Improved nonlinear optical behaviour of ball type indium (III) phthalocyanine linked to glutathione capped nanoparticles
- Nwaji, Njemuwa, Oluwole, David O, Mack, John, Louzada, Marcel, Khene, Samson M, Britton, Jonathan, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Oluwole, David O , Mack, John , Louzada, Marcel , Khene, Samson M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239654 , vital:50752 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.066"
- Description: The synthesis of ball–type indium phthalocyanine (complex 4) and its covalent attachment to glutathione (GSH–) capped (Ag, Au, CdTeSe, CdTeSe/ZnO) nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical behaviour were investigated. We observed a decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield of the nanoconjugates in comparison to complex 4 alone. The reverse saturable absorption was found to be dependent on excited state absorption. The optical limiting threshold ranges from 0.40–0.78 (J/cm2). The nanoconjugate of the complex 4 with GSH–CdTeSe/ZnO (QD1) accounted for the most improved triplet state parameters and nonlinear optical behaviour in comparison to complex 4 and the other nanoconjugates studied in this work.
- Full Text:
- Date Issued: 2017
- Authors: Nwaji, Njemuwa , Oluwole, David O , Mack, John , Louzada, Marcel , Khene, Samson M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239654 , vital:50752 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.066"
- Description: The synthesis of ball–type indium phthalocyanine (complex 4) and its covalent attachment to glutathione (GSH–) capped (Ag, Au, CdTeSe, CdTeSe/ZnO) nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical behaviour were investigated. We observed a decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield of the nanoconjugates in comparison to complex 4 alone. The reverse saturable absorption was found to be dependent on excited state absorption. The optical limiting threshold ranges from 0.40–0.78 (J/cm2). The nanoconjugate of the complex 4 with GSH–CdTeSe/ZnO (QD1) accounted for the most improved triplet state parameters and nonlinear optical behaviour in comparison to complex 4 and the other nanoconjugates studied in this work.
- Full Text:
- Date Issued: 2017
Synthesis, photophysical and nonlinear optical properties of a series of ball-type phthalocyanines in solution and thin films
- Nwaji, Njemuwa, Mack, John, Britton, Jonathan, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Mack, John , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188976 , vital:44803 , xlink:href="https://doi.org/10.1039/C6NJ03662G"
- Description: In this study, we report on the enhanced nonlinear optical properties of novel tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato zinc(II)) (4), tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato gallium chloride) (5) and tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato indium chloride) (6) both in solution and when embedded in polymer thin films. Complexes 5 and 6 bearing heavy atoms showed enhanced triplet quantum yield and nonlinear optical response. The nonlinear third-order susceptibility and second-order hyperpolarizability values are also reported. Time dependent density functional theory (TD-DFT) calculations were performed in order to explain the origin of the observed UV-vis and magnetic circular dichroism (MCD) spectra of the complexes.
- Full Text:
- Date Issued: 2017
- Authors: Nwaji, Njemuwa , Mack, John , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188976 , vital:44803 , xlink:href="https://doi.org/10.1039/C6NJ03662G"
- Description: In this study, we report on the enhanced nonlinear optical properties of novel tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato zinc(II)) (4), tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato gallium chloride) (5) and tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato indium chloride) (6) both in solution and when embedded in polymer thin films. Complexes 5 and 6 bearing heavy atoms showed enhanced triplet quantum yield and nonlinear optical response. The nonlinear third-order susceptibility and second-order hyperpolarizability values are also reported. Time dependent density functional theory (TD-DFT) calculations were performed in order to explain the origin of the observed UV-vis and magnetic circular dichroism (MCD) spectra of the complexes.
- Full Text:
- Date Issued: 2017
Spectroscopic and nonlinear optical properties of the four positional isomers of 4α-(4-tert-butylphenoxy) phthalocyanine
- Ngubeni, Grace N, Britton, Jonathan, Mack, John, New, Edward, Hancox, Ian, Walker, Marc, Nyokong, Tebello, Jones, Tim S, Khene,Samson M
- Authors: Ngubeni, Grace N , Britton, Jonathan , Mack, John , New, Edward , Hancox, Ian , Walker, Marc , Nyokong, Tebello , Jones, Tim S , Khene,Samson M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241448 , vital:50940 , xlink:href="https://doi.org/10.1039/C5TC01601K"
- Description: The spectroscopic and nonlinear optical properties of the positional isomers of metal free 4α-(4-tert-butylphenoxy) phthalocyanine are presented. Second order nonlinear polarizability (β), imaginary hyperpolarizability (Im(γ)) and imaginary susceptibility (Im[χ(3)]) values were determined for the four positional isomers. The measured β values of the four isomers displayed the following trend, C4h (34.0 × 10−5 m MW−1) > D2h (28.8 × 10−5 m MW−1) > C2v (22.8 × 10−5 m MW−1) > Cs (13.7 × 10−5 m MW−1).
- Full Text:
- Date Issued: 2015
- Authors: Ngubeni, Grace N , Britton, Jonathan , Mack, John , New, Edward , Hancox, Ian , Walker, Marc , Nyokong, Tebello , Jones, Tim S , Khene,Samson M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241448 , vital:50940 , xlink:href="https://doi.org/10.1039/C5TC01601K"
- Description: The spectroscopic and nonlinear optical properties of the positional isomers of metal free 4α-(4-tert-butylphenoxy) phthalocyanine are presented. Second order nonlinear polarizability (β), imaginary hyperpolarizability (Im(γ)) and imaginary susceptibility (Im[χ(3)]) values were determined for the four positional isomers. The measured β values of the four isomers displayed the following trend, C4h (34.0 × 10−5 m MW−1) > D2h (28.8 × 10−5 m MW−1) > C2v (22.8 × 10−5 m MW−1) > Cs (13.7 × 10−5 m MW−1).
