Synthesis and photophysical properties of a covalently linked porphyrin-phthalocyanine conjugate
- Zhao, Zhixin, Ogunsipe, Abimbola O, Maree, M David, Nyokong, Tebello
- Authors: Zhao, Zhixin , Ogunsipe, Abimbola O , Maree, M David , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300358 , vital:57922 , xlink:href="https://doi.org/10.1142/S1088424605000253"
- Description: The synthesis of a phthalocyanine-porphyrin heteropentamer (zinc(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin)) zinc(II) phthalocyanine, (ZnPc-(ZnTPP)4), containing four units of zinc tetraphenylporphyrin linked to a central zinc phthalocyanine macrocycle via an ether linkage is reported. The photophysical parameters of the pentamer are reported in toluene and dimethyl sulfoxide (DMSO). The observed differences in the fluorescence behavior of the pentamer in the two solvents is explained in terms of emission from different states; charge transfer state in DMSO and locally excited state in toluene. The rate constants for fluorescence, intersystem crossing, internal conversion, and of charge and energy transfer are reported for the pentamer. Quantum yields for fluorescence, internal conversion, triplet state and of charge and energy transfer are also reported for the pentamer, ZnPc-(ZnTPP)4 and the mixture of ZnPc and ZnTPP. The latter two parameters are higher in the pentamer compared to a mixture containing ZnPc and ZnTPP.
- Full Text:
- Date Issued: 2005
- Authors: Zhao, Zhixin , Ogunsipe, Abimbola O , Maree, M David , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300358 , vital:57922 , xlink:href="https://doi.org/10.1142/S1088424605000253"
- Description: The synthesis of a phthalocyanine-porphyrin heteropentamer (zinc(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin)) zinc(II) phthalocyanine, (ZnPc-(ZnTPP)4), containing four units of zinc tetraphenylporphyrin linked to a central zinc phthalocyanine macrocycle via an ether linkage is reported. The photophysical parameters of the pentamer are reported in toluene and dimethyl sulfoxide (DMSO). The observed differences in the fluorescence behavior of the pentamer in the two solvents is explained in terms of emission from different states; charge transfer state in DMSO and locally excited state in toluene. The rate constants for fluorescence, intersystem crossing, internal conversion, and of charge and energy transfer are reported for the pentamer. Quantum yields for fluorescence, internal conversion, triplet state and of charge and energy transfer are also reported for the pentamer, ZnPc-(ZnTPP)4 and the mixture of ZnPc and ZnTPP. The latter two parameters are higher in the pentamer compared to a mixture containing ZnPc and ZnTPP.
- Full Text:
- Date Issued: 2005
Influence of cyclodextrins on the fluorescence, photostability and singlet oxygen quantum yields of zinc phthalocyanine and naphthalocyanine complexes
- Tau, Prudence, Ogunsipe, Abimbola O, Maree, Suzanne, Maree, M David, Nyokong, Tebello
- Authors: Tau, Prudence , Ogunsipe, Abimbola O , Maree, Suzanne , Maree, M David , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304775 , vital:58488 , xlink:href="https://doi.org/10.1142/S1088424603000562"
- Description: The effects of formation of cyclodextrin inclusion complexes on the photochemical and photophysical properties of zinc phthalocyanine (ZnPc) and various peripherally substituted zinc phthalocyanines as well as zinc naphthalocyanine (ZnNPc) are investigated. The cyclodextrins employed were the hydroxypropyl-γ-cyclodextrin and unsubstituted β-cyclodextrin. Job's plots were employed to confirm the stoichiometry of the inclusion complexes and showed 2:1 and 4:1 (cyclodextrin:phthalocyanine) inclusion behavior. The phthalocyanine inclusion complexes showed larger singlet oxygen quantum yield (ϕΔ) values when compared to the free phthalocyanines before inclusion, for complexes 1 (zinc naphthalocyanine), 2 (zinc tetranitrophthalocyanine) and 4 (zinc tetra-tert-butylphenoxyphthalocyanine). The fluorescence quantum yields generally remained unchanged following inclusion.
- Full Text:
- Date Issued: 2003
- Authors: Tau, Prudence , Ogunsipe, Abimbola O , Maree, Suzanne , Maree, M David , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304775 , vital:58488 , xlink:href="https://doi.org/10.1142/S1088424603000562"
- Description: The effects of formation of cyclodextrin inclusion complexes on the photochemical and photophysical properties of zinc phthalocyanine (ZnPc) and various peripherally substituted zinc phthalocyanines as well as zinc naphthalocyanine (ZnNPc) are investigated. The cyclodextrins employed were the hydroxypropyl-γ-cyclodextrin and unsubstituted β-cyclodextrin. Job's plots were employed to confirm the stoichiometry of the inclusion complexes and showed 2:1 and 4:1 (cyclodextrin:phthalocyanine) inclusion behavior. The phthalocyanine inclusion complexes showed larger singlet oxygen quantum yield (ϕΔ) values when compared to the free phthalocyanines before inclusion, for complexes 1 (zinc naphthalocyanine), 2 (zinc tetranitrophthalocyanine) and 4 (zinc tetra-tert-butylphenoxyphthalocyanine). The fluorescence quantum yields generally remained unchanged following inclusion.
