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:
- Date Issued: 2019
- 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:
- Date Issued: 2019
Morphological influence of deposition routes on lead sulfide thin films
- Mlowe, Sixberth, Shombe, Ginena B, Akerman, Matthew P, Mubofu, Egid B, O'Brien, Paul, Mashazi, Philani N, Nyokong, Tebello, Revaprasadu, Neerish
- Authors: Mlowe, Sixberth , Shombe, Ginena B , Akerman, Matthew P , Mubofu, Egid B , O'Brien, Paul , Mashazi, Philani N , Nyokong, Tebello , Revaprasadu, Neerish
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186780 , vital:44533 , xlink:href="https://doi.org/10.1016/j.ica.2019.119116"
- Description: A distorted single crystal structure of bis(piperidinedithiocarbamato)lead(II) complex and its subsequent use to deposit thin films is reported. Two deposition routes namely, aerosol-assisted chemical vapour deposition (AACVD) and spin coating deposition have been employed to obtain anisotropic lead sulfide (PbS) nanostructures. The thin films displayed rod to cubic shaped crystals for AACVD, and a range of cubes, star and dendritic morphologies with variation of temperatures were displayed for spin coated films. Optical band gaps between 1.32 and 1.55 eV as controlled by the change in temperature were observed for thin films deposited by AACVD. Powder X-ray diffraction (P-XRD) studies show that the films formed are composed of cubic crystalline PbS. The X-ray photoelectron spectroscopy (XPS) was used to investigate the effect of activation temperatures (350, 400 and 450 °C) on the chemical composition and oxidation states of PbS samples.
- Full Text:
- Date Issued: 2019
- Authors: Mlowe, Sixberth , Shombe, Ginena B , Akerman, Matthew P , Mubofu, Egid B , O'Brien, Paul , Mashazi, Philani N , Nyokong, Tebello , Revaprasadu, Neerish
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186780 , vital:44533 , xlink:href="https://doi.org/10.1016/j.ica.2019.119116"
- Description: A distorted single crystal structure of bis(piperidinedithiocarbamato)lead(II) complex and its subsequent use to deposit thin films is reported. Two deposition routes namely, aerosol-assisted chemical vapour deposition (AACVD) and spin coating deposition have been employed to obtain anisotropic lead sulfide (PbS) nanostructures. The thin films displayed rod to cubic shaped crystals for AACVD, and a range of cubes, star and dendritic morphologies with variation of temperatures were displayed for spin coated films. Optical band gaps between 1.32 and 1.55 eV as controlled by the change in temperature were observed for thin films deposited by AACVD. Powder X-ray diffraction (P-XRD) studies show that the films formed are composed of cubic crystalline PbS. The X-ray photoelectron spectroscopy (XPS) was used to investigate the effect of activation temperatures (350, 400 and 450 °C) on the chemical composition and oxidation states of PbS samples.
- Full Text:
- Date Issued: 2019
New type of metal-free and Zinc (II), In (III), Ga (III) phthalocyanines carrying biologically active substituents: Synthesis and photophysicochemical properties and photodynamic therapy activity
- Sen, Pinar, Managa, Muthumuni, Nyokong, Tebello
- Authors: Sen, Pinar , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186971 , vital:44552 , xlink:href="https://doi.org/10.1016/j.ica.2019.03.010"
- Description: This study reports on novel phthalocyanines having benzimidazole units which are known to have biological properties. 4-(4-(5-chloro-1H-benzo[d]imidazol-2-yl) substituted metal-free, Zn(II), In(III) and Ga(III) phthalocyanines were synthesized, these newly synthesized molecules that were substituted by oxygen bridges were fully characterized. For the purpose of determining their potency for photodynamic therapy, the photophysicochemical properties were investigated in DMSO. The H2Pc (4) showed higher fluorescence quantum yield and fluorescence lifetime as compared to metallated phthalocyanines derivatives. However, the highest singlet oxygen (ΦΔ) and triplet state quantum yields (ΦT) values were obtained with the In(III)Pc (5).