- Full Text:
- Date Issued: 2015
The photodynamic activities of the gold nanoparticle conjugates of phosphorus (V) and gallium (III) A3 meso-triarylcorroles
- Soy, Rodah C, Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Soy, Rodah C , Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184978 , vital:44313 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109631"
- Description: The synthesis and characterization of series of P(V) and Ga(III) A3 triarylcorrole complexes with 4-methylthiophenyl (2a, 3a), thien-3-yl (2b, 3b) and thien-2-yl (2c, 3c) meso-groups are reported along with the physicochemical and photodynamic activity properties of the dyes and their gold nanoparticle (AuNP) conjugates. The Ga(III) corrole series have lower fluorescence quantum yields and higher singlet oxygen quantum yields than the analogous P(V) complexes. Upon conjugation to AuNPs, the fluorescence quantum yields of the P(V) and Ga(III) corroles decrease, while the singlet oxygen quantum yields increase due to an external heavy atom effect. The P(V) and Ga(III) corroles exhibit relatively low in vitro dark cytotoxicity, which was further enhanced upon conjugation to AuNPs. The P(V) complexes and their AuNP conjugates display more favorable PDT activity properties upon illumination with a Thorlabs 625 nm light-emitting diode (288 J cm−2) with phototoxicity indices > 18.5 and 20.8, respectively, for the meso-thienyl-substituted 2b-AuNP and 2c-AuNP conjugates. Optical spectroscopy analyses demonstrate that this can be attributed to there being significantly less aggregation due to the presence of two trans-hydroxy axial ligands.
- Full Text:
- Date Issued: 2021
- Authors: Soy, Rodah C , Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184978 , vital:44313 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109631"
- Description: The synthesis and characterization of series of P(V) and Ga(III) A3 triarylcorrole complexes with 4-methylthiophenyl (2a, 3a), thien-3-yl (2b, 3b) and thien-2-yl (2c, 3c) meso-groups are reported along with the physicochemical and photodynamic activity properties of the dyes and their gold nanoparticle (AuNP) conjugates. The Ga(III) corrole series have lower fluorescence quantum yields and higher singlet oxygen quantum yields than the analogous P(V) complexes. Upon conjugation to AuNPs, the fluorescence quantum yields of the P(V) and Ga(III) corroles decrease, while the singlet oxygen quantum yields increase due to an external heavy atom effect. The P(V) and Ga(III) corroles exhibit relatively low in vitro dark cytotoxicity, which was further enhanced upon conjugation to AuNPs. The P(V) complexes and their AuNP conjugates display more favorable PDT activity properties upon illumination with a Thorlabs 625 nm light-emitting diode (288 J cm−2) with phototoxicity indices > 18.5 and 20.8, respectively, for the meso-thienyl-substituted 2b-AuNP and 2c-AuNP conjugates. Optical spectroscopy analyses demonstrate that this can be attributed to there being significantly less aggregation due to the presence of two trans-hydroxy axial ligands.
- Full Text:
- Date Issued: 2021
Solar Driven Photocatalytic Activity of Porphyrin Sensitized TiO2
- Otieno, Sebastien, Lanterna, Anabel E, Mack, John, Derese, Solomon, Amuhaya, Edith K, Nyokong, Tebello, Scaiano, Juan C
- Authors: Otieno, Sebastien , Lanterna, Anabel E , Mack, John , Derese, Solomon , Amuhaya, Edith K , Nyokong, Tebello , Scaiano, Juan C
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190612 , vital:45010 , xlink:href="https://doi.org/10.3390/molecules26113131"
- Description: The absence of a secure long-term sustainable energy supply is recognized as a major worldwide technological challenge. The generation of H2 through photocatalysis is an environmentally friendly alternative that can help solve the energy problem. Thus, the development of semiconductor materials that can absorb solar light is an attractive approach. TiO2 has a wide bandgap that suffers from no activity in the visible spectrum, limiting its use of solar radiation. In this research, the semiconductor absorption profile was extended into the visible region of the solar spectrum by preparing porphyrin-TiO2 (P-TiO2 ) composites of meso-tetra(4-bromophenyl)porphyrin (PP1) and meso-tetra(5-bromo-2-thienyl)porphyrin (PP2) and their In(III), Zn(II) and Ga(III) metal complexes. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were performed on the porphyrins to gain insight into their electron injection capability. The results demonstrate that P-TiO2 systems merit further in-depth study for applications that require efficient photocatalytic H2 generation.
- Full Text:
- Date Issued: 2021
- Authors: Otieno, Sebastien , Lanterna, Anabel E , Mack, John , Derese, Solomon , Amuhaya, Edith K , Nyokong, Tebello , Scaiano, Juan C
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190612 , vital:45010 , xlink:href="https://doi.org/10.3390/molecules26113131"
- Description: The absence of a secure long-term sustainable energy supply is recognized as a major worldwide technological challenge. The generation of H2 through photocatalysis is an environmentally friendly alternative that can help solve the energy problem. Thus, the development of semiconductor materials that can absorb solar light is an attractive approach. TiO2 has a wide bandgap that suffers from no activity in the visible spectrum, limiting its use of solar radiation. In this research, the semiconductor absorption profile was extended into the visible region of the solar spectrum by preparing porphyrin-TiO2 (P-TiO2 ) composites of meso-tetra(4-bromophenyl)porphyrin (PP1) and meso-tetra(5-bromo-2-thienyl)porphyrin (PP2) and their In(III), Zn(II) and Ga(III) metal complexes. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were performed on the porphyrins to gain insight into their electron injection capability. The results demonstrate that P-TiO2 systems merit further in-depth study for applications that require efficient photocatalytic H2 generation.