- Full Text:
- Date Issued: 2003
Photophysics and photochemistry of octaglucosylated zinc phthalocyanine derivatives
- Iqbal, Zafar, Ogunsipe, Abimbola, Nyokong, Tebello, Lyubimtsev, Alexey, Hanack, Michael, Ziegler, Thomas
- Authors: Iqbal, Zafar , Ogunsipe, Abimbola , Nyokong, Tebello , Lyubimtsev, Alexey , Hanack, Michael , Ziegler, Thomas
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244416 , vital:51255 , xlink:href="https://doi.org/10.1142/S1088424612500630"
- Description: The ground state electronic absorption spectra, photophysics and photochemistry of amphiphilic octaglucosylated zinc phthalocyanines containing oxygen or sulfur bridges are presented. Triplet quantum yield values for the two dyes (in DMF and DMSO) vary between 0.71 and 0.84, while singlet quantum yield values lie between 0.63 and 0.75. Fluorescence lifetimes were determined experimentally by time correlated single photon counting and semi-empirically by fluorescence quenching techniques; and values from both methods were within the same range. Kinetic data were obtained for the quenching of the triplet state of the phthalocyanines by ground state molecular oxygen; the bimolecular collisional quenching rate constant range between 2.35 × 108 and 1.13 × 109 M-1.s-1. These values suggest that triplet states of the dyes are effectively quenched by ground molecular oxygen.
- Full Text:
- Date Issued: 2012
- Authors: Iqbal, Zafar , Ogunsipe, Abimbola , Nyokong, Tebello , Lyubimtsev, Alexey , Hanack, Michael , Ziegler, Thomas
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/244416 , vital:51255 , xlink:href="https://doi.org/10.1142/S1088424612500630"
- Description: The ground state electronic absorption spectra, photophysics and photochemistry of amphiphilic octaglucosylated zinc phthalocyanines containing oxygen or sulfur bridges are presented. Triplet quantum yield values for the two dyes (in DMF and DMSO) vary between 0.71 and 0.84, while singlet quantum yield values lie between 0.63 and 0.75. Fluorescence lifetimes were determined experimentally by time correlated single photon counting and semi-empirically by fluorescence quenching techniques; and values from both methods were within the same range. Kinetic data were obtained for the quenching of the triplet state of the phthalocyanines by ground state molecular oxygen; the bimolecular collisional quenching rate constant range between 2.35 × 108 and 1.13 × 109 M-1.s-1. These values suggest that triplet states of the dyes are effectively quenched by ground molecular oxygen.
- Full Text:
- Date Issued: 2012
Effects of central metal on the photophysical and photochemical properties of non-transition metal sulfophthalocyanine
- Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289337 , vital:56623 , xlink:href="https://doi.org/10.1142/S1088424605000186"
- Description: The photophysical and photochemical properties and quenching (by 1,4-benzoquinone) of metallophthalocyanine sulfonates of aluminium (AlPcSmix), zinc (ZnPcSmix), silicon (SiPcSmix), germanium (GePcSmix) and tin (SnPcSmix) are presented. The quantum yield values of fluorescence (ΦF), triplet state (ΦT), singlet oxygen (ΦΔ) and photodegradation (Φd) were determined and the observed trends in their variation among the complexes discussed in terms of aggregation and the heavy atom effect. 1,4-benzoquinone effectively quenched the fluorescence of the complexes. Quenching analyses gave positive deviations from Stern-Volmer behavior, suggesting the existence of static quenching in addition to dynamic quenching. The static and dynamic components of the quenching were separated using a modified Stern-Volmer equation and the “sphere of action quenching model”. The quenching constant was found to be a function of the radius of the central metal ion.
- Full Text:
- Date Issued: 2005
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289337 , vital:56623 , xlink:href="https://doi.org/10.1142/S1088424605000186"
- Description: The photophysical and photochemical properties and quenching (by 1,4-benzoquinone) of metallophthalocyanine sulfonates of aluminium (AlPcSmix), zinc (ZnPcSmix), silicon (SiPcSmix), germanium (GePcSmix) and tin (SnPcSmix) are presented. The quantum yield values of fluorescence (ΦF), triplet state (ΦT), singlet oxygen (ΦΔ) and photodegradation (Φd) were determined and the observed trends in their variation among the complexes discussed in terms of aggregation and the heavy atom effect. 1,4-benzoquinone effectively quenched the fluorescence of the complexes. Quenching analyses gave positive deviations from Stern-Volmer behavior, suggesting the existence of static quenching in addition to dynamic quenching. The static and dynamic components of the quenching were separated using a modified Stern-Volmer equation and the “sphere of action quenching model”. The quenching constant was found to be a function of the radius of the central metal ion.
- Full Text:
- Date Issued: 2005
Novel gallium (III) phthalocyanine derivatives–Synthesis, photophysics and photochemistry
- Chauke, Vongani, Ogunsipe, Abimbola, Durmus, Mahmut, Nyokong, Tebello
- Authors: Chauke, Vongani , Ogunsipe, Abimbola , Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283118 , vital:55912 , xlink:href="https://doi.org/10.1016/j.poly.2007.01.016"
- Description: The syntheses of gallium(III) chloride phthalocyanine {(Cl)GaPc}, octaphenoxyphthalocyaninato gallium(III) chloride {(Cl)GaOPPc} and octakis(4-tert-butylphenoxy)phthalocyaninato gallium(III) chloride {(Cl)GaOTBPPc}; as well as their photophysical and photochemical parameters are hereby presented. Fluorescence quantum yields do not vary much among the three metallophthalocyanines (MPcs); therefore it was concluded that the effect of the substituents is not significant amongst (Cl)GaPc, (Cl)GaOPPc and (Cl)GaOTBPPc. Solvents effects, however, had an effect on the results. Triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. We have also reported photodegradation and singlet oxygen quantum yields. There was no clear correlation between the later parameters. It was, however, established that the three MPcs were stable.
