Photoelectrochemical characterization of electrodeposited ZnO thin films sensitized by octacarboxymetallophthalocyanine derivatives
- Authors: Idowu, Mopelola , Loewenstein, Thomas , Hastall, Andreas , Nyokong, Tebello , Schlettwein, Derck
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262655 , vital:53541 , xlink:href="https://doi.org/10.1142/S1088424610001854"
- Description: Hybrid thin films of crystalline zinc oxide (ZnO) modified by different octacarboxymetallophthalocyanines (MOCPc) were prepared by the readsorption method. Homogeneously blue or green thin films were formed. The photoelectrochemical characteristics of the electrodes were studied by time-resolved photocurrent measurements. Zinc(II) 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine (ZnOCPc) showed considerably large quantum efficiency in sensitization of ZnO, one of the highest quantum efficiencies obtained so far with phthalocyanine-type sensitizers on nanocrystalline ZnO films.
- Full Text:
- Date Issued: 2010
Spectroscopic behavior of cationic metallophthalocyanines in the presence of anionic quantum dots
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262699 , vital:53545 , xlink:href="https://doi.org/10.1016/j.saa.2009.10.050"
- Description: The interactions and spectroscopic properties between cationic zinc phthalocyanine derivatives (peripherally and non-peripherally tetrasubstituted and peripherally octa substituted with 2-diethylmethylaminoethylsulfanyl (βTZnPc, αTZnPc and βOZnPc)) and CdTe core quantum dots (QDs) capped with mercaptopropionic acid or thioglycolic acid (represented as CdTe@MPA and CdTe@TGA, respectively) have been studied in methanol:water mixture. Strong coupling of MPcs was deduced from the interaction since the UV–vis spectroscopic studies of the ground state complex formed on mixing both components showed loss of the phthalocyanine monomeric band with the formation of a dimeric band (spectrum of aggregated species). The dimerization constants were of the order of 104 M−1.
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- Date Issued: 2010
Interaction of water-soluble CdTe quantum dots with octacarboxy metallophthalocyanines
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264197 , vital:53708 , xlink:href="https://doi.org/10.1016/j.jlumin.2008.11.005"
- Description: Water-soluble CdTe quantum dots capped with L-cysteine (QD-CYS) were found to improve the photophysical and photochemical properties of octacarboxy metallophthalocyanine (MOCPc, M=Zn(II), Al(III)(OH), Ge(IV)(OH)2 and Si(IV)(OH)2) complexes. Increased diffusional interactions between the molecules and the ground-state molecular oxygen were established resulting from the increase in the triplet-state quantum yield and lifetimes of the MOCPcs in the presence of QD-CYS. Energy transfer occurred from QD-CYS to the MOCPcs upon excitation of QD-CYS. It was found that an efficient energy transfer process, which is not directly related to the amount of spectral overlap between the donor (QD-CYS) and the acceptor (MOCPc) can occur. Singlet oxygen via fluorescence resonance energy transfer (FRET) mechanism was produced in the QD-MPc mixture.
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- Date Issued: 2009
Photophysical, photochemical and electrochemical properties of water soluble silicon, titanium and zinc phthalocyanines
- Authors: Masilela, Nkosiphile , Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264496 , vital:53739 , xlink:href="https://doi.org/10.1016/j.jphotochem.2008.10.009"
- Description: The photophysical, and photochemical properties of titanium, silicon and zinc octacarboxy phthalocyanine (OTiOCPc, (OH)2SiOCPc and ZnOCPc) and their tetrasulfonated counterparts (OTiTSPc, (OH)2SiTSPc and ZnTSPc) in phosphate-buffer solution (PBS), pH 10 were studied. The tetrasulfonated derivatives were also studied in the presence of a surfactant, cremophore EL (CEL) due to their high aggregation tendency in aqueous solutions. Triplet quantum yields ranged from 0.20 to 0.48 for MOCPcs and 0.32–0.65 for MTSPcs in the presence of CEL and in pH 10. High triplet lifetimes were observed for ZnTSPc (270 μs, in the presence of CEL) or ZnOCPc (130 μs) compared to values ranging from 50 to 70 μs for the rest of the complexes.
