Photophysicochemical and fluorescence quenching studies of tetra-and octa-carboxy substituted silicon and germanium phthalocyanines
- Idowu, Mopelola A I, Nyokong, Tebello
- Authors: Idowu, Mopelola A I , 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:
- Authors: Idowu, Mopelola A I , 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.
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Solvent and central metal effects on the photophysical and photochemical properties of peripherally tetra mercaptopyridine substituted metallophthalocyanines
- Moeno, Sharon, Nyokong, Tebello
- Authors: Moeno, Sharon , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263522 , vital:53635 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.01.021"
- Description: The synthesis of peripherally tetra 2-mercaptopyridine substituted phthalocyanines containing Si, Ga, Sn and In as central metal ions is reported for the first time in this study. Photophysical and photochemical studies were carried out on these compounds in order to determine the potential of the complexes as photosensitizers for use in photodynamic therapy. Fluorescence quantum yields (ΦF) ranged from 0.012 to 0.2 and triplet quantum yields (ΦT) from 0.54 to 0.89 in dimethylformamide (DMF) and from 0.65 to 0.93 in dimethylsulfoxide (DMSO). The triplet lifetimes ranged from 20 to 130 μs, the low values are due to the heavy atom effects of the central metal. The triplet lifetimes were larger in DMSO when compared with DMF.
- Full Text:
- Authors: Moeno, Sharon , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263522 , vital:53635 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.01.021"
- Description: The synthesis of peripherally tetra 2-mercaptopyridine substituted phthalocyanines containing Si, Ga, Sn and In as central metal ions is reported for the first time in this study. Photophysical and photochemical studies were carried out on these compounds in order to determine the potential of the complexes as photosensitizers for use in photodynamic therapy. Fluorescence quantum yields (ΦF) ranged from 0.012 to 0.2 and triplet quantum yields (ΦT) from 0.54 to 0.89 in dimethylformamide (DMF) and from 0.65 to 0.93 in dimethylsulfoxide (DMSO). The triplet lifetimes ranged from 20 to 130 μs, the low values are due to the heavy atom effects of the central metal. The triplet lifetimes were larger in DMSO when compared with DMF.
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Study of the photophysical behavior of tetrasulfonated metallophthalocyanines in the presence of CdTe quantum dots
- Idowu, Mopelola A I, Nyokong, Tebello
- Authors: Idowu, Mopelola A I , 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:
- Authors: Idowu, Mopelola A I , 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.
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Synthesis and characterization of electrocatalytic conjugates of tetraamino cobalt (II) phthalocyanine and single wall carbon nanotubes
- Mugadza, Tawanda, Nyokong, Tebello
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263341 , vital:53619 , xlink:href="https://doi.org/10.1016/j.electacta.2009.05.074"
- Description: In this paper we report on the synthesis and characterization of electrocatalytic conjugates of tetraamino cobalt (II) phthalocyanine and single walled carbon nanotubes (CoTAPc–SWCNT-linked) for use as electrode surface modifiers. FTIR, UV–vis and Raman spectroscopies were used to ascertain the chemical linkage between CoTAPc and SWCNT while cyclic voltammetry and rotating disk electrode voltammetry were used to assess the electrocatalytic efficiency of the linked product towards the oxidation of 2-mercaptoethanol. The CoTAPc–SWCNT-linked-GCE demonstrated very good catalytic efficiency relative to CoTAPc–SWCNT-mixed-GCE, CoTAPc-GCE and f-SWCNTs-GCE (functionalised SWCNT). CoTAPc–SWCNT-linked-GCE gave a sensitivity of 0.2 μA/μM and a limit of detection (LOD) of 1.2 × 10−7 M for 2-mercaptoethanol (2-ME) at pH 4.
- Full Text:
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263341 , vital:53619 , xlink:href="https://doi.org/10.1016/j.electacta.2009.05.074"
- Description: In this paper we report on the synthesis and characterization of electrocatalytic conjugates of tetraamino cobalt (II) phthalocyanine and single walled carbon nanotubes (CoTAPc–SWCNT-linked) for use as electrode surface modifiers. FTIR, UV–vis and Raman spectroscopies were used to ascertain the chemical linkage between CoTAPc and SWCNT while cyclic voltammetry and rotating disk electrode voltammetry were used to assess the electrocatalytic efficiency of the linked product towards the oxidation of 2-mercaptoethanol. The CoTAPc–SWCNT-linked-GCE demonstrated very good catalytic efficiency relative to CoTAPc–SWCNT-mixed-GCE, CoTAPc-GCE and f-SWCNTs-GCE (functionalised SWCNT). CoTAPc–SWCNT-linked-GCE gave a sensitivity of 0.2 μA/μM and a limit of detection (LOD) of 1.2 × 10−7 M for 2-mercaptoethanol (2-ME) at pH 4.