- Full Text:
- Date Issued: 2007
- Authors: Chauke, Vongani , Ogunsipe, Abimbola , Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283118 , vital:55912 , xlink:href="https://doi.org/10.1016/j.poly.2007.01.016"
- Description: The syntheses of gallium(III) chloride phthalocyanine {(Cl)GaPc}, octaphenoxyphthalocyaninato gallium(III) chloride {(Cl)GaOPPc} and octakis(4-tert-butylphenoxy)phthalocyaninato gallium(III) chloride {(Cl)GaOTBPPc}; as well as their photophysical and photochemical parameters are hereby presented. Fluorescence quantum yields do not vary much among the three metallophthalocyanines (MPcs); therefore it was concluded that the effect of the substituents is not significant amongst (Cl)GaPc, (Cl)GaOPPc and (Cl)GaOTBPPc. Solvents effects, however, had an effect on the results. Triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. We have also reported photodegradation and singlet oxygen quantum yields. There was no clear correlation between the later parameters. It was, however, established that the three MPcs were stable.
- Full Text:
- Date Issued: 2007
Microwave synthesis and photophysics of new tetrasulfonated tin (II) macrocycles
- Khene, Samson, Ogunsipe, Abimbola, Antunes, Edith M, Nyokong, Tebello
- Authors: Khene, Samson , Ogunsipe, Abimbola , Antunes, Edith M , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281269 , vital:55708 , xlink:href="https://doi.org/10.1142/S108842460700014X"
- Description: This work reports on the microwave synthesis of tetrasulfonated tin phthalocyanine and tetrasulfonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (more than 1:8) of 4-sulfophthalic acid to urea. Both complexes are aggregated in aqueous media, but can be partly or fully disaggregated by the addition of Triton X-100. The α,β,γ-tetrabenzcorrole complex has lower triplet life times and yields, while the binding constant and quenching (of bovine serum albumin) constant are lower for α,β,γ-tetrabenzcorrole compared to tetrasulfonated tin phthalocyanine.
- Full Text:
- Date Issued: 2007
- Authors: Khene, Samson , Ogunsipe, Abimbola , Antunes, Edith M , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281269 , vital:55708 , xlink:href="https://doi.org/10.1142/S108842460700014X"
- Description: This work reports on the microwave synthesis of tetrasulfonated tin phthalocyanine and tetrasulfonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (more than 1:8) of 4-sulfophthalic acid to urea. Both complexes are aggregated in aqueous media, but can be partly or fully disaggregated by the addition of Triton X-100. The α,β,γ-tetrabenzcorrole complex has lower triplet life times and yields, while the binding constant and quenching (of bovine serum albumin) constant are lower for α,β,γ-tetrabenzcorrole compared to tetrasulfonated tin phthalocyanine.
- Full Text:
- Date Issued: 2007
Photophysical, photochemical and bovine serum albumin binding studies on water-soluble gallium (III) phthalocyanine derivatives
- Ogunsipe, Abimbola, Nyokong, Tebello, Durmus, Mahmut
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello , Durmus, Mahmut
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271239 , vital:54524 , xlink:href="https://doi.org/10.1142/S1088424607000746"
- Description: Spectral, photophysical, photochemical and bovine serum albumin binding studies on some gallium(III) derivatives - {1,(4)-(tetrapyridyloxyphthalocyaninato)gallium(III), (αGaPc); 2,(3)-(tetrapyridyloxyphthalocyaninato)gallium(III), (βGaPc); and their quaternized derivatives: QαGaPc and QβGaPc)} are hereby presented. β-Substituted complexes are more fluorescent, but show lower tendencies to undergo intersystem crossing than the α-substituted, as judged by their fluorescence and triplet quantum yield values. The quaternized derivatives (QGaPc) are water-soluble and non-aggregated, which makes them potential photosensitizers of choice for photodynamic therapy applications; these amphiphilic compounds also bind strongly to bovine serum albumin in 1:1 stoichiometries, and with binding constants (Kb) in the order of 106 M−1.
- Full Text:
- Date Issued: 2007
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello , Durmus, Mahmut
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271239 , vital:54524 , xlink:href="https://doi.org/10.1142/S1088424607000746"
- Description: Spectral, photophysical, photochemical and bovine serum albumin binding studies on some gallium(III) derivatives - {1,(4)-(tetrapyridyloxyphthalocyaninato)gallium(III), (αGaPc); 2,(3)-(tetrapyridyloxyphthalocyaninato)gallium(III), (βGaPc); and their quaternized derivatives: QαGaPc and QβGaPc)} are hereby presented. β-Substituted complexes are more fluorescent, but show lower tendencies to undergo intersystem crossing than the α-substituted, as judged by their fluorescence and triplet quantum yield values. The quaternized derivatives (QGaPc) are water-soluble and non-aggregated, which makes them potential photosensitizers of choice for photodynamic therapy applications; these amphiphilic compounds also bind strongly to bovine serum albumin in 1:1 stoichiometries, and with binding constants (Kb) in the order of 106 M−1.