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- Date Issued: 2009
Photophysicochemical and fluorescence quenching studies of tetra-and octa-carboxy substituted silicon and germanium phthalocyanines
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263500 , vital:53633 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.02.002"
- Description: Spectral, photophysical and photochemical properties of tetra- and octa-carboxy substituted metallophthalocyanines containing silicon and germanium as central metals ((OH)2GeTCPc, (OH)2SiTCPc, (OH)2GeOCPc and (OH)2SiOCPc) have been studied in dimethylsulfoxide (DMSO) and the trends in triplet, fluorescence, singlet oxygen quantum yields and triplet lifetimes are described for these compounds. The GePc derivatives exhibited high triplet quantum yields (ΦT = 0.79 for (OH)2GeOCPc and 0.82 for (OH)2GeTCPc compared to ΦT = 0.66 for (OH)2SiTCPc and 0.48 for (OH)2SiOCPc) due to the spin–orbit coupling induced by Ge(IV). The triplet lifetimes were higher for MOCPc (τT = 760 μs for (OH)2SiOCPc and 480 μs for (OH)2GeOCPc compared to τT = 210 μs for (OH)2SiTCPc and 260 μs for (OH)2GeTCPc). The fluorescent states of the metallophthalocyanine (MPc) complexes were effectively quenched by benzoquinone (BQ) and the quenching course was found to follow a diffusion-controlled (dynamic) bimolecular mechanism. Theoretical values of bimolecular rate constant for the interaction of the complexes with BQ were determined using the Stokes–Einstein–Smoluchowski model, and values together with the Stern–Volmer quenching constants were used in calculating the fluorescence lifetimes of the complexes.
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- Date Issued: 2009
Study of the photophysical behavior of tetrasulfonated metallophthalocyanines in the presence of CdTe quantum dots
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264138 , vital:53701 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: Förster resonance energy transfer (FRET) studies were carried out with CdTe quantum dots (QDs) synthesized in aqueous phase and various tetrasulfonated metallophthalocyanines (MPcS4, M = aluminum ((OH)AlPcS4), zinc (ZnPcS4), silicon ((OH)2SiPcS4) and germanium ((OH)2GePcS4) in a H2O:MeOH (1:1) solvent mixture. The QDs studied were capped with thioglycolic acid (TGA) or mercaptopropionic acid (MPA) with sizes ranging from 2.3 to 3.7 nm. Non-radiative energy transfer from QDs emission to MPcS4 complexes was observed. Study of the photophysics of the MPcs in the presence of the QDs revealed high triplet state quantum yields (ΦT, ranging from 0.41 to 0.85 in the presence of QDs), with corresponding long triplet state lifetimes (τT, which ranged from 140 to 610 μs in the presence of QDs) to allow for photosensitized reactions to occur. The efficiency of energy transfer and the donor–acceptor distance between the MPcs and the QDs were also evaluated.
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- Date Issued: 2009
Synthesis, photophysical and photochemical studies of water soluble cationic zinc phthalocyanine derivatives
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264245 , vital:53712 , xlink:href="https://doi.org/10.1016/j.poly.2008.11.021"
- Description: Peripherally and non-peripherally 2-diethylaminoethanethiol tetra-substituted zinc phthalocyanine (5a and 6a) and their quaternized derivatives (5b and 6b) have been synthesized and characterized. The quaternized derivatives (5b and 6b) show excellent solubility in aqueous medium. The photophysical and photochemical properties of the 2-diethylaminoethanethiol appended zinc phthalocyanine in dimethylsulfoxide (DMSO) for the non-ionic (5a and 6a) and in both DMSO and aqueous medium (phosphate buffered saline solution PBS, pH 7.4) (in the presence and absence of cremophore EL (CEL)) for the quaternized (5b and 6b) derivatives were studied and compared with that of the peripherally octa-substituted derivatives (7a and 7b). The complexes have intense absorption in the visible/near-IR region though the quaternized forms (5b, 6b and 7b) were slightly blue shifted and highly aggregate in aqueous solution. The triplet state quantum yields (ΦT) and the triplet lifetimes (τT) were found to be higher in DMSO (ΦT values ranged from 0.57 to 0.75 while τT values ranged from 190 to 220 μs in DMSO for all complexes) compared to aqueous medium (ΦT values ranged from 0.15 to 0.17 while τT values ranged from 20 to 70 μs in pH 7.4 buffer). Addition of cremophore EL in aqueous solution resulted in induced disaggregation leading to increased ΦT and τT.
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- Date Issued: 2009
Interaction of water-soluble thiol capped CdTe quantum dots and bovine serum albumin
- Authors: Idowu, Mopelola , Lamprecht, Emmanuel , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265974 , vital:53906 , xlink:href="https://doi.org/10.1016/j.jphotochem.2008.02.008"
- Description: Luminescent water-soluble CdTe quantum dots (QDs) capped with different thiol carboxylic acids were synthesized in aqueous medium and then cross linked to bovine serum albumin (BSA) with 1-ethyl3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC). Enhancement of fluorescence emission intensity occurred for QDs in the presence of bovine serum albumin (BSA, mixed or linked) signifying inhibition of non-radiative recombination of the surface vacancies. Fluorescence studies reveal a positive deviation behaviour suggesting the occurrence of static and dynamic mechanisms of quenching together which was accounted for by the modified Stern–Volmer equation.
