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
Trends in the TD-DFT calculations of porphyrin and phthalocyanine analogs
- Mack, John, Stone, Justin, Nyokong, Tebello
- Authors: Mack, John , Stone, Justin , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193882 , vital:45402 , xlink:href="https://doi.org/10.1142/S108842461450045X"
- Description: In 2005, Kobayashi and coworkers reported trends in the TD-DFT spectra of 17 Zn (II) porphyrinoids [J. Am. Chem. Soc. 2005; 127: 17697] that were analyzed using Michl's perimeter model as part of a study of the anomalous magnetic circular dichroism (MCD) spectroscopy of zinc tetraphenyltetraacenaphthoporphyrin. In recent years, it has become increasingly clear that TD-DFT calculations with the commonly used hybrid B3LYP exchange-correlation functional of the Gaussian software package are problematic in the B-band region of porphyrinoid spectra, since the degree of configurational interaction between the B and higher energy ππ* state appears to be significantly overestimated. The CAM-B3LYP functional is now often preferred for analyzing the optical properties of porphyrinoids, since it includes a long-range correction of the exchange potential, which incorporates an increasing fraction of Hartree–Fock (HF) exchange as the interelectronic separation increases, making it better suited for studying compounds where there is significant charge transfer in the electronic excited states. The trends in the TD-DFT calculations are reexamined with a wider range porphyrinoid compounds including several with pyrazino moieties and are found to provide a closer agreement with the experimental in the B-band region for complexes such as zinc tetraphenylporphyrin and phthalocyanine.
- Full Text:
- Date Issued: 2014
- Authors: Mack, John , Stone, Justin , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193882 , vital:45402 , xlink:href="https://doi.org/10.1142/S108842461450045X"
- Description: In 2005, Kobayashi and coworkers reported trends in the TD-DFT spectra of 17 Zn (II) porphyrinoids [J. Am. Chem. Soc. 2005; 127: 17697] that were analyzed using Michl's perimeter model as part of a study of the anomalous magnetic circular dichroism (MCD) spectroscopy of zinc tetraphenyltetraacenaphthoporphyrin. In recent years, it has become increasingly clear that TD-DFT calculations with the commonly used hybrid B3LYP exchange-correlation functional of the Gaussian software package are problematic in the B-band region of porphyrinoid spectra, since the degree of configurational interaction between the B and higher energy ππ* state appears to be significantly overestimated. The CAM-B3LYP functional is now often preferred for analyzing the optical properties of porphyrinoids, since it includes a long-range correction of the exchange potential, which incorporates an increasing fraction of Hartree–Fock (HF) exchange as the interelectronic separation increases, making it better suited for studying compounds where there is significant charge transfer in the electronic excited states. The trends in the TD-DFT calculations are reexamined with a wider range porphyrinoid compounds including several with pyrazino moieties and are found to provide a closer agreement with the experimental in the B-band region for complexes such as zinc tetraphenylporphyrin and phthalocyanine.
- Full Text:
- Date Issued: 2014
Trends in the optical and redox properties of tetraphenyltetraphenanthroporphyrins
- Mack, John, Lobb, Kevin, Nyokong, Tebello, Shen, Zhen, Kobayashi, Nagao
- Authors: Mack, John , Lobb, Kevin , Nyokong, Tebello , Shen, Zhen , Kobayashi, Nagao
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245809 , vital:51407 , xlink:href="https://doi.org/10.1142/S1088424612500885"
- Description: The results of TD-DFT calculations for a series of tetraaryltetraphenanthroporphyrins containing para-substituents with differing electron donating and accepting properties are compared to the observed optical and redox properties and Michl's perimeter model is used as a conceptual framework for analyzing the results.
- Full Text:
- Date Issued: 2012
- Authors: Mack, John , Lobb, Kevin , Nyokong, Tebello , Shen, Zhen , Kobayashi, Nagao
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245809 , vital:51407 , xlink:href="https://doi.org/10.1142/S1088424612500885"
- Description: The results of TD-DFT calculations for a series of tetraaryltetraphenanthroporphyrins containing para-substituents with differing electron donating and accepting properties are compared to the observed optical and redox properties and Michl's perimeter model is used as a conceptual framework for analyzing the results.