- Full Text:
- Date Issued: 2021
Thien-2-yl substituted chlorins as photosensitizers for photodynamic therapy and photodynamic antimicrobial chemotherapy
- Babu, Balaji, Sindelo, Azole, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Sindelo, Azole , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190578 , vital:45007 , xlink:href="https://doi.org/10.1016/j.dyepig.2020.108886"
- Description: The synthesis and characterization of meso-tetra(thien-2-yl)chlorin (1) and meso-tetra(5-bromothien-2-yl)chlorin (2) is reported. These dyes have red-shifted absorption maxima compared to those of the analogous meso-tetraphenylchlorin (3). 1 and 2 have Q bands at 660 and 664 nm, respectively, singlet oxygen quantum yields of 0.60 and 0.64 and exhibit good photostability. The triplet states were found to have lifetimes of 8.6 μs in N2 purged DMF. Time-dependent cellular uptake of chlorins reached a maximum in MCF-7 cancer cells after 12 h. Upon irradiation with a Thorlabs M660L3 LED (280 mW cm−2), 2 exhibited better photocytotoxicity with an IC50 value of 2.7 μM against MCF-7 cells. The 2ʹ,7ʹ-dichlorodihydrofluorescein diacetate (DCFDA) assay provided evidence for intracellular generation of reactive oxygen species. Photodynamic inactivation of bacteria by the chlorins was also studied. 2 exhibits better activity with log reduction values of 7.42 and 8.34 towards Staphylococcus aureus and Escherichia coli, respectively, under illumination for 60 min at 660 nm with a Thorlabs M660L3 LED (280 mW cm−2). These results demonstrate that 2 is a promising candidate for future in vivo experiments and merits further in-depth investigation.
- Full Text:
- Date Issued: 2021
- Authors: Babu, Balaji , Sindelo, Azole , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190578 , vital:45007 , xlink:href="https://doi.org/10.1016/j.dyepig.2020.108886"
- Description: The synthesis and characterization of meso-tetra(thien-2-yl)chlorin (1) and meso-tetra(5-bromothien-2-yl)chlorin (2) is reported. These dyes have red-shifted absorption maxima compared to those of the analogous meso-tetraphenylchlorin (3). 1 and 2 have Q bands at 660 and 664 nm, respectively, singlet oxygen quantum yields of 0.60 and 0.64 and exhibit good photostability. The triplet states were found to have lifetimes of 8.6 μs in N2 purged DMF. Time-dependent cellular uptake of chlorins reached a maximum in MCF-7 cancer cells after 12 h. Upon irradiation with a Thorlabs M660L3 LED (280 mW cm−2), 2 exhibited better photocytotoxicity with an IC50 value of 2.7 μM against MCF-7 cells. The 2ʹ,7ʹ-dichlorodihydrofluorescein diacetate (DCFDA) assay provided evidence for intracellular generation of reactive oxygen species. Photodynamic inactivation of bacteria by the chlorins was also studied. 2 exhibits better activity with log reduction values of 7.42 and 8.34 towards Staphylococcus aureus and Escherichia coli, respectively, under illumination for 60 min at 660 nm with a Thorlabs M660L3 LED (280 mW cm−2). These results demonstrate that 2 is a promising candidate for future in vivo experiments and merits further in-depth investigation.
- Full Text:
- Date Issued: 2021
Push-pull type Co (III) corroles
- Niu, Yingjie, Zhu, Weihua, Mack, John, Dubazana, Nadine, Nyokong, Tebello, Fu, Bo, Xu, Haijun, Liang, Xu
- Authors: Niu, Yingjie , Zhu, Weihua , Mack, John , Dubazana, Nadine , Nyokong, Tebello , Fu, Bo , Xu, Haijun , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190826 , vital:45032 , xlink:href="https://doi.org/10.1142/S1088424621500279"
- Description: The rational design and preparation of three A2B type Co(III)triarylcorroles with push- and pull-substituents are reported. The structure-property relationships were identified by comparing their optically spectroscopic and electrochemical properties to trends predicted in DFT and TD-DFT calculations. The results demonstrate that the Co(III)triarylcorroles are highly efficient catalysts for electrocatalyzed hydrogen evolutions (HERs) and oxygen reductions (ORRs), and that their reactivity can be modulated by changing the meso-B-substituent of the Co(III)Corroles.
- Full Text:
- Date Issued: 2021
- Authors: Niu, Yingjie , Zhu, Weihua , Mack, John , Dubazana, Nadine , Nyokong, Tebello , Fu, Bo , Xu, Haijun , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190826 , vital:45032 , xlink:href="https://doi.org/10.1142/S1088424621500279"
- Description: The rational design and preparation of three A2B type Co(III)triarylcorroles with push- and pull-substituents are reported. The structure-property relationships were identified by comparing their optically spectroscopic and electrochemical properties to trends predicted in DFT and TD-DFT calculations. The results demonstrate that the Co(III)triarylcorroles are highly efficient catalysts for electrocatalyzed hydrogen evolutions (HERs) and oxygen reductions (ORRs), and that their reactivity can be modulated by changing the meso-B-substituent of the Co(III)Corroles.
