Methodological Survey of Simplified TD-DFT Methods for Fast and Accurate Interpretation of UV−Vis−NIR Spectra of Phthalocyanines
- Martynov, Alexander G, Mack, John, May, Aviwe K, Nyokong, Tebello, Gorbunova, Yulia G, Tsivadze, Aslan Yu
- Authors: Martynov, Alexander G , Mack, John , May, Aviwe K , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186915 , vital:44547 , xlink:href="https://doi.org/10.1021/acsomega.8b03500"
- Description: A methodological survey of density functional theory (DFT) methods for the prediction of UV−visible (vis)−near-infrared (NIR) spectra of phthalocyanines is reported. Four methods, namely, full time-dependent (TD)-DFT and its Tamm−Dancoff approximation (TDA), together with their simplified modifications (sTD-DFT and sTDA, respectively), were tested by using the examples of unsubstituted and alkoxy-substituted metal-free ligands and zinc complexes. The theoretical results were compared with experimental data derived from UV−visible absorption and magnetic circular dichroism spectroscopy. Seven popular exchange-correlation functionals (BP86, B3LYP, TPSSh, M06, CAM-B3LYP, LC-BLYP, and ωB97X) were tested within these four approaches starting at a relatively modest level using 6-31G(d) basis sets and gas-phase BP86/def2-SVP optimized geometries. A gradual augmentation of the computational levels was used to identify the influence of starting geometry, solvation effects, and basis sets on the results of TD-DFT and sTD-DFT calculations. It was found that although these factors do influence the predicted energies of the vertical excitations, they do not affect the trends predicted in the spectral properties across series of structurally related substituted free bases and metallophthalocyanines. The best accuracy for the gas-phase vertical excitations was observed in the lower-energy Q-band region for calculations that made use of range-separated hybrids for both full and simplified TD-DFT approaches. The CAMB3LYP functional provided particularly accurate results in the context of the sTD-DFT approach. The description of the higherenergy B-band region is considerably less accurate, and this demonstrates the need for further advances in the accuracy of theoretical calculations. Together with a general increase in accuracy, the application of simplified TD-DFT methods affords a 2−3 orders of magnitude speedup of the calculations in comparison to the full TD-DFT approach. It is anticipated that this approach will be widely used on desktop computers during the interpretation of UV−vis−NIR spectra of phthalocyanines and related macrocycles in the years ahead.
- Full Text:
- Authors: Martynov, Alexander G , Mack, John , May, Aviwe K , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186915 , vital:44547 , xlink:href="https://doi.org/10.1021/acsomega.8b03500"
- Description: A methodological survey of density functional theory (DFT) methods for the prediction of UV−visible (vis)−near-infrared (NIR) spectra of phthalocyanines is reported. Four methods, namely, full time-dependent (TD)-DFT and its Tamm−Dancoff approximation (TDA), together with their simplified modifications (sTD-DFT and sTDA, respectively), were tested by using the examples of unsubstituted and alkoxy-substituted metal-free ligands and zinc complexes. The theoretical results were compared with experimental data derived from UV−visible absorption and magnetic circular dichroism spectroscopy. Seven popular exchange-correlation functionals (BP86, B3LYP, TPSSh, M06, CAM-B3LYP, LC-BLYP, and ωB97X) were tested within these four approaches starting at a relatively modest level using 6-31G(d) basis sets and gas-phase BP86/def2-SVP optimized geometries. A gradual augmentation of the computational levels was used to identify the influence of starting geometry, solvation effects, and basis sets on the results of TD-DFT and sTD-DFT calculations. It was found that although these factors do influence the predicted energies of the vertical excitations, they do not affect the trends predicted in the spectral properties across series of structurally related substituted free bases and metallophthalocyanines. The best accuracy for the gas-phase vertical excitations was observed in the lower-energy Q-band region for calculations that made use of range-separated hybrids for both full and simplified TD-DFT approaches. The CAMB3LYP functional provided particularly accurate results in the context of the sTD-DFT approach. The description of the higherenergy B-band region is considerably less accurate, and this demonstrates the need for further advances in the accuracy of theoretical calculations. Together with a general increase in accuracy, the application of simplified TD-DFT methods affords a 2−3 orders of magnitude speedup of the calculations in comparison to the full TD-DFT approach. It is anticipated that this approach will be widely used on desktop computers during the interpretation of UV−vis−NIR spectra of phthalocyanines and related macrocycles in the years ahead.
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Nonlinear optical responses of carbazole-substituted phthalocyanines conjugated to graphene quantum dots and in thin films
- Majeed, Shereen A, Nwaji, Njemuwa, Mack, John, Nyokong, Tebello, Makhseed, Saad
- Authors: Majeed, Shereen A , Nwaji, Njemuwa , Mack, John , Nyokong, Tebello , Makhseed, Saad
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186938 , vital:44549 , xlink:href="https://doi.org/10.1016/j.jlumin.2019.04.034"
- Description: Three different phthalocyanine complexes substituted with carbazoles were conjugated to graphene quantum dots (GQDs) through π–π stacking. The morphologies, sizes, and crystallinities of the nanoconjugates were determined using Raman spectroscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray diffraction. The nonlinear optical (NLO) properties of the metallophthalocyanines alone and when conjugated to the GQD nanomaterial in different solvents, as well as after having been embedded in thin films, were studied. The effects of the different substituents and solvents on the NLO properties of the metallophthalocyanines were evaluated. Enhancements in the photophysical properties of the complexes upon conjugation with the nanomaterial were observed. Fluorescence quantum yields, fluorescence lifetimes, triplet quantum yields, and triplet lifetimes were measured for the complexes, and for their conjugates in DMSO.