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Synthesis, photophysical and nonlinear optical properties of microwave synthesized 4-tetra and octa-substituted lead phthalocyanines
- Modibane, Desmond K, Nyokong, Tebello
- Authors: Modibane, Desmond K , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263452 , vital:53629 , xlink:href="https://doi.org/10.1016/j.poly.2009.03.013"
- Description: This work presents the photophysical and nonlinear optical behaviour of newly synthesized complexes: 2,(3)-tetrakis(4-benzyloxyphenoxyphthalocyaninato) lead (5a) and 2,3-octakis(4-benzyloxyphenoxyphthalocyaninato) lead (6a). The nonlinear optical behaviour of complexes 5a and 6a are compared with those of 2,(3)-tetraphenoxyphthalocyaninato lead (5b), 2,(3)-tetrakis(4-t-butylphenoxyphthalocyaninato) lead (5c), 2,3-octaphenoxyphthalocyaninato lead (6b) and 2,3-octakis(4-t-butylphenoxyphthalocyaninato) lead (6c). The synthesis of 5a and 6a was performed using microwave irradiation. Photophysical properties were studied for these complexes in 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 0.80 to 0.86 (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. Nonlinear optical properties were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.6 W/cm2.
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- Authors: Modibane, Desmond K , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263452 , vital:53629 , xlink:href="https://doi.org/10.1016/j.poly.2009.03.013"
- Description: This work presents the photophysical and nonlinear optical behaviour of newly synthesized complexes: 2,(3)-tetrakis(4-benzyloxyphenoxyphthalocyaninato) lead (5a) and 2,3-octakis(4-benzyloxyphenoxyphthalocyaninato) lead (6a). The nonlinear optical behaviour of complexes 5a and 6a are compared with those of 2,(3)-tetraphenoxyphthalocyaninato lead (5b), 2,(3)-tetrakis(4-t-butylphenoxyphthalocyaninato) lead (5c), 2,3-octaphenoxyphthalocyaninato lead (6b) and 2,3-octakis(4-t-butylphenoxyphthalocyaninato) lead (6c). The synthesis of 5a and 6a was performed using microwave irradiation. Photophysical properties were studied for these complexes in 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 0.80 to 0.86 (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. Nonlinear optical properties were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.6 W/cm2.
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Synthesis, photophysical and photochemical properties of novel soluble tetra [4-(thiophen-3yl)-phenoxy] phthalocyaninato zinc (II) and Ti (IV) O complexes
- Erdoğmuş, Ali, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263318 , vital:53617 , xlink:href="https://doi.org/10.1016/j.ica.2009.07.015"
- Description: The synthesis, photophysical and photochemical properties of zinc and oxo-titanium phthalocyanine derivatives 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)zinc(II), (2); and 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)oxo-titanium(IV), (3), are described for the first time. These peripherally substituted complexes (2 and 3) have been synthesized and characterized by elemental analysis, IR, 1H NMR and electronic spectroscopy. The compounds (2 and 3) have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated within a wide concentration range. General trends are described for singlet oxygen, photodegradation, fluorescence quantum yields, triplet quantum yields and triplet life times of these complexes in DMSO, DMF and THF. Compound 2 has higher fluorescence quantum yields, triplet quantum yields and triplet life times than 3, however, the former has lower singlet oxygen quantum yields and photodegradation quantum yields than the latter.
- Full Text:
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263318 , vital:53617 , xlink:href="https://doi.org/10.1016/j.ica.2009.07.015"
- Description: The synthesis, photophysical and photochemical properties of zinc and oxo-titanium phthalocyanine derivatives 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)zinc(II), (2); and 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)oxo-titanium(IV), (3), are described for the first time. These peripherally substituted complexes (2 and 3) have been synthesized and characterized by elemental analysis, IR, 1H NMR and electronic spectroscopy. The compounds (2 and 3) have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated within a wide concentration range. General trends are described for singlet oxygen, photodegradation, fluorescence quantum yields, triplet quantum yields and triplet life times of these complexes in DMSO, DMF and THF. Compound 2 has higher fluorescence quantum yields, triplet quantum yields and triplet life times than 3, however, the former has lower singlet oxygen quantum yields and photodegradation quantum yields than the latter.