- Full Text:
- Date Issued: 2021
Photodynamic activity of Sn (IV) tetrathien-2-ylchlorin against MCF-7 breast cancer cells
- Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185920 , vital:44448 , xlink:href="https://doi.org/10.1039/d0dt03958f"
- Description: A new readily-synthesized Sn(IV) tetraarylchlorin with thien-2-yl substituents (SnC) has been prepared and fully characterized by various spectroscopic techniques and its photophysical and photochemical properties, such as the singlet oxygen quantum yield (ΦΔ), fluorescence quantum yield (ΦF), triplet lifetime (τT) and photostability, have been evaluated. SnC has an unusually high ΦΔ value of 0.89 in DMF. Studies on the photodynamic activity against MCF-7 breast cancer cells exhibited a very low IC50 value of 0.9 μM and high phototoxicity (dark versus light) indices of >27.8 after irradiation with a 660 nm Thorlabs LED (280 mW cm−2). The results demonstrate that Sn(IV) tetraarylchlorins of this type are suitable candidates for further in-depth PDT studies.
- Full Text:
- Date Issued: 2021
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185920 , vital:44448 , xlink:href="https://doi.org/10.1039/d0dt03958f"
- Description: A new readily-synthesized Sn(IV) tetraarylchlorin with thien-2-yl substituents (SnC) has been prepared and fully characterized by various spectroscopic techniques and its photophysical and photochemical properties, such as the singlet oxygen quantum yield (ΦΔ), fluorescence quantum yield (ΦF), triplet lifetime (τT) and photostability, have been evaluated. SnC has an unusually high ΦΔ value of 0.89 in DMF. Studies on the photodynamic activity against MCF-7 breast cancer cells exhibited a very low IC50 value of 0.9 μM and high phototoxicity (dark versus light) indices of >27.8 after irradiation with a 660 nm Thorlabs LED (280 mW cm−2). The results demonstrate that Sn(IV) tetraarylchlorins of this type are suitable candidates for further in-depth PDT studies.
- Full Text:
- Date Issued: 2021
Naked Eye and Colorimetric Detection of Cyanide with a 1, 3‐Diethyl‐2‐thiobarbituric Acid Substituted Ferrocene Chemosensor
- Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190567 , vital:45006 , xlink:href="https://doi.org/10.1002/slct.202100163"
- Description: A 1,3-diethyl-2-thiobarbituric-acid-substituted ferrocene (FET) has been evaluated for its cyanide sensing ability by UV-visible absorption spectroscopy and other characterization methods. FET provides a ratiometric colorimetric chemosensor for the CN− anion detection in 1 : 1 DMSO/H2O (v/v) solution. The addition of CN− results in an immediate color change from dark blue to pale orange that is visible to the naked eye. Mechanism studies and molecular modelling with TD-DFT calculations demonstrate that nucleophilic addition of CN− to an electrophilic sp2-hybridized carbon atom blocks charge transfer from the ferrocene ring complex to the thiobarbituric acid moiety. The FET sensor exhibits excellent selectivity for CN− and a limit of detection of 0.2 μM.
- Full Text:
- Date Issued: 2021
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190567 , vital:45006 , xlink:href="https://doi.org/10.1002/slct.202100163"
- Description: A 1,3-diethyl-2-thiobarbituric-acid-substituted ferrocene (FET) has been evaluated for its cyanide sensing ability by UV-visible absorption spectroscopy and other characterization methods. FET provides a ratiometric colorimetric chemosensor for the CN− anion detection in 1 : 1 DMSO/H2O (v/v) solution. The addition of CN− results in an immediate color change from dark blue to pale orange that is visible to the naked eye. Mechanism studies and molecular modelling with TD-DFT calculations demonstrate that nucleophilic addition of CN− to an electrophilic sp2-hybridized carbon atom blocks charge transfer from the ferrocene ring complex to the thiobarbituric acid moiety. The FET sensor exhibits excellent selectivity for CN− and a limit of detection of 0.2 μM.
- Full Text:
- Date Issued: 2021
Modulation of the optical properties of chiral porphyrin dimers by introducing bridged chiral amide-bonds
- Qin, Mingfeng, Zhang, Zhen, Zhu, Weihua, Mack, John, Soy, Rodah C, Nyokong, Tebello, Liang, Xu
- Authors: Qin, Mingfeng , Zhang, Zhen , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190815 , vital:45031 , xlink:href="https://doi.org/10.1142/S1088424620500492"
- Description: The d/l-enantiomers of a series of three Zn(II)tetraarylporphyrin dimers were synthesized and isolated by incorporating a bridging amide-bonded xanthene moiety at the para-position of one of the meso-aryl rings. The electronic structures and optical properties were modulated by incorporating chiral amino acid moieties into the amide-bonding moieties of the xanthene bridge that contain methyl, tolyl and 2-methylindole substituents. A cofacial dimer was formed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) resulting in a significant red shift of the B band, due to a relative destabilization of the HOMO, which has large MO coefficients on the pyrrole nitrogens. The sign sequences observed in the B band region of the CD spectra due to the presence of the chiral amino acid moieties were modified due to this change in geometry. Significant CD intensity is also observed in the B band region of the CD spectra of anion radical species during in situ spectroelectrochemical measurements.
