The study of the interactions of cobalt (II) tetrasulfophthalocyanine with cysteine and histidine
- Sekota, Mantoa, Nyokong, Tebello
- Authors: Sekota, Mantoa , Nyokong, Tebello
- Date: 1997
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293458 , vital:57087 , xlink:href="https://doi.org/10.1016/S0277-5387(97)00096-X"
- Description: Kinetics for the interaction of cobalt(II) tetrasulfophthalocyanine ([CoIITSPc]4−, Pc(−2) = phthalocyanine dianion) with the amino acids, histidine and cysteine, in pH 7.2 phosphate buffer were studied. The rates were found to be first order in both the [CoIITSPc]4− and the amino acid. The formation of the [CoIIITSPc]3− species in the presence of histidine occurred with a rate constant of 0.16 dm3 mol−s−1, whereas the formation of the [CoITSPc]5− species in the presence of cysteine gave a rate constant of 2.2 dm3 mol−1.
- Full Text:
- Date Issued: 1997
- Authors: Sekota, Mantoa , Nyokong, Tebello
- Date: 1997
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293458 , vital:57087 , xlink:href="https://doi.org/10.1016/S0277-5387(97)00096-X"
- Description: Kinetics for the interaction of cobalt(II) tetrasulfophthalocyanine ([CoIITSPc]4−, Pc(−2) = phthalocyanine dianion) with the amino acids, histidine and cysteine, in pH 7.2 phosphate buffer were studied. The rates were found to be first order in both the [CoIITSPc]4− and the amino acid. The formation of the [CoIIITSPc]3− species in the presence of histidine occurred with a rate constant of 0.16 dm3 mol−s−1, whereas the formation of the [CoITSPc]5− species in the presence of cysteine gave a rate constant of 2.2 dm3 mol−1.
- Full Text:
- Date Issued: 1997
The renaissance in optical spectroscopy of phthalocyanines and other tetraazaporphyrins
- Nyokong, Tebello, Isago, Hiroaki
- Authors: Nyokong, Tebello , Isago, Hiroaki
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289388 , vital:56628 , xlink:href="https://doi.org/10.1142/S1088424604000453"
- Description: Spectral properties of metallophthalocyanines and other tetraazaporphyrins are governed mainly by the Q band which originates from the π-π* transitions within the ring. The position and intensity of the Q band is important in tailoring new phthalocyanine derivatives for particular applications. Aggregation, the nature of the central metal, π conjugation, symmetry of the molecules, and axial, peripheral or non-peripheral substitutions affect the spectra and hence the properties of the phthalocyanine molecule. This review gives a brief outline on how optical spectroscopy provides useful informations on molecular and electronic structures, chemistry and physics of phthalocyanines and other tetraazaporphyrins.
- Full Text:
- Date Issued: 2004
- Authors: Nyokong, Tebello , Isago, Hiroaki
- Date: 2004
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289388 , vital:56628 , xlink:href="https://doi.org/10.1142/S1088424604000453"
- Description: Spectral properties of metallophthalocyanines and other tetraazaporphyrins are governed mainly by the Q band which originates from the π-π* transitions within the ring. The position and intensity of the Q band is important in tailoring new phthalocyanine derivatives for particular applications. Aggregation, the nature of the central metal, π conjugation, symmetry of the molecules, and axial, peripheral or non-peripheral substitutions affect the spectra and hence the properties of the phthalocyanine molecule. This review gives a brief outline on how optical spectroscopy provides useful informations on molecular and electronic structures, chemistry and physics of phthalocyanines and other tetraazaporphyrins.
- Full Text:
- Date Issued: 2004
The reaction of cyanide with iron (II) hexadecachlorophthalocyanine
- Authors: Nyokong, Tebello
- Date: 1995
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293447 , vital:57086 , xlink:href="https://doi.org/10.1016/0277-5387(94)00291-L"
- Description: Kinetics and equilibria for the reaction between cyanide and iron(II) hexadecachlorophthalocyanine ((Cl)16PcFe(DMSO)2, where Pc(−2) = phthalocyanine dianion) in dimethyl sulphoxide (DMSO) are reported. Only the spectrophotometric changes due to the formation of the dicyano, [(Cl)16PcFe(CN)2]2−, complex were observed. This complex is formed with the equilibrium constant, K3 = 1.6 × 103 dm3 mol−1 and a rate constant of k3f = 4.2 × 10−3 dm3 mol−1 s−1. The K2[(Cl)16PcFe(CN)2] complex dissolves in DMSO and dimethyl formamide (DMF) with ϵ = 110 000 and 92 000 dm3 mol−1 cm−1, respectively.
- Full Text:
- Date Issued: 1995
- Authors: Nyokong, Tebello
- Date: 1995
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293447 , vital:57086 , xlink:href="https://doi.org/10.1016/0277-5387(94)00291-L"
- Description: Kinetics and equilibria for the reaction between cyanide and iron(II) hexadecachlorophthalocyanine ((Cl)16PcFe(DMSO)2, where Pc(−2) = phthalocyanine dianion) in dimethyl sulphoxide (DMSO) are reported. Only the spectrophotometric changes due to the formation of the dicyano, [(Cl)16PcFe(CN)2]2−, complex were observed. This complex is formed with the equilibrium constant, K3 = 1.6 × 103 dm3 mol−1 and a rate constant of k3f = 4.2 × 10−3 dm3 mol−1 s−1. The K2[(Cl)16PcFe(CN)2] complex dissolves in DMSO and dimethyl formamide (DMF) with ϵ = 110 000 and 92 000 dm3 mol−1 cm−1, respectively.
- Full Text:
- Date Issued: 1995
The Primary Demonstration of Exciton Coupling Effects on Optical Limiting Properties of Blue Double-Decker Lanthanide Phthalocyanine Salts
- Sekhosana, Kutloano E, Nkhahle, Reitumetse, Nyokong, Tebello
- Authors: Sekhosana, Kutloano E , Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234614 , vital:50213 , xlink:href="https://doi.org/10.1002/slct.201800597"
- Description: In this manuscript, novel green and blue sandwich-type rare-earth phthalocyanines (LnPc2) are presented. This parent green LnPc2 complex is named bis-{2(3),9(10),16(17),23(24)-tetra(4-tert-buylphenoxy) phthalocyaninato} neodymium (III) (2) and modified into blue LnPc2 complexes (3), (4) and (5) based on hexadecyltrimethylammonium ion, mononeodymium(III) diacetate and monodysprosium(III) diacetate as counter ions, respectively. These stable blue lanthanide Pc salts are highly soluble in many organic and inorganic solvents. All complexes 2, 3, 4 and 5 were studied for optical limiting for the first time using Z-scan at nanosecond regime in the visible absorption spectral wavelength (532 nm). Our studies reveal the advantage of exciton coupling in blue sandwich-type rare-earth phthalocyanines over the π-radicals (characterized by blue valence at 485 nm) in the green counterpart which are in resonance with the 532 nm wavelength for optical limiting application. Large singlet ground state to excited state absorption cross section ratios were found, particularly for complex 5 in comparison to that of complex 2.