- Full Text:
- Authors: Majeed, Shereen A , Nwaji, Njemuwa , Mack, John , Nyokong, Tebello , Makhseed, Saad
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186938 , vital:44549 , xlink:href="https://doi.org/10.1016/j.jlumin.2019.04.034"
- Description: Three different phthalocyanine complexes substituted with carbazoles were conjugated to graphene quantum dots (GQDs) through π–π stacking. The morphologies, sizes, and crystallinities of the nanoconjugates were determined using Raman spectroscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray diffraction. The nonlinear optical (NLO) properties of the metallophthalocyanines alone and when conjugated to the GQD nanomaterial in different solvents, as well as after having been embedded in thin films, were studied. The effects of the different substituents and solvents on the NLO properties of the metallophthalocyanines were evaluated. Enhancements in the photophysical properties of the complexes upon conjugation with the nanomaterial were observed. Fluorescence quantum yields, fluorescence lifetimes, triplet quantum yields, and triplet lifetimes were measured for the complexes, and for their conjugates in DMSO.
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Optical limiting and femtosecond pump-probe transient absorbance properties of a 3, 5-distyrylBODIPY dye
- Ngoy, Bokolombe P, May, Aviwe K, Mack, John, Nyokong, Tebello
- Authors: Ngoy, Bokolombe P , May, Aviwe K , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186835 , vital:44538 , xlink:href="https://doi.org/10.3389/fchem.2019.00740"
- Description: The optical limiting (OL) properties of a 3,5-di-p-benzyloxystyrylBODIPY dye with an p-acetamidophenyl moiety at the meso-position have been investigated by using the open-aperture Z-scan technique at 532 nm with 10 ns laser pulses. There is a ca. 140 nm red shift of the main spectral band to 644 nm relative to the corresponding BODIPY core dye, due to the incorporation of p-benzyloxystyryl groups at the 3,5-positions. As a result, there is relatively weak absorbance across most of the visible region under ambient light conditions. Analysis of the observed reverse saturable absorbance (RSA) profiles demonstrates that the dye is potentially suitable for use in optical limiting applications as has been reported previously for other 3,5-distyrylBODIPY dyes. Time-resolved transient absorption spectroscopy and kinetic studies with femtosecond and nanosecond scale laser pulses provide the first direct spectral evidence that excited state absorption (ESA) from the S1 state is responsible for the observed OL properties.
- Full Text:
- Authors: Ngoy, Bokolombe P , May, Aviwe K , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186835 , vital:44538 , xlink:href="https://doi.org/10.3389/fchem.2019.00740"
- Description: The optical limiting (OL) properties of a 3,5-di-p-benzyloxystyrylBODIPY dye with an p-acetamidophenyl moiety at the meso-position have been investigated by using the open-aperture Z-scan technique at 532 nm with 10 ns laser pulses. There is a ca. 140 nm red shift of the main spectral band to 644 nm relative to the corresponding BODIPY core dye, due to the incorporation of p-benzyloxystyryl groups at the 3,5-positions. As a result, there is relatively weak absorbance across most of the visible region under ambient light conditions. Analysis of the observed reverse saturable absorbance (RSA) profiles demonstrates that the dye is potentially suitable for use in optical limiting applications as has been reported previously for other 3,5-distyrylBODIPY dyes. Time-resolved transient absorption spectroscopy and kinetic studies with femtosecond and nanosecond scale laser pulses provide the first direct spectral evidence that excited state absorption (ESA) from the S1 state is responsible for the observed OL properties.
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Photophysical and enhanced nonlinear optical response in asymmetric benzothiazole substituted phthalocyanine covalently linked to semiconductor quantum dots
- Nwaji, Njemuwa, Dingiswayo, Somila, Mack, John, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Dingiswayo, Somila , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187851 , vital:44703 , xlink:href="https://doi.org/10.1016/j.saa.2018.06.098"
- Description: The synthesis of asymmetric benzothiazole substituted phthalocyanines (complexes 3 to 5) and their covalent attachment to glutathione (GSH) functionalized quantum dots (QDs) are reported in this work. Additionally, their photophysical and nonlinear optical properties were investigated. A decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield was observed when the complexes were covalently linked to glutathione (GSH) functionalized cadmium telluride (CdTe) quantum dots. Reverse saturable absorption was found to be predominantly dominated by excited state absorption. The observed limiting threshold values range from 0.29–0.75 J/cm2.
- Full Text:
- Authors: Nwaji, Njemuwa , Dingiswayo, Somila , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187851 , vital:44703 , xlink:href="https://doi.org/10.1016/j.saa.2018.06.098"
- Description: The synthesis of asymmetric benzothiazole substituted phthalocyanines (complexes 3 to 5) and their covalent attachment to glutathione (GSH) functionalized quantum dots (QDs) are reported in this work. Additionally, their photophysical and nonlinear optical properties were investigated. A decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield was observed when the complexes were covalently linked to glutathione (GSH) functionalized cadmium telluride (CdTe) quantum dots. Reverse saturable absorption was found to be predominantly dominated by excited state absorption. The observed limiting threshold values range from 0.29–0.75 J/cm2.
