet oxygen via fluorescence resonance energy transfer (FRET) mechanism was produced in the QD-MPc mixture.
- Full Text:
- Date Issued: 2009
Spectroscopic behavior of cationic metallophthalocyanines in the presence of anionic quantum dots
- Idowu, Mopelola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262699 , vital:53545 , xlink:href="https://doi.org/10.1016/j.saa.2009.10.050"
- Description: The interactions and spectroscopic properties between cationic zinc phthalocyanine derivatives (peripherally and non-peripherally tetrasubstituted and peripherally octa substituted with 2-diethylmethylaminoethylsulfanyl (βTZnPc, αTZnPc and βOZnPc)) and CdTe core quantum dots (QDs) capped with mercaptopropionic acid or thioglycolic acid (represented as CdTe@MPA and CdTe@TGA, respectively) have been studied in methanol:water mixture. Strong coupling of MPcs was deduced from the interaction since the UV–vis spectroscopic studies of the ground state complex formed on mixing both components showed loss of the phthalocyanine monomeric band with the formation of a dimeric band (spectrum of aggregated species). The dimerization constants were of the order of 104 M−1.
- Full Text:
- Date Issued: 2010
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262699 , vital:53545 , xlink:href="https://doi.org/10.1016/j.saa.2009.10.050"
- Description: The interactions and spectroscopic properties between cationic zinc phthalocyanine derivatives (peripherally and non-peripherally tetrasubstituted and peripherally octa substituted with 2-diethylmethylaminoethylsulfanyl (βTZnPc, αTZnPc and βOZnPc)) and CdTe core quantum dots (QDs) capped with mercaptopropionic acid or thioglycolic acid (represented as CdTe@MPA and CdTe@TGA, respectively) have been studied in methanol:water mixture. Strong coupling of MPcs was deduced from the interaction since the UV–vis spectroscopic studies of the ground state complex formed on mixing both components showed loss of the phthalocyanine monomeric band with the formation of a dimeric band (spectrum of aggregated species). The dimerization constants were of the order of 104 M−1.
- Full Text:
- Date Issued: 2010
Synthesis, photophysical and photochemical studies of water soluble cationic zinc phthalocyanine derivatives
- Idowu, Mopelola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264245 , vital:53712 , xlink:href="https://doi.org/10.1016/j.poly.2008.11.021"
- Description: Peripherally and non-peripherally 2-diethylaminoethanethiol tetra-substituted zinc phthalocyanine (5a and 6a) and their quaternized derivatives (5b and 6b) have been synthesized and characterized. The quaternized derivatives (5b and 6b) show excellent solubility in aqueous medium. The photophysical and photochemical properties of the 2-diethylaminoethanethiol appended zinc phthalocyanine in dimethylsulfoxide (DMSO) for the non-ionic (5a and 6a) and in both DMSO and aqueous medium (phosphate buffered saline solution PBS, pH 7.4) (in the presence and absence of cremophore EL (CEL)) for the quaternized (5b and 6b) derivatives were studied and compared with that of the peripherally octa-substituted derivatives (7a and 7b). The complexes have intense absorption in the visible/near-IR region though the quaternized forms (5b, 6b and 7b) were slightly blue shifted and highly aggregate in aqueous solution. The triplet state quantum yields (ΦT) and the triplet lifetimes (τT) were found to be higher in DMSO (ΦT values ranged from 0.57 to 0.75 while τT values ranged from 190 to 220 μs in DMSO for all complexes) compared to aqueous medium (ΦT values ranged from 0.15 to 0.17 while τT values ranged from 20 to 70 μs in pH 7.4 buffer). Addition of cremophore EL in aqueous solution resulted in induced disaggregation leading to increased ΦT and τT.
- Full Text:
- Date Issued: 2009
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264245 , vital:53712 , xlink:href="https://doi.org/10.1016/j.poly.2008.11.021"
- Description: Peripherally and non-peripherally 2-diethylaminoethanethiol tetra-substituted zinc phthalocyanine (5a and 6a) and their quaternized derivatives (5b and 6b) have been synthesized and characterized. The quaternized derivatives (5b and 6b) show excellent solubility in aqueous medium. The photophysical and photochemical properties of the 2-diethylaminoethanethiol appended zinc phthalocyanine in dimethylsulfoxide (DMSO) for the non-ionic (5a and 6a) and in both DMSO and aqueous medium (phosphate buffered saline solution PBS, pH 7.4) (in the presence and absence of cremophore EL (CEL)) for the quaternized (5b and 6b) derivatives were studied and compared with that of the peripherally octa-substituted derivatives (7a and 7b). The complexes have intense absorption in the visible/near-IR region though the quaternized forms (5b, 6b and 7b) were slightly blue shifted and highly aggregate in aqueous solution. The triplet state quantum yields (ΦT) and the triplet lifetimes (τT) were found to be higher in DMSO (ΦT values ranged from 0.57 to 0.75 while τT values ranged from 190 to 220 μs in DMSO for all complexes) compared to aqueous medium (ΦT values ranged from 0.15 to 0.17 while τT values ranged from 20 to 70 μs in pH 7.4 buffer). Addition of cremophore EL in aqueous solution resulted in induced disaggregation leading to increased ΦT and τT.