- Full Text:
- Date Issued: 2018
- Authors: Sekhosana, Kutloano E , Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234614 , vital:50213 , xlink:href="https://doi.org/10.1002/slct.201800597"
- Description: In this manuscript, novel green and blue sandwich-type rare-earth phthalocyanines (LnPc2) are presented. This parent green LnPc2 complex is named bis-{2(3),9(10),16(17),23(24)-tetra(4-tert-buylphenoxy) phthalocyaninato} neodymium (III) (2) and modified into blue LnPc2 complexes (3), (4) and (5) based on hexadecyltrimethylammonium ion, mononeodymium(III) diacetate and monodysprosium(III) diacetate as counter ions, respectively. These stable blue lanthanide Pc salts are highly soluble in many organic and inorganic solvents. All complexes 2, 3, 4 and 5 were studied for optical limiting for the first time using Z-scan at nanosecond regime in the visible absorption spectral wavelength (532 nm). Our studies reveal the advantage of exciton coupling in blue sandwich-type rare-earth phthalocyanines over the π-radicals (characterized by blue valence at 485 nm) in the green counterpart which are in resonance with the 532 nm wavelength for optical limiting application. Large singlet ground state to excited state absorption cross section ratios were found, particularly for complex 5 in comparison to that of complex 2.
- Full Text:
- Date Issued: 2018
The photophysicochemical properties and photodynamic therapy activity of Schiff base substituted phthalocyanines doped into silica nanoparticles and conjugated to folic acid
- Magadla, Aviwe, Babu, Balaji, Sen, Pinar, Nyokong, Tebello
- Authors: Magadla, Aviwe , Babu, Balaji , Sen, Pinar , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185407 , vital:44384 , xlink:href="https://doi.org/10.1016/j.poly.2021.115227"
- Description: This work explores the synthesis, photophysicochemical properties and photodynamic activity (PDT) of tetrakis [N,N’–bis (4-(diethylamino)benzylidene) amino)propan-2-yl)oxy) phthalocyaninato] Zn (II) (3) and tetra-phenoxy N,N-dimethyl-4-((methylimino) Zn (II) (4) when the encapsulated into silica nanoparticles (SiNPs) followed by conjugation of folic acid (FA). The synthesised complexes and their doped analogues are examined for their PDT activity using MCF-7 cells. All the complexes showed dark toxicity that is >80%. The folic acid conjugates, MPc@SiNPs-FA showed greater photocytoxicity against MCF-7 cells upon irradiation with laser light.
- Full Text:
- Date Issued: 2021
- Authors: Magadla, Aviwe , Babu, Balaji , Sen, Pinar , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185407 , vital:44384 , xlink:href="https://doi.org/10.1016/j.poly.2021.115227"
- Description: This work explores the synthesis, photophysicochemical properties and photodynamic activity (PDT) of tetrakis [N,N’–bis (4-(diethylamino)benzylidene) amino)propan-2-yl)oxy) phthalocyaninato] Zn (II) (3) and tetra-phenoxy N,N-dimethyl-4-((methylimino) Zn (II) (4) when the encapsulated into silica nanoparticles (SiNPs) followed by conjugation of folic acid (FA). The synthesised complexes and their doped analogues are examined for their PDT activity using MCF-7 cells. All the complexes showed dark toxicity that is >80%. The folic acid conjugates, MPc@SiNPs-FA showed greater photocytoxicity against MCF-7 cells upon irradiation with laser light.
- Full Text:
- Date Issued: 2021
The photophysicochemical properties and photodynamic therapy activity of phenyldiazenyl phenoxy substituted phthalocyanines when incorporated into Pluronic® F127 micelles
- Motloung, Banele M, Sekhosana, Kutloano E, Managa, Muthumuni, Prinsloo, Earl, Nyokong, Tebello
- Authors: Motloung, Banele M , Sekhosana, Kutloano E , Managa, Muthumuni , Prinsloo, Earl , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186769 , vital:44532 , xlink:href="https://doi.org/10.1016/j.poly.2019.114157"
- Description: The synthesis, photophysicochemical properties and photodynamic activity (PDT) of 4(4-phenyldiazenyl) phenoxy substituted indium (III) (InPc) and zinc (ZnPc) phthalocyanines when alone or incorporated into Pluronic_ F127 micelles are presented in this study. The InPc exhibited higher singlet oxygen (UD) at 0.47 compared to the ZnPc at 0.20 in dimethylsulfoxide. The UD values in the presence of Pluronic_ F127 and in water, were 0.32 for InPc and 0.09 for ZnPc. The triplet quantum yields (UT) were 0.92 for InPc and 0.32 for ZnPc in DMSO. The PDT activity followed the same trend as the singlet oxygen quantum yields. At the highest concentration, InPc in Pluronic_ F127 gave 22% cell viability compared to 34% for complex ZnPc. The partition coefficient Kp values were determined using the water and octanol system. InPc had a larger Kp suggesting that it is more likely to be taken up by the cancer cells, hence it exhibited better PDT activity.
- Full Text:
- Date Issued: 2019
- Authors: Motloung, Banele M , Sekhosana, Kutloano E , Managa, Muthumuni , Prinsloo, Earl , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186769 , vital:44532 , xlink:href="https://doi.org/10.1016/j.poly.2019.114157"
- Description: The synthesis, photophysicochemical properties and photodynamic activity (PDT) of 4(4-phenyldiazenyl) phenoxy substituted indium (III) (InPc) and zinc (ZnPc) phthalocyanines when alone or incorporated into Pluronic_ F127 micelles are presented in this study. The InPc exhibited higher singlet oxygen (UD) at 0.47 compared to the ZnPc at 0.20 in dimethylsulfoxide. The UD values in the presence of Pluronic_ F127 and in water, were 0.32 for InPc and 0.09 for ZnPc. The triplet quantum yields (UT) were 0.92 for InPc and 0.32 for ZnPc in DMSO. The PDT activity followed the same trend as the singlet oxygen quantum yields. At the highest concentration, InPc in Pluronic_ F127 gave 22% cell viability compared to 34% for complex ZnPc. The partition coefficient Kp values were determined using the water and octanol system. InPc had a larger Kp suggesting that it is more likely to be taken up by the cancer cells, hence it exhibited better PDT activity.