- Full Text:
- Date Issued: 2012
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
The photophysicochemical behavior of symmetric and asymmetric zinc phthalocyanines, surface assembled onto gold nanotriangles
- Dube, Edith, Nwaji, Njemuwa, Mack, John, Nyokong, Tebello
- Authors: Dube, Edith , Nwaji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233310 , vital:50079 , xlink:href="https://doi.org/10.1039/C8NJ02746C"
- Description: The synthesis of a novel asymmetric phthalocyanine, (4-(4-(benzo[d]thiazol-2-yl)phenoxy)-2,10,17-tris(4-(2-carboxyethyl)phenoxy)phthalocyaninatol)zinc(II), complex 3, is reported. Complex 3 together with the previously reported complexes tetrakis[(benzo[d]thiazol-2-yl phenoxy)phthalocyaninato]zinc(II) (4) and 3-(4-((3,17,23-tris(4-(benzo[d]thiazol-2-yl)phenoxy)phthalocyaninatol)oxy)phenyl)propanoic acid zinc(II) (5), were linked to gold nanotriangles (AuNTs) through S–Au/Au–N self-assembly to afford the conjugates (3-AuNTs, 4-AuNTs and 5-AuNTs). The photophysicochemical behaviour of the complexes and their conjugates were studied. The asymmetric complexes 3 and 5, displayed improved triplet and singlet oxygen quantum yields compared to the symmetric complex 4, while all conjugates displayed improved triplet and singlet oxygen quantum yields compared to their respective complexes alone. The complexes and their conjugates could serve as good candidates for photodynamic therapy.
- Full Text:
- Date Issued: 2018
- Authors: Dube, Edith , Nwaji, Njemuwa , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233310 , vital:50079 , xlink:href="https://doi.org/10.1039/C8NJ02746C"
- Description: The synthesis of a novel asymmetric phthalocyanine, (4-(4-(benzo[d]thiazol-2-yl)phenoxy)-2,10,17-tris(4-(2-carboxyethyl)phenoxy)phthalocyaninatol)zinc(II), complex 3, is reported. Complex 3 together with the previously reported complexes tetrakis[(benzo[d]thiazol-2-yl phenoxy)phthalocyaninato]zinc(II) (4) and 3-(4-((3,17,23-tris(4-(benzo[d]thiazol-2-yl)phenoxy)phthalocyaninatol)oxy)phenyl)propanoic acid zinc(II) (5), were linked to gold nanotriangles (AuNTs) through S–Au/Au–N self-assembly to afford the conjugates (3-AuNTs, 4-AuNTs and 5-AuNTs). The photophysicochemical behaviour of the complexes and their conjugates were studied. The asymmetric complexes 3 and 5, displayed improved triplet and singlet oxygen quantum yields compared to the symmetric complex 4, while all conjugates displayed improved triplet and singlet oxygen quantum yields compared to their respective complexes alone. The complexes and their conjugates could serve as good candidates for photodynamic therapy.
- Full Text:
- Date Issued: 2018
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
The investigation of in vitro dark cytotoxicity and photodynamic therapy effect of a 2, 6-dibromo-3, 5-distyryl BODIPY dye encapsulated in Pluronic® F-127 micelles
- Molupe, Nthabeleng, Babu, Balaji, Oluwole, David O, Prinsloo, Earl, Mack, John, Nyokong, Tebello
- Authors: Molupe, Nthabeleng , Babu, Balaji , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187862 , vital:44704 , xlink:href="https://doi.org/10.1080/00958972.2018.1522536"
- Description: A 2,6-dibrominated 3,5-distyryl boron-dipyrromethene (BODIPY) dye with a moderately high singlet oxygen quantum yield was encapsulated in Pluronic® F-127 micelles, and its dark cytotoxicity and photodynamic activity were investigated on the human breast adenocarcinoma MCF-7 cell line. The BODIPY dye exhibited very low dark toxicity and a significant PDT effect when added in drug formulations consisting of 5.0% (v/v) DMSO in supplemented Dulbecco’s modified Eagle’s medium (DMEM) and as Pluronic® F-127 micelle encapsulation complexes in supplemented DMEM alone. An IC50 value of 4 ± 2 μM was obtained when the BODIPY dye was encapsulated in Pluronic® F-127 micelles during in vitro photodynamic activity studies in MCF-7 cancer cells with a 660 nm light emitting diode.