- Full Text:
- Date Issued: 2009
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
Study of the photophysical behavior of tetrasulfonated metallophthalocyanines in the presence of CdTe quantum dots
- Idowu, Mopelola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264138 , vital:53701 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: Förster resonance energy transfer (FRET) studies were carried out with CdTe quantum dots (QDs) synthesized in aqueous phase and various tetrasulfonated metallophthalocyanines (MPcS4, M = aluminum ((OH)AlPcS4), zinc (ZnPcS4), silicon ((OH)2SiPcS4) and germanium ((OH)2GePcS4) in a H2O:MeOH (1:1) solvent mixture. The QDs studied were capped with thioglycolic acid (TGA) or mercaptopropionic acid (MPA) with sizes ranging from 2.3 to 3.7 nm. Non-radiative energy transfer from QDs emission to MPcS4 complexes was observed. Study of the photophysics of the MPcs in the presence of the QDs revealed high triplet state quantum yields (ΦT, ranging from 0.41 to 0.85 in the presence of QDs), with corresponding long triplet state lifetimes (τT, which ranged from 140 to 610 μs in the presence of QDs) to allow for photosensitized reactions to occur. The efficiency of energy transfer and the donor–acceptor distance between the MPcs and the QDs were also evaluated.
- Full Text:
- Date Issued: 2009
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264138 , vital:53701 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: Förster resonance energy transfer (FRET) studies were carried out with CdTe quantum dots (QDs) synthesized in aqueous phase and various tetrasulfonated metallophthalocyanines (MPcS4, M = aluminum ((OH)AlPcS4), zinc (ZnPcS4), silicon ((OH)2SiPcS4) and germanium ((OH)2GePcS4) in a H2O:MeOH (1:1) solvent mixture. The QDs studied were capped with thioglycolic acid (TGA) or mercaptopropionic acid (MPA) with sizes ranging from 2.3 to 3.7 nm. Non-radiative energy transfer from QDs emission to MPcS4 complexes was observed. Study of the photophysics of the MPcs in the presence of the QDs revealed high triplet state quantum yields (ΦT, ranging from 0.41 to 0.85 in the presence of QDs), with corresponding long triplet state lifetimes (τT, which ranged from 140 to 610 μs in the presence of QDs) to allow for photosensitized reactions to occur. The efficiency of energy transfer and the donor–acceptor distance between the MPcs and the QDs were also evaluated.
- Full Text:
- Date Issued: 2009
Spectral properties and photophysical behaviour of water soluble cationic Mg (II) and Al (III) phthalocyanines
- Idowu, Mopelola A, Arslanoğlu, Yasin, Nyokong, Tebello
- Authors: Idowu, Mopelola A , Arslanoğlu, Yasin , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241549 , vital:50949 , xlink:href="https://doi.org/10.2478/s11532-013-0388-z"
- Description: Peripherally and non-peripherally tetrasubstituted-[(N-methyl-2-pyridylthio)]phthalocyaninato magnesium (II) (5 and 6) and chloro aluminium (III) (7 and 8) tetraiodide have been synthesized and characterized. The photophysical properties of the complexes in dimethyl sulfoxide (DMSO) and aqueous medium in the presence and absence of cremophore EL have been studied. These complexes show high solubility in aqueous medium though they were aggregated. The triplet state quantum yields (FT) and the triplet lifetimes (tT) were found to be higher in DMSO with ΦT ranging from 0.32 to 0.51, while tT ranged from 282 to 622 ms in DMSO, compared to aqueous medium (pH 7.4 buffer) where ΦT ranged from 0.15 to 0.19 and tT from 26 to 35 ms. Addition of cremophore EL in aqueous solution resulted in partial disaggregation and increased photoactivity. The fluorescence lifetimes of the complexes showed strong dependence on their immediate environment. The ionic magnesium(II) and aluminium(III) phthalocyanines strongly bind to bovine serum albumin (BSA).
- Full Text:
- Date Issued: 2014
- Authors: Idowu, Mopelola A , Arslanoğlu, Yasin , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241549 , vital:50949 , xlink:href="https://doi.org/10.2478/s11532-013-0388-z"
- Description: Peripherally and non-peripherally tetrasubstituted-[(N-methyl-2-pyridylthio)]phthalocyaninato magnesium (II) (5 and 6) and chloro aluminium (III) (7 and 8) tetraiodide have been synthesized and characterized. The photophysical properties of the complexes in dimethyl sulfoxide (DMSO) and aqueous medium in the presence and absence of cremophore EL have been studied. These complexes show high solubility in aqueous medium though they were aggregated. The triplet state quantum yields (FT) and the triplet lifetimes (tT) were found to be higher in DMSO with ΦT ranging from 0.32 to 0.51, while tT ranged from 282 to 622 ms in DMSO, compared to aqueous medium (pH 7.4 buffer) where ΦT ranged from 0.15 to 0.19 and tT from 26 to 35 ms. Addition of cremophore EL in aqueous solution resulted in partial disaggregation and increased photoactivity. The fluorescence lifetimes of the complexes showed strong dependence on their immediate environment. The ionic magnesium(II) and aluminium(III) phthalocyanines strongly bind to bovine serum albumin (BSA).
- Full Text:
- Date Issued: 2014