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Photophysical properties and photodynamic therapy activities of detonated nanodiamonds-BODIPY-phthalocyanines nanoassemblies
- Matshitse, Refilwe, Ngoy, Bokolombe P, Managa, Muthumuni, Mack, John, Nyokong, Tebello
- Authors: Matshitse, Refilwe , Ngoy, Bokolombe P , Managa, Muthumuni , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186981 , vital:44553 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.03.007"
- Description: This work reports on the synthesis of nanoassemblies of supramolecular hybrids containing detonated nanodiamonds (DNDs) covalently linked to halogenated BODIPY (DNDs-BODIPY) by an amide bond, followed by π–π stacking of 2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ) on the DNDs-BODIPY conjugate, to form nanoassembly represented as ZnTPPcQ-DNDs-BODIPY. ZnTPPcQ-DNDs-BODIPY has a higher singlet oxygen quantum yield of 0.50 in water. Therefore, the construction of a three component photodynamic therapy agent (ZnTPPcQ-DNDs-BODIPY) as a single photosentisiser improved singlet quantum yields of the Pc. Zeta potential studies of ZnTPPcQ-DNDs-BODIPY under various temperatures, concentrations and pH conditions, showed the conjugate is more stable at pHs 2, 4 and 7 and at high concentrations (50 μg/mL) and temperatures (80 °C). ZnTPPcQ-DNDs-BODIPY showed high photodynamic therapy (PDT) activity with a low MCF-7 cell viability of 21 ± 5% when compared to 31 ± 2%, 30 ± 2% and 28 ± 2% cell viability at the highest tested concentration of 50 μg/mL for DNDs, ZnTPPcQ-DND and DNDs-BODIPY, respectively.
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- Authors: Matshitse, Refilwe , Ngoy, Bokolombe P , Managa, Muthumuni , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186981 , vital:44553 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.03.007"
- Description: This work reports on the synthesis of nanoassemblies of supramolecular hybrids containing detonated nanodiamonds (DNDs) covalently linked to halogenated BODIPY (DNDs-BODIPY) by an amide bond, followed by π–π stacking of 2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ) on the DNDs-BODIPY conjugate, to form nanoassembly represented as ZnTPPcQ-DNDs-BODIPY. ZnTPPcQ-DNDs-BODIPY has a higher singlet oxygen quantum yield of 0.50 in water. Therefore, the construction of a three component photodynamic therapy agent (ZnTPPcQ-DNDs-BODIPY) as a single photosentisiser improved singlet quantum yields of the Pc. Zeta potential studies of ZnTPPcQ-DNDs-BODIPY under various temperatures, concentrations and pH conditions, showed the conjugate is more stable at pHs 2, 4 and 7 and at high concentrations (50 μg/mL) and temperatures (80 °C). ZnTPPcQ-DNDs-BODIPY showed high photodynamic therapy (PDT) activity with a low MCF-7 cell viability of 21 ± 5% when compared to 31 ± 2%, 30 ± 2% and 28 ± 2% cell viability at the highest tested concentration of 50 μg/mL for DNDs, ZnTPPcQ-DND and DNDs-BODIPY, respectively.
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Preparation of NIR absorbing axial substituted tin (iv) porphyrins and their photocytotoxic properties
- Babu, Balaji, Amuhaya, Edith K, Oluwole, David O, Prinsloo, Earl, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Amuhaya, Edith K , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234592 , vital:50211 , xlink:href="https://doi.org/10.1039/C8MD00373D"
- Description: Sn(IV) porphyrins ([Sn(IV)TTP(3PyO)2] (5) and [Sn(IV)TPP(3PyO)2] (6) [tetrathienylporphyrin (TTP), tetraphenylporphyrin (TPP), and pyridyloxy (PyO)]) were prepared and characterized and their photocytotoxicity upon irradiation with 625 nm light has been studied. The presence of the 3PyO axial ligands was found to limit the aggregation and enhance the solubility of 5 and 6 in DMF/H2O (1 : 1). The photophysical properties and photodynamic therapy (PDT) activity of the meso-2-thienyl and meso-phenyl-substituted Sn(IV) porphyrins are compared. 5 and 6 were found to be photocytotoxic in MCF-7 cancer cells when irradiated with a Thorlabs M625L3 LED at 625 nm but remained nontoxic in the dark. The PDT activity of Sn(IV) meso-tetra-2-thienylporphyrin 5 was found to be significantly enhanced relative to its analogous tetraphenylporphyrin 6. There is a marked red-shift of the Q00 band of 5 into the therapeutic window due to the meso-2-thienyl rings, and 5 has an unusually high singlet oxygen quantum yield value of 0.83 in DMF. The results demonstrate that readily synthesized axially ligated Sn(IV) meso-arylporphyrins are potentially suitable for use as singlet oxygen photosensitizers in biomedical applications and merit further in depth investigation in this context.
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- Authors: Babu, Balaji , Amuhaya, Edith K , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234592 , vital:50211 , xlink:href="https://doi.org/10.1039/C8MD00373D"
- Description: Sn(IV) porphyrins ([Sn(IV)TTP(3PyO)2] (5) and [Sn(IV)TPP(3PyO)2] (6) [tetrathienylporphyrin (TTP), tetraphenylporphyrin (TPP), and pyridyloxy (PyO)]) were prepared and characterized and their photocytotoxicity upon irradiation with 625 nm light has been studied. The presence of the 3PyO axial ligands was found to limit the aggregation and enhance the solubility of 5 and 6 in DMF/H2O (1 : 1). The photophysical properties and photodynamic therapy (PDT) activity of the meso-2-thienyl and meso-phenyl-substituted Sn(IV) porphyrins are compared. 5 and 6 were found to be photocytotoxic in MCF-7 cancer cells when irradiated with a Thorlabs M625L3 LED at 625 nm but remained nontoxic in the dark. The PDT activity of Sn(IV) meso-tetra-2-thienylporphyrin 5 was found to be significantly enhanced relative to its analogous tetraphenylporphyrin 6. There is a marked red-shift of the Q00 band of 5 into the therapeutic window due to the meso-2-thienyl rings, and 5 has an unusually high singlet oxygen quantum yield value of 0.83 in DMF. The results demonstrate that readily synthesized axially ligated Sn(IV) meso-arylporphyrins are potentially suitable for use as singlet oxygen photosensitizers in biomedical applications and merit further in depth investigation in this context.