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- Date Issued: 2008
Photoinduced energy transfer between water-soluble CdTe quantum dots and aluminium tetrasulfonated phthalocyanine
- Authors: Idowu, Mopelola , Chen, Ji-Yao , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268564 , vital:54210 , xlink:href="https://doi.org/10.1039/B707808K"
- Description: Thiol stabilized CdTe quantum dots (QDs) synthesized in aqueous phase were used as energy donors to aluminium tetrasulfonated phthalocyanine (AlTSPc) through fluorescence resonance energy transfer (FRET). Energy transfer occurred from the QDs to AlTSPc upon photoexcitation of the QDs. An enhancement in efficiency of energy transfer with the nature of the carboxylic thiol stabilizers on the QDs was observed. The results showed that for enhanced FRET to occur, the donor–acceptor distance has to be lower than the critical distance. The quenching constant K as well as the binding constant kb values were calculated suggesting strong interaction of the QDs with the AlTSPc. Study of the photophysics of AlTSPc in the presence of the QDs revealed a high triplet state yield, hence the possibility of using QDs in combination with phthalocyanines as photosensitizers in photodynamic therapy. The triplet state lifetimes of AlTSPc in the presence of the QDs were calculated and the lifetime in the presence of CdTe capped with 3-mercaptopropionic acid (MPA) was found to be the longest. MPA capped QD in a mixture with AlTSPc resulted in long triplet lifetime and high triplet yield of the latter, and high energy transfer efficiency, hence was found to be most suitable as a potential candidate for photodynamic therapy of cancer studies.
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- Date Issued: 2008
Photosensitizing properties of octacarboxy metallophthalocyanines in aqueous medium and their interaction with bovine serum albumin
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264552 , vital:53744 , xlink:href="https://doi.org/10.1016/j.jphotochem.2008.09.003"
- Description: Photosensitizing properties of aluminium, silicon, zinc and germanium octacarboxy phthalocyanines ((OH)AlOCPc, (OH)2SiOCPc, ZnOCPc and (OH)2GeOCPc) were studied in aqueous medium and in the presence of bovine serum albumin (BSA). Triplet quantum yields increased with increasing atomic number of the central metals of the metallophthalocyanine. The efficiency of singlet oxygen generation via energy transfer from the excited triplet state of the octacarboxy metallophthalocyanines (MOCPcs) to ground state oxygen increased markedly in the presence of BSA. The triplet state lifetimes of the MOCPc complexes in the presence of BSA were found to be longer than in the absence of BSA, ranging from 110 to 580 μs. These complexes bind readily to BSA. Stern–Volmer quenching constant KSV as well as the binding constant kb values were calculated. The probable mechanism of quenching of BSA fluorescence by the MOCPc complexes is by static quenching.
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- Date Issued: 2008
Spontaneous charge transfer between zinc tetramethyl-tetra-2, 3-pyridinoporphyrazine and CdTe and ZnS quantum dots
- Authors: Moeno, Sharon , Idowu, Mopelola , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/265997 , vital:53908 , xlink:href="https://doi.org/10.1016/j.ica.2008.02.048"
- Description: Zinc tetramethyl-tetra-2,3-pyridinoporphyrazine (ZnTmtppa(-2)) gets reduced to the ZnTmtppa(-3) species on interaction with CdTe QDs capped with 2-mercaptoethanol (2-ME) or thioglycolic acid (TGA) and ZnS QDs capped with 2-ME. The interaction occurs without photolysis. The fluorescence of the QDs is quenched by ZnTmtppa resulting in large quenching constants. Binding of ZnTmtppa to QDs occurs with two molecules of the former binding to the latter.
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- Date Issued: 2008
Excited state dynamics of zinc and aluminum phthalocyanine carboxylates
- 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.
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- Date Issued: 2007
Photophysical and photochemical properties of zinc and aluminum phthalocyanines in the presence of magnetic fluid
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281298 , vital:55710 , xlink:href="https://doi.org/10.1016/j.jphotochem.2006.12.013"
- Description: The effect of magnetic fluid (MF) on the photophysical and photochemical parameters of zinc and aluminum phthalocyanines are reported. The complexes studied are zinc (II) phthalocyanine (ZnPc), chloroaluminum phthalocyanine ((Cl)AlPc) and tetrasulfonated aluminum phthalocyanine ((Cl)AlTSPc). The parameters are studied in dimethylsulfoxide (DMSO) for all complexes and also in aqueous media for (Cl)AlTSPc. The triplet lifetimes for (Cl)AlTSPc and ZnPc decreased while the triplet quantum yields increased in the presence of MF. For (Cl)AlPc, the triplet lifetimes were found to increase with decrease in laser energy while there was photoreduction to the Pc−3 species. Singlet oxygen and photodegradation quantum yields decreased in the presence of MF, suggesting quenching.
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- Date Issued: 2007