Structural modification of RhIIItriarylcorroles for enhanced electrocatalyzed hydrogen evolution reactions
- Zhu, Weihua, Li, Lihua, Wang, Yu, Mack, John, Dingiswayo, Somila, Nyokong, Tebello, Liang, Xu
- Authors: Zhu, Weihua , Li, Lihua , Wang, Yu , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229933 , vital:49724 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.110046"
- Description: A series of A3 type RhIIItriarylcorroles 2a-c with different meso-substituents with differing electron-donating and withdrawing properties and two A2B type RhIIItriarylcorroles 4a-b with meso-methylthiophenyls at the B position have been prepared and characterized. An analysis of structure-property relationships of 2a-c and 4a-b has been carried out by comparing the optical spectroscopy and electrochemistry of the dyes to trends predicted in DFT and TD-DFT calculations. Rational structural modification strategies that enhance the suitability of 2a-c for use as highly efficient catalysts for hydrogen evolution reactions on glassy carbon electrodes coated with 2a-c/reduced graphene oxide composites and of 4a-b in surface-modified Au electrodes are explored.
- Full Text:
- Date Issued: 2022
- Authors: Zhu, Weihua , Li, Lihua , Wang, Yu , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229933 , vital:49724 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.110046"
- Description: A series of A3 type RhIIItriarylcorroles 2a-c with different meso-substituents with differing electron-donating and withdrawing properties and two A2B type RhIIItriarylcorroles 4a-b with meso-methylthiophenyls at the B position have been prepared and characterized. An analysis of structure-property relationships of 2a-c and 4a-b has been carried out by comparing the optical spectroscopy and electrochemistry of the dyes to trends predicted in DFT and TD-DFT calculations. Rational structural modification strategies that enhance the suitability of 2a-c for use as highly efficient catalysts for hydrogen evolution reactions on glassy carbon electrodes coated with 2a-c/reduced graphene oxide composites and of 4a-b in surface-modified Au electrodes are explored.
- Full Text:
- Date Issued: 2022
The synthesis and characterisation of Sn(IV) porphyrin derivatives and their potential application in anti-cancer and antimicrobial photodynamic therapy
- Authors: Dingiswayo, Somila
- Date: 2021-10
- Subjects: Porphyrins , Photochemotherapy , Cancer Photochemotherapy , Active oxygen Physiological effect , Aromaticity (Chemistry) , Tetrapyrroles , Magnetic circular dichroism , Corroles , Chlorins , Photodynamic antimicrobial chemotherapy (PACT)
- Language: English
- Type: Masters theses , text
- Identifier: http://hdl.handle.net/10962/188843 , vital:44791
- Description: In photodynamic therapy (PDT), the activation of light-sensitive drugs in tumour cells produces reactive singlet oxygen species, which cause tumour destruction through a cascade of biochemical reactions. Over the years, the wavelength of activation has been shown to be a critical factor in the penetration of light. Hence the properties of photosensitiser dyes in this context shape their ability to treat deep-seated tumours. In this study, the synthesis, structural characterisation and photophysicochemical properties of a series of Sn(IV) porphyrins with meso-methylthiophenyl rings that have been prepared to study their PDT and photodynamic antimicrobial chemotherapy (PACT) activity properties are reported. The series of Sn(IV) complexes is comprised of a porphyrin (1-Sn), a corrole (2-Sn), a chlorin (3-Sn) and an N-confused porphyrin (4-Sn). Herein, the low symmetry Sn(IV) porphyrin derivatives are shown to have excellent singlet oxygen generation capabilities, and lifetimes of the triplet excited states were in the microsecond range. For example, 4-Sn had a singlet oxygen quantum yield (ФΔ) and an excited triplet state lifetime (τT) of 0.88 and 27 μs, respectively. The complexes were studied using UV-visible and magnetic circular dichroism (MCD) spectroscopies. Interestingly, the positive-to-negative sign sequences of the Faraday B0 terms of 2-Sn and 3-Sn reveal that the structural modifications involved break the degeneracy of the MOs derived from the 1eg* LUMO of the porphyrin 1-Sn. In contrast, a conventional negative-to-positive sign sequence is observed for 4-Sn, since the confusion of a pyrrole moiety also results in a large separation of the 1a1u and 1a2u MOs of the porphyrin 1-Sn that are derived from the HOMO of a C16H162−parent hydrocarbon