- Full Text:
- Date Issued: 2007
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:
- Date Issued: 2009
- 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:
- Date Issued: 2009
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
Photophysical and photochemical studies of sulphonated non-transition metal phthalocyanines in aqueous and non-aqueous media
- Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289271 , vital:56614 , xlink:href="https://doi.org/10.1016/j.jphotochem.2005.03.001"
- Description: The photophysical and photochemical parameters for mixed sulphonated metallophthalocyanine complexes (AlPcSmix, SiPcSmix, GePcSmix, SnPcSmix, and ZnPcSmix) are reported in phosphate buffer saline (PBS, pH 7.4), PBS containing the surfactant Triton X-100, and in dimethylsulphoxide (DMSO). The ground state spectra of SiPcSmix, GePcSmix and SnPcSmix show splitting of the Q-band in DMSO, but the fluorescence spectra have only one band, suggesting that only some components of the mixed complexes fluoresce. In general the quantum yields of fluorescence (ΦF) were smaller in DMSO compared to the aqueous solvents, while quantum yields of triplet state (ΦT) were larger in DMSO. Triplet lifetimes were much lower in aqueous solutions (compared to DMSO) due to the fact that water absorbs strongly around 1108 nm, which corresponds to the triplet energy of a metallophthalocyanine complex. The MPcSmix complexes quenched hydroquinone, and the Stern–Volmer constants follow the order: AlPcSmix > SiPcSmix > GePcSmix > ZnPcSmix > SnPcSmix which is the order of the extinction coefficients (of the low energy band for complexes with split Q-band) of these molecules. The rate constants for fluorescence, intersystem crossing, internal conversion, and photodegradation were determined from the hydroquinone quenching data.
- Full Text:
- Date Issued: 2005
- Authors: Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2005
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289271 , vital:56614 , xlink:href="https://doi.org/10.1016/j.jphotochem.2005.03.001"
- Description: The photophysical and photochemical parameters for mixed sulphonated metallophthalocyanine complexes (AlPcSmix, SiPcSmix, GePcSmix, SnPcSmix, and ZnPcSmix) are reported in phosphate buffer saline (PBS, pH 7.4), PBS containing the surfactant Triton X-100, and in dimethylsulphoxide (DMSO). The ground state spectra of SiPcSmix, GePcSmix and SnPcSmix show splitting of the Q-band in DMSO, but the fluorescence spectra have only one band, suggesting that only some components of the mixed complexes fluoresce. In general the quantum yields of fluorescence (ΦF) were smaller in DMSO compared to the aqueous solvents, while quantum yields of triplet state (ΦT) were larger in DMSO. Triplet lifetimes were much lower in aqueous solutions (compared to DMSO) due to the fact that water absorbs strongly around 1108 nm, which corresponds to the triplet energy of a metallophthalocyanine complex. The MPcSmix complexes quenched hydroquinone, and the Stern–Volmer constants follow the order: AlPcSmix > SiPcSmix > GePcSmix > ZnPcSmix > SnPcSmix which is the order of the extinction coefficients (of the low energy band for complexes with split Q-band) of these molecules. The rate constants for fluorescence, intersystem crossing, internal conversion, and photodegradation were determined from the hydroquinone quenching data.
- Full Text:
- Date Issued: 2005
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:
- Date Issued: 2009
- 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:
- Date Issued: 2009
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:
- Date Issued: 2009
- 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:
- Date Issued: 2009
Synthesis, photophysical and photochemical studies on long chain zinc phthalocyanine derivatives
- Ogunsipe, Abimbola, Durmus, Mahmut, Atilla, Devrim, Gürek, Ayşe Gül, Ahsen, Vefa, Nyokong, Tebello
- Authors: Ogunsipe, Abimbola , Durmus, Mahmut , Atilla, Devrim , Gürek, Ayşe Gül , Ahsen, Vefa , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/266019 , vital:53910 , xlink:href="https://doi.org/10.1016/j.synthmet.2008.06.007"
- Description: The synthesis and characterization of 2,9,16,23-chloro-3,10,17,24-triethyleneoxysulphanylphthalocyaninato zinc(II) (CTESZnPc) is described. The photophysics and photochemistry of CTESZnPc and those of tetrakis(triethyleneoxysulphanyl)zinc phthalocyanine (TTESZnPc) and octakis(triethyleneoxysulphanyl)zinc phthalocyanine (OTESZnPc), are presented and compared with those of unsubstituted zinc phthalocyanine (ZnPc). The presence of triethyleneoxysulphanyl substituents on the ZnPc ring gave rise to higher values of singlet oxygen (ΦΔ) and photodegradation (ΦPd) quantum yields in DMF. However, TTESZnPc, OTESZnPc and CTESZnPc are less fluorescent than ZnPc, judging from their fluorescence quantum yield (ΦF) values. Fluorescence was lower in toluene than in DMF due to aggregation in the former solvent. Triplet quantum yield (ΦT) values were found to increase with the presence of substituents on the ZnPc ring, while triplet lifetimes (τT) were found to vary linearly with the logarithms of solvent viscosities. The fluorescences of the substituted ZnPc complexes were effectively quenched by benzoquinone (BQ), and the quenching data analyzed by the Stern–Volmer equation. The Stern–Volmer constants and the diffusion-controlled bimolecular rate constants were calculated.
