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
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
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
Turn-on detection of cysteine by a donor-acceptor type quinoline fluorophore: Exploring the sensing strategy and performance in bioimaging
- Muthusamy, Selvaraj, Zhao, Long, Rajalakshmi, Kanagaraj, Zhu, Dongwei, Soy, Rodah, Mack, John, Nyokong, Tebello, Wang, Shengjun, Lee, Kang-Bong, Zhu, Weihua
- Authors: Muthusamy, Selvaraj , Zhao, Long , Rajalakshmi, Kanagaraj , Zhu, Dongwei , Soy, Rodah , Mack, John , Nyokong, Tebello , Wang, Shengjun , Lee, Kang-Bong , Zhu, Weihua
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185644 , vital:44406 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109556"
- Description: Tracking the biothiol cysteine (Cys) in living systems is a significant responsibility to balance the redox environment and oxidative stress. A quinoline-7-nitro-1,2,3-benzoxadiazole (Q-NBD) fluorophore has been synthesized and characterized towards examination of Cys. The probe forms a quinoline-substituted phenol (Q-Ph-OH) after thiolysis of the NBD ether bond, leading to an increase of fluorescence at green channel. The turn-on sensing mechanism originates from the change in intramolecular charge transfer (ICT-OFF) along with an aggregation-induced emission (AIE) as suggested by spectroscopy measurements in solutions, time-dependent density-functional theory (TD-DFT) calculations and 1H NMR titration examination. Importantly, Q-NBD exhibited great sensitivity with a low limit of detection value of 89.5 nM and remarkable selectivity in various biothiols towards Cys. The sensor probe was successfully used for detecting both endogenous and exogenous Cys in PC3 living cells and spiked Cys in human urine samples.
- Full Text:
- Date Issued: 2021
- Authors: Muthusamy, Selvaraj , Zhao, Long , Rajalakshmi, Kanagaraj , Zhu, Dongwei , Soy, Rodah , Mack, John , Nyokong, Tebello , Wang, Shengjun , Lee, Kang-Bong , Zhu, Weihua
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/185644 , vital:44406 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.109556"
- Description: Tracking the biothiol cysteine (Cys) in living systems is a significant responsibility to balance the redox environment and oxidative stress. A quinoline-7-nitro-1,2,3-benzoxadiazole (Q-NBD) fluorophore has been synthesized and characterized towards examination of Cys. The probe forms a quinoline-substituted phenol (Q-Ph-OH) after thiolysis of the NBD ether bond, leading to an increase of fluorescence at green channel. The turn-on sensing mechanism originates from the change in intramolecular charge transfer (ICT-OFF) along with an aggregation-induced emission (AIE) as suggested by spectroscopy measurements in solutions, time-dependent density-functional theory (TD-DFT) calculations and 1H NMR titration examination. Importantly, Q-NBD exhibited great sensitivity with a low limit of detection value of 89.5 nM and remarkable selectivity in various biothiols towards Cys. The sensor probe was successfully used for detecting both endogenous and exogenous Cys in PC3 living cells and spiked Cys in human urine samples.
- 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
An octabrominated Sn (iv) tetraisopropylporphyrin as a photosensitizer dye for singlet oxygen biomedical applications
- Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186679 , vital:44524 , xlink:href="https://doi.org/10.1039/D0DT01915A"
- Description: Two novel Sn(IV) tetraisopropylphenylporphyrins have been synthesized to explore the effect of octabromination at the β-pyrrole positions on their photophysical properties and photodynamic activity. The lower energy Q band of an octabrominated complex lies at 675 nm well within the therapeutic window. The octabrominated dye has a relatively high singlet oxygen quantum yield of 0.78 in DMF and exhibits favorable photodynamic activity against MCF-7 cells with an IC50 value of 10.7 μM and a 5.74 log reduction value (5 μM) towards S. aureus under illumination at 660 nm for 60 min with a Thorlabs M660L3 LED (280 mW cm−2).
- Full Text:
- Date Issued: 2020
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186679 , vital:44524 , xlink:href="https://doi.org/10.1039/D0DT01915A"
- Description: Two novel Sn(IV) tetraisopropylphenylporphyrins have been synthesized to explore the effect of octabromination at the β-pyrrole positions on their photophysical properties and photodynamic activity. The lower energy Q band of an octabrominated complex lies at 675 nm well within the therapeutic window. The octabrominated dye has a relatively high singlet oxygen quantum yield of 0.78 in DMF and exhibits favorable photodynamic activity against MCF-7 cells with an IC50 value of 10.7 μM and a 5.74 log reduction value (5 μM) towards S. aureus under illumination at 660 nm for 60 min with a Thorlabs M660L3 LED (280 mW cm−2).
