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:
- 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:
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:
- 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.
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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:
- 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.
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