- Full Text:
- Date Issued: 2008
- Authors: Ogunsipe, Abimbola , Durmus, Mahmut , Atilla, Devrim , Gürek, Ayşe Gül , Ahsen, Vefa , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/266019 , vital:53910 , xlink:href="https://doi.org/10.1016/j.synthmet.2008.06.007"
- Description: The synthesis and characterization of 2,9,16,23-chloro-3,10,17,24-triethyleneoxysulphanylphthalocyaninato zinc(II) (CTESZnPc) is described. The photophysics and photochemistry of CTESZnPc and those of tetrakis(triethyleneoxysulphanyl)zinc phthalocyanine (TTESZnPc) and octakis(triethyleneoxysulphanyl)zinc phthalocyanine (OTESZnPc), are presented and compared with those of unsubstituted zinc phthalocyanine (ZnPc). The presence of triethyleneoxysulphanyl substituents on the ZnPc ring gave rise to higher values of singlet oxygen (ΦΔ) and photodegradation (ΦPd) quantum yields in DMF. However, TTESZnPc, OTESZnPc and CTESZnPc are less fluorescent than ZnPc, judging from their fluorescence quantum yield (ΦF) values. Fluorescence was lower in toluene than in DMF due to aggregation in the former solvent. Triplet quantum yield (ΦT) values were found to increase with the presence of substituents on the ZnPc ring, while triplet lifetimes (τT) were found to vary linearly with the logarithms of solvent viscosities. The fluorescences of the substituted ZnPc complexes were effectively quenched by benzoquinone (BQ), and the quenching data analyzed by the Stern–Volmer equation. The Stern–Volmer constants and the diffusion-controlled bimolecular rate constants were calculated.
- Full Text:
- Date Issued: 2008
Effects of substituents and solvents on the photochemical properties of zinc phthalocyanine complexes and their protonated derivatives
- Ogunsipe, Abimbola Olukayode, Nyokong, Tebello
- Authors: Ogunsipe, Abimbola Olukayode , Nyokong, Tebello
- Date: 2004
- Language: English
- Type: Article
- Identifier: vital:6585 , http://hdl.handle.net/10962/d1004161
- Description: Zinc phthalocyanine derivatives containing various ring substituents and axial ligands were studied with respect to the effect of substituents on protonation. Aggregation resulted in failure of some of the ZnPc derivatives to protonate. In fact addition of protonating agents to aggregated ZnPc derivatives resulted in increase in aggregation followed by slow degradation. Axial ligands were lost on protonation. Photobleaching, fluorescence and singlet oxygen quantum yields of the protonated derivatives were compared with those of the unprotonated derivatives. In all cases protonation decreases the singlet oxygen and fluorescence quantum yields. However, photobleaching quantum yields decreased (i.e. stability increased) for the protonated derivatives except when axial ligands were present, where protonation resulted in decrease in stability.
- Full Text:
- Date Issued: 2004
- Authors: Ogunsipe, Abimbola Olukayode , Nyokong, Tebello
- Date: 2004
- Language: English
- Type: Article
- Identifier: vital:6585 , http://hdl.handle.net/10962/d1004161
- Description: Zinc phthalocyanine derivatives containing various ring substituents and axial ligands were studied with respect to the effect of substituents on protonation. Aggregation resulted in failure of some of the ZnPc derivatives to protonate. In fact addition of protonating agents to aggregated ZnPc derivatives resulted in increase in aggregation followed by slow degradation. Axial ligands were lost on protonation. Photobleaching, fluorescence and singlet oxygen quantum yields of the protonated derivatives were compared with those of the unprotonated derivatives. In all cases protonation decreases the singlet oxygen and fluorescence quantum yields. However, photobleaching quantum yields decreased (i.e. stability increased) for the protonated derivatives except when axial ligands were present, where protonation resulted in decrease in stability.
- Full Text:
- Date Issued: 2004
Solvent effects on the photochemical and fluorescence properties of zinc phthalocyanine derivatives
- Ogunsipe, Abimbola Olukayode, Maree, D, Nyokong, Tebello
- Authors: Ogunsipe, Abimbola Olukayode , Maree, D , Nyokong, Tebello
- Date: 2003
- Language: English
- Type: Article
- Identifier: vital:6586 , http://hdl.handle.net/10962/d1004162 , http://dx.doi.org/10.1016/S0022-2860(03)00155-8
- Description: The effects of solvents on the singlet oxygen, photobleaching and fluorescence quantum yields for zinc phthalocyanine (ZnPc) and its derivatives; (pyridino)zinc phthalocyanine ((py)ZnPc), zinc octaphenoxyphthalocyanine (ZnOPPc) and zinc octaestronephthalocyanine (ZnOEPc), is presented. The effects of the solvents on the ground state spectra are also discussed. The largest red shift of the Q band was observed in aromatic solvents, the highest shift being observed for 1-chloronaphthalene. Higher singlet fluorescence quantum yields were observed in THF for ZnPc and ZnOPPC. Also in the same solvent phototransformation rather than photobleaching was observed for ZnOPPc. Split Q band in the emission and excitation spectra of ZnOPPc was observed in some solvents and this is explained in terms of the lowering of symmetry following excitation.