- Full Text:
- Date Issued: 2020
High genetic diversity and limited spatial structure in an endangered, endemic South African sparid, the red steenbras Petrus rupestris:
- Tang, Wei, Qiu, Yuanyuan, Li, Xiaonan, Soy, Rodah C, Mack, John, Nyokong, Tebello
- Authors: Tang, Wei , Qiu, Yuanyuan , Li, Xiaonan , Soy, Rodah C , Mack, John , Nyokong, Tebello
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/160390 , vital:40441 , DOI: 10.6060/mhc200183l
- Description: Earth-abundant first row transition metal corrole complexes have played an important role in fundamental research due to their unique molecular structures and attractive properties. In comparison to porphyrins, corroles have three inner N-H protons and are ring-contracted with a smaller macrocyclic cavity. First row transition metal corroles have been widely used as effective electrochemical catalysts for small molecule activations, such as hydrogen evolution, oxygen reduction/evolution and CO2 reduction reactions (HERs, ORRs/OERs and CO2 RRs) through homogenous and/or heterogenous prodecures. Several strategies have been used to modulate the catalytic efficiency of synthetic metallocorroles.
- Full Text:
- Date Issued: 2020
- Authors: Tang, Wei , Qiu, Yuanyuan , Li, Xiaonan , Soy, Rodah C , Mack, John , Nyokong, Tebello
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/160390 , vital:40441 , DOI: 10.6060/mhc200183l
- Description: Earth-abundant first row transition metal corrole complexes have played an important role in fundamental research due to their unique molecular structures and attractive properties. In comparison to porphyrins, corroles have three inner N-H protons and are ring-contracted with a smaller macrocyclic cavity. First row transition metal corroles have been widely used as effective electrochemical catalysts for small molecule activations, such as hydrogen evolution, oxygen reduction/evolution and CO2 reduction reactions (HERs, ORRs/OERs and CO2 RRs) through homogenous and/or heterogenous prodecures. Several strategies have been used to modulate the catalytic efficiency of synthetic metallocorroles.
- Full Text:
- Date Issued: 2020
New difluoroboron complexes based on N, O-chelated Schiff base ligands: Synthesis, characterization, DFT calculations and photophysical and electrochemical properties
- Sen, Pinar, Mpeta, Lekhetho S, Mack, John, Nyokong, Tebello
- Authors: Sen, Pinar , Mpeta, Lekhetho S , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186207 , vital:44473 , xlink:href="https://doi.org/10.1016/j.jlumin.2020.117262"
- Description: The synthesis of new Schiff bases and their dinuclear boron complexes is described, along with their characterization by 1H and 13C NMR, FT-IR, and UV–visible absorption spectroscopy, mass spectrometry, and EDX for elemental analysis. The optical and photophysical properties were examined in terms of their absorption and emission behavior, fluorescence quantum yields and fluorescence lifetimes. The flexible dinuclear boron complexes that are linked by a flexible carbon chain exhibited large Stokes shifts in the range from 92 nm to 115 nm in contrast to BODIPY dyes. Those properties make these complexes precious for applications in fluorescence materials. And also theoretical calculations were obtained by using Density Functional Theory (DFT) methods.
- Full Text:
- Date Issued: 2020
- Authors: Sen, Pinar , Mpeta, Lekhetho S , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186207 , vital:44473 , xlink:href="https://doi.org/10.1016/j.jlumin.2020.117262"
- Description: The synthesis of new Schiff bases and their dinuclear boron complexes is described, along with their characterization by 1H and 13C NMR, FT-IR, and UV–visible absorption spectroscopy, mass spectrometry, and EDX for elemental analysis. The optical and photophysical properties were examined in terms of their absorption and emission behavior, fluorescence quantum yields and fluorescence lifetimes. The flexible dinuclear boron complexes that are linked by a flexible carbon chain exhibited large Stokes shifts in the range from 92 nm to 115 nm in contrast to BODIPY dyes. Those properties make these complexes precious for applications in fluorescence materials. And also theoretical calculations were obtained by using Density Functional Theory (DFT) methods.