- Full Text:
- Date Issued: 2019
The photophysicochemical properties and photodynamic therapy activity of In and Zn phthalocyanines when incorporated into individual or mixed Pluronic® micelles
- Motloung, Banele M, Babu, Balaji, Prinsloo, Earl, Nyokong, Tebello
- Authors: Motloung, Banele M , Babu, Balaji , Prinsloo, Earl , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186124 , vital:44465 , xlink:href="https://doi.org/10.1016/j.poly.2020.114683"
- Description: The synthesis, photophysicochemical properties and photodynamic activity (PDT) of tetra-pyridyloxy (1,2) and benzothiazole (3, 4) substituted indium (III) (1,3) and zinc (2, 4) phthalocyanines (Pcs) and their incorporation into Pluronic® F127 and Pluronic L121/F127 mixed micelles (the latter for 3 and 4 only) are presented in this study. The InPcs exhibited higher singlet oxygen (ΦΔ) at 0.76 and 0.68 compared to the ZnPc’s at 0.47 and 0.44 in dimethyl sulfoxide. The ΦΔ values in the presence of Pluronic® F127 and in water, were 0.39 and 0.42 for InPcs and 0.23 and 0.37 for ZnPc. The ΦΔ values in the presence of Pluronic F127/L121 mixed micelles for complex 3 and 4 were 0.51 and 0.29 in water. The Kp was determined using the water and octanol system. InPcs had larger Kp values suggesting that they are more likely to be taken up by the cancer cells hence they showed better PDT activity
- Full Text:
- Date Issued: 2020
- Authors: Motloung, Banele M , Babu, Balaji , Prinsloo, Earl , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186124 , vital:44465 , xlink:href="https://doi.org/10.1016/j.poly.2020.114683"
- Description: The synthesis, photophysicochemical properties and photodynamic activity (PDT) of tetra-pyridyloxy (1,2) and benzothiazole (3, 4) substituted indium (III) (1,3) and zinc (2, 4) phthalocyanines (Pcs) and their incorporation into Pluronic® F127 and Pluronic L121/F127 mixed micelles (the latter for 3 and 4 only) are presented in this study. The InPcs exhibited higher singlet oxygen (ΦΔ) at 0.76 and 0.68 compared to the ZnPc’s at 0.47 and 0.44 in dimethyl sulfoxide. The ΦΔ values in the presence of Pluronic® F127 and in water, were 0.39 and 0.42 for InPcs and 0.23 and 0.37 for ZnPc. The ΦΔ values in the presence of Pluronic F127/L121 mixed micelles for complex 3 and 4 were 0.51 and 0.29 in water. The Kp was determined using the water and octanol system. InPcs had larger Kp values suggesting that they are more likely to be taken up by the cancer cells hence they showed better PDT activity
- Full Text:
- Date Issued: 2020
The photophysicochemical behavior of symmetric and asymmetric zinc phthalocyanines, surface assembled onto gold nanotriangles
- Dube, Edith, Nwaji, Njemuwa, Mack, John, Nyokong, Tebello
- Authors: Dube, Edith , Nwaji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233310 , vital:50079 , xlink:href="https://doi.org/10.1039/C8NJ02746C"
- Description: The synthesis of a novel asymmetric phthalocyanine, (4-(4-(benzo[d]thiazol-2-yl)phenoxy)-2,10,17-tris(4-(2-carboxyethyl)phenoxy)phthalocyaninatol)zinc(II), complex 3, is reported. Complex 3 together with the previously reported complexes tetrakis[(benzo[d]thiazol-2-yl phenoxy)phthalocyaninato]zinc(II) (4) and 3-(4-((3,17,23-tris(4-(benzo[d]thiazol-2-yl)phenoxy)phthalocyaninatol)oxy)phenyl)propanoic acid zinc(II) (5), were linked to gold nanotriangles (AuNTs) through S–Au/Au–N self-assembly to afford the conjugates (3-AuNTs, 4-AuNTs and 5-AuNTs). The photophysicochemical behaviour of the complexes and their conjugates were studied. The asymmetric complexes 3 and 5, displayed improved triplet and singlet oxygen quantum yields compared to the symmetric complex 4, while all conjugates displayed improved triplet and singlet oxygen quantum yields compared to their respective complexes alone. The complexes and their conjugates could serve as good candidates for photodynamic therapy.
- Full Text:
- Date Issued: 2018
- Authors: Dube, Edith , Nwaji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233310 , vital:50079 , xlink:href="https://doi.org/10.1039/C8NJ02746C"
- Description: The synthesis of a novel asymmetric phthalocyanine, (4-(4-(benzo[d]thiazol-2-yl)phenoxy)-2,10,17-tris(4-(2-carboxyethyl)phenoxy)phthalocyaninatol)zinc(II), complex 3, is reported. Complex 3 together with the previously reported complexes tetrakis[(benzo[d]thiazol-2-yl phenoxy)phthalocyaninato]zinc(II) (4) and 3-(4-((3,17,23-tris(4-(benzo[d]thiazol-2-yl)phenoxy)phthalocyaninatol)oxy)phenyl)propanoic acid zinc(II) (5), were linked to gold nanotriangles (AuNTs) through S–Au/Au–N self-assembly to afford the conjugates (3-AuNTs, 4-AuNTs and 5-AuNTs). The photophysicochemical behaviour of the complexes and their conjugates were studied. The asymmetric complexes 3 and 5, displayed improved triplet and singlet oxygen quantum yields compared to the symmetric complex 4, while all conjugates displayed improved triplet and singlet oxygen quantum yields compared to their respective complexes alone. The complexes and their conjugates could serve as good candidates for photodynamic therapy.