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Synthesis and properties of chiral amide-bonded porphyrin dimers with various functional bridging blocks
- Zhu, Weihua, Haider, Syed Najeeb-uz-Zaman, Zhang, Honglin, Attatsi, Isaac K, Mack, John, Dingiswayo, Somila, Nyokong, Tebello, Song, Yuting, Xu, Haijun, Liang, Xu
- Authors: Zhu, Weihua , Haider, Syed Najeeb-uz-Zaman , Zhang, Honglin , Attatsi, Isaac K , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Song, Yuting , Xu, Haijun , Liang, Xu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186791 , vital:44534 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107740"
- Description: Eight porphyrin dimers with various functional bridging blocks and chiral amide-bonds were synthesized and characterized. An analysis of the spectroscopy and electrochemistry has been carried out to demonstrate that the chiral properties can be modified by changing the interchromophoric through-space coupling distance between the two porphyrin chromophores by introducing various bonding and bridging blocks.
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- Authors: Zhu, Weihua , Haider, Syed Najeeb-uz-Zaman , Zhang, Honglin , Attatsi, Isaac K , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Song, Yuting , Xu, Haijun , Liang, Xu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186791 , vital:44534 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107740"
- Description: Eight porphyrin dimers with various functional bridging blocks and chiral amide-bonds were synthesized and characterized. An analysis of the spectroscopy and electrochemistry has been carried out to demonstrate that the chiral properties can be modified by changing the interchromophoric through-space coupling distance between the two porphyrin chromophores by introducing various bonding and bridging blocks.
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Synthesis, characterization and photodynamic activity of Sn (iv) triarylcorroles with red-shifted Q bands
- Babu, Balaji, Prinsloo, Earl, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187521 , vital:44668 , xlink:href="https://doi.org/10.1039/C9NJ03391B"
- Description: Two Sn(IV) triarylcorroles were synthesised and characterized. The absorption spectrum of a meso-thien-2-yl substituted tin(IV)corrole (1-Sn) is red shifted compared to its phenyl analogue (2-Sn) and shows no sign of aggregation in solution. 1-Sn and 2-Sn exhibited singlet oxygen quantum yields of 0.87 and 0.54 in DMF, and have a triplet lifetime of 31 and 50 μs, respectively. Time dependent cellular uptake in MCF-7 cells for 1-Sn reached a peak at 24 h, and 1-Sn was found to be more lipophilic than 2-Sn. 1-Sn showed good photo-cytotoxicity on exposure to a Thorlabs 625 nm LED with an IC50 value of 3.2 μM and remained inactive in the dark.
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- Authors: Babu, Balaji , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187521 , vital:44668 , xlink:href="https://doi.org/10.1039/C9NJ03391B"
- Description: Two Sn(IV) triarylcorroles were synthesised and characterized. The absorption spectrum of a meso-thien-2-yl substituted tin(IV)corrole (1-Sn) is red shifted compared to its phenyl analogue (2-Sn) and shows no sign of aggregation in solution. 1-Sn and 2-Sn exhibited singlet oxygen quantum yields of 0.87 and 0.54 in DMF, and have a triplet lifetime of 31 and 50 μs, respectively. Time dependent cellular uptake in MCF-7 cells for 1-Sn reached a peak at 24 h, and 1-Sn was found to be more lipophilic than 2-Sn. 1-Sn showed good photo-cytotoxicity on exposure to a Thorlabs 625 nm LED with an IC50 value of 3.2 μM and remained inactive in the dark.
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Core-modified rubyrins with phenanthrene-fused pyrrole rings
- Yuan, Xuemei, Li, Minzhi, Meng, Ting, Mack, John, Soy, Rodah, Nyokong, Tebello, Zhu, Weihua, Xu, Haijun, Liang, Xu
- Authors: Yuan, Xuemei , Li, Minzhi , Meng, Ting , Mack, John , Soy, Rodah , Nyokong, Tebello , Zhu, Weihua , Xu, Haijun , Liang, Xu
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234568 , vital:50209 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.05.045"
- Description: Three fused-ring-expanded rubyrins with modified macrocyclic core have been synthesized and characterized. A series of spectroscopic, electrochemical measurements and a set of theoretical calculations demonstrate that the core-modification of the inner core of rubyrins has a large influence on the electronic structure. Colorimetric changes are observe that demonstrate that these core-modified rubyrins could be used as selective Hg2+ ion sensors. These properties can be fine-tuned by introducing lipophilic substituents on the meso-aryl rings.
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- Authors: Yuan, Xuemei , Li, Minzhi , Meng, Ting , Mack, John , Soy, Rodah , Nyokong, Tebello , Zhu, Weihua , Xu, Haijun , Liang, Xu
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234568 , vital:50209 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.05.045"
- Description: Three fused-ring-expanded rubyrins with modified macrocyclic core have been synthesized and characterized. A series of spectroscopic, electrochemical measurements and a set of theoretical calculations demonstrate that the core-modification of the inner core of rubyrins has a large influence on the electronic structure. Colorimetric changes are observe that demonstrate that these core-modified rubyrins could be used as selective Hg2+ ion sensors. These properties can be fine-tuned by introducing lipophilic substituents on the meso-aryl rings.