- Full Text:
- Date Issued: 2003
- Authors: Ogunsipe, Abimbola Olukayode , Maree, D , Nyokong, Tebello
- Date: 2003
- Language: English
- Type: Article
- Identifier: vital:6586 , http://hdl.handle.net/10962/d1004162 , http://dx.doi.org/10.1016/S0022-2860(03)00155-8
- Description: The effects of solvents on the singlet oxygen, photobleaching and fluorescence quantum yields for zinc phthalocyanine (ZnPc) and its derivatives; (pyridino)zinc phthalocyanine ((py)ZnPc), zinc octaphenoxyphthalocyanine (ZnOPPc) and zinc octaestronephthalocyanine (ZnOEPc), is presented. The effects of the solvents on the ground state spectra are also discussed. The largest red shift of the Q band was observed in aromatic solvents, the highest shift being observed for 1-chloronaphthalene. Higher singlet fluorescence quantum yields were observed in THF for ZnPc and ZnOPPC. Also in the same solvent phototransformation rather than photobleaching was observed for ZnOPPc. Split Q band in the emission and excitation spectra of ZnOPPc was observed in some solvents and this is explained in terms of the lowering of symmetry following excitation.
- Full Text:
- Date Issued: 2003
Syntheses and photophysics of new phthalocyanine derivatives of zinc, cadmium and mercury
- Chidawanyika, Wadzanai, Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283940 , vital:56005 , xlink:href="https://doi.org/10.1039/B615663K"
- Description: The syntheses of novel tetra{2,(3)-pyridyloxyphthalocyaninato} complexes of zinc, cadmium and mercury (TPyZnPc, TPyCdPc and TPyHgPc) are presented. Their spectral and photophysical properties (as well as those of their unsubstituted counterparts: ZnPc, CdPc and HgPc) are investigated. TPyZnPc and TPyCdPc are aggregated in non-coordinating solvents such as chloroform, while TPyHgPc is demetallated, as evident from their respective absorption spectra. The trends in fluorescence (ΦF), triplet (ΦT) and singlet oxygen (ΦΔ) quantum yields are explained in terms of relative strengths of spin–orbit coupling induced by the respective central metal ions in the complexes. The effect of the pyridyloxy substituents is a decrease in ΦF and an increase in ΦT values. The complexes are less fluorescent in DMSO but possess higher ΦT, triplet lifetimes (τT) and ΦΔ therein.
- Full Text:
- Date Issued: 2007
- Authors: Chidawanyika, Wadzanai , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283940 , vital:56005 , xlink:href="https://doi.org/10.1039/B615663K"
- Description: The syntheses of novel tetra{2,(3)-pyridyloxyphthalocyaninato} complexes of zinc, cadmium and mercury (TPyZnPc, TPyCdPc and TPyHgPc) are presented. Their spectral and photophysical properties (as well as those of their unsubstituted counterparts: ZnPc, CdPc and HgPc) are investigated. TPyZnPc and TPyCdPc are aggregated in non-coordinating solvents such as chloroform, while TPyHgPc is demetallated, as evident from their respective absorption spectra. The trends in fluorescence (ΦF), triplet (ΦT) and singlet oxygen (ΦΔ) quantum yields are explained in terms of relative strengths of spin–orbit coupling induced by the respective central metal ions in the complexes. The effect of the pyridyloxy substituents is a decrease in ΦF and an increase in ΦT values. The complexes are less fluorescent in DMSO but possess higher ΦT, triplet lifetimes (τT) and ΦΔ therein.
- Full Text:
- Date Issued: 2007
Synthesis, photochemical and photophysical properties of gallium and indium phthalocyanine derivatives
- Authors: Chauke, Vongani Portia
- Date: 2008
- Subjects: Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4375 , http://hdl.handle.net/10962/d1005040 , Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Description: The syntheses of octasubstituted and unsusbstitituted Gallium(III) chloride and indium(III) chloride phthalocyanines (GaPc and InPc), their photophysical, photochemical and nonlinear optical parameters are hereby presented. The photocatalytic oxidation of 1-hexene using the synthesized GaPc and InPc complexes as well as electrochemical characterization is also presented in this thesis. Fluorescence quantum yields do not vary much among the four Ga complexes, except for complex 21c; therefore it was concluded that the effect of substituents is not significant among them. Solvents however, had an effect on the results. Lower Φ[subscript F] values were obtained in low viscosity solvents like toluene, relative to highly viscous solvents, such as DMSO. The triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. Photodegradation and singlet oxygen quantum yields have also been reported. There was no clear correlation between the latter parameters. It was however established that the four gallium MPcs were stable, within the allowed stability range for phthalocyanines. High quantum yields of triplet state (Φ[subscript T] ranging from 0.70 to 0.91 in dimethysulfoxide, DMSO) and singlet oxygen generation (Φ[subscript greek capital letter delta], ranging from 0.61 to 0.79 in DMSO) were obtained. Short triplet lifetimes 50 to 60 μs were obtained in DMSO). Calculated non-linear parameters of these complexes are compared with those of the corresponding GaPc derivatives and tetrasubstituted GaPc and InPc complexes. The optical limiting threshold intensity (I[subscript lim]) values for the InPc and GaPc derivatives were calculated and compared with those of corresponding tetrasubstituted InPc and GaPc complexes. The octasubstituted were found to be better optical limiters. Photocatalytic oxidation of 1-hexene by GaPc (21a-c) and InPc (22a-c) derivatives is also presented. The photocatalytic oxidation products for 1-hexene were 1,2- epoxyhexane and 1-hexen-3-ol. The % conversion values of 1-hexene and % selectivity of 1,2-epoxyhexane were generally higher for InPc derivatives. Even though InPc derivatives showed better photocatalytic results than GaPc derivatives, the former were less stable relative to the latter. Both type I and type II mechanism were implicated in the photocatalysis mechanism.