- Full Text:
- Date Issued: 2018
The photophysical studies of Pluronic F127/P123 micelle mixture system loaded with metal free and Zn 5, 10, 15, 20-tetrakis [4-(benzyloxy) phenyl] porphyrins
- Managa, Muthumuni, Ngoy, Bokolombe P, Nyokong, Tebello
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188932 , vital:44799 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.02.018"
- Description: Binary mixtures of Pluronics are studied as drug nanocarriers in this work. H2 and Zn 5,10,15,20-tetrakis[4-(benzyloxy) phenyl] porphyrin were encapsulated onto binary micelle mixture of Pluronic F127/P123. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. The fluorescence quantum yield for H2TBnOPP (ΦF = 0.034) was higher than that of ZnTBnOPP (ΦF = 0.023) and decreased when ZnTBnOPP or H2TBnOPP when in the presence of Pluronic F127/P123 binary mixtures. The kq values were 2.8 × 108 and 3.7 × 108 M−1 s−1, for H2TBnOPP + Pluronic F127/P123 and ZnTBnOPP + Pluronic F127/P123 in water, respectively. The binding constants (Kb) were 1.58 × 105 M−1 and 1.02 × 105 M−1 for ZnTBnOPP + Pluronic F127/P123 and H2TBnOPP + Pluronic F127/P123, respectively.
- Full Text:
- Date Issued: 2017
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188932 , vital:44799 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.02.018"
- Description: Binary mixtures of Pluronics are studied as drug nanocarriers in this work. H2 and Zn 5,10,15,20-tetrakis[4-(benzyloxy) phenyl] porphyrin were encapsulated onto binary micelle mixture of Pluronic F127/P123. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. The fluorescence quantum yield for H2TBnOPP (ΦF = 0.034) was higher than that of ZnTBnOPP (ΦF = 0.023) and decreased when ZnTBnOPP or H2TBnOPP when in the presence of Pluronic F127/P123 binary mixtures. The kq values were 2.8 × 108 and 3.7 × 108 M−1 s−1, for H2TBnOPP + Pluronic F127/P123 and ZnTBnOPP + Pluronic F127/P123 in water, respectively. The binding constants (Kb) were 1.58 × 105 M−1 and 1.02 × 105 M−1 for ZnTBnOPP + Pluronic F127/P123 and H2TBnOPP + Pluronic F127/P123, respectively.
- Full Text:
- Date Issued: 2017
The photophysical studies of a mixture of CdTe quantum dots and negatively charged zinc phthalocyanines
- Moeno, Sharon, Nyokong, Tebello
- Authors: Moeno, Sharon , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268663 , vital:54220 , xlink:href="https://doi.org/10.1016/j.poly.2008.03.007"
- Description: Fluorescence resonance energy transfer (FRET) studies were carried out with quantum dots capped with thioglycolic acid (TGA) and 2-mercaptoethanol (2-ME) and negatively charged phthalocyanines {Zn tetracarboxy (ZnTCPc), Zn octacarboxy (ZnOCPc) and Zn tetrasulfo (ZnTSPc) phthalocyinines} in a 0.1 NaOH:EtOH (50:50) solvent mixture. The best overlap between emission spectra of the donor (QDs) and the absorption spectra of the acceptor (ZnPc derivatives) was observed for TGA capped QDs, very little overlap was obtained for 2-ME QDs. ZnTSPc gave the highest FRET efficiency (0.3), with ZnOCPc and ZnTCPc giving a FRET efficiency of 0.2. The ΦT values of the MPcs generally decreased in the presence of the QD whereas the triplet lifetimes (τT) of the ZnPc derivatives were higher in the presence of QDs.
- Full Text:
- Date Issued: 2008
- Authors: Moeno, Sharon , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268663 , vital:54220 , xlink:href="https://doi.org/10.1016/j.poly.2008.03.007"
- Description: Fluorescence resonance energy transfer (FRET) studies were carried out with quantum dots capped with thioglycolic acid (TGA) and 2-mercaptoethanol (2-ME) and negatively charged phthalocyanines {Zn tetracarboxy (ZnTCPc), Zn octacarboxy (ZnOCPc) and Zn tetrasulfo (ZnTSPc) phthalocyinines} in a 0.1 NaOH:EtOH (50:50) solvent mixture. The best overlap between emission spectra of the donor (QDs) and the absorption spectra of the acceptor (ZnPc derivatives) was observed for TGA capped QDs, very little overlap was obtained for 2-ME QDs. ZnTSPc gave the highest FRET efficiency (0.3), with ZnOCPc and ZnTCPc giving a FRET efficiency of 0.2. The ΦT values of the MPcs generally decreased in the presence of the QD whereas the triplet lifetimes (τT) of the ZnPc derivatives were higher in the presence of QDs.
- Full Text:
- Date Issued: 2008
The photophysical properties of multi-functional quantum dots-magnetic nanoparticles—indium octacarboxyphthalocyanine nanocomposite
- Tshangana, Charmaine, Nyokong, Tebello
- Authors: Tshangana, Charmaine , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189876 , vital:44942 , xlink:href="https://doi.org/10.1007/s10895-014-1497-6"
- Description: This work presents the development of a multifunctional hybrid nanoparticle made of L-glutathione capped quantum dots (GSH-CdSe@ZnS), amino functionalized Fe3O4 magnetic nanoparticles and indium octacarboxy phthalocyanine (ClInPc(COOH)8). In this work we investigate the photophysical properties of the individual components and the hybrid nanoparticle, in addition we study the energy transfer (Förster Resonance Energy Transfer (FRET)) in the complex. FRET efficiencies of ~48 % were obtained for energy transfer between the QDs (when alone or linked to MNPs). Both triplet yields and lifetimes of ClInPc(COOH)8 increase in the nanocomposite, with a decrease in fluorescence lifetime. The hybrid nanoparticle showed improved photophysical properties and as a result can be used in photodynamic therapy.
- Full Text:
- Date Issued: 2015
- Authors: Tshangana, Charmaine , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189876 , vital:44942 , xlink:href="https://doi.org/10.1007/s10895-014-1497-6"
- Description: This work presents the development of a multifunctional hybrid nanoparticle made of L-glutathione capped quantum dots (GSH-CdSe@ZnS), amino functionalized Fe3O4 magnetic nanoparticles and indium octacarboxy phthalocyanine (ClInPc(COOH)8). In this work we investigate the photophysical properties of the individual components and the hybrid nanoparticle, in addition we study the energy transfer (Förster Resonance Energy Transfer (FRET)) in the complex. FRET efficiencies of ~48 % were obtained for energy transfer between the QDs (when alone or linked to MNPs). Both triplet yields and lifetimes of ClInPc(COOH)8 increase in the nanocomposite, with a decrease in fluorescence lifetime. The hybrid nanoparticle showed improved photophysical properties and as a result can be used in photodynamic therapy.