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Electrospun 3, 5-dithienylvinyleneBODIPY embedded polystyrene nanofibers for the photocatalytic degradation of azo dyes in industrial wastewaters
- Lebechi, Augustus K, Gai, Lizhi, Shen, Zhen, Nyokong, Tebello, Mack, John
- Authors: Lebechi, Augustus K , Gai, Lizhi , Shen, Zhen , Nyokong, Tebello , Mack, John
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187679 , vital:44686 , xlink:href="https://doi.org/10.1142/S1088424618500360"
- Description: The potential utility of electrospun polystyrene (PS) nanofibers embedded with 2,6-diiodo-8-phenyl-1,7-dimethyl-3,5-di-2-thienylvinyleneBODIPY for the photocatalytic degradation of azo dyes is investigated. A comparison of the singlet oxygen quantum yield of the ππ-extended BODIPY dye in solution and in the PS nanofibers demonstrates that its photosensitizer properties are retained when it is embedded in the solid phase. The photocatalytic degradation properties of the PS nanofibers for Methyl Orange and Orange G were determined by using a Thorlabs 625 nm light emitting diode. The rate of photodegradation increases with the Orange G and Methyl Orange concentration and follows pseudo-first order kinetics at pH 6.7.
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- Authors: Lebechi, Augustus K , Gai, Lizhi , Shen, Zhen , Nyokong, Tebello , Mack, John
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187679 , vital:44686 , xlink:href="https://doi.org/10.1142/S1088424618500360"
- Description: The potential utility of electrospun polystyrene (PS) nanofibers embedded with 2,6-diiodo-8-phenyl-1,7-dimethyl-3,5-di-2-thienylvinyleneBODIPY for the photocatalytic degradation of azo dyes is investigated. A comparison of the singlet oxygen quantum yield of the ππ-extended BODIPY dye in solution and in the PS nanofibers demonstrates that its photosensitizer properties are retained when it is embedded in the solid phase. The photocatalytic degradation properties of the PS nanofibers for Methyl Orange and Orange G were determined by using a Thorlabs 625 nm light emitting diode. The rate of photodegradation increases with the Orange G and Methyl Orange concentration and follows pseudo-first order kinetics at pH 6.7.
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Enhanced nonlinear optical response of benzothiazole substituted ball-type phthalocyanines in the presence of metallic nanoparticles
- Nwaji, Njemuwa, Mack, John, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188149 , vital:44727 , xlink:href="https://doi.org/10.1016/j.optmat.2018.05.052"
- Description: The synthesis of zinc-zinc, gallium-gallium and indium-indium ball-type phthalocyanines (complexes 4, 5 and 6) and the surface assembly of the complexes onto metallic gold and silver nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical dynamics were investigated. Decreases in the fluorescence quantum yields with a corresponding increase in the triplet quantum yields of the nanoconjugates in comparison to complexes 4, 5 and 6 alone were observed. The mechanism of strong reverse saturable absorption observed was found to be predominantly dependent on excited state absorption. The optical limiting thresholds range from 0.09 to 0.19 J/cm2. Enhanced triplet parameters and nonlinear optical responses were found when the complexes were conjugated to metallic nanoparticles.
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- Authors: Nwaji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188149 , vital:44727 , xlink:href="https://doi.org/10.1016/j.optmat.2018.05.052"
- Description: The synthesis of zinc-zinc, gallium-gallium and indium-indium ball-type phthalocyanines (complexes 4, 5 and 6) and the surface assembly of the complexes onto metallic gold and silver nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical dynamics were investigated. Decreases in the fluorescence quantum yields with a corresponding increase in the triplet quantum yields of the nanoconjugates in comparison to complexes 4, 5 and 6 alone were observed. The mechanism of strong reverse saturable absorption observed was found to be predominantly dependent on excited state absorption. The optical limiting thresholds range from 0.09 to 0.19 J/cm2. Enhanced triplet parameters and nonlinear optical responses were found when the complexes were conjugated to metallic nanoparticles.
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Iron (iii) porphyrin electrocatalyzed enantioselective carbon-chloride bond cleavage of hexachlorocyclohexanes (HCHs): combined experimental investigation and theoretical calculations
- Liang, Xu, Li, Minzhi, Mack, John, Lobb, Kevin A, Zhu, Weihua
- Authors: Liang, Xu , Li, Minzhi , Mack, John , Lobb, Kevin A , Zhu, Weihua
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/447979 , vital:74688 , xlink:href="https://pubs.rsc.org/en/content/articlehtml/2018/dt/c8dt02510j"
- Description: Enantioselective electrocatalysis of α-, β-, γ- and δ-hexachlorocyclohexanes (HCHs) by tetrakis-pentafluorophenyl-Fe(III)porphyrin is described. The first example of the combined use of electrochemical measurements and theoretical calculations to determine the mechanism of the enantioselective C–Cl bond cleavage of the electrocatalysis is reported. The electrochemical measurements demonstrate that the reactivity of the HCHs follows the order γ-HCH > α-HCH > δ-HCH > β-HCH. Steric considerations and a molecular orbital theory approach can be used to rationalize the enantioselective nature of the catalysis based on the ease of approach of each Cl atom to the central Fe(I) ion and a consideration of the nodes on the C–Cl bonds that weaken these bonds in a manner that results in bond cleavage and the formation of an Fe–Cl bond.