- Full Text:
- Date Issued: 2019
- Authors: Sen, Pinar , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186971 , vital:44552 , xlink:href="https://doi.org/10.1016/j.ica.2019.03.010"
- Description: This study reports on novel phthalocyanines having benzimidazole units which are known to have biological properties. 4-(4-(5-chloro-1H-benzo[d]imidazol-2-yl) substituted metal-free, Zn(II), In(III) and Ga(III) phthalocyanines were synthesized, these newly synthesized molecules that were substituted by oxygen bridges were fully characterized. For the purpose of determining their potency for photodynamic therapy, the photophysicochemical properties were investigated in DMSO. The H2Pc (4) showed higher fluorescence quantum yield and fluorescence lifetime as compared to metallated phthalocyanines derivatives. However, the highest singlet oxygen (ΦΔ) and triplet state quantum yields (ΦT) values were obtained with the In(III)Pc (5).
- Full Text:
- Date Issued: 2019
Nonlinear optical behavior of n-tuple decker phthalocyanines at the nanosecond regime
- Sekhosana, Kutloana E, Nyokong, Tebello
- Authors: Sekhosana, Kutloana E , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234603 , vital:50212 , xlink:href="https://doi.org/10.1039/C9RA01836K"
- Description: The coordination system of rare-earth n-tuple decker phthalocyanines would be better suited with appropriate metal ions with the correct coordination number and the solvent system of the reaction, amongst other reasons, for the formation of n-tuple decker phthalocyanines. As a result, these complexes are very rare. In this manuscript, we present new n-tuple decker phthalocyanines in the form of double- (complex 2), quadruple- (complex 3a) and sextuple-decker phthalocyanines (complex 3b), all of which contain neodymium and cadmium metal ions. The primary focus is the investigation of the nonlinear optical (NLO) mechanisms responsible for the observed reverse saturable absorption. While the extension of the π-electron system has been found to enhance the nonlinear optical behavior of complexes 3a and 3b, a change in the NLO mechanisms has been observed, with complex 2 lacking the triplet state population, as revealed by a laser flash photolysis technique. It has also been established that the excited state absorption cross sections follow a clear order of magnitude for the complexes under investigation: σ23 (for 3b) > σ23 (for 3a) > σ1m (for 2). This trend evidences the effects of the extension of the π-electron system.
- Full Text:
- Date Issued: 2019
- Authors: Sekhosana, Kutloana E , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234603 , vital:50212 , xlink:href="https://doi.org/10.1039/C9RA01836K"
- Description: The coordination system of rare-earth n-tuple decker phthalocyanines would be better suited with appropriate metal ions with the correct coordination number and the solvent system of the reaction, amongst other reasons, for the formation of n-tuple decker phthalocyanines. As a result, these complexes are very rare. In this manuscript, we present new n-tuple decker phthalocyanines in the form of double- (complex 2), quadruple- (complex 3a) and sextuple-decker phthalocyanines (complex 3b), all of which contain neodymium and cadmium metal ions. The primary focus is the investigation of the nonlinear optical (NLO) mechanisms responsible for the observed reverse saturable absorption. While the extension of the π-electron system has been found to enhance the nonlinear optical behavior of complexes 3a and 3b, a change in the NLO mechanisms has been observed, with complex 2 lacking the triplet state population, as revealed by a laser flash photolysis technique. It has also been established that the excited state absorption cross sections follow a clear order of magnitude for the complexes under investigation: σ23 (for 3b) > σ23 (for 3a) > σ1m (for 2). This trend evidences the effects of the extension of the π-electron system.
- Full Text:
- Date Issued: 2019
Nonlinear optical properties of metal free and nickel binuclear phthalocyanines
- Kabwe, Kapambwe P, Louzada, Marcel, Britton, Jonathan, Olomola,Temitope O, Nyokong, Tebello, Khene, Samson M
- Authors: Kabwe, Kapambwe P , Louzada, Marcel , Britton, Jonathan , Olomola,Temitope O , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186846 , vital:44539 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.05.003"
- Description: This work employs the open and closed Z-scan aperture technique to comparatively study the nonlinear optical (NLO) properties of nickel and metal free 4-tert-butylphenoxy phthalocyanine, biphenyl bridged bis-4-tert-butylphenoxy phthalocyanine and naphthalene bridged bis-4-tert-butylphenoxy phthalocyanine. Density functional theory (DFT) calculations of dipolar and octupolar ( J=1 and J=3) contribution were determined theoretically from hyper-Rayleigh scattering (HRS) response ( HRS) values.