- Full Text:
- Date Issued: 2020
NIR Absorbing AzaBODIPY Dyes for pH Sensing
- Kubheka, Gugu, Mack, John, Nyokong, Tebello, Zhen, Shen
- Authors: Kubheka, Gugu , Mack, John , Nyokong, Tebello , Zhen, Shen
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186668 , vital:44523 , xlink:href="https://doi.org/10.3390/molecules25163689"
- Description: Two near-infrared (NIR) absorbing di(thien-2-nyl)-di(dimethylanilino)azaBODIPY dyes 2a and 2b were synthesized and characterized that differ depending on whether the dimethylaniline substituents are introduced at the 3,5- or 1,7-positions of the azaBODIPY core. The main spectral bands lie at 824 and 790 nm, respectively, in CH2Cl2. The effect of substituent position on the photophysical and pH sensing properties was analyzed through a comparison of the optical properties with the results of time-dependent density functional theory (TD-DFT) calculations. Protonation of the dimethylamino nitrogen atoms eliminates the intramolecular charge transfer properties of these compounds, and this results in a marked blue-shift of the main absorption bands to 696 and 730 nm, respectively, in CH2Cl2, and a fluorescence “turn-on” effect in the NIR region. The pH dependence studies reveal that the pKa values of the non-protonated 2a and 2b molecules are ca. 6.9 (±0.05) and 7.3 (±0.05), respectively, while that of the monoprotonated species for both dyes is ca. 1.4 (±0.05) making them potentially suitable for use as colorimetric pH indicators under highly acidic conditions.
- Full Text:
- Date Issued: 2020
- Authors: Kubheka, Gugu , Mack, John , Nyokong, Tebello , Zhen, Shen
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186668 , vital:44523 , xlink:href="https://doi.org/10.3390/molecules25163689"
- Description: Two near-infrared (NIR) absorbing di(thien-2-nyl)-di(dimethylanilino)azaBODIPY dyes 2a and 2b were synthesized and characterized that differ depending on whether the dimethylaniline substituents are introduced at the 3,5- or 1,7-positions of the azaBODIPY core. The main spectral bands lie at 824 and 790 nm, respectively, in CH2Cl2. The effect of substituent position on the photophysical and pH sensing properties was analyzed through a comparison of the optical properties with the results of time-dependent density functional theory (TD-DFT) calculations. Protonation of the dimethylamino nitrogen atoms eliminates the intramolecular charge transfer properties of these compounds, and this results in a marked blue-shift of the main absorption bands to 696 and 730 nm, respectively, in CH2Cl2, and a fluorescence “turn-on” effect in the NIR region. The pH dependence studies reveal that the pKa values of the non-protonated 2a and 2b molecules are ca. 6.9 (±0.05) and 7.3 (±0.05), respectively, while that of the monoprotonated species for both dyes is ca. 1.4 (±0.05) making them potentially suitable for use as colorimetric pH indicators under highly acidic conditions.
- Full Text:
- Date Issued: 2020
Non-aggregated lipophilic water-soluble tin porphyrins as photosensitizers for photodynamic therapy and photodynamic antimicrobial chemotherapy:
- Babu, Balaji, Soy, Rodah C, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Soy, Rodah C , Mack, John , Nyokong, Tebello
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/158241 , vital:40165 , DOI: 10.1039/d0nj01564d
- Description: Two readily synthesized water-soluble Sn(IV) porphyrins have been prepared with quaternized pyridyl nitrogens and 2-naphthalato trans-axial ligands. Methyl and hexyl groups were attached to the quaternized nitrogens to form lipophilic dyes with high singlet oxygen quantum yields (ca. 0.90) and unusually long triplet state lifetimes. The dyes exhibit good photodynamic activity against MCF-7 cells with IC50 values of 14.3 and 8.5 μM, respectively. The hexyl quaternized dye exhibited a 9.69 log reduction value (0.5 μM) towards S. aureus under illumination for 90 min (250 mW cm−2). The results demonstrate that this set of structural modification strategies for photosensitizer dyes merits further in depth study.
- Full Text:
- Date Issued: 2020
- Authors: Babu, Balaji , Soy, Rodah C , Mack, John , Nyokong, Tebello
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/158241 , vital:40165 , DOI: 10.1039/d0nj01564d
- Description: Two readily synthesized water-soluble Sn(IV) porphyrins have been prepared with quaternized pyridyl nitrogens and 2-naphthalato trans-axial ligands. Methyl and hexyl groups were attached to the quaternized nitrogens to form lipophilic dyes with high singlet oxygen quantum yields (ca. 0.90) and unusually long triplet state lifetimes. The dyes exhibit good photodynamic activity against MCF-7 cells with IC50 values of 14.3 and 8.5 μM, respectively. The hexyl quaternized dye exhibited a 9.69 log reduction value (0.5 μM) towards S. aureus under illumination for 90 min (250 mW cm−2). The results demonstrate that this set of structural modification strategies for photosensitizer dyes merits further in depth study.