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- Authors: Liang, Xu , Li, Minzhi , Mack, John , Lobb, Kevin A , Zhu, Weihua
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/447979 , vital:74688 , xlink:href="https://pubs.rsc.org/en/content/articlehtml/2018/dt/c8dt02510j"
- Description: Enantioselective electrocatalysis of α-, β-, γ- and δ-hexachlorocyclohexanes (HCHs) by tetrakis-pentafluorophenyl-Fe(III)porphyrin is described. The first example of the combined use of electrochemical measurements and theoretical calculations to determine the mechanism of the enantioselective C–Cl bond cleavage of the electrocatalysis is reported. The electrochemical measurements demonstrate that the reactivity of the HCHs follows the order γ-HCH > α-HCH > δ-HCH > β-HCH. Steric considerations and a molecular orbital theory approach can be used to rationalize the enantioselective nature of the catalysis based on the ease of approach of each Cl atom to the central Fe(I) ion and a consideration of the nodes on the C–Cl bonds that weaken these bonds in a manner that results in bond cleavage and the formation of an Fe–Cl bond.
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Optical limiting properties of 3, 5-dipyrenylvinyleneBODIPY dyes at 532 nm
- Kubheka, Gugu, Sanusi, Kayode, Mack, John, Nyokong, Tebello
- Authors: Kubheka, Gugu , Sanusi, Kayode , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/237938 , vital:50567 , xlink:href="https://doi.org/10.1016/j.saa.2017.10.021"
- Description: The optical limiting (OL) properties of 3,5-dipyrenylvinyleneBODIPY dyes that contain both electron withdrawing and donating moieties have been investigated by using the z-scan technique at 532 nm in the nanosecond pulse range. The extension of the π-conjugation at the 3,5-positions with pyrenylvinylene groups results in a ca. 200 nm red shift of the main BODIPY spectral band to ca. 700 nm, so there is relatively weak absorbance at 532 nm under ambient light conditions. Reverse saturable absorbance (RSA) profiles are observed in response to incident pulsed laser light that is consistent with a two photon absorption-assisted excited state absorption (ESA) mechanism in CH2Cl2 solution and when the dyes are embedded in poly(bisphenol carbonate A) (PBC) polymer thin films. This demonstrates that 3,5-divinyleneBODIPY dyes are potentially suitable for use in OL applications, since limiting threshold fluence (Ilim) values of below 0.95 J cm−2 are observed when thin films are prepared.
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- Authors: Kubheka, Gugu , Sanusi, Kayode , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/237938 , vital:50567 , xlink:href="https://doi.org/10.1016/j.saa.2017.10.021"
- Description: The optical limiting (OL) properties of 3,5-dipyrenylvinyleneBODIPY dyes that contain both electron withdrawing and donating moieties have been investigated by using the z-scan technique at 532 nm in the nanosecond pulse range. The extension of the π-conjugation at the 3,5-positions with pyrenylvinylene groups results in a ca. 200 nm red shift of the main BODIPY spectral band to ca. 700 nm, so there is relatively weak absorbance at 532 nm under ambient light conditions. Reverse saturable absorbance (RSA) profiles are observed in response to incident pulsed laser light that is consistent with a two photon absorption-assisted excited state absorption (ESA) mechanism in CH2Cl2 solution and when the dyes are embedded in poly(bisphenol carbonate A) (PBC) polymer thin films. This demonstrates that 3,5-divinyleneBODIPY dyes are potentially suitable for use in OL applications, since limiting threshold fluence (Ilim) values of below 0.95 J cm−2 are observed when thin films are prepared.
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Photophysical and strong optical limiting properties of ball-type phthalocyanines dimers and their monomeric analogues
- Nwaji, Njemuwa, Mack, John, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187930 , vital:44711 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.10.045"
- Description: The nonlinear optical behaviors of ball-type phthalocyanine complexes: 1′,11,’15′,25′-tetrakis-[4,4′-((4-formyl-1,2-bisphenoxyl))bis(phthalocyaninato zinc (II)] (5), 1′,11,’15′,25′-tetrakis-[4,4′-((4-formyl-1,2-bisphenoxyl) bis(phthalocyaninato gallium (III) chloride)] (6), and 1′, 11,’15′,25′-tetrakis-4,4′-((4-formyl-1,2-phenoxyl)bis(phthalocyaninato indium (III) chloride)] (7) and the corresponding monomeric derivatives 8–10 were investigated using nanosecond pulse open aperture Z-scan technique at 532 nm. The nonlinear response showed strong reverse saturable absorption for all the complexes both in solution and when embedded in polymer matrix. The dimeric complexes showed better optical limiting properties compared to the monomeric derivatives. The βeff values for the dimeric complexes 5–7 were found to be 48.5, 55.2, and 60.1 cm/GW for 5, 6A, and 7 respectively, higher than the corresponding monomeric derivatives 8–10. Enhanced optical limiting properties were observed when the complexes were formulated in thin films. The second order hyperpolarizability values were in order of 10−28–10−26 esu in solution and 10−27–10−26 in films.