- Full Text:
- Date Issued: 2021
- Authors: Qin, Mingfeng , Zhang, Zhen , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190815 , vital:45031 , xlink:href="https://doi.org/10.1142/S1088424620500492"
- Description: The d/l-enantiomers of a series of three Zn(II)tetraarylporphyrin dimers were synthesized and isolated by incorporating a bridging amide-bonded xanthene moiety at the para-position of one of the meso-aryl rings. The electronic structures and optical properties were modulated by incorporating chiral amino acid moieties into the amide-bonding moieties of the xanthene bridge that contain methyl, tolyl and 2-methylindole substituents. A cofacial dimer was formed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) resulting in a significant red shift of the B band, due to a relative destabilization of the HOMO, which has large MO coefficients on the pyrrole nitrogens. The sign sequences observed in the B band region of the CD spectra due to the presence of the chiral amino acid moieties were modified due to this change in geometry. Significant CD intensity is also observed in the B band region of the CD spectra of anion radical species during in situ spectroelectrochemical measurements.
- Full Text:
- Date Issued: 2021
Positively charged styryl pyridine substituted Zn (II) Phthalocyanines for Photodynamic Therapy and Photoantimicrobial Chemotherapy
- Magadla, Aviwe, Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Magadla, Aviwe , Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190600 , vital:45009 , xlink:href="https://doi.org/10.1039/D1DT01047F"
- Description: Cationic Zn phthalocyanine complexes were synthesized using Knoevenagel reaction starting from a Zn(II) tetrakis(2-formylphenoxy)phthalocyanine (1) to form Zn(II) tetrakis(1-butyl-4-(4-(tetraphenoxy)styryl)pyridin-1-ium) phthalocyanine (2) and Zn(II) tetrakis(4-(4-(tetraphenoxy)styryl)-1-(4-(triphenylphosphonio)butyl)pyridin-1-ium)phthalocyanine (3). The photophysicochemical behaviours of the Pc complexes were assessed. The cationic complexes display high water-solubility and gave moderate singlet oxygen quantum yield in water. The cationic Pcs demonstrate good cellular uptake and photodynamic activity against MCF-7 cells with IC50 values of 8.2 and 4.9 μM for 2 and 3, respectively. The cationic Pcs also demonstrate high photoantimicrobial activity against Escherichia coli with log reductions of 5.3 and 6.0 for 2 and 3, respectively.
- Full Text:
- Date Issued: 2021
- Authors: Magadla, Aviwe , Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190600 , vital:45009 , xlink:href="https://doi.org/10.1039/D1DT01047F"
- Description: Cationic Zn phthalocyanine complexes were synthesized using Knoevenagel reaction starting from a Zn(II) tetrakis(2-formylphenoxy)phthalocyanine (1) to form Zn(II) tetrakis(1-butyl-4-(4-(tetraphenoxy)styryl)pyridin-1-ium) phthalocyanine (2) and Zn(II) tetrakis(4-(4-(tetraphenoxy)styryl)-1-(4-(triphenylphosphonio)butyl)pyridin-1-ium)phthalocyanine (3). The photophysicochemical behaviours of the Pc complexes were assessed. The cationic complexes display high water-solubility and gave moderate singlet oxygen quantum yield in water. The cationic Pcs demonstrate good cellular uptake and photodynamic activity against MCF-7 cells with IC50 values of 8.2 and 4.9 μM for 2 and 3, respectively. The cationic Pcs also demonstrate high photoantimicrobial activity against Escherichia coli with log reductions of 5.3 and 6.0 for 2 and 3, respectively.
- Full Text:
- Date Issued: 2021
Photocytotoxicity of heavy-atom-free thiobarbituric acid functionalized pyrene derivatives against MCF-7 cancer cells
- Babu, Balaji, Ali, Thaslima A, Ochappan, Thivagar, Mack, John, Nyokong, Tebello, Sethuraman, Mathur G
- Authors: Babu, Balaji , Ali, Thaslima A , Ochappan, Thivagar , Mack, John , Nyokong, Tebello , Sethuraman, Mathur G
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190556 , vital:45005 , xlink:href="https://doi.org/10.1016/j.pdpdt.2020.102102"
- Description: Two thiobarbituric acid-functionalized pyrene derivatives (P1, P2) have been synthesized to explore the photophysical properties and photodynamic activity of dyes of this type. Both compounds exhibit an intense intramolecular charge transfer (ICT) band at ca. 470 nm, which is absent in the spectra of the precursor. P1 and P2 exhibit singlet oxygen generation on irradiation with light with moderate singlet oxygen yields of 0.36 and 0.32, respectively, in DMSO. P1 showed better photodynamic activity against MCF-7 cells with an IC50 value of 18.3 μM under illumination at 455 nm for 60 min with a Thorlabs M455L3 LED (330 mW.cm−2).
- Full Text:
- Date Issued: 2021
- Authors: Babu, Balaji , Ali, Thaslima A , Ochappan, Thivagar , Mack, John , Nyokong, Tebello , Sethuraman, Mathur G
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190556 , vital:45005 , xlink:href="https://doi.org/10.1016/j.pdpdt.2020.102102"
- Description: Two thiobarbituric acid-functionalized pyrene derivatives (P1, P2) have been synthesized to explore the photophysical properties and photodynamic activity of dyes of this type. Both compounds exhibit an intense intramolecular charge transfer (ICT) band at ca. 470 nm, which is absent in the spectra of the precursor. P1 and P2 exhibit singlet oxygen generation on irradiation with light with moderate singlet oxygen yields of 0.36 and 0.32, respectively, in DMSO. P1 showed better photodynamic activity against MCF-7 cells with an IC50 value of 18.3 μM under illumination at 455 nm for 60 min with a Thorlabs M455L3 LED (330 mW.cm−2).