- Full Text:
- Date Issued: 2019
- Authors: Kabwe, Kapambwe P , Louzada, Marcel , Britton, Jonathan , Olomola,Temitope O , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186846 , vital:44539 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.05.003"
- Description: This work employs the open and closed Z-scan aperture technique to comparatively study the nonlinear optical (NLO) properties of nickel and metal free 4-tert-butylphenoxy phthalocyanine, biphenyl bridged bis-4-tert-butylphenoxy phthalocyanine and naphthalene bridged bis-4-tert-butylphenoxy phthalocyanine. Density functional theory (DFT) calculations of dipolar and octupolar ( J=1 and J=3) contribution were determined theoretically from hyper-Rayleigh scattering (HRS) response ( HRS) values.
- Full Text:
- Date Issued: 2019
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:
- Date Issued: 2019
- 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:
- Date Issued: 2019
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:
- Date Issued: 2019
- 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:
- Date Issued: 2019
Photo-physicochemical properties and in vitro photodynamic therapy activity of morpholine-substituted Zinc (II)-Phthalocyanines π-π stacked on biotinylated graphene quantum dots
- Nene, Lindokuhle, Managa, Muthumuni, Nyokong, Tebello
- Authors: Nene, Lindokuhle , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186993 , vital:44554 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.03.002"
- Description: Two morpholine-substituted Zn(II) phthalocyanines, complex 4 and the cationic 5, were synthesized and conjugated to graphene quantum dots (GQDs) and biotinylated GQDs (GQDs-biotin) by non-covalent π-π interactions. The GQDs-biotin are prepared as potential nanoparticle-based Pc delivery vector combined with a receptor-mediated transport system using biotin. The photo-physicochemical properties of the Pc complexes and their corresponding conjugates were studied. Upon conjugation, the fluorescence quantum yields decrease for 4 and 5, however, the triplet quantum yields were increased for the conjugates. All samples demonstrated singlet oxygen generation. For conjugated complexes, the singlet quantum yields decreased due to the screening effect in some cases. An increase in the photodynamic therapy activities upon quaternization was observed for the conjugates, with the cell viability decreasing from 66.2% to 51.2% after treatment for 4-GQDs and 5-GQDs, respectively. A relatively better performance was also observed for the cationic complex in combination with the biotin functionalized GQDs, 5-GQDs-biotin, where the cell viability was 34.9% after treatment. Moreover, the cellular uptake of 5-GQDs-biotin over 24 h was relatively higher compared to Pc complex alone and other PcsGQDs conjugates.
- Full Text:
- Date Issued: 2019
- Authors: Nene, Lindokuhle , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186993 , vital:44554 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.03.002"
- Description: Two morpholine-substituted Zn(II) phthalocyanines, complex 4 and the cationic 5, were synthesized and conjugated to graphene quantum dots (GQDs) and biotinylated GQDs (GQDs-biotin) by non-covalent π-π interactions. The GQDs-biotin are prepared as potential nanoparticle-based Pc delivery vector combined with a receptor-mediated transport system using biotin. The photo-physicochemical properties of the Pc complexes and their corresponding conjugates were studied. Upon conjugation, the fluorescence quantum yields decrease for 4 and 5, however, the triplet quantum yields were increased for the conjugates. All samples demonstrated singlet oxygen generation. For conjugated complexes, the singlet quantum yields decreased due to the screening effect in some cases. An increase in the photodynamic therapy activities upon quaternization was observed for the conjugates, with the cell viability decreasing from 66.2% to 51.2% after treatment for 4-GQDs and 5-GQDs, respectively. A relatively better performance was also observed for the cationic complex in combination with the biotin functionalized GQDs, 5-GQDs-biotin, where the cell viability was 34.9% after treatment. Moreover, the cellular uptake of 5-GQDs-biotin over 24 h was relatively higher compared to Pc complex alone and other PcsGQDs conjugates.