- Full Text:
- Date Issued: 2015
The Photophysical Properties of Multi-Functional Quantum Dots-Magnetic Nanoparticles—Indium Octacarboxyphthalocyanine Nanocomposite
- Tshangana, Charmaine, Nyokong, Tebello
- Authors: Tshangana, Charmaine , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7248 , http://hdl.handle.net/10962/d1020254
- Description: This work presents the development of a multifunctional hybrid nanoparticle made of L-glutathione capped quantum dots (GSH-CdSe@ZnS), amino functionalized Fe3O4 magnetic nanoparticles and indium octacarboxy phthalocyanine (ClInPc(COOH)8). In this work we investigate the photophysical properties of the individual components and the hybrid nanoparticle, in addition we study the energy transfer (Förster Resonance Energy Transfer (FRET)) in the complex. FRET efficiencies of ~48 % were obtained for energy transfer between the QDs (when alone or linked to MNPs). Both triplet yields and lifetimes of ClInPc(COOH)8 increase in the nanocomposite, with a decrease in fluorescence lifetime. The hybrid nanoparticle showed improved photophysical properties and as a result can be used in photodynamic therapy. , Original publication is available at http://dx.doi.org/10.1007/s10895-014-1497-6
- Full Text: false
- Authors: Tshangana, Charmaine , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7248 , http://hdl.handle.net/10962/d1020254
- Description: This work presents the development of a multifunctional hybrid nanoparticle made of L-glutathione capped quantum dots (GSH-CdSe@ZnS), amino functionalized Fe3O4 magnetic nanoparticles and indium octacarboxy phthalocyanine (ClInPc(COOH)8). In this work we investigate the photophysical properties of the individual components and the hybrid nanoparticle, in addition we study the energy transfer (Förster Resonance Energy Transfer (FRET)) in the complex. FRET efficiencies of ~48 % were obtained for energy transfer between the QDs (when alone or linked to MNPs). Both triplet yields and lifetimes of ClInPc(COOH)8 increase in the nanocomposite, with a decrease in fluorescence lifetime. The hybrid nanoparticle showed improved photophysical properties and as a result can be used in photodynamic therapy. , Original publication is available at http://dx.doi.org/10.1007/s10895-014-1497-6
- Full Text: false
The photophysical and photochemical behaviour of coumarin-derivatized zinc phthalocyanine when conjugated with gold nanoparticles and electrospun into polymer fibers
- Tombe, Sekai, Antunes, Edith M, Nyokong, Tebello
- Authors: Tombe, Sekai , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232534 , vital:50000 , xlink:href="https://doi.org/10.1039/C2NJ40984D"
- Description: Polymer composite fibers doped with phthalocyanines and phthalocyanine-functionalized gold nanoparticles were developed. The phthalocyanine and phthalocyanine-functionalized gold nanoparticles have been characterized using UV/Vis, fluorescence and X-ray photoelectron spectroscopy (XPS), time correlated single photon counting (TCSPC), time-resolved emission spectra (TRES) and transmission electron microscopy (TEM). The changes in photophysical and photochemical behavior of the phthalocyanines induced by their interaction with gold nanoparticles and polystyrene were also investigated. In the presence of gold nanoparticles, the fluorescence lifetimes and quantum yields of the phthalocyanine decreased, whereas the singlet oxygen quantum yield increased. This work shows that polymer composite fibers could be used as functional fibers for a variety of applications such as gas sensing when using the advantageous properties of phthalocyanines and gold nanoparticles.
- Full Text:
- Date Issued: 2013
- Authors: Tombe, Sekai , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232534 , vital:50000 , xlink:href="https://doi.org/10.1039/C2NJ40984D"
- Description: Polymer composite fibers doped with phthalocyanines and phthalocyanine-functionalized gold nanoparticles were developed. The phthalocyanine and phthalocyanine-functionalized gold nanoparticles have been characterized using UV/Vis, fluorescence and X-ray photoelectron spectroscopy (XPS), time correlated single photon counting (TCSPC), time-resolved emission spectra (TRES) and transmission electron microscopy (TEM). The changes in photophysical and photochemical behavior of the phthalocyanines induced by their interaction with gold nanoparticles and polystyrene were also investigated. In the presence of gold nanoparticles, the fluorescence lifetimes and quantum yields of the phthalocyanine decreased, whereas the singlet oxygen quantum yield increased. This work shows that polymer composite fibers could be used as functional fibers for a variety of applications such as gas sensing when using the advantageous properties of phthalocyanines and gold nanoparticles.
- Full Text:
- Date Issued: 2013
The photophysical and energy transfer behaviour of low symmetry phthalocyanine complexes conjugated to coreshell quantum dots
- Masilela, Nkosiphile, Nyokong, Tebello
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243051 , vital:51111 , xlink:href="https://doi.org/10.1016/j.jphotochem.2012.07.016"
- Description: This work reports on the synthesis of new coreshell quantum dots (QDs)-low symmetry phthalocyanines conjugates. The energy transfer from QDs (donor) to phthalocyanines (acceptor) was investigated when the two are mixed together or chemically linked to each other. Ti monocarboxy phthalocyanine QDs-linked and Sn monocarboxy phthalocyanine QDs-linked gave the smallest centre-to-centre separation distance (r) corresponding to their higher Förster resonance energy transfer efficiencies which are estimated at 0.76 and 0.85 respectively. Higher energy transfer behaviour was achieved for all the covalently linked conjugates compared to their corresponding mixed counterparts. An improvement in triplet quantum yields and lifetimes was achieved for all the complexes in the presence of quantum dots, with the linked counterparts displaying excellent triplet state behaviour.
- Full Text:
- Date Issued: 2012
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/243051 , vital:51111 , xlink:href="https://doi.org/10.1016/j.jphotochem.2012.07.016"
- Description: This work reports on the synthesis of new coreshell quantum dots (QDs)-low symmetry phthalocyanines conjugates. The energy transfer from QDs (donor) to phthalocyanines (acceptor) was investigated when the two are mixed together or chemically linked to each other. Ti monocarboxy phthalocyanine QDs-linked and Sn monocarboxy phthalocyanine QDs-linked gave the smallest centre-to-centre separation distance (r) corresponding to their higher Förster resonance energy transfer efficiencies which are estimated at 0.76 and 0.85 respectively. Higher energy transfer behaviour was achieved for all the covalently linked conjugates compared to their corresponding mixed counterparts. An improvement in triplet quantum yields and lifetimes was achieved for all the complexes in the presence of quantum dots, with the linked counterparts displaying excellent triplet state behaviour.