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Synthesis, photophysical and photochemical properties of octa-substituted antimony phthalocyanines
- Modibane, Desmond Kwena, Nyokong, Tebello
- Authors: Modibane, Desmond Kwena , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264226 , vital:53711 , xlink:href="https://doi.org/10.1016/j.poly.2008.11.052"
- Description: This work reports on the synthesis and photophysicochemical parameters of unsubstituted [SbIIIPc]+I3- and octa-phenoxy ([SbIIIOPPc]+I3-) and -4-t-butylphenoxy ([SbIIIOTBPPc]+I3-) substituted antimony phthalocyanines. Photophysical and photochemical properties were studied for these complexes in dimethylsulfoxide, dimethylformamide and toluene. The excitation spectra of oxidized antimony (Sb(V)Pc) derivates were similar to absorption spectra. Low fluorescence quantum yields, high triplet quantum yields and low triplet lifetimes were observed as the result of heavy atom (antimony ion).
- Full Text:
- Authors: Modibane, Desmond Kwena , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264226 , vital:53711 , xlink:href="https://doi.org/10.1016/j.poly.2008.11.052"
- Description: This work reports on the synthesis and photophysicochemical parameters of unsubstituted [SbIIIPc]+I3- and octa-phenoxy ([SbIIIOPPc]+I3-) and -4-t-butylphenoxy ([SbIIIOTBPPc]+I3-) substituted antimony phthalocyanines. Photophysical and photochemical properties were studied for these complexes in dimethylsulfoxide, dimethylformamide and toluene. The excitation spectra of oxidized antimony (Sb(V)Pc) derivates were similar to absorption spectra. Low fluorescence quantum yields, high triplet quantum yields and low triplet lifetimes were observed as the result of heavy atom (antimony ion).
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Synthesis, photophysical and photochemical studies of water soluble cationic zinc phthalocyanine derivatives
- Idowu, Mopelola A I, Nyokong, Tebello
- Authors: Idowu, Mopelola A I , 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:
- Authors: Idowu, Mopelola A I , 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.
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Synthesis, photophysics and photochemistry of novel tetra (quinoxalinyl) phthalocyaninato zinc (II) complexes
- Erdoğmuş, Ali, Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263441 , vital:53628 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.04.007"
- Description: The syntheses and spectral, photophysical and photochemical properties of some zinc phthalocyanine derivatives – {2, (3)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (β-ZnPc) and 1, (4)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (α-ZnPc)} – are presented. The β-substituted complex is more fluorescent and exhibits lower tendencies to undergo intersystem crossing than its α-substituted counterpart, as judged by the former's higher fluorescence quantum yield (ΦF) and lower triplet quantum yield (ΦT) than the latter's in three solvents (DMSO, DMF and toluene). Singlet oxygen quantum yield (ΦΔ) values show the same trends as ΦT values. The differences in the spectral and photophysical properties of α-ZnPc and β-ZnPc are partly attributed to greater molecular distortions in the former. Studies of the interaction of the triplet states of α-ZnPc and β-ZnPc with triplet oxygen showed that α-ZnPc is more vulnerable to oxygen quenching than β-ZnPc. Also, the smallest quenching rate constants were observed in DMSO, which is attributed to the higher viscosity of DMSO than DMF and toluene.
- Full Text:
- Authors: Erdoğmuş, Ali , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263441 , vital:53628 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.04.007"
- Description: The syntheses and spectral, photophysical and photochemical properties of some zinc phthalocyanine derivatives – {2, (3)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (β-ZnPc) and 1, (4)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (α-ZnPc)} – are presented. The β-substituted complex is more fluorescent and exhibits lower tendencies to undergo intersystem crossing than its α-substituted counterpart, as judged by the former's higher fluorescence quantum yield (ΦF) and lower triplet quantum yield (ΦT) than the latter's in three solvents (DMSO, DMF and toluene). Singlet oxygen quantum yield (ΦΔ) values show the same trends as ΦT values. The differences in the spectral and photophysical properties of α-ZnPc and β-ZnPc are partly attributed to greater molecular distortions in the former. Studies of the interaction of the triplet states of α-ZnPc and β-ZnPc with triplet oxygen showed that α-ZnPc is more vulnerable to oxygen quenching than β-ZnPc. Also, the smallest quenching rate constants were observed in DMSO, which is attributed to the higher viscosity of DMSO than DMF and toluene.