- Full Text:
- Date Issued: 2020
Optical limiting properties of D-π-A BODIPY dyes in the presence and absence of methyl groups at the 1, 7-positions
- May, Aviwe K, Mack, John, Nyokong, Tebello
- Authors: May, Aviwe K , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186146 , vital:44468 , xlink:href="https://doi.org/10.1142/S1088424620500315"
- Description: The optical limiting properties of three meso-pentafluorophenylstyrylBODIPY dyes are investigated in the presence and absence of methyl groups at the 1,7-positions that hinder free rotation of the meso-aryl group. Pentafluorophenyl groups are introduced at the meso-position, while 4-diethylaminostyryl groups are introduced at the 3- and/or 5-positions to form dyes with strong donor-ππ-acceptor (D-ππ-A) properties to enhance the dipole moment of the molecule. Favorable optical limiting properties are obtained for all three dyes, with the highest second-order hyperpolarizability value obtained for a monostyryl dye with no methyl groups at the 1,7-position. Bromination at the 2,6-positions of a 1,7-methyl substituted dye is found to result in second-order hyperpolarizability that is an order of magnitude lower than that calculated for the analogous non-halogenated dye.
- Full Text:
- Date Issued: 2020
- Authors: May, Aviwe K , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186146 , vital:44468 , xlink:href="https://doi.org/10.1142/S1088424620500315"
- Description: The optical limiting properties of three meso-pentafluorophenylstyrylBODIPY dyes are investigated in the presence and absence of methyl groups at the 1,7-positions that hinder free rotation of the meso-aryl group. Pentafluorophenyl groups are introduced at the meso-position, while 4-diethylaminostyryl groups are introduced at the 3- and/or 5-positions to form dyes with strong donor-ππ-acceptor (D-ππ-A) properties to enhance the dipole moment of the molecule. Favorable optical limiting properties are obtained for all three dyes, with the highest second-order hyperpolarizability value obtained for a monostyryl dye with no methyl groups at the 1,7-position. Bromination at the 2,6-positions of a 1,7-methyl substituted dye is found to result in second-order hyperpolarizability that is an order of magnitude lower than that calculated for the analogous non-halogenated dye.
- Full Text:
- Date Issued: 2020
Optical limiting properties, structure and simplified TD-DFT calculations of scandium tetra-15-crown-5 phthalocyaninates:
- May, Aviwe K, Majumdar, Poulomi, Martynov, Alexander G, Lapkina, Lyudmila A, Troyanov, Sergey I, Gorbunova, Yulia G, Tsivadze, Aslan Yu, Mack, John, Nyokong, Tebello
- Authors: May, Aviwe K , Majumdar, Poulomi , Martynov, Alexander G , Lapkina, Lyudmila A , Troyanov, Sergey I , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Mack, John , Nyokong, Tebello
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/163553 , vital:41048 , https://0-doi.org.wam.seals.ac.za/10.1142/S108842462050011X
- Description: The optical limiting properties of crown-ether-substituted scandium(III) phthalocyaninate complexes, bis-tetra-15-crown-5-phthalocyaninates Sc[(15C5)4Pc]∙022•0 (I) and Sc[(15C5)4Pc]−22− (Ia), together with monophthalocyaninate [(15C5)4Pc]Sc(OAc) (II) were measured by using the Z-scan technique (532 nm laser and pulse rate of 10 ns).
- Full Text:
- Date Issued: 2020
- Authors: May, Aviwe K , Majumdar, Poulomi , Martynov, Alexander G , Lapkina, Lyudmila A , Troyanov, Sergey I , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Mack, John , Nyokong, Tebello
- Date: 2020
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/163553 , vital:41048 , https://0-doi.org.wam.seals.ac.za/10.1142/S108842462050011X
- Description: The optical limiting properties of crown-ether-substituted scandium(III) phthalocyaninate complexes, bis-tetra-15-crown-5-phthalocyaninates Sc[(15C5)4Pc]∙022•0 (I) and Sc[(15C5)4Pc]−22− (Ia), together with monophthalocyaninate [(15C5)4Pc]Sc(OAc) (II) were measured by using the Z-scan technique (532 nm laser and pulse rate of 10 ns).