- Full Text:
- Date Issued: 2012
The photodynamic antimicrobial chemotherapy of Stapphylococcus aureus using an asymmetrical zinc phthalocyanine conjugated to silver and iron oxide based nanoparticles
- Mapukata, Sivuyisiwe, Nwahara, Nnamdi, Nyokong, Tebello
- Authors: Mapukata, Sivuyisiwe , Nwahara, Nnamdi , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186078 , vital:44461 , xlink:href="https://doi.org/10.1016/j.jphotochem.2020.112813"
- Description: The synthesis and characterisation of asymmetrical zinc(II) 2(3)-mono-isophthalic acid-9(10),16(17),23 (24)-tri (tert-butylphenoxy) phthalocyanine (complex 4) are reported. The phthalocyanine is conjugated to cysteamine capped silver nanoparticles (Cys-Ag NPs), amine functionalised iron oxide magnetic nanoparticles (NH2-Fe3O4 NPs) and a core-shell composite of the two (Cys-Fe3O4@Ag) via amide bonds. The photo-physico-chemical properties of complex 4 and its respective nanoconjugates (4-Ag, 4-Fe3O4 NPs and 4-Fe3O4@Ag NPs) are also reported. The nanoconjugates showed improved triplet and singlet oxygen quantum yields compared to complex 4. The antibacterial activity of complex 4 and its nanoconjugates were also evaluated on S. aureus wherein their activity was found to be mainly visible light driven with the best catalyst being 4-Fe3O4@Ag. The work therefore demonstrates the feasibility of phthalocyanine-nanoparticle based compounds as potential agents in real life antibacterial treatment
- Full Text:
- Date Issued: 2020
- Authors: Mapukata, Sivuyisiwe , Nwahara, Nnamdi , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186078 , vital:44461 , xlink:href="https://doi.org/10.1016/j.jphotochem.2020.112813"
- Description: The synthesis and characterisation of asymmetrical zinc(II) 2(3)-mono-isophthalic acid-9(10),16(17),23 (24)-tri (tert-butylphenoxy) phthalocyanine (complex 4) are reported. The phthalocyanine is conjugated to cysteamine capped silver nanoparticles (Cys-Ag NPs), amine functionalised iron oxide magnetic nanoparticles (NH2-Fe3O4 NPs) and a core-shell composite of the two (Cys-Fe3O4@Ag) via amide bonds. The photo-physico-chemical properties of complex 4 and its respective nanoconjugates (4-Ag, 4-Fe3O4 NPs and 4-Fe3O4@Ag NPs) are also reported. The nanoconjugates showed improved triplet and singlet oxygen quantum yields compared to complex 4. The antibacterial activity of complex 4 and its nanoconjugates were also evaluated on S. aureus wherein their activity was found to be mainly visible light driven with the best catalyst being 4-Fe3O4@Ag. The work therefore demonstrates the feasibility of phthalocyanine-nanoparticle based compounds as potential agents in real life antibacterial treatment
- Full Text:
- Date Issued: 2020
The photodynamic activities of the gold nanoparticle conjugates of phosphorus (V) and gallium (III) A3 meso-triarylcorroles
- Soy, Rodah C, Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Soy, Rodah C , Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184978 , vital:44313 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109631"
- Description: The synthesis and characterization of series of P(V) and Ga(III) A3 triarylcorrole complexes with 4-methylthiophenyl (2a, 3a), thien-3-yl (2b, 3b) and thien-2-yl (2c, 3c) meso-groups are reported along with the physicochemical and photodynamic activity properties of the dyes and their gold nanoparticle (AuNP) conjugates. The Ga(III) corrole series have lower fluorescence quantum yields and higher singlet oxygen quantum yields than the analogous P(V) complexes. Upon conjugation to AuNPs, the fluorescence quantum yields of the P(V) and Ga(III) corroles decrease, while the singlet oxygen quantum yields increase due to an external heavy atom effect. The P(V) and Ga(III) corroles exhibit relatively low in vitro dark cytotoxicity, which was further enhanced upon conjugation to AuNPs. The P(V) complexes and their AuNP conjugates display more favorable PDT activity properties upon illumination with a Thorlabs 625 nm light-emitting diode (288 J cm−2) with phototoxicity indices > 18.5 and 20.8, respectively, for the meso-thienyl-substituted 2b-AuNP and 2c-AuNP conjugates. Optical spectroscopy analyses demonstrate that this can be attributed to there being significantly less aggregation due to the presence of two trans-hydroxy axial ligands.
- Full Text:
- Date Issued: 2021
- Authors: Soy, Rodah C , Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184978 , vital:44313 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109631"
- Description: The synthesis and characterization of series of P(V) and Ga(III) A3 triarylcorrole complexes with 4-methylthiophenyl (2a, 3a), thien-3-yl (2b, 3b) and thien-2-yl (2c, 3c) meso-groups are reported along with the physicochemical and photodynamic activity properties of the dyes and their gold nanoparticle (AuNP) conjugates. The Ga(III) corrole series have lower fluorescence quantum yields and higher singlet oxygen quantum yields than the analogous P(V) complexes. Upon conjugation to AuNPs, the fluorescence quantum yields of the P(V) and Ga(III) corroles decrease, while the singlet oxygen quantum yields increase due to an external heavy atom effect. The P(V) and Ga(III) corroles exhibit relatively low in vitro dark cytotoxicity, which was further enhanced upon conjugation to AuNPs. The P(V) complexes and their AuNP conjugates display more favorable PDT activity properties upon illumination with a Thorlabs 625 nm light-emitting diode (288 J cm−2) with phototoxicity indices > 18.5 and 20.8, respectively, for the meso-thienyl-substituted 2b-AuNP and 2c-AuNP conjugates. Optical spectroscopy analyses demonstrate that this can be attributed to there being significantly less aggregation due to the presence of two trans-hydroxy axial ligands.