- Full Text:
- Date Issued: 2019
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:
- Date Issued: 2019
- 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:
- Date Issued: 2019
Photophysical and nonlinear optical characteristics of pyridyl substituted phthalocyanine-detonation nanodiamond conjugated systems in solution
- Matshitse, Refilwe, Khene, Samson M, Nyokong, Tebello
- Authors: Matshitse, Refilwe , Khene, Samson M , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187079 , vital:44563 , xlink:href="https://doi.org/10.1016/j.diamond.2019.03.013"
- Description: In this study photophysical, nonlinear absorption and optical limiting properties of detonation nanodiamonds (DNDs)-phthalocyanine nanoconjugate systems containing: 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyaninato (H2TPPc), 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato zinc(II) (ZnTPPc) and 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato silicon(IV) hydroxide (Si(OH)2TPPc), were investigated in dimethylsulfoxide solution. Pcs were non-covalently linked to nanondiamonds (also covalently linked for Si(OH)2TPPc) and investigated using 532 nm laser excitation at 10 ns pulses for their optical limiting properties. Complexes that have higher triplet state absorption also possessed enhanced nonlinear optical behaviour following reverse saturable absorption mechanism. Superior optical performance is observed when the Pcs had a central metal with axial ligands conjugated to DNDs in solution. Nanoconjugate of DNDs-Si(OH)2TPPc and respective Pc in solution gave the highest imaginary third-order susceptibility (Im[X(3)]) and hyperpolarizability (γ) at 2.91 × 10−8 and 3.17 × 10−8 esu and 3.88 × 10−28 and 4.22 × 10−28 esu, respectively, with Ilim value of 0.47 and 0.39 J·cm−2.
- Full Text:
- Date Issued: 2019
- Authors: Matshitse, Refilwe , Khene, Samson M , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187079 , vital:44563 , xlink:href="https://doi.org/10.1016/j.diamond.2019.03.013"
- Description: In this study photophysical, nonlinear absorption and optical limiting properties of detonation nanodiamonds (DNDs)-phthalocyanine nanoconjugate systems containing: 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyaninato (H2TPPc), 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato zinc(II) (ZnTPPc) and 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato silicon(IV) hydroxide (Si(OH)2TPPc), were investigated in dimethylsulfoxide solution. Pcs were non-covalently linked to nanondiamonds (also covalently linked for Si(OH)2TPPc) and investigated using 532 nm laser excitation at 10 ns pulses for their optical limiting properties. Complexes that have higher triplet state absorption also possessed enhanced nonlinear optical behaviour following reverse saturable absorption mechanism. Superior optical performance is observed when the Pcs had a central metal with axial ligands conjugated to DNDs in solution. Nanoconjugate of DNDs-Si(OH)2TPPc and respective Pc in solution gave the highest imaginary third-order susceptibility (Im[X(3)]) and hyperpolarizability (γ) at 2.91 × 10−8 and 3.17 × 10−8 esu and 3.88 × 10−28 and 4.22 × 10−28 esu, respectively, with Ilim value of 0.47 and 0.39 J·cm−2.
- Full Text:
- Date Issued: 2019
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.
- Full Text:
- Date Issued: 2019
- 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.