- Full Text:
- Date Issued: 2020
Photodynamic activity of 2, 6-diiodo-3, 5-dithienylvinyleneBODIPYs and their folate-functionalized chitosan-coated Pluronic® F-127 micelles on MCF-7 breast cancer cells
- Molupe, Nthabeleng, Babu, Balaji, Oluwole, David O, Prinsloo, Earl, Gai, Lizhi, Shen, Zhen, Mack, John, Nyokong, Tebello
- Authors: Molupe, Nthabeleng , Babu, Balaji , Oluwole, David O , Prinsloo, Earl , Gai, Lizhi , Shen, Zhen , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186222 , vital:44474 , xlink:href="https://doi.org/10.1142/S1088424619501773"
- Description: A 2,6-diiodo-3,5-dithienylvinyleneBODIPY dye was prepared and encapsulated with folate-chitosan capped Pluronic®® F-127 to provide drug delivery systems for photodynamic therapy (PDT). Moderately enhanced singlet oxygen quantum yields were observed for the dye encapsulation complexes in water. The in vitro dark cytotoxicity and photodynamic activity were investigated on the human breast adenocarcinoma (MCF-7) cell line. Minimal dark cytotoxicity was observed for the BODIPY dyes in 5% DMSO and when encapsulated in folate-functionalized chitosan-coated Pluronic®® F-127 micelles, since the cell viability values are consistently greater than 80% over the 0-40 μg⋅mL−1μg⋅mL−1 concentration range. Upon irradiation of the samples, significant cytocidal activity was observed for the encapsulation complex of a 2,6-diiodo-8-dimethylaminophenyl-3,5-dithienylvinyleneBODIPY dye with less than 50% viable cells observed at concentrations ≥20μg⋅mL−1≥20μg⋅mL−1.
- Full Text:
- Date Issued: 2020
- Authors: Molupe, Nthabeleng , Babu, Balaji , Oluwole, David O , Prinsloo, Earl , Gai, Lizhi , Shen, Zhen , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186222 , vital:44474 , xlink:href="https://doi.org/10.1142/S1088424619501773"
- Description: A 2,6-diiodo-3,5-dithienylvinyleneBODIPY dye was prepared and encapsulated with folate-chitosan capped Pluronic®® F-127 to provide drug delivery systems for photodynamic therapy (PDT). Moderately enhanced singlet oxygen quantum yields were observed for the dye encapsulation complexes in water. The in vitro dark cytotoxicity and photodynamic activity were investigated on the human breast adenocarcinoma (MCF-7) cell line. Minimal dark cytotoxicity was observed for the BODIPY dyes in 5% DMSO and when encapsulated in folate-functionalized chitosan-coated Pluronic®® F-127 micelles, since the cell viability values are consistently greater than 80% over the 0-40 μg⋅mL−1μg⋅mL−1 concentration range. Upon irradiation of the samples, significant cytocidal activity was observed for the encapsulation complex of a 2,6-diiodo-8-dimethylaminophenyl-3,5-dithienylvinyleneBODIPY dye with less than 50% viable cells observed at concentrations ≥20μg⋅mL−1≥20μg⋅mL−1.
- Full Text:
- Date Issued: 2020
Sn (iv) N-confused porphyrins as photosensitizer dyes for photodynamic therapy in the near IR region
- Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186648 , vital:44521 , xlink:href="https://doi.org/10.1039/D0DT03296D"
- Description: The utility of Sn(IV) N-confused porphyrin (SnNCP) for use as photosensitizer dyes in photodynamic therapy is investigated. SnNCP has an unusually high singlet oxygen quantum yield of 0.72 in DMSO. IC50 values of 1.6 and 12.8 μM were obtained against MCF-7 cells upon irradiation with 660 and 780 nm LEDs.
- Full Text:
- Date Issued: 2020
Sn (iv) N-confused porphyrins as photosensitizer dyes for photodynamic therapy in the near IR region
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186648 , vital:44521 , xlink:href="https://doi.org/10.1039/D0DT03296D"
- Description: The utility of Sn(IV) N-confused porphyrin (SnNCP) for use as photosensitizer dyes in photodynamic therapy is investigated. SnNCP has an unusually high singlet oxygen quantum yield of 0.72 in DMSO. IC50 values of 1.6 and 12.8 μM were obtained against MCF-7 cells upon irradiation with 660 and 780 nm LEDs.