- Full Text:
- Date Issued: 2021
The photocatalytic properties of zinc phthalocyanines supported on hematite nanofibers for use against methyl orange and Staphylococcus aureus
- Mapukata, Sivuyisiwe, Britton, Jonathan, Nwahara, Nnamdi, Nyokong, Tebello
- Authors: Mapukata, Sivuyisiwe , Britton, Jonathan , Nwahara, Nnamdi , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230184 , vital:49751 , xlink:href="https://doi.org/10.1016/j.jphotochem.2021.113637"
- Description: Heterogeneous photocatalysis is a promising approach for environmental remediation from contaminants including microorganisms and organic pollutants. In this work, hematite nanofibers are fabricated and modified with a novel monosubstituted Pc (4) as well as an asymmetrical tetrasubstituted Pc (5) with the aim of creating hybrid photocatalysts. The photocatalytic activities of the unmodified and phthalocyanine modified hematite nanofibers were compared based on their efficiencies in the photoinactivation of S. aureus and photooxidation of methyl orange. For both applications, the hybrid nanofibers were found to be more efficient photocatalysts than the unmodified hematite nanofibers. Comparison of the modified nanofibers (4-Fe2O3 and 5-Fe2O3) showed that they have comparable antibacterial activity while the 5-Fe2O3 nanofibers are the best for the photooxidation of methyl orange. The singlet oxygen generation efficiency, high activity, versatility, regenerability and thus reusability of the fabricated hybrid nanofibers makes them ideal candidates for real life water treatment studies.
- Full Text:
- Date Issued: 2022
- Authors: Mapukata, Sivuyisiwe , Britton, Jonathan , Nwahara, Nnamdi , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230184 , vital:49751 , xlink:href="https://doi.org/10.1016/j.jphotochem.2021.113637"
- Description: Heterogeneous photocatalysis is a promising approach for environmental remediation from contaminants including microorganisms and organic pollutants. In this work, hematite nanofibers are fabricated and modified with a novel monosubstituted Pc (4) as well as an asymmetrical tetrasubstituted Pc (5) with the aim of creating hybrid photocatalysts. The photocatalytic activities of the unmodified and phthalocyanine modified hematite nanofibers were compared based on their efficiencies in the photoinactivation of S. aureus and photooxidation of methyl orange. For both applications, the hybrid nanofibers were found to be more efficient photocatalysts than the unmodified hematite nanofibers. Comparison of the modified nanofibers (4-Fe2O3 and 5-Fe2O3) showed that they have comparable antibacterial activity while the 5-Fe2O3 nanofibers are the best for the photooxidation of methyl orange. The singlet oxygen generation efficiency, high activity, versatility, regenerability and thus reusability of the fabricated hybrid nanofibers makes them ideal candidates for real life water treatment studies.
- Full Text:
- Date Issued: 2022
The photobleaching of the free and encapsulated metallic phthalocyanine and its effect on the photooxidation of simple molecules
- Fanchiotti, Brenda Gomes, Machado, Marcella Piffer Zamprogno, de Paula, Letícia Camilato, Durmuş, Mahmut, Nyokong, Tebello, da Silva, Gonçalves, da Silva, André Romero
- Authors: Fanchiotti, Brenda Gomes , Machado, Marcella Piffer Zamprogno , de Paula, Letícia Camilato , Durmuş, Mahmut , Nyokong, Tebello , da Silva, Gonçalves , da Silva, André Romero
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239687 , vital:50755 , xlink:href="https://doi.org/10.1016/j.jphotobiol.2016.10.007"
- Description: The photobleaching of an unsubstituted phthalocyanine (gallium(III) phthalocyanine chloride (GaPc)) and a substituted phthalocyanine (1,4-(tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato) indium(III) chloride (InTBPPc)) was monitored for the free photosensitizers and for the phthalocyanines encapsulated into nanoparticles of PEGylated poly(D,L-lactide-co-glycolide) (PLGA-PEG). Phosphate-buffered solutions (PBS) and organic solutions of the free GaPc or the free InTBPPc, and suspensions of each encapsulated photosensitizer (2–15 μmol/L) were irradiated using a laser diode of 665 nm with a power of 1–104 mW and a light dose of 7.5 J/cm2. The relative absorbance (RA) of the free GaPc dissolved in 1-methyl-2-pyrrolidone (MP) decreased 8.4 times when the laser power increased from 1 mW to 104 mW. However, the free or encapsulated GaPc did not suffer the photobleaching in PBS solution. The RA values decreased 2.4 times and 22.2 times for the free InTBPPc dissolved in PBS solution and in dimethylformamide (DMF), respectively, but the encapsulated InTBPPc was only photobleached when the laser power was 104 mW at 8 μmol/L. The increase of the free GaPc concentration favored the photobleaching in MP until 8 μmol/L while the increase from 2 μmol/L to 5 μmol/L reduced the photodegradation in PBS solution. However, the photobleaching of the free InTBPPc in DMF or in PBS solution, and of each encapsulated photosensitizer was not influenced by increasing the concentration. The influence of the photobleaching on the capability of the free and encapsulated GaPc and InTBPPc to photooxidate the simple molecules was investigated monitoring the fluorescence of dimethylanthracene (DMA) and the tryptophan (Trp). Free InTBPPc was 2.0 and 1.8 times faster to photooxidate the DMA and Trp than it was the free GaPc, but the encapsulated GaPc was 3.4 times more efficient to photooxidize the Trp than it was the encapsulated InTBPPc due to the photodegradation suffered by the encapsulated InTBPPc. The participation of the singlet oxygen was confirmed with the sodium azide in the photobleaching of all free and encapsulated photosensitizer, and in the photooxidation of the DMA and Trp. The asymmetry of InTBPPc increased the solubility of the free compound, decreasing the aggregation state of the photosensitizer and favoring the photobleaching process. The encapsulation shows capability in decreasing the photobleaching of both photosensitizers but the confocal micrographs showed that the increase of the solubility favored the InTBPPc photobleaching during the acquisition of optical cross section. A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2016
- Authors: Fanchiotti, Brenda Gomes , Machado, Marcella Piffer Zamprogno , de Paula, Letícia Camilato , Durmuş, Mahmut , Nyokong, Tebello , da Silva, Gonçalves , da Silva, André Romero
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239687 , vital:50755 , xlink:href="https://doi.org/10.1016/j.jphotobiol.2016.10.007"