perimeter. The trends in the electronic structures of the Sn(IV) complexes were further investigated through a series of time-dependent density functional theory calculations, so that the suitability of the different types of complex for use in singlet oxygen applications could be further explored. During in vitro photodynamic antimicrobial chemotherapy (PACT) studies, chlorin derivative 3-Sn had the highest activity towards S. aureus and E. coli with log10 reductions of 10.5 and 8.74, respectively. The unusually high activity of 3-Sn against E.coli suggests that the interaction of neutral photosensitisers with gram-negativebacteria is more complex than previously understood. Anti-cancer PDT studies demonstrated that the photosensitisers had negligible dark cytotoxicity. Upon photoirradiation, the Sn(IV) complexes consistently exhibited IC50 values lower than 15 μM against MCF-7 adenocarcinoma cells. An IC50 value of 1.4 μM for 4-Sn after activation at the deep-red region of the spectrum demonstrates that complexes of this type merit further in-depth investigation. The results provide evidence that the low-symmetry Sn(IV) chlorins and N-confused porphyrins merit further in-depth study for use in singlet oxygen applications. , Thesis (MSc) -- Faculty of Science, Chemistry, 2021
- Full Text:
- Date Issued: 2021-10
- Authors: Dingiswayo, Somila
- Date: 2021-10
- Subjects: Porphyrins , Photochemotherapy , Cancer Photochemotherapy , Active oxygen Physiological effect , Aromaticity (Chemistry) , Tetrapyrroles , Magnetic circular dichroism , Corroles , Chlorins , Photodynamic antimicrobial chemotherapy (PACT)
- Language: English
- Type: Masters theses , text
- Identifier: http://hdl.handle.net/10962/188843 , vital:44791
- Description: In photodynamic therapy (PDT), the activation of light-sensitive drugs in tumour cells produces reactive singlet oxygen species, which cause tumour destruction through a cascade of biochemical reactions. Over the years, the wavelength of activation has been shown to be a critical factor in the penetration of light. Hence the properties of photosensitiser dyes in this context shape their ability to treat deep-seated tumours. In this study, the synthesis, structural characterisation and photophysicochemical properties of a series of Sn(IV) porphyrins with meso-methylthiophenyl rings that have been prepared to study their PDT and photodynamic antimicrobial chemotherapy (PACT) activity properties are reported. The series of Sn(IV) complexes is comprised of a porphyrin (1-Sn), a corrole (2-Sn), a chlorin (3-Sn) and an N-confused porphyrin (4-Sn). Herein, the low symmetry Sn(IV) porphyrin derivatives are shown to have excellent singlet oxygen generation capabilities, and lifetimes of the triplet excited states were in the microsecond range. For example, 4-Sn had a singlet oxygen quantum yield (ФΔ) and an excited triplet state lifetime (τT) of 0.88 and 27 μs, respectively. The complexes were studied using UV-visible and magnetic circular dichroism (MCD) spectroscopies. Interestingly, the positive-to-negative sign sequences of the Faraday B0 terms of 2-Sn and 3-Sn reveal that the structural modifications involved break the degeneracy of the MOs derived from the 1eg* LUMO of the porphyrin 1-Sn. In contrast, a conventional negative-to-positive sign sequence is observed for 4-Sn, since the confusion of a pyrrole moiety also results in a large separation of the 1a1u and 1a2u MOs of the porphyrin 1-Sn that are derived from the HOMO of a C16H162−parent hydrocarbon perimeter. The trends in the electronic structures of the Sn(IV) complexes were further investigated through a series of time-dependent density functional theory calculations, so that the suitability of the different types of complex for use in singlet oxygen applications could be further explored. During in vitro photodynamic antimicrobial chemotherapy (PACT) studies, chlorin derivative 3-Sn had the highest activity towards S. aureus and E. coli with log10 reductions of 10.5 and 8.74, respectively. The unusually high activity of 3-Sn against E.coli suggests that the interaction of neutral photosensitisers with gram-negativebacteria is more complex than previously understood. Anti-cancer PDT studies demonstrated that the photosensitisers had negligible dark cytotoxicity. Upon photoirradiation, the Sn(IV) complexes consistently exhibited IC50 values lower than 15 μM against MCF-7 adenocarcinoma cells. An IC50 value of 1.4 μM for 4-Sn after activation at the deep-red region of the spectrum demonstrates that complexes of this type merit further in-depth investigation. The results provide evidence that the low-symmetry Sn(IV) chlorins and N-confused porphyrins merit further in-depth study for use in singlet oxygen applications. , Thesis (MSc) -- Faculty of Science, Chemistry, 2021