- Full Text:
- Date Issued: 2019
Photophysical properties and photodynamic therapy activity of a meso-tetra (4-carboxyphenyl) porphyrin tetramethyl ester–graphene quantum dot conjugate
- Managa, Muthumuni, Ngoy, Bokolombe P, Nyokong, Tebello
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187533 , vital:44669 , xlink:href="https://doi.org/10.1039/C8NJ06175K"
- Description: Novel meso-tetra(4-carboxyphenyl)porphyrin tetramethyl ester metal derivatives were synthesised and characterized. These derivatives were interacted with graphene quantum dots (GDQs). Spectroscopic evidence that was obtained showed that the resultant conjugates were stable due to the strong π–π stacking interaction between the GQDs and the porphyrins. The fluorescence and singlet oxygen generating behaviour of the porphyrins and the nanoconjugates were investigated following incorporation. The dark toxicity and photodynamic therapy activities of the porphyrins and the nanoconjugates were successfully studied using MCF-7 breast cancer cells. Cell viability for the dark toxicity was more than 90% for all complexes. The PDT activities at the highest concentration of 120 μg ml−1 showed a decrease in cell viability down to 15.2% for the GaClTMPP–GQDs.
- Full Text:
- Date Issued: 2019
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187533 , vital:44669 , xlink:href="https://doi.org/10.1039/C8NJ06175K"
- Description: Novel meso-tetra(4-carboxyphenyl)porphyrin tetramethyl ester metal derivatives were synthesised and characterized. These derivatives were interacted with graphene quantum dots (GDQs). Spectroscopic evidence that was obtained showed that the resultant conjugates were stable due to the strong π–π stacking interaction between the GQDs and the porphyrins. The fluorescence and singlet oxygen generating behaviour of the porphyrins and the nanoconjugates were investigated following incorporation. The dark toxicity and photodynamic therapy activities of the porphyrins and the nanoconjugates were successfully studied using MCF-7 breast cancer cells. Cell viability for the dark toxicity was more than 90% for all complexes. The PDT activities at the highest concentration of 120 μg ml−1 showed a decrease in cell viability down to 15.2% for the GaClTMPP–GQDs.
- Full Text:
- Date Issued: 2019
Photophysicochemical and photodynamic therapy properties of metallophthalocyanines linked to gold speckled silica nanoparticles
- Dube, Edith, Oluwole, David O, Niemuwa, Nwaji, Prinsloo, Earl, Nyokong, Tebello
- Authors: Dube, Edith , Oluwole, David O , Niemuwa, Nwaji , Prinsloo, Earl , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187472 , vital:44657 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.01.019"
- Description: This work reports on the linkage of 2(3),9(10),16(17),23(24) tetrakis [(benzo[d]thiazol-2-yl phenoxy) phthalocyaninato] zinc(II) (1) and indium(III) chloride (2) to gold speckled silica (GSS) nanoparticles via gold to sulphur (Au-S) and gold to nitrogen (Au-N) self-assembly to form the conjugates: 1-GSS and 2-GSS. The formed conjugates were characterized using microscopic and spectroscopic techniques, and the photophysicochemical properties and photodynamic therapy (PDT) activity against human breast adenocarcinoma cell line (MCF-7 cells) were studied. The conjugates afforded decrease in fluorescence quantum yields with corresponding increase in triplet and singlet oxygen quantum yields when compared to phthalocyanines alone. Singlet oxygen is cytotoxic to cancer cells hence it is important for PDT. The in vitro dark toxicity of complex 2 and 2-GSS against MCF–7 cells showed ≥93% viable cells within concentration ranges of 10–160 μg/mL. 2–GSS showed enhanced PDT activity with less than 50% viable cells at 80 μg/mL as compared to 2 and GSS alone which showed > 60% viable cells within 10–160 μg/mL. The observed improvements in the PDT activity of 2-GSS could be attributed to the high singlet oxygen generation of 2-GSS compared to 2 alone in addition to the phototoxicity of GSS.