- Full Text:
- Date Issued: 2021
Ga III triarylcorroles with push–pull substitutions
- Niu, Yingjie, Wang, Lin, Guo, Yingxin, Zhu, Weihua, Soy, Rodah C, Babu, Balaji, Mack, John, Nyokong, Tebello, Xu, Haijun, Liang, Xu
- Authors: Niu, Yingjie , Wang, Lin , Guo, Yingxin , Zhu, Weihua , Soy, Rodah C , Babu, Balaji , Mack, John , Nyokong, Tebello , Xu, Haijun , Liang, Xu
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300079 , vital:57890 , xlink:href="https://doi.org/10.1039/D2DT01262F"
- Description: Two A2B type H3corroles and two GaIIItriarylcorroles with carbazole substitutions at 10-positions were synthesized and characterized. An analysis of structure–property relationships of the corroles has been carried out by investigating the optical spectroscopy of the dyes to trends predicted in DFT and TD-DFT calculations. Interestingly, the photodynamic therapy (PDT) and photodynamic antimicrobial chemotherapy (PACT) activity properties of the GaIIItriarylcorroles were determined against the MCF-7 breast cancer line, and Staphyloccocus aureus (S. aureus) and Escherichia coli (E. coli), respectively. The cationic G-2Q species exhibited the most favorable properties with an IC50 value of 7.8 μM against MCF-7 cells, and Log reduction values of 7.78 and 3.26 against planktonic S. aureus and E. coli at 0.5 and 10 μM, respectively.
- Full Text:
- Date Issued: 2022
- Authors: Niu, Yingjie , Wang, Lin , Guo, Yingxin , Zhu, Weihua , Soy, Rodah C , Babu, Balaji , Mack, John , Nyokong, Tebello , Xu, Haijun , Liang, Xu
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300079 , vital:57890 , xlink:href="https://doi.org/10.1039/D2DT01262F"
- Description: Two A2B type H3corroles and two GaIIItriarylcorroles with carbazole substitutions at 10-positions were synthesized and characterized. An analysis of structure–property relationships of the corroles has been carried out by investigating the optical spectroscopy of the dyes to trends predicted in DFT and TD-DFT calculations. Interestingly, the photodynamic therapy (PDT) and photodynamic antimicrobial chemotherapy (PACT) activity properties of the GaIIItriarylcorroles were determined against the MCF-7 breast cancer line, and Staphyloccocus aureus (S. aureus) and Escherichia coli (E. coli), respectively. The cationic G-2Q species exhibited the most favorable properties with an IC50 value of 7.8 μM against MCF-7 cells, and Log reduction values of 7.78 and 3.26 against planktonic S. aureus and E. coli at 0.5 and 10 μM, respectively.
- Full Text:
- Date Issued: 2022
Indium phthalocyanines
- Pinar, Sen, Mack, John, Nyokong, Tebello
- Authors: Pinar, Sen , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229998 , vital:49731 , xlink:href="https://doi.org/10.1016/j.molstruc.2021.131850"
- Description: In this study, the photodynamic antimicrobial activities of a series of new tetra-substituted indium phthalocyanine (InPc) complexes are assessed. An aldehyde substituted complex (2) was initially prepared, which was converted through a condensatioreaction to an imine-pyrrolidine substituted complex (3), which in turn was quaternized to form a tetracationic species (4). Favorable photophysicochemical properties were obtained by incorporating a heavy In(III) ion into the central cavity. Aggregation studies revealed that 2–4 remain non-aggregated in DMSO at concentration below 25 µM. The photodeactivation of S.aureus and E.coli was studied. Log reduction values > 9.0 were obtained for cationic InPc 4 after 30 min of incubation and exposure to light for 75 min.
- Full Text:
- Date Issued: 2022
- Authors: Pinar, Sen , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229998 , vital:49731 , xlink:href="https://doi.org/10.1016/j.molstruc.2021.131850"
- Description: In this study, the photodynamic antimicrobial activities of a series of new tetra-substituted indium phthalocyanine (InPc) complexes are assessed. An aldehyde substituted complex (2) was initially prepared, which was converted through a condensatioreaction to an imine-pyrrolidine substituted complex (3), which in turn was quaternized to form a tetracationic species (4). Favorable photophysicochemical properties were obtained by incorporating a heavy In(III) ion into the central cavity. Aggregation studies revealed that 2–4 remain non-aggregated in DMSO at concentration below 25 µM. The photodeactivation of S.aureus and E.coli was studied. Log reduction values > 9.0 were obtained for cationic InPc 4 after 30 min of incubation and exposure to light for 75 min.
- Full Text:
- Date Issued: 2022
A heavy-atom-free π-extended N-confused porphyrin as a photosensitizer for photodynamic therapy
- Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185909 , vital:44447 , xlink:href="https://doi.org/10.1039/d1nj00112d"
- Description: The synthesis and characterization of a novel 1,3-diethyl-2-thiobarbituric-acid-substituted N-confused porphyrin (NCP-TB) is reported, along with a study of its photodynamic activity against MCF-7 cells using 530 (110 mW cm−2) and 660 nm (280 mW cm−2) Thorlabs light-emitting diodes for 30 min. The singlet oxygen quantum yield for NCP-TB is 0.38 compared to 0.23 for the parent unsubstituted N-confused porphyrin (NCP) due to the presence of a sulfur atom. NCP-TB exhibits enhanced PDT activity compared to NCP at both wavelengths. A significantly lower IC50 value of 5.2 μM was obtained at 530 nm (14.7 μM at 660 nm) despite a smaller light dose, due to a large red shift of the intense B band into the green region of the spectrum. 2′,7′-Dichlorofluorescein diacetate (DCFDA) assays demonstrate that there is intracellular generation of reactive oxygen species upon exposure to light.