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The formation of self-assembled monolayers of thiophthalocyanine complexes of titanium, vanadium and manganese and their use in l-cysteine electrocatalysis
- Mbambisa, Gcineka, Nombona, Nolwazi, Nyokong, Tebello
- Authors: Mbambisa, Gcineka , Nombona, Nolwazi , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263375 , vital:53622 , xlink:href="https://doi.org/10.1016/j.microc.2009.04.009"
- Description: Self-assembled monolayers (SAMs) based on octapentylthiophthalocyanine complexes of oxovanadium (IV) (OVOPThPc), titanium(IV) (OTiOPThPc), and manganese (III) acetate (AcMnOPThPc), and of tetraphenylthiophthalocyanine complexes of hydroxo manganese(III) (OHMnTPPc) and oxotitanium(IV) (OTiTPPc) are described. The oxidation of l-cysteine was observed at potentials which ranged from 0.52 V to 0.67 V. The detection limits for l-cysteine analysis were of the order of 10− 7 to 10− 6 M.
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- Authors: Mbambisa, Gcineka , Nombona, Nolwazi , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263375 , vital:53622 , xlink:href="https://doi.org/10.1016/j.microc.2009.04.009"
- Description: Self-assembled monolayers (SAMs) based on octapentylthiophthalocyanine complexes of oxovanadium (IV) (OVOPThPc), titanium(IV) (OTiOPThPc), and manganese (III) acetate (AcMnOPThPc), and of tetraphenylthiophthalocyanine complexes of hydroxo manganese(III) (OHMnTPPc) and oxotitanium(IV) (OTiTPPc) are described. The oxidation of l-cysteine was observed at potentials which ranged from 0.52 V to 0.67 V. The detection limits for l-cysteine analysis were of the order of 10− 7 to 10− 6 M.
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The role of macrophytes as a refuge and food source for the estuarine isopod Exosphaeroma hylocoetes ()
- Henninger, Tony O, Froneman, P William, Richoux, Nicole B, Hodgson, Alan N
- Authors: Henninger, Tony O , Froneman, P William , Richoux, Nicole B , Hodgson, Alan N
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/458360 , vital:75735 , xlink:href="https://doi.org/10.1016/j.ecss.2009.01.01"
- Description: The role of submerged macrophytes as refugia from fish predation and as possible food sources for the estuarine isopod Exosphaeroma hylocoetes (Barnard, K.H., 1940) was investigated. Laboratory experiments tested the effectiveness of artificial vegetation, replicating submerged vegetation, in enabling isopods to elude selected fish predators Rhabdosargus holubi, Glossogobius callidus, Monodactylus falciformis and Clinus cottoides. Isopods preferentially hid in the vegetation (>90%), even in absence of fish. The predatory fish had varying success in finding isopods within the vegetation. Isopod mortality ranged from 2% (R. holubi) to a maximum of 87% (C. cottoides) within vegetation, depending on the fish predator present. Stable isotope and fatty acid analyses ruled out the submerged macrophyte Ruppia maritima and inundated fringing grasses as direct food sources, but highlighted the epiphytic biota (mainly diatoms) found on the submerged vegetation and sediments as more likely food sources. These findings are consistent with gut content analyses. The results suggest that the close association of E. hylocoetes with R. maritima is the result of the vegetation providing the isopod with a refuge against fish predation as well as areas of increased food availability.
- Full Text:
- Authors: Henninger, Tony O , Froneman, P William , Richoux, Nicole B , Hodgson, Alan N
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/458360 , vital:75735 , xlink:href="https://doi.org/10.1016/j.ecss.2009.01.01"
- Description: The role of submerged macrophytes as refugia from fish predation and as possible food sources for the estuarine isopod Exosphaeroma hylocoetes (Barnard, K.H., 1940) was investigated. Laboratory experiments tested the effectiveness of artificial vegetation, replicating submerged vegetation, in enabling isopods to elude selected fish predators Rhabdosargus holubi, Glossogobius callidus, Monodactylus falciformis and Clinus cottoides. Isopods preferentially hid in the vegetation (>90%), even in absence of fish. The predatory fish had varying success in finding isopods within the vegetation. Isopod mortality ranged from 2% (R. holubi) to a maximum of 87% (C. cottoides) within vegetation, depending on the fish predator present. Stable isotope and fatty acid analyses ruled out the submerged macrophyte Ruppia maritima and inundated fringing grasses as direct food sources, but highlighted the epiphytic biota (mainly diatoms) found on the submerged vegetation and sediments as more likely food sources. These findings are consistent with gut content analyses. The results suggest that the close association of E. hylocoetes with R. maritima is the result of the vegetation providing the isopod with a refuge against fish predation as well as areas of increased food availability.