- Full Text:
- Date Issued: 2020
A 3, 5-DistyrylBODIPY Dye Functionalized with Boronic Acid Groups for Direct Electrochemical Glucose Sensing
- Ndebele, Nobuhle, Mack, John, Nyokong, Tebello
- Authors: Ndebele, Nobuhle , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187556 , vital:44671 , xlink:href="https://doi.org/10.1002/elan.201800651"
- Description: The synthesis and characterization of a novel BODIPY dye functionalized with bis-boronic acid groups to enable direct glucose sensing through selective recognition of carbohydrates is reported. Styrylation with boronic acid groups at the 3,5-positions of the BODIPY core results in an extension of the π-conjugation system of the dye and in a red-shift of the main absorption band from 500 to 637 nm. The functionalized BODIPY dye was adsorbed on a glassy carbon electrode using the drop and dry method. Modified and bare electrodes were characterized using cyclic voltammetry and scanning electrochemical microscopy, while glucose detection was carried out by using differential pulse voltammetry and chronoamperometry. The detection limit was determined to be 1.42 μM. The dye was found to be selective and sensitive towards glucose, since likely interferences have only minor effects on the glucose detection.
- Full Text:
- Date Issued: 2019
- Authors: Ndebele, Nobuhle , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187556 , vital:44671 , xlink:href="https://doi.org/10.1002/elan.201800651"
- Description: The synthesis and characterization of a novel BODIPY dye functionalized with bis-boronic acid groups to enable direct glucose sensing through selective recognition of carbohydrates is reported. Styrylation with boronic acid groups at the 3,5-positions of the BODIPY core results in an extension of the π-conjugation system of the dye and in a red-shift of the main absorption band from 500 to 637 nm. The functionalized BODIPY dye was adsorbed on a glassy carbon electrode using the drop and dry method. Modified and bare electrodes were characterized using cyclic voltammetry and scanning electrochemical microscopy, while glucose detection was carried out by using differential pulse voltammetry and chronoamperometry. The detection limit was determined to be 1.42 μM. The dye was found to be selective and sensitive towards glucose, since likely interferences have only minor effects on the glucose detection.
- Full Text:
- Date Issued: 2019
Chiral Modulation from Molecular to Macroscopic levels by synthetic chiral-amide-bonded porphyrin dimers
- Liang, Xu, Qin, Mingfeng, Zhang, Xiaomei, Mack, John, Soy, Rodah, Nyokong, Tebello, Zhu, Weihua
- Authors: Liang, Xu , Qin, Mingfeng , Zhang, Xiaomei , Mack, John , Soy, Rodah , Nyokong, Tebello , Zhu, Weihua
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186802 , vital:44535 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107637"
- Description: Six different nanoarchitectures were constructed by a series of synthetic bio-inspired chiral porphyrin dimers through molecular self-assembly behaviour. A plausible mechanism of chiral expression from the molecular to the macroscopic levels was investigated through an analysis of the optical spectroscopy and theoretical calculations.
- Full Text:
- Date Issued: 2019
- Authors: Liang, Xu , Qin, Mingfeng , Zhang, Xiaomei , Mack, John , Soy, Rodah , Nyokong, Tebello , Zhu, Weihua
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186802 , vital:44535 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107637"
- Description: Six different nanoarchitectures were constructed by a series of synthetic bio-inspired chiral porphyrin dimers through molecular self-assembly behaviour. A plausible mechanism of chiral expression from the molecular to the macroscopic levels was investigated through an analysis of the optical spectroscopy and theoretical calculations.
- Full Text:
- Date Issued: 2019
Co (ii) Tetraphenyltetraphenanthroporphyrin@ MWCNTs
- Gu, Tingting, Tao, Jaiyu, Zhu, Weihua, Mack, John, Soy, Rodah C, Nyokong, Tebello, Xu, Haijin, Li, Minzhi, Liang, Xu
- Authors: Gu, Tingting , Tao, Jaiyu , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Xu, Haijin , Li, Minzhi , Liang, Xu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234580 , vital:50210 , xlink:href="https://doi.org/10.1039/C9NJ01707K"
- Description: Herein, a cobalt(II)tetraphenyltetraphenanthroporphyrin (Co(II)TPTPP) with phenanthrene-fused pyrrole rings was synthesized and characterized. Moreover, a detailed analysis of its optical and redox properties was carried out by comparing the results obtained via optical spectroscopy and electrochemistry with the trends predicted via a series of DFT and TD-DFT calculations. The electrochemistry results demonstrated that the π-expanded Co(II)TPTPP interacted strongly with multiwall carbon nanotubes (MWCNTs), which were finally immobilized on carbon nanotubes via noncovalent interactions and further deposited on glassy carbon. This strong immobilization via π–π stacking between Co(II)TPTPP and MWCNTs leads to significantly stable electrochemically catalyzed hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), which provides a new insight into the understanding electron transfer channels.