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- Authors: Nwaji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187930 , vital:44711 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.10.045"
- Description: The nonlinear optical behaviors of ball-type phthalocyanine complexes: 1′,11,’15′,25′-tetrakis-[4,4′-((4-formyl-1,2-bisphenoxyl))bis(phthalocyaninato zinc (II)] (5), 1′,11,’15′,25′-tetrakis-[4,4′-((4-formyl-1,2-bisphenoxyl) bis(phthalocyaninato gallium (III) chloride)] (6), and 1′, 11,’15′,25′-tetrakis-4,4′-((4-formyl-1,2-phenoxyl)bis(phthalocyaninato indium (III) chloride)] (7) and the corresponding monomeric derivatives 8–10 were investigated using nanosecond pulse open aperture Z-scan technique at 532 nm. The nonlinear response showed strong reverse saturable absorption for all the complexes both in solution and when embedded in polymer matrix. The dimeric complexes showed better optical limiting properties compared to the monomeric derivatives. The βeff values for the dimeric complexes 5–7 were found to be 48.5, 55.2, and 60.1 cm/GW for 5, 6A, and 7 respectively, higher than the corresponding monomeric derivatives 8–10. Enhanced optical limiting properties were observed when the complexes were formulated in thin films. The second order hyperpolarizability values were in order of 10−28–10−26 esu in solution and 10−27–10−26 in films.
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Photophysical properties of a novel styryl-BODIPY with a fused crown ether moiety
- Stone, Justin, Mack, John, Nyokong, Tebello, Kimura, Mitsumi, Kobayashi, Nagao
- Authors: Stone, Justin , Mack, John , Nyokong, Tebello , Kimura, Mitsumi , Kobayashi, Nagao
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188227 , vital:44736 , xlink:href="https://doi.org/10.1142/S1088424617500699"
- Description: The synthesis and characterization of a crown-ether-substituted 3-styrylBODIPY dye with a 4-isopropylphenyl group at the meso-position is reported. The effect that the incorporation of Na++ ions into the crown ether moiety has on the photophysical properties is investigated.
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- Authors: Stone, Justin , Mack, John , Nyokong, Tebello , Kimura, Mitsumi , Kobayashi, Nagao
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188227 , vital:44736 , xlink:href="https://doi.org/10.1142/S1088424617500699"
- Description: The synthesis and characterization of a crown-ether-substituted 3-styrylBODIPY dye with a 4-isopropylphenyl group at the meso-position is reported. The effect that the incorporation of Na++ ions into the crown ether moiety has on the photophysical properties is investigated.
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Porphyrin dimers with a bridging chiral amide-bonded benzo-moiety
- Liang, Xu, Qin, Mingfeng, Zhou, Lin, Liu, Tingting, Li, Minzhi, Mack, John, Ndebele, Nobuhle, Nyokong, Tebello, Zhu, Weihua
- Authors: Liang, Xu , Qin, Mingfeng , Zhou, Lin , Liu, Tingting , Li, Minzhi , Mack, John , Ndebele, Nobuhle , Nyokong, Tebello , Zhu, Weihua
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233433 , vital:50090 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.02.043"
- Description: The facile synthesis and characterization of four porphyrin dimers which introduced stereomeric centers with chiral amide-bonded para- and meta-disubstituted benzo-moiety is reported. Trends in the electronic structures and optical and redox properties are analyzed through a comparison with theoretical calculations to explore the effect of positional isomerism of the bridging benzene rings.
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- Authors: Liang, Xu , Qin, Mingfeng , Zhou, Lin , Liu, Tingting , Li, Minzhi , Mack, John , Ndebele, Nobuhle , Nyokong, Tebello , Zhu, Weihua
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233433 , vital:50090 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.02.043"
- Description: The facile synthesis and characterization of four porphyrin dimers which introduced stereomeric centers with chiral amide-bonded para- and meta-disubstituted benzo-moiety is reported. Trends in the electronic structures and optical and redox properties are analyzed through a comparison with theoretical calculations to explore the effect of positional isomerism of the bridging benzene rings.
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Pyridone substituted phthalocyanines: Photophysico-chemical properties and TD-DFT calculations
- Abdurrahmanoğlu, Şaziye, Canlica, Mevlüde, Mack, John, Nyokong, Tebello
- Authors: Abdurrahmanoğlu, Şaziye , Canlica, Mevlüde , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188216 , vital:44735 , xlink:href="https://doi.org/10.1142/S1088424617500730"
- Description: 4-(6-methyl-3-nitro-2-oxo-1,2-dihydropyridin-4-yloxy)phthalonitrile has been used to prepare a novel Zn(II) phthalocyanines with four peripheral pyridone substituents. The compound has been characterized by UV-visible absorption, FT-IR and 11H-NMR spectroscopy, elemental analysis and MALDI-TOF mass spectroscopy. The fluorescence, triplet quantum and singlet oxygen quantum yields have been determined and TD-DFT calculations have been used to identify trends in the electronic structure.
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- Authors: Abdurrahmanoğlu, Şaziye , Canlica, Mevlüde , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188216 , vital:44735 , xlink:href="https://doi.org/10.1142/S1088424617500730"
- Description: 4-(6-methyl-3-nitro-2-oxo-1,2-dihydropyridin-4-yloxy)phthalonitrile has been used to prepare a novel Zn(II) phthalocyanines with four peripheral pyridone substituents. The compound has been characterized by UV-visible absorption, FT-IR and 11H-NMR spectroscopy, elemental analysis and MALDI-TOF mass spectroscopy. The fluorescence, triplet quantum and singlet oxygen quantum yields have been determined and TD-DFT calculations have been used to identify trends in the electronic structure.