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The syntheses, characterization and fluorescence spectra of novel, octakis (alkylthiophthalocyanato) nickel (II) and palladium (II) complexes
- Ogunbayo, Taofeek Babatunde, Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Ogunbayo, Taofeek Babatunde , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263386 , vital:53623 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.03.009"
- Description: The syntheses, characterization and fluorescence studies of several {octakis(alkylthio)phthalocyanato} palladium(II) and nickel(II) complexes are presented. The absorption spectra of some of the complexes showed extra peaks which are attributable to non-planar distortion, the extent of which, was found to dependent on alkyl chain length. The fluorescence excitation spectra of the nickel(II) derivatives were not in agreement with their absorption spectra, owing to structural changes upon excitation. Fluorescence quantum yields were very low (more than 1%) for all complexes as a consequence of the open-shell electronic structures of nickel(II) and palladium(II).
- Full Text:
- Authors: Ogunbayo, Taofeek Babatunde , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263386 , vital:53623 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.03.009"
- Description: The syntheses, characterization and fluorescence studies of several {octakis(alkylthio)phthalocyanato} palladium(II) and nickel(II) complexes are presented. The absorption spectra of some of the complexes showed extra peaks which are attributable to non-planar distortion, the extent of which, was found to dependent on alkyl chain length. The fluorescence excitation spectra of the nickel(II) derivatives were not in agreement with their absorption spectra, owing to structural changes upon excitation. Fluorescence quantum yields were very low (more than 1%) for all complexes as a consequence of the open-shell electronic structures of nickel(II) and palladium(II).
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The synthesis and photophysicochemical behaviour of novel water-soluble cationic indium (III) phthalocyanine
- Durmus, Mahmut, Erdoğmuş, Ali, Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Durmus, Mahmut , Erdoğmuş, Ali , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263419 , vital:53626 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.01.008"
- Description: The syntheses and characterization of 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) and quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) are described. The ground state electronic absorption spectra, photophysics and photochemistry of both dyes in DMSO as well as that of the quaternized compound in aqueous solution are also presented. A comparison of the photophysical and photochemical parameters of the two dyes revealed that quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) was a better photosensitizer than its unquaternized counterpart. The quantum yield values of fluorescence (ΦF), triplet state formation (ΦT) and singlet oxygen formation (ΦΔ) for the cationic dye were found to be 0.03, 0.68 and 0.66 respectively in DMSO; these values were higher than those for 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III), which exhibited values of 0.02, 0.66 and 0.63, respectively in DMSO. The values for the cationic dye in aq. solution were 0.02, 0.59 and 0.56 respectively, suggesting that the water-soluble quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) offers potential as a photosensitizer in photodynamic therapy treatment.
- Full Text:
- Authors: Durmus, Mahmut , Erdoğmuş, Ali , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263419 , vital:53626 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.01.008"
- Description: The syntheses and characterization of 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) and quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) are described. The ground state electronic absorption spectra, photophysics and photochemistry of both dyes in DMSO as well as that of the quaternized compound in aqueous solution are also presented. A comparison of the photophysical and photochemical parameters of the two dyes revealed that quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) was a better photosensitizer than its unquaternized counterpart. The quantum yield values of fluorescence (ΦF), triplet state formation (ΦT) and singlet oxygen formation (ΦΔ) for the cationic dye were found to be 0.03, 0.68 and 0.66 respectively in DMSO; these values were higher than those for 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III), which exhibited values of 0.02, 0.66 and 0.63, respectively in DMSO. The values for the cationic dye in aq. solution were 0.02, 0.59 and 0.56 respectively, suggesting that the water-soluble quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) offers potential as a photosensitizer in photodynamic therapy treatment.