- Description: The photobleaching of an unsubstituted phthalocyanine (gallium(III) phthalocyanine chloride (GaPc)) and a substituted phthalocyanine (1,4-(tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato) indium(III) chloride (InTBPPc)) was monitored for the free photosensitizers and for the phthalocyanines encapsulated into nanoparticles of PEGylated poly(D,L-lactide-co-glycolide) (PLGA-PEG). Phosphate-buffered solutions (PBS) and organic solutions of the free GaPc or the free InTBPPc, and suspensions of each encapsulated photosensitizer (2–15 μmol/L) were irradiated using a laser diode of 665 nm with a power of 1–104 mW and a light dose of 7.5 J/cm2. The relative absorbance (RA) of the free GaPc dissolved in 1-methyl-2-pyrrolidone (MP) decreased 8.4 times when the laser power increased from 1 mW to 104 mW. However, the free or encapsulated GaPc did not suffer the photobleaching in PBS solution. The RA values decreased 2.4 times and 22.2 times for the free InTBPPc dissolved in PBS solution and in dimethylformamide (DMF), respectively, but the encapsulated InTBPPc was only photobleached when the laser power was 104 mW at 8 μmol/L. The increase of the free GaPc concentration favored the photobleaching in MP until 8 μmol/L while the increase from 2 μmol/L to 5 μmol/L reduced the photodegradation in PBS solution. However, the photobleaching of the free InTBPPc in DMF or in PBS solution, and of each encapsulated photosensitizer was not influenced by increasing the concentration. The influence of the photobleaching on the capability of the free and encapsulated GaPc and InTBPPc to photooxidate the simple molecules was investigated monitoring the fluorescence of dimethylanthracene (DMA) and the tryptophan (Trp). Free InTBPPc was 2.0 and 1.8 times faster to photooxidate the DMA and Trp than it was the free GaPc, but the encapsulated GaPc was 3.4 times more efficient to photooxidize the Trp than it was the encapsulated InTBPPc due to the photodegradation suffered by the encapsulated InTBPPc. The participation of the singlet oxygen was confirmed with the sodium azide in the photobleaching of all free and encapsulated photosensitizer, and in the photooxidation of the DMA and Trp. The asymmetry of InTBPPc increased the solubility of the free compound, decreasing the aggregation state of the photosensitizer and favoring the photobleaching process. The encapsulation shows capability in decreasing the photobleaching of both photosensitizers but the confocal micrographs showed that the increase of the solubility favored the InTBPPc photobleaching during the acquisition of optical cross section. A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2016
The photo-physicochemical properties and in vitro photodynamic therapy activity of differently substituted-zinc (II)-phthalocyanines and graphene quantum dots conjugates on MCF7 breast cancer cell line
- Nene, Lindokuhle C, Managa, Muthumuni E, Oluwole, David O, Mafukidze, Donovan M, Sindelo, Azole, Nyokong, Tebello
- Authors: Nene, Lindokuhle C , Managa, Muthumuni E , Oluwole, David O , Mafukidze, Donovan M , Sindelo, Azole , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187449 , vital:44653 , xlink:href="https://doi.org/10.1016/j.ica.2019.01.012"
- Description: Several differently substituted Zn(II) phthalocyanines (ZnPcs) were prepared and conjugated to GQDs. The photophysical properties were determined for both the Pcs and their respective conjugates including the fluorescence/triplet quantum yields and lifetimes as well as the singlet oxygen generating abilities. Upon conjugation to GQDs, the fluorescence of the Pcs decreased (insignificant decrease in some cases), with an increase in the triplet quantum yields. However, the singlet quantum yields of the Pcs in the conjugates did not show an increase with the increase in the triplet quantum yields, this is suspected to be due to the screening effect. The cytotoxicity of the complexes in vitro decreased upon conjugation, as a result of the reduced actual number of Pcs units provided in the conjugate for therapy. Upon introduction of cationic charges, the photodynamic therapy activity of the complexes increased.
- Full Text:
- Date Issued: 2019
- Authors: Nene, Lindokuhle C , Managa, Muthumuni E , Oluwole, David O , Mafukidze, Donovan M , Sindelo, Azole , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187449 , vital:44653 , xlink:href="https://doi.org/10.1016/j.ica.2019.01.012"
- Description: Several differently substituted Zn(II) phthalocyanines (ZnPcs) were prepared and conjugated to GQDs. The photophysical properties were determined for both the Pcs and their respective conjugates including the fluorescence/triplet quantum yields and lifetimes as well as the singlet oxygen generating abilities. Upon conjugation to GQDs, the fluorescence of the Pcs decreased (insignificant decrease in some cases), with an increase in the triplet quantum yields. However, the singlet quantum yields of the Pcs in the conjugates did not show an increase with the increase in the triplet quantum yields, this is suspected to be due to the screening effect. The cytotoxicity of the complexes in vitro decreased upon conjugation, as a result of the reduced actual number of Pcs units provided in the conjugate for therapy. Upon introduction of cationic charges, the photodynamic therapy activity of the complexes increased.
- Full Text:
- Date Issued: 2019
The optical limiting of blue and green ytterbium double-decker phthalocyanines in solution and in poly (acrylic acid) as thin films
- Sekhosana, Kutloana E, Nyokong, Tebello
- Authors: Sekhosana, Kutloana E , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188585 , vital:44767 , xlink:href="https://doi.org/10.1016/j.ica.2016.05.026"
- Description: Bis{1(4), 8(11), 15(18), 22(25)-tetra(4-tert-butylphenoxy)phthalocyaninato} ytterbium(III) (2a) (the green form) was synthesized and reduced to form 2b (the blue form). Nonlinear optical parameters for complex 2 in green and blue forms were determined using the Z-scan technique and the values of third-order imaginary susceptibility (Im[χ(3)]) and second-order hyperpolarizability (γ) of the order of 10−9 (for 2b) and 10−27 esu, respectively, were obtained in solution. In poly(acrylic acid) as a thin film, complex 2a showed extremely high Im[χ(3)] and γ values of the order 10−8 and 10−25 respectively. A low optical limiting threshold value of 0.075 J cm−2 was obtained for the thin film 2a.
- Full Text:
- Date Issued: 2016
- Authors: Sekhosana, Kutloana E , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188585 , vital:44767 , xlink:href="https://doi.org/10.1016/j.ica.2016.05.026"
- Description: Bis{1(4), 8(11), 15(18), 22(25)-tetra(4-tert-butylphenoxy)phthalocyaninato} ytterbium(III) (2a) (the green form) was synthesized and reduced to form 2b (the blue form). Nonlinear optical parameters for complex 2 in green and blue forms were determined using the Z-scan technique and the values of third-order imaginary susceptibility (Im[χ(3)]) and second-order hyperpolarizability (γ) of the order of 10−9 (for 2b) and 10−27 esu, respectively, were obtained in solution. In poly(acrylic acid) as a thin film, complex 2a showed extremely high Im[χ(3)] and γ values of the order 10−8 and 10−25 respectively. A low optical limiting threshold value of 0.075 J cm−2 was obtained for the thin film 2a.
- Full Text:
- Date Issued: 2016