- Full Text:
- Date Issued: 2019
- Authors: Dube, Edith , Oluwole, David O , Niemuwa, Nwaji , Prinsloo, Earl , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187472 , vital:44657 , xlink:href="https://doi.org/10.1016/j.pdpdt.2019.01.019"
- Description: This work reports on the linkage of 2(3),9(10),16(17),23(24) tetrakis [(benzo[d]thiazol-2-yl phenoxy) phthalocyaninato] zinc(II) (1) and indium(III) chloride (2) to gold speckled silica (GSS) nanoparticles via gold to sulphur (Au-S) and gold to nitrogen (Au-N) self-assembly to form the conjugates: 1-GSS and 2-GSS. The formed conjugates were characterized using microscopic and spectroscopic techniques, and the photophysicochemical properties and photodynamic therapy (PDT) activity against human breast adenocarcinoma cell line (MCF-7 cells) were studied. The conjugates afforded decrease in fluorescence quantum yields with corresponding increase in triplet and singlet oxygen quantum yields when compared to phthalocyanines alone. Singlet oxygen is cytotoxic to cancer cells hence it is important for PDT. The in vitro dark toxicity of complex 2 and 2-GSS against MCF–7 cells showed ≥93% viable cells within concentration ranges of 10–160 μg/mL. 2–GSS showed enhanced PDT activity with less than 50% viable cells at 80 μg/mL as compared to 2 and GSS alone which showed > 60% viable cells within 10–160 μg/mL. The observed improvements in the PDT activity of 2-GSS could be attributed to the high singlet oxygen generation of 2-GSS compared to 2 alone in addition to the phototoxicity of GSS.
- Full Text:
- Date Issued: 2019
Physicochemical and antimicrobial photodynamic chemotherapy (against E. coli) by indium phthalocyanines in the presence of silver–iron bimetallic nanoparticles
- Magadla, Aviwe, Oluwole, David O, Managa, Muthumuni, Nyokong, Tebello
- Authors: Magadla, Aviwe , Oluwole, David O , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187091 , vital:44564 , xlink:href="https://doi.org/10.1016/j.poly.2019.01.032"
- Description: In this work, Schiff base indium phthalocyanines: In–Cl tetrakis N,N-dimethyl-4-(methylimino) phthalocyanine (complex 1b) and In–Cl tetrakis phenoxy N,N-dimethyl-4-(methylimino) phthalocyanine (complex 2b) are synthesized from tetra amino and tetra phenoxy amino phthalocyanines, respectively. These complexes were further quartenised with 1,3-propanesultone to form zwitterionic complexes 1 and 2, respectively. Silver–iron dimers (Ag–Fe3O4) and silver-iron core shell (Ag@Fe3O4) nanoparticles (NPs) were linked to the synthesised complexes. The photophysical and photochemical behaviour of the complexes and their conjugates with NPs were investigated in dimethyl sulfoxide. Complexes 2 and 2b and their conjugates were then used for photodynamic antimicrobial chemotherapy on Escherichia coli. The zwitter ionic photosensitiser 2 and its conjugates showed better efficiency for photodynamic antimicrobial chemotherapy compared to their neutral counterparts.
- Full Text:
- Date Issued: 2019
- Authors: Magadla, Aviwe , Oluwole, David O , Managa, Muthumuni , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187091 , vital:44564 , xlink:href="https://doi.org/10.1016/j.poly.2019.01.032"
- Description: In this work, Schiff base indium phthalocyanines: In–Cl tetrakis N,N-dimethyl-4-(methylimino) phthalocyanine (complex 1b) and In–Cl tetrakis phenoxy N,N-dimethyl-4-(methylimino) phthalocyanine (complex 2b) are synthesized from tetra amino and tetra phenoxy amino phthalocyanines, respectively. These complexes were further quartenised with 1,3-propanesultone to form zwitterionic complexes 1 and 2, respectively. Silver–iron dimers (Ag–Fe3O4) and silver-iron core shell (Ag@Fe3O4) nanoparticles (NPs) were linked to the synthesised complexes. The photophysical and photochemical behaviour of the complexes and their conjugates with NPs were investigated in dimethyl sulfoxide. Complexes 2 and 2b and their conjugates were then used for photodynamic antimicrobial chemotherapy on Escherichia coli. The zwitter ionic photosensitiser 2 and its conjugates showed better efficiency for photodynamic antimicrobial chemotherapy compared to their neutral counterparts.