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The synthesis and photophysicochemical properties of low-symmetry zinc phthalocyanine analogues
- Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263397 , vital:53624 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.06.005"
- Description: The synthesis of a low-symmetry derivative, zinc mono-carboxy substituted phthalocyanine, ZnPc-COOH (4) has been reported. The photochemical and photophysical properties of ZnPc-COOH (4), ZnTMPyPc (5), ZnttbPc (6) and a previously synthesized low-symmetry derivative, ZnttbIPc (7), in various organic solvents are reported. The red-shifting of the spectra of 4 and 5 (relative to that of unsubstituted zinc phthalocyanine, ZnPc) is a function of the electron-donating sulfur-containing substituents attached to the periphery of the molecule. High triplet quantum yields (ФT) generally occur in response to substitution on the zinc phthalocyanine ring periphery. The highest ФT values and triplet lifetimes (τT) occur in DMSO for all derivatives as a result of the solvent's high viscosity. The strongly electron-withdrawing imido fused ring of ZnttbIPc (7) stabilizes it against photo-oxidative degradation relative to the other derivatives.
- Full Text:
- Authors: Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263397 , vital:53624 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.06.005"
- Description: The synthesis of a low-symmetry derivative, zinc mono-carboxy substituted phthalocyanine, ZnPc-COOH (4) has been reported. The photochemical and photophysical properties of ZnPc-COOH (4), ZnTMPyPc (5), ZnttbPc (6) and a previously synthesized low-symmetry derivative, ZnttbIPc (7), in various organic solvents are reported. The red-shifting of the spectra of 4 and 5 (relative to that of unsubstituted zinc phthalocyanine, ZnPc) is a function of the electron-donating sulfur-containing substituents attached to the periphery of the molecule. High triplet quantum yields (ФT) generally occur in response to substitution on the zinc phthalocyanine ring periphery. The highest ФT values and triplet lifetimes (τT) occur in DMSO for all derivatives as a result of the solvent's high viscosity. The strongly electron-withdrawing imido fused ring of ZnttbIPc (7) stabilizes it against photo-oxidative degradation relative to the other derivatives.
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The synthesis, cyclic voltammetry and spectroelectrochemical studies of Co (II) phthalocyanines tetra-substituted at the α and β positions with phenylthio groups
- Nombona, Nolwazi, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264529 , vital:53742 , xlink:href="https://doi.org/10.1016/j.dyepig.2008.06.002"
- Description: Non-peripherally substituted cobalt 1,(4)-(tetraphenylthiophthalocyaninato) and peripherally substituted cobalt 2,(3)-(tetraphenylthiophthalocyaninato) complexes were synthesized. Redox processes were observed at E1/2 = −1.44 V (I), −0.39 V (II), +0.37 V (III), +0.78 V (IV) and 1.15 V (V) for the non-peripherally substituted and at E1/2 = −1.42 V (I), −0.57, −0.39 V (II), +0.27 V (III), +0.79 V (IV) and +1.10 V (V) for the peripherally substituted complexes, respectively. The couples were assigned to CoIPc−2/CoIPc−3 (I), CoIIPc−2/CoIPc−2 (II), CoIIIPc−2/CoIIPc−2 (III), and CoIIIPc−1/CoIIIPc−2 (IV) using spectroelectrochemistry. The last process (V) could not be ascertained by spectroelectrochemistry but is associated with ring oxidation. Upon reduction or oxidation, the Q band of the non-peripherally substituted complex became less red shifted compared to that of its peripherally substituted counterpart.
- Full Text:
- Authors: Nombona, Nolwazi , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264529 , vital:53742 , xlink:href="https://doi.org/10.1016/j.dyepig.2008.06.002"
- Description: Non-peripherally substituted cobalt 1,(4)-(tetraphenylthiophthalocyaninato) and peripherally substituted cobalt 2,(3)-(tetraphenylthiophthalocyaninato) complexes were synthesized. Redox processes were observed at E1/2 = −1.44 V (I), −0.39 V (II), +0.37 V (III), +0.78 V (IV) and 1.15 V (V) for the non-peripherally substituted and at E1/2 = −1.42 V (I), −0.57, −0.39 V (II), +0.27 V (III), +0.79 V (IV) and +1.10 V (V) for the peripherally substituted complexes, respectively. The couples were assigned to CoIPc−2/CoIPc−3 (I), CoIIPc−2/CoIPc−2 (II), CoIIIPc−2/CoIIPc−2 (III), and CoIIIPc−1/CoIIIPc−2 (IV) using spectroelectrochemistry. The last process (V) could not be ascertained by spectroelectrochemistry but is associated with ring oxidation. Upon reduction or oxidation, the Q band of the non-peripherally substituted complex became less red shifted compared to that of its peripherally substituted counterpart.
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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.
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- 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.
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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.
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- 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.
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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.
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- 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.
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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.
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- 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.
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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.
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- 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.
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