- Full Text:
- Date Issued: 2021-10
Borneol-triarylcorrole hybrids with chiral-optical response and anticancer behaviours
- Fu, Bo, Wang, Lin, Yu, Xiaoxiao, Fang, Xianying, Mack, John, Dingiswayo, Somila, Nyokong, Tebello, Liang, Xu, Xu, Haijun
- Authors: Fu, Bo , Wang, Lin , Yu, Xiaoxiao , Fang, Xianying , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu , Xu, Haijun
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185294 , vital:44362 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109699"
- Description: A series of four multifunctional A2B type H3corroles with meso-borneol substituents at the B position have been synthesized and characterized. A detailed analysis of the optical properties was carried out, and a comparison was made with theoretical calculations to identify the key trends in the structure-property relationships. The meso-borneol substituent couples with the corrole core leading to clear CD signals in the B band region. Enhanced anti-cancer properties are observed in vitro relative to (−)-borneol with cell inhibition rates of up to 94%.
- Full Text:
- Date Issued: 2021
- Authors: Fu, Bo , Wang, Lin , Yu, Xiaoxiao , Fang, Xianying , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu , Xu, Haijun
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185294 , vital:44362 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109699"
- Description: A series of four multifunctional A2B type H3corroles with meso-borneol substituents at the B position have been synthesized and characterized. A detailed analysis of the optical properties was carried out, and a comparison was made with theoretical calculations to identify the key trends in the structure-property relationships. The meso-borneol substituent couples with the corrole core leading to clear CD signals in the B band region. Enhanced anti-cancer properties are observed in vitro relative to (−)-borneol with cell inhibition rates of up to 94%.
- Full Text:
- Date Issued: 2021
A comparative study of the photophysicochemical and photodynamic activity properties of meso-4-methylthiophenyl functionalized Sn (IV) tetraarylporphyrins and triarylcorroles
- Dingiswayo, Somila, Babu, Balaji, Prinsloo, Earl, Mack, John, Nyokong, Tebello
- Authors: Dingiswayo, Somila , Babu, Balaji , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186157 , vital:44469 , xlink:href="https://doi.org/10.1142/S1088424620500273"
- Description: Tin(IV) complexes of a 4-methylthiophenyl functionalized porphyrin (1-Sn) and its corrole analogue (2-Sn) were synthesized so that their photophysicochemical properties and photodynamic activities against MCF-7 breast cancer cells could be compared. Singlet oxygen luminescence studies revealed that 1-Sn and 2-Sn have comparable ΦΔΦΔ values in DMF of 0.59 and 0.60, respectively, while the IC5050 values after irradiation of MCF-7 cells for 30 min with a Thorlabs 625 nm LED (432 J · cm−2)−2) were determined to be 12.4 and 8.9 μμM. The results demonstrate that the cellular uptake of 2-Sn and its molar absorptivity at the irradiation wavelength play a crucial role during in vitro cytotoxicity studies.
- Full Text:
- Date Issued: 2020
- Authors: Dingiswayo, Somila , Babu, Balaji , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186157 , vital:44469 , xlink:href="https://doi.org/10.1142/S1088424620500273"
- Description: Tin(IV) complexes of a 4-methylthiophenyl functionalized porphyrin (1-Sn) and its corrole analogue (2-Sn) were synthesized so that their photophysicochemical properties and photodynamic activities against MCF-7 breast cancer cells could be compared. Singlet oxygen luminescence studies revealed that 1-Sn and 2-Sn have comparable ΦΔΦΔ values in DMF of 0.59 and 0.60, respectively, while the IC5050 values after irradiation of MCF-7 cells for 30 min with a Thorlabs 625 nm LED (432 J · cm−2)−2) were determined to be 12.4 and 8.9 μμM. The results demonstrate that the cellular uptake of 2-Sn and its molar absorptivity at the irradiation wavelength play a crucial role during in vitro cytotoxicity studies.
- Full Text:
- Date Issued: 2020
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
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
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