- Full Text:
- Date Issued: 2019
Physicochemical and photodynamic antimicrobial chemotherapy activity of morpholine-substituted phthalocyanines: Effect of point of substitution and central metal
- Sindelo, Azole, Kobayashi, Nagao, Kimura, Mutsumi, Nyokong, Tebello
- Authors: Sindelo, Azole , Kobayashi, Nagao , Kimura, Mutsumi , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187438 , vital:44652 , xlink:href="https://doi.org/10.1016/j.jphotochem.2019.01.025"
- Description: In this study, novel metal-free, zinc and indium 1(4),8(11),15(18),22(25)-tetramorpholine (1a, 2a, 3a respectively) and 2(3), 9(10), 16(17),23(24)-tetramorpholine (1b, 2b, 3b respectively) phthalocyanines were synthesized and complexes 2 and 3 were quaternized. The photophysical and photochemical properties were investigated in dimethylsulfoxide. The non-peripherally substituted phthalocyanines generated higher singlet oxygen than the peripherally substituted phthalocyanines. Photodynamic antimicrobial chemotherapy activities towards inactivation of Escherichia coli, Staphylococcus aureus and Candida albican were evaluated, where all the quaternized Pcs showed total elimination of the micro-organism with log reductions greater than 9. Though the neutral Pcs had log reductions less than 2, for C. albican the percentage reduction was 68.5% for 2b showing the antifungal properties of the morpholine group.
- Full Text:
- Date Issued: 2019
- Authors: Sindelo, Azole , Kobayashi, Nagao , Kimura, Mutsumi , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187438 , vital:44652 , xlink:href="https://doi.org/10.1016/j.jphotochem.2019.01.025"
- Description: In this study, novel metal-free, zinc and indium 1(4),8(11),15(18),22(25)-tetramorpholine (1a, 2a, 3a respectively) and 2(3), 9(10), 16(17),23(24)-tetramorpholine (1b, 2b, 3b respectively) phthalocyanines were synthesized and complexes 2 and 3 were quaternized. The photophysical and photochemical properties were investigated in dimethylsulfoxide. The non-peripherally substituted phthalocyanines generated higher singlet oxygen than the peripherally substituted phthalocyanines. Photodynamic antimicrobial chemotherapy activities towards inactivation of Escherichia coli, Staphylococcus aureus and Candida albican were evaluated, where all the quaternized Pcs showed total elimination of the micro-organism with log reductions greater than 9. Though the neutral Pcs had log reductions less than 2, for C. albican the percentage reduction was 68.5% for 2b showing the antifungal properties of the morpholine group.
- Full Text:
- Date Issued: 2019
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.
- Full Text:
- Date Issued: 2019
- 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.
- Full Text:
- Date Issued: 2019
Spectroscopic and nonlinear optical properties of alkyl thio substituted binuclear phthalocyanines
- Makinde, Zainab O, Louzada, Marcel S, Britton, Jonathan, Nyokong, Tebello, Khene, Samson M
- Authors: Makinde, Zainab O , Louzada, Marcel S , Britton, Jonathan , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187485 , vital:44661 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.10.022"
- Description: This work presents the spectroscopic and nonlinear optical properties of metal free binuclear and monomeric 4- (pentylthio)phthalocyanine and cobalt 4,5-(bipentylthio)phthalocyanine. Second order nonlinear absorption coefficient (β) values for the complexes were determined and compared.
- Full Text:
- Date Issued: 2019
- Authors: Makinde, Zainab O , Louzada, Marcel S , Britton, Jonathan , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187485 , vital:44661 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.10.022"
- Description: This work presents the spectroscopic and nonlinear optical properties of metal free binuclear and monomeric 4- (pentylthio)phthalocyanine and cobalt 4,5-(bipentylthio)phthalocyanine. Second order nonlinear absorption coefficient (β) values for the complexes were determined and compared.