- Full Text:
- Date Issued: 2021
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185909 , vital:44447 , xlink:href="https://doi.org/10.1039/d1nj00112d"
- Description: The synthesis and characterization of a novel 1,3-diethyl-2-thiobarbituric-acid-substituted N-confused porphyrin (NCP-TB) is reported, along with a study of its photodynamic activity against MCF-7 cells using 530 (110 mW cm−2) and 660 nm (280 mW cm−2) Thorlabs light-emitting diodes for 30 min. The singlet oxygen quantum yield for NCP-TB is 0.38 compared to 0.23 for the parent unsubstituted N-confused porphyrin (NCP) due to the presence of a sulfur atom. NCP-TB exhibits enhanced PDT activity compared to NCP at both wavelengths. A significantly lower IC50 value of 5.2 μM was obtained at 530 nm (14.7 μM at 660 nm) despite a smaller light dose, due to a large red shift of the intense B band into the green region of the spectrum. 2′,7′-Dichlorofluorescein diacetate (DCFDA) assays demonstrate that there is intracellular generation of reactive oxygen species upon exposure to light.
- Full Text:
- Date Issued: 2021
Low-Symmetry Phthalocyanines Bearing Carboxy-Groups
- Bunin, Dmitry A, Ndebele, Nobuhle, Martynov, Alexander G, Mack, John, Gorbunova, Yulia G, Nyokong, Tebello
- Authors: Bunin, Dmitry A , Ndebele, Nobuhle , Martynov, Alexander G , Mack, John , Gorbunova, Yulia G , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231262 , vital:49870 , xlink:href="https://doi.org/10.3390/molecules27020524" "
- Description: The synthesis and characterization of A3B-type phthalocyanines, ZnPc1–4, bearing bulky 2,6-diisopropylphenoxy-groups or chlorine atoms on isoindoline units “A” and either one or two carboxylic anchors on isoindoline unit “B” are reported. A comparison of molecular modelling with the conventional time dependent—density functional theory (TD-DFT) approach and its simplified sTD-DFT approximation provides further evidence that the latter method accurately reproduces the key trends in the spectral properties, providing colossal savings in computer time for quite large molecules. This demonstrates that it is a valuable tool for guiding the rational design of new phthalocyanines for practical applications.
- Full Text:
- Date Issued: 2022
- Authors: Bunin, Dmitry A , Ndebele, Nobuhle , Martynov, Alexander G , Mack, John , Gorbunova, Yulia G , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231262 , vital:49870 , xlink:href="https://doi.org/10.3390/molecules27020524" "
- Description: The synthesis and characterization of A3B-type phthalocyanines, ZnPc1–4, bearing bulky 2,6-diisopropylphenoxy-groups or chlorine atoms on isoindoline units “A” and either one or two carboxylic anchors on isoindoline unit “B” are reported. A comparison of molecular modelling with the conventional time dependent—density functional theory (TD-DFT) approach and its simplified sTD-DFT approximation provides further evidence that the latter method accurately reproduces the key trends in the spectral properties, providing colossal savings in computer time for quite large molecules. This demonstrates that it is a valuable tool for guiding the rational design of new phthalocyanines for practical applications.
- Full Text:
- Date Issued: 2022
A Sn (iv) porphyrin with mitochondria targeting properties for enhanced photodynamic activity against MCF-7 cells
- Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230897 , vital:49829 , xlink:href="https://doi.org/10.1039/D2NJ00350C"
- Description: Two readily synthesized Sn(IV) porphyrins (SnP, SnPH) have been prepared with and without the cationic triphenylphosphonium moiety (TPP+), which have high singlet oxygen quantum yields (ca. 0.72) and long triplet state lifetimes. The Sn(IV) porphyrin with a TPP+ moiety (SnPH) exhibits favorable photodynamic activity against MCF-7 cells with IC50 values of 2.9 μM. SnPH exhibits higher cellular uptake than SnP in MCF-7 cells. A Rhodamine 123 (Rh123) assay showed that SnPH targets mitochondria and induces apoptosis by generating reactive oxygen species. The results demonstrate that this structural modification strategy merits further in-depth study.
- Full Text:
- Date Issued: 2022
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230897 , vital:49829 , xlink:href="https://doi.org/10.1039/D2NJ00350C"
- Description: Two readily synthesized Sn(IV) porphyrins (SnP, SnPH) have been prepared with and without the cationic triphenylphosphonium moiety (TPP+), which have high singlet oxygen quantum yields (ca. 0.72) and long triplet state lifetimes. The Sn(IV) porphyrin with a TPP+ moiety (SnPH) exhibits favorable photodynamic activity against MCF-7 cells with IC50 values of 2.9 μM. SnPH exhibits higher cellular uptake than SnP in MCF-7 cells. A Rhodamine 123 (Rh123) assay showed that SnPH targets mitochondria and induces apoptosis by generating reactive oxygen species. The results demonstrate that this structural modification strategy merits further in-depth study.