- Full Text:
- Date Issued: 2019
- Authors: Gu, Tingting , Tao, Jaiyu , Zhu, Weihua , Mack, John , Soy, Rodah C , Nyokong, Tebello , Xu, Haijin , Li, Minzhi , Liang, Xu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234580 , vital:50210 , xlink:href="https://doi.org/10.1039/C9NJ01707K"
- Description: Herein, a cobalt(II)tetraphenyltetraphenanthroporphyrin (Co(II)TPTPP) with phenanthrene-fused pyrrole rings was synthesized and characterized. Moreover, a detailed analysis of its optical and redox properties was carried out by comparing the results obtained via optical spectroscopy and electrochemistry with the trends predicted via a series of DFT and TD-DFT calculations. The electrochemistry results demonstrated that the π-expanded Co(II)TPTPP interacted strongly with multiwall carbon nanotubes (MWCNTs), which were finally immobilized on carbon nanotubes via noncovalent interactions and further deposited on glassy carbon. This strong immobilization via π–π stacking between Co(II)TPTPP and MWCNTs leads to significantly stable electrochemically catalyzed hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), which provides a new insight into the understanding electron transfer channels.
- Full Text:
- Date Issued: 2019
Corrosion resistance of aluminum against acid activation: Impact of benzothiazole-substituted gallium phthalocyanine
- Nnaji, Nnaemeka, Nwaji, Njemuwa N, Mack, John, Nyokong, Tebello
- Authors: Nnaji, Nnaemeka , Nwaji, Njemuwa N , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187545 , vital:44670 , xlink:href="https://doi.org/10.3390/molecules24010207"
- Description: This study describes the adsorption behavior of organic inhibitors at the aluminum-HCl solution interface and their corrosion inhibition performance. The organic inhibitors employed are: 4-(benzo [d]thiazol-2ylthio)phthalonitrile (BTThio) and tetrakis[(benzo[d]thiazol-2-yl-thio)phthalocyaninato]gallium(III) chloride (ClGaBTThioPc). The corrosion behavior of these inhibitors is investigated using electrochemical and computational techniques. Open circuit potential results reveal predominant cathodic character for the mechanism of aluminum corrosion inhibition by the inhibitors. Inhibition efficiency values from potentiodynamic polarization measurements increase from 46.9 to 70.8% for BTThio and 59.7 to 81.0% for ClGaBTThioPc within the concentration range of 2 to 10 µM. Scanning electron microscopy (SEM) measurements reveal protection of the metal surface from acid attack, in the presence of the inhibitors and energy dispersive X-ray (EDX) measurements show that the most probable way by which the inhibitors protect the metal surface would be by shielding it from the corrosion attacks of Cl− from the acid. Quantum chemical parameters corroborate well with experimental findings.
- Full Text:
- Date Issued: 2019
- Authors: Nnaji, Nnaemeka , Nwaji, Njemuwa N , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187545 , vital:44670 , xlink:href="https://doi.org/10.3390/molecules24010207"
- Description: This study describes the adsorption behavior of organic inhibitors at the aluminum-HCl solution interface and their corrosion inhibition performance. The organic inhibitors employed are: 4-(benzo [d]thiazol-2ylthio)phthalonitrile (BTThio) and tetrakis[(benzo[d]thiazol-2-yl-thio)phthalocyaninato]gallium(III) chloride (ClGaBTThioPc). The corrosion behavior of these inhibitors is investigated using electrochemical and computational techniques. Open circuit potential results reveal predominant cathodic character for the mechanism of aluminum corrosion inhibition by the inhibitors. Inhibition efficiency values from potentiodynamic polarization measurements increase from 46.9 to 70.8% for BTThio and 59.7 to 81.0% for ClGaBTThioPc within the concentration range of 2 to 10 µM. Scanning electron microscopy (SEM) measurements reveal protection of the metal surface from acid attack, in the presence of the inhibitors and energy dispersive X-ray (EDX) measurements show that the most probable way by which the inhibitors protect the metal surface would be by shielding it from the corrosion attacks of Cl− from the acid. Quantum chemical parameters corroborate well with experimental findings.