- Full Text:
- Date Issued: 2019
Spectroscopic characterization and photodynamic antimicrobial chemotherapy of phthalocyanine-silver triangular nanoprism conjugates when supported on asymmetric polymer membranes
- Mafukidze, Donovan M, Sindelo, Azole, Nyokong, Tebello
- Authors: Mafukidze, Donovan M , Sindelo, Azole , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186927 , vital:44548 , xlink:href="https://doi.org/10.1016/j.saa.2019.04.054"
- Description: Silver triangular nanoprisms were synthesized and conjugated to zinc (ZnPc) and indium (InPc) phthalocyanines prior to embedding in asymmetric membranes. Conjugation of nanoparticles increased triplet state and singlet oxygen quantum yields of the phthalocyanines as well as enhancing photodynamic antimicrobial chemotherapy (PACT) activity against bacteria (S. aureus). The ZnPc derivative showed higher PACT activity when compared to the InPc, possibly due to degradation of the latter in aqueous media.
- Full Text:
- Date Issued: 2019
- Authors: Mafukidze, Donovan M , Sindelo, Azole , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186927 , vital:44548 , xlink:href="https://doi.org/10.1016/j.saa.2019.04.054"
- Description: Silver triangular nanoprisms were synthesized and conjugated to zinc (ZnPc) and indium (InPc) phthalocyanines prior to embedding in asymmetric membranes. Conjugation of nanoparticles increased triplet state and singlet oxygen quantum yields of the phthalocyanines as well as enhancing photodynamic antimicrobial chemotherapy (PACT) activity against bacteria (S. aureus). The ZnPc derivative showed higher PACT activity when compared to the InPc, possibly due to degradation of the latter in aqueous media.
- Full Text:
- Date Issued: 2019
Synthesis and photophysicochemical properties of novel axially di-substituted silicon (IV) phthalocyanines and their photodynamic antimicrobial chemotherapy (PACT) activity against Staphylococcus aureus
- Sen, Pinar, Sindelo, Azole, Mafukidze, Donovan M, Nyokong, Tebello
- Authors: Sen, Pinar , Sindelo, Azole , Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186757 , vital:44531 , xlink:href="https://doi.org/10.1016/j.synthmet.2019.116203"
- Description: In this study, novel silicon (IV) phthalocyanine axially di-substituted with benzimidazole moieties (3) and its quaternized derivative (4) have been synthesized and fully characterized. The photophysical and photochemical properties of both phthalocyanines such as absorption, fluorescence and, singlet oxygen quantum yields, triplet state quantum yields and exited state lifetimes were investigated in solutions. These new silicon phthalocyanines exhibited low fluorescence but produced high singlet oxygen yields in both DMSO (compound 3 and 4) and aqueous media (compound 4). The quaternization of Si(IV)Pc (3) improved the triplet state quantum yield (ΦT) 0.61 to 0.83, consequently singlet oxygen generation (ΦΔ) increased to 0.69 from 0.42. Photodynamic antimicrobial chemotherapy activities (PACT) of Si(IV)Pc photosensitizers were determined towards Staphylococcus aureus. The higher efficiency was obtained with cationic derivative (4) giving reduction percentage value of 99.75%.
- Full Text:
- Date Issued: 2019
- Authors: Sen, Pinar , Sindelo, Azole , Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186757 , vital:44531 , xlink:href="https://doi.org/10.1016/j.synthmet.2019.116203"
- Description: In this study, novel silicon (IV) phthalocyanine axially di-substituted with benzimidazole moieties (3) and its quaternized derivative (4) have been synthesized and fully characterized. The photophysical and photochemical properties of both phthalocyanines such as absorption, fluorescence and, singlet oxygen quantum yields, triplet state quantum yields and exited state lifetimes were investigated in solutions. These new silicon phthalocyanines exhibited low fluorescence but produced high singlet oxygen yields in both DMSO (compound 3 and 4) and aqueous media (compound 4). The quaternization of Si(IV)Pc (3) improved the triplet state quantum yield (ΦT) 0.61 to 0.83, consequently singlet oxygen generation (ΦΔ) increased to 0.69 from 0.42. Photodynamic antimicrobial chemotherapy activities (PACT) of Si(IV)Pc photosensitizers were determined towards Staphylococcus aureus. The higher efficiency was obtained with cationic derivative (4) giving reduction percentage value of 99.75%.
- Full Text:
- Date Issued: 2019
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.
- Full Text:
- Date Issued: 2019
- 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.
- Full Text:
- Date Issued: 2019