- Full Text:
- Date Issued: 2022
Promotion of Catalytic Oxygen Reduction Reactions
- Wei, Yuqin, Zhao, Long, Yuan, Rui, Xue, Zhaoli, Mack, John, Chivumba, Choonzo, Nyokong, Tebello, Zhang, Jianming
- Authors: Wei, Yuqin , Zhao, Long , Yuan, Rui , Xue, Zhaoli , Mack, John , Chivumba, Choonzo , Nyokong, Tebello , Zhang, Jianming
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300347 , vital:57919 , xlink:href="https://doi.org/10.1021/acs.inorgchem.2c01591"
- Description: Three ABAB-type cobalt meso-tetraarylporphyrins with fluorine (F-CoPor), acetic acid (AC-CoPor), and cyanoacetic acid (CN-CoPor) groups at the para-positions of phenyl rings at the 10,20-positions are synthesized and evaluated as catalysts for oxygen reduction reactions (ORRs). In density functional theory calculations, the frontier molecular orbitals of these complexes were found to be stabilized relative to model complexes with electron-withdrawing atoms or moieties on the meso-aryl rings. Electrochemical measurements suggest that electrodes with CN-CoPor (CN-CoPor/C) exhibit the most positive ORR potential values and the highest limiting current density in both acidic and alkali electrolytes, while the F-CoPor/C electrocatalyst exhibits extremely low ORR performance. The electron transfer numbers for the electrocatalysts are more than 3.0, indicating that a mixture of 2- and 4-electron transfer pathways occurs. The results demonstrate that coupling the hydrogen bonding properties and electron-withdrawing abilities through rational design of the substituent at the meso-position is an efficient way to modify the ORR performance.
- Full Text:
- Date Issued: 2022
- Authors: Wei, Yuqin , Zhao, Long , Yuan, Rui , Xue, Zhaoli , Mack, John , Chivumba, Choonzo , Nyokong, Tebello , Zhang, Jianming
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300347 , vital:57919 , xlink:href="https://doi.org/10.1021/acs.inorgchem.2c01591"
- Description: Three ABAB-type cobalt meso-tetraarylporphyrins with fluorine (F-CoPor), acetic acid (AC-CoPor), and cyanoacetic acid (CN-CoPor) groups at the para-positions of phenyl rings at the 10,20-positions are synthesized and evaluated as catalysts for oxygen reduction reactions (ORRs). In density functional theory calculations, the frontier molecular orbitals of these complexes were found to be stabilized relative to model complexes with electron-withdrawing atoms or moieties on the meso-aryl rings. Electrochemical measurements suggest that electrodes with CN-CoPor (CN-CoPor/C) exhibit the most positive ORR potential values and the highest limiting current density in both acidic and alkali electrolytes, while the F-CoPor/C electrocatalyst exhibits extremely low ORR performance. The electron transfer numbers for the electrocatalysts are more than 3.0, indicating that a mixture of 2- and 4-electron transfer pathways occurs. The results demonstrate that coupling the hydrogen bonding properties and electron-withdrawing abilities through rational design of the substituent at the meso-position is an efficient way to modify the ORR performance.
- Full Text:
- Date Issued: 2022
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
Ball-type phthalocyanines and reduced graphene oxide nanoparticles as separate and combined corrosion inhibitors of aluminium in HCl
- Nnaji, Nnaemeka, Nawji, Njemuwa, Mack, John, Nyokong, Tebello
- Authors: Nnaji, Nnaemeka , Nawji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185421 , vital:44385 , xlink:href="https://doi.org/10.1016/j.molstruc.2021.130279"
- Description: Corrosion inhibition performances and adsorption behaviour at the aluminum-HCl solution interface were investigated for reduced graphene oxide nanosheets (rGONS), tetrakis-[4,4′-((4-(benzo[d]thiazol-2-yl)-1,2-bis(phenoxy)] (diphthalocyaninato gallium (III) chloride) (2) and tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato gallium(III) chloride) (1). Corrosion inhibition effects of rGONS, 1 and 2 were evaluated alone and in combination in 1.0 M hydrochloric acid solution using electrochemical techniques. The mechanism of aluminum corrosion inhibition revealed predominantly anodic character for rGONS and predominantly cathodic character for 1, 2, and conjugates with rGONS . The polarization technique gave inhibition efficiency values of 96.5% and 96.9% respectively for 1 and 2, which increased in the presence of rGONS to 97.4% and 98.1%, respectively, for the highest concentrations of 1 and 2. Scanning electron microscopy revealed effective metal surface protection by the inhibitors by formation of protective films.
- Full Text:
- Date Issued: 2021
- Authors: Nnaji, Nnaemeka , Nawji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185421 , vital:44385 , xlink:href="https://doi.org/10.1016/j.molstruc.2021.130279"
- Description: Corrosion inhibition performances and adsorption behaviour at the aluminum-HCl solution interface were investigated for reduced graphene oxide nanosheets (rGONS), tetrakis-[4,4′-((4-(benzo[d]thiazol-2-yl)-1,2-bis(phenoxy)] (diphthalocyaninato gallium (III) chloride) (2) and tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato gallium(III) chloride) (1). Corrosion inhibition effects of rGONS, 1 and 2 were evaluated alone and in combination in 1.0 M hydrochloric acid solution using electrochemical techniques. The mechanism of aluminum corrosion inhibition revealed predominantly anodic character for rGONS and predominantly cathodic character for 1, 2, and conjugates with rGONS . The polarization technique gave inhibition efficiency values of 96.5% and 96.9% respectively for 1 and 2, which increased in the presence of rGONS to 97.4% and 98.1%, respectively, for the highest concentrations of 1 and 2. Scanning electron microscopy revealed effective metal surface protection by the inhibitors by formation of protective films.
- Full Text:
- Date Issued: 2021