- Full Text:
- Date Issued: 2019
Effect of bromination on the optical limiting properties at 532 nm of BODIPY dyes with p-benzyloxystyryl groups at the 3, 5-positions
- 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/10962/187507 , vital:44665 , xlink:href="https://doi.org/10.1016/j.molstruc.2018.08.012"
- Description: The optical limiting (OL) properties of 3,5-di-p-benzyloxystyrylBODIPY dyes that contain both protons and bromine atoms at the 2,6-positions have been investigated by using the Z-scan technique at 532 nm on the nanosecond timescale. There is relatively weak absorbance at 532 nm under ambient light conditions, because the incorporation of p-benzyloxystyryl groups at the 3,5-positions results in a ca. 140 nm red shift of the main BODIPY spectral band to the 640–670 nm range. Reverse saturable absorbance (RSA) profiles that are consistent with an excited state absorption (ESA) mechanism involving the T1 and/or S1 states are observed in CH2Cl2 solution. Second order hyperpolarizability values of ca. 8 × 10−30 esu are obtained and this demonstrates that the dyes are potentially suitable for use in OL applications at 532 nm. There is a slight enhancement of the OL properties upon bromination, due to increased intersystem crossing to the triplet manifold, but the enhancement of the OL properties is less significant than has been observed with metal phthalocyanine complexes.
- 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/10962/187507 , vital:44665 , xlink:href="https://doi.org/10.1016/j.molstruc.2018.08.012"
- Description: The optical limiting (OL) properties of 3,5-di-p-benzyloxystyrylBODIPY dyes that contain both protons and bromine atoms at the 2,6-positions have been investigated by using the Z-scan technique at 532 nm on the nanosecond timescale. There is relatively weak absorbance at 532 nm under ambient light conditions, because the incorporation of p-benzyloxystyryl groups at the 3,5-positions results in a ca. 140 nm red shift of the main BODIPY spectral band to the 640–670 nm range. Reverse saturable absorbance (RSA) profiles that are consistent with an excited state absorption (ESA) mechanism involving the T1 and/or S1 states are observed in CH2Cl2 solution. Second order hyperpolarizability values of ca. 8 × 10−30 esu are obtained and this demonstrates that the dyes are potentially suitable for use in OL applications at 532 nm. There is a slight enhancement of the OL properties upon bromination, due to increased intersystem crossing to the triplet manifold, but the enhancement of the OL properties is less significant than has been observed with metal phthalocyanine complexes.
- Full Text:
- Date Issued: 2019
Inhibition of aluminium corrosion using benzothiazole and its phthalocyanine derivative
- Nnaji, Nnaemeka, Nwaji, Njemuwa, Fomo, Gertrude, Mack, John, Nyokong, Tebello
- Authors: Nnaji, Nnaemeka , Nwaji, Njemuwa , Fomo, Gertrude , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186949 , vital:44550 , xlink:href="https://doi.org/10.1007/s12678-019-00538-1"
- Description: Cyclic voltammetry and potentiodynamic polarization techniques were used to study the effects of 4-[4-(1,3-benzothiazol2yl)phenoxy] phthalonitrile (BT) and tetrakis[(benzo[d]thiazol-2ylphenoxy) phthalocyaninato] gallium(III)chloride (ClGaBTPc) as aluminium corrosion inhibitors in 1.0 M hydrochloric acid. The presence of the inhibitors in the concentration range of 2 to 10 μM was found to retard the aluminium corrosion process such that the inhibition efficiency was found to range from 28.2 to 76.1% for BT and from 71.5 to 82.7% for ClGaBTPc. The latter was a better inhibitor. Scanning electron microscopy and energy-dispersive X-ray measurements reveal effective metal surface protection by the inhibitors, most probably by shielding it from the corrosion attacks of Cl− from the acid. The calculated quantum chemical parameters agreed with experimental results.
- Full Text:
- Date Issued: 2019
- Authors: Nnaji, Nnaemeka , Nwaji, Njemuwa , Fomo, Gertrude , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186949 , vital:44550 , xlink:href="https://doi.org/10.1007/s12678-019-00538-1"
- Description: Cyclic voltammetry and potentiodynamic polarization techniques were used to study the effects of 4-[4-(1,3-benzothiazol2yl)phenoxy] phthalonitrile (BT) and tetrakis[(benzo[d]thiazol-2ylphenoxy) phthalocyaninato] gallium(III)chloride (ClGaBTPc) as aluminium corrosion inhibitors in 1.0 M hydrochloric acid. The presence of the inhibitors in the concentration range of 2 to 10 μM was found to retard the aluminium corrosion process such that the inhibition efficiency was found to range from 28.2 to 76.1% for BT and from 71.5 to 82.7% for ClGaBTPc. The latter was a better inhibitor. Scanning electron microscopy and energy-dispersive X-ray measurements reveal effective metal surface protection by the inhibitors, most probably by shielding it from the corrosion attacks of Cl− from the acid. The calculated quantum chemical parameters agreed with experimental results.
- Full Text:
- Date Issued: 2019