- Full Text:
- Date Issued: 2008
- Authors: Chauke, Vongani Portia
- Date: 2008
- Subjects: Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4375 , http://hdl.handle.net/10962/d1005040 , Phthalocyanines , Photochemotherapy , Electrochemistry , Gallium , Indium
- Description: The syntheses of octasubstituted and unsusbstitituted Gallium(III) chloride and indium(III) chloride phthalocyanines (GaPc and InPc), their photophysical, photochemical and nonlinear optical parameters are hereby presented. The photocatalytic oxidation of 1-hexene using the synthesized GaPc and InPc complexes as well as electrochemical characterization is also presented in this thesis. Fluorescence quantum yields do not vary much among the four Ga complexes, except for complex 21c; therefore it was concluded that the effect of substituents is not significant among them. Solvents however, had an effect on the results. Lower Φ[subscript F] values were obtained in low viscosity solvents like toluene, relative to highly viscous solvents, such as DMSO. The triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. Photodegradation and singlet oxygen quantum yields have also been reported. There was no clear correlation between the latter parameters. It was however established that the four gallium MPcs were stable, within the allowed stability range for phthalocyanines. High quantum yields of triplet state (Φ[subscript T] ranging from 0.70 to 0.91 in dimethysulfoxide, DMSO) and singlet oxygen generation (Φ[subscript greek capital letter delta], ranging from 0.61 to 0.79 in DMSO) were obtained. Short triplet lifetimes 50 to 60 μs were obtained in DMSO). Calculated non-linear parameters of these complexes are compared with those of the corresponding GaPc derivatives and tetrasubstituted GaPc and InPc complexes. The optical limiting threshold intensity (I[subscript lim]) values for the InPc and GaPc derivatives were calculated and compared with those of corresponding tetrasubstituted InPc and GaPc complexes. The octasubstituted were found to be better optical limiters. Photocatalytic oxidation of 1-hexene by GaPc (21a-c) and InPc (22a-c) derivatives is also presented. The photocatalytic oxidation products for 1-hexene were 1,2- epoxyhexane and 1-hexen-3-ol. The % conversion values of 1-hexene and % selectivity of 1,2-epoxyhexane were generally higher for InPc derivatives. Even though InPc derivatives showed better photocatalytic results than GaPc derivatives, the former were less stable relative to the latter. Both type I and type II mechanism were implicated in the photocatalysis mechanism.
- Full Text:
- Date Issued: 2008
African Oral Literature and the Humanities: Challenges and Prospects
- Authors: Enongene Mirabeau Sone
- Date: 2018
- Subjects: folklore; oral literature; humanities; Africa; education; place; education; universities; curriculum
- Language: English
- Type: Journal Article
- Identifier: http://hdl.handle.net/11260/2664 , vital:42311
- Description: This paper examines the origin, evolution and emergence of folklore (oral literature) as an academic discipline in Africa and its place in the humanities. It draws attention to the richness of indigenous knowledge contained in oral literature and demonstrates how the ethical and moral gap in the existing educational system can be filled by the moral precepts embedded in oral literature. The paper argues that African oral literature has not received the attention it deserves among other disciplines of the humanities in institutions of higher learning in Africa. It concludes that any discussion on African literature will be incomplete, and indeed irrelevant, if it does not equally give adequate attention to the oral literature of the African people. As a result, a new curriculum and pedagogy must be designed to give pride of place to folklore and oral literature as the best repository of our cultural norms and values especially in African tertiary institutions.
- Full Text:
- Authors: Enongene Mirabeau Sone
- Date: 2018
- Subjects: folklore; oral literature; humanities; Africa; education; place; education; universities; curriculum
- Language: English
- Type: Journal Article
- Identifier: http://hdl.handle.net/11260/2664 , vital:42311
- Description: This paper examines the origin, evolution and emergence of folklore (oral literature) as an academic discipline in Africa and its place in the humanities. It draws attention to the richness of indigenous knowledge contained in oral literature and demonstrates how the ethical and moral gap in the existing educational system can be filled by the moral precepts embedded in oral literature. The paper argues that African oral literature has not received the attention it deserves among other disciplines of the humanities in institutions of higher learning in Africa. It concludes that any discussion on African literature will be incomplete, and indeed irrelevant, if it does not equally give adequate attention to the oral literature of the African people. As a result, a new curriculum and pedagogy must be designed to give pride of place to folklore and oral literature as the best repository of our cultural norms and values especially in African tertiary institutions.