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Synthesis and photophysical properties of BODIPY-decorated graphene quantum dot–phthalocyanine conjugates
- Nwahara, Nnamdi, Nkhahle, Reitumetse, Ngoy, Bokolombe P, Mack, John, Nyokong, Tebello
- Authors: Nwahara, Nnamdi , Nkhahle, Reitumetse , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233409 , vital:50088 , xlink:href="https://doi.org/10.1039/C8NJ00758F"
- Description: This work reports on the synthesis and characterisation of novel supramolecular hybrids containing BODIPY-decorated graphene quantum dots (BODIPY@GQDs) and zinc phthalocyanine. Graphene quantum dots (GQDs) were functionalized with L-glutathione (GSH) in order to assist coupling to the BODIPY dye. {2,9(10)16(17)23(24)-Tetrakis-[3-(diethylamino)phenoxy]phthalocyaninato}zinc(II) (1) was immobilized via π–π stacking interaction on the BODIPY-decorated GQDs and pristine GQDs to form the supramolecular hybrids 1-BODIPY@GQDs and 1-GQDs, respectively. The photophysical and photochemical properties of these conjugates were investigated. Energy transfer occurred from the (i) GQDs to BODIPY, (ii) GQDs to 1, and (iii) BODIPY@GQDs to 1via fluorescence resonance energy transfer (FRET). The highest FRET efficiency was observed for the BODIPY@GQDs (0.93). The introduction of the BODIPY core to the GQD structure resulted in higher triplet, and singlet oxygen quantum yields for the resultant Pc/GQD hybrid (1-BODIPY@GQDs). The zeta potential values obtained imply a high colloidal stability for the supramolecular hybrids. The results suggest that such hybrids may be applied in fields such as photodynamic therapy (PDT), where a high singlet oxygen quantum yield is desired.
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- Authors: Nwahara, Nnamdi , Nkhahle, Reitumetse , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233409 , vital:50088 , xlink:href="https://doi.org/10.1039/C8NJ00758F"
- Description: This work reports on the synthesis and characterisation of novel supramolecular hybrids containing BODIPY-decorated graphene quantum dots (BODIPY@GQDs) and zinc phthalocyanine. Graphene quantum dots (GQDs) were functionalized with L-glutathione (GSH) in order to assist coupling to the BODIPY dye. {2,9(10)16(17)23(24)-Tetrakis-[3-(diethylamino)phenoxy]phthalocyaninato}zinc(II) (1) was immobilized via π–π stacking interaction on the BODIPY-decorated GQDs and pristine GQDs to form the supramolecular hybrids 1-BODIPY@GQDs and 1-GQDs, respectively. The photophysical and photochemical properties of these conjugates were investigated. Energy transfer occurred from the (i) GQDs to BODIPY, (ii) GQDs to 1, and (iii) BODIPY@GQDs to 1via fluorescence resonance energy transfer (FRET). The highest FRET efficiency was observed for the BODIPY@GQDs (0.93). The introduction of the BODIPY core to the GQD structure resulted in higher triplet, and singlet oxygen quantum yields for the resultant Pc/GQD hybrid (1-BODIPY@GQDs). The zeta potential values obtained imply a high colloidal stability for the supramolecular hybrids. The results suggest that such hybrids may be applied in fields such as photodynamic therapy (PDT), where a high singlet oxygen quantum yield is desired.
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The investigation of in vitro dark cytotoxicity and photodynamic therapy effect of a 2, 6-dibromo-3, 5-distyryl BODIPY dye encapsulated in Pluronic® F-127 micelles
- Molupe, Nthabeleng, Babu, Balaji, Oluwole, David O, Prinsloo, Earl, Mack, John, Nyokong, Tebello
- Authors: Molupe, Nthabeleng , Babu, Balaji , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187862 , vital:44704 , xlink:href="https://doi.org/10.1080/00958972.2018.1522536"
- Description: A 2,6-dibrominated 3,5-distyryl boron-dipyrromethene (BODIPY) dye with a moderately high singlet oxygen quantum yield was encapsulated in Pluronic® F-127 micelles, and its dark cytotoxicity and photodynamic activity were investigated on the human breast adenocarcinoma MCF-7 cell line. The BODIPY dye exhibited very low dark toxicity and a significant PDT effect when added in drug formulations consisting of 5.0% (v/v) DMSO in supplemented Dulbecco’s modified Eagle’s medium (DMEM) and as Pluronic® F-127 micelle encapsulation complexes in supplemented DMEM alone. An IC50 value of 4 ± 2 μM was obtained when the BODIPY dye was encapsulated in Pluronic® F-127 micelles during in vitro photodynamic activity studies in MCF-7 cancer cells with a 660 nm light emitting diode.
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- Authors: Molupe, Nthabeleng , Babu, Balaji , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187862 , vital:44704 , xlink:href="https://doi.org/10.1080/00958972.2018.1522536"
- Description: A 2,6-dibrominated 3,5-distyryl boron-dipyrromethene (BODIPY) dye with a moderately high singlet oxygen quantum yield was encapsulated in Pluronic® F-127 micelles, and its dark cytotoxicity and photodynamic activity were investigated on the human breast adenocarcinoma MCF-7 cell line. The BODIPY dye exhibited very low dark toxicity and a significant PDT effect when added in drug formulations consisting of 5.0% (v/v) DMSO in supplemented Dulbecco’s modified Eagle’s medium (DMEM) and as Pluronic® F-127 micelle encapsulation complexes in supplemented DMEM alone. An IC50 value of 4 ± 2 μM was obtained when the BODIPY dye was encapsulated in Pluronic® F-127 micelles during in vitro photodynamic activity studies in MCF-7 cancer cells with a 660 nm light emitting diode.
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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.
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- 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.
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