- Full Text:
African Oral Literature and the Humanities: Challenges and Prospects
- Authors: Enongene Mirabeau Sone
- Date: 2018
- Subjects: folklore; oral literature; humanities; Africa; education; place; education; universities; curriculum
- Language: English
- Type: Journal Article
- Identifier: http://hdl.handle.net/11260/2656 , vital:42310
- Description: This paper examines the origin, evolution and emergence of folklore (oral literature) as an academic discipline in Africa and its place in the humanities. It draws attention to the richness of indigenous knowledge contained in oral literature and demonstrates how the ethical and moral gap in the existing educational system can be filled by the moral precepts embedded in oral literature. The paper argues that African oral literature has not received the attention it deserves among other disciplines of the humanities in institutions of higher learning in Africa. It concludes that any discussion on African literature will be incomplete, and indeed irrelevant, if it does not equally give adequate attention to the oral literature of the African people. As a result, a new curriculum and pedagogy must be designed to give pride of place to folklore and oral literature as the best repository of our cultural norms and values especially in African tertiary institutions.
- Full Text:
- Authors: Enongene Mirabeau Sone
- Date: 2018
- Subjects: folklore; oral literature; humanities; Africa; education; place; education; universities; curriculum
- Language: English
- Type: Journal Article
- Identifier: http://hdl.handle.net/11260/2656 , vital:42310
- Description: This paper examines the origin, evolution and emergence of folklore (oral literature) as an academic discipline in Africa and its place in the humanities. It draws attention to the richness of indigenous knowledge contained in oral literature and demonstrates how the ethical and moral gap in the existing educational system can be filled by the moral precepts embedded in oral literature. The paper argues that African oral literature has not received the attention it deserves among other disciplines of the humanities in institutions of higher learning in Africa. It concludes that any discussion on African literature will be incomplete, and indeed irrelevant, if it does not equally give adequate attention to the oral literature of the African people. As a result, a new curriculum and pedagogy must be designed to give pride of place to folklore and oral literature as the best repository of our cultural norms and values especially in African tertiary institutions.
- Full Text:
Photophysical and photochemical studies of non-transition metal phthalocyanine derivatives
- Ogunsipe, Abimbola Olukayode
- Authors: Ogunsipe, Abimbola Olukayode
- Date: 2005
- Subjects: Photochemotherapy Phthalocyanines Spectrum analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4445 , http://hdl.handle.net/10962/d1007721
- Description: A detailed photophysicochemical study of some non-transition metal (AI, Zn, Si, Ge, and Sn) metallophthalocyanine (MPc) derivatives is presented. The effects of substituents, central metal ions and solvents on the photophysical and photochemical properties are investigated and rationalized accordingly. The presence of peripheral substituents on the macrocycle enhances the yield of the triplet state. Near infra-red absorptions of the solvents reveal that solvents which absorb around 1100 nm and around 1270 nm, quench the triplet state of the MPc derivative and singlet oxygen, respectively. Although water has a high singlet oxygen quenching effect, the singlet oxygen quantum yield (Φ∆) value for sulphonated zinc phthalocyanine in water is still reasonably high at 0.48, which may provide an explanation for the efficient photosensitization by this molecule in photodynamic studies. The lowering of Φ∆ following protonation of the MPc macrocycle is attributed to the lowering of triplet energy to the level where energy transfer to ground state oxygen is no longer favourable. MPc inclusion complexes with cyclodextrins showed larger Φ∆ values when compared to the complexes before inclusion. Job's plots show that 2:1 and 4:1 (CD:MPc) complexes may be formed. Fluorescence quenching by electron donors and acceptors were analysed by StemVolmer relationship and the results used in determining fluorescence lifetimes of the complexes. Qualitative and quantitative interpretations of the interaction of sulphonated MPcs with bovine serum albumin (BSA) are provided in this thesis. 1:1 adducts were formed with BSA, but the binding feasibilities varied markedly. Spectral, photophysical and photochemical properties of the complexes are altered in the presence of BSA.
- Full Text:
- Date Issued: 2005
- Authors: Ogunsipe, Abimbola Olukayode
- Date: 2005
- Subjects: Photochemotherapy Phthalocyanines Spectrum analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4445 , http://hdl.handle.net/10962/d1007721
- Description: A detailed photophysicochemical study of some non-transition metal (AI, Zn, Si, Ge, and Sn) metallophthalocyanine (MPc) derivatives is presented. The effects of substituents, central metal ions and solvents on the photophysical and photochemical properties are investigated and rationalized accordingly. The presence of peripheral substituents on the macrocycle enhances the yield of the triplet state. Near infra-red absorptions of the solvents reveal that solvents which absorb around 1100 nm and around 1270 nm, quench the triplet state of the MPc derivative and singlet oxygen, respectively. Although water has a high singlet oxygen quenching effect, the singlet oxygen quantum yield (Φ∆) value for sulphonated zinc phthalocyanine in water is still reasonably high at 0.48, which may provide an explanation for the efficient photosensitization by this molecule in photodynamic studies. The lowering of Φ∆ following protonation of the MPc macrocycle is attributed to the lowering of triplet energy to the level where energy transfer to ground state oxygen is no longer favourable. MPc inclusion complexes with cyclodextrins showed larger Φ∆ values when compared to the complexes before inclusion. Job's plots show that 2:1 and 4:1 (CD:MPc) complexes may be formed. Fluorescence quenching by electron donors and acceptors were analysed by StemVolmer relationship and the results used in determining fluorescence lifetimes of the complexes. Qualitative and quantitative interpretations of the interaction of sulphonated MPcs with bovine serum albumin (BSA) are provided in this thesis. 1:1 adducts were formed with BSA, but the binding feasibilities varied markedly. Spectral, photophysical and photochemical properties of the complexes are altered in the presence of BSA.
- Full Text:
- Date Issued: 2005