- Full Text:
- Date Issued: 2018
- Authors: Molupe, Nthabeleng , Babu, Balaji , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187862 , vital:44704 , xlink:href="https://doi.org/10.1080/00958972.2018.1522536"
- Description: A 2,6-dibrominated 3,5-distyryl boron-dipyrromethene (BODIPY) dye with a moderately high singlet oxygen quantum yield was encapsulated in Pluronic® F-127 micelles, and its dark cytotoxicity and photodynamic activity were investigated on the human breast adenocarcinoma MCF-7 cell line. The BODIPY dye exhibited very low dark toxicity and a significant PDT effect when added in drug formulations consisting of 5.0% (v/v) DMSO in supplemented Dulbecco’s modified Eagle’s medium (DMEM) and as Pluronic® F-127 micelle encapsulation complexes in supplemented DMEM alone. An IC50 value of 4 ± 2 μM was obtained when the BODIPY dye was encapsulated in Pluronic® F-127 micelles during in vitro photodynamic activity studies in MCF-7 cancer cells with a 660 nm light emitting diode.
- Full Text:
- Date Issued: 2018
Synthesis, photophysicochemical properties and TD-DFT calculations of tetrakis (2-benzoyl-4-chlorophenoxy) phthalocyanines
- Yilmaz, Yusuf, Mack, John, Sener, M Kasim, Sönmez, Mehmet, Nyokong, Tebello
- Authors: Yilmaz, Yusuf , Mack, John , Sener, M Kasim , Sönmez, Mehmet , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241538 , vital:50948 , xlink:href="https://doi.org/10.1142/S1088424614500047"
- Description: The synthesis of metal free, magnesium and zinc tetrakis(2-benzoyl-4-chlorophenoxy) phthalocyanine derivatives (2–4) is described along with their characterization by elemental analysis, IR, UV-visible absorption, and 1H NMR spectroscopy and mass spectrometry. Trends observed in the fluorescence, triplet state, singlet oxygen and photodegradation quantum yields and the triplet state lifetimes are also analyzed. The compounds exhibit high solubility in a wide range of organic solvents and no evidence of aggregation was observed over a wide concentration range. The Zn(II) complex (4) was found to have a very high singlet oxygen quantum yield (ΦΔ = 0.78) in dimethylsulfoxide (DMSO) and a reasonably large triplet state quantum yield (ΦT = 0.82). The photophysical and photochemical properties clearly demonstrate that these compounds could prove useful in singlet oxygen applications such as photodynamic therapy (PDT). DFT and TD-DFT calculations were used to assess the impact of the positional isomerism of the 2-benzoyl-4-chlorophenoxy substituents on the electronic structures and optical spectroscopy.
- Full Text:
- Date Issued: 2014
- Authors: Yilmaz, Yusuf , Mack, John , Sener, M Kasim , Sönmez, Mehmet , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241538 , vital:50948 , xlink:href="https://doi.org/10.1142/S1088424614500047"
- Description: The synthesis of metal free, magnesium and zinc tetrakis(2-benzoyl-4-chlorophenoxy) phthalocyanine derivatives (2–4) is described along with their characterization by elemental analysis, IR, UV-visible absorption, and 1H NMR spectroscopy and mass spectrometry. Trends observed in the fluorescence, triplet state, singlet oxygen and photodegradation quantum yields and the triplet state lifetimes are also analyzed. The compounds exhibit high solubility in a wide range of organic solvents and no evidence of aggregation was observed over a wide concentration range. The Zn(II) complex (4) was found to have a very high singlet oxygen quantum yield (ΦΔ = 0.78) in dimethylsulfoxide (DMSO) and a reasonably large triplet state quantum yield (ΦT = 0.82). The photophysical and photochemical properties clearly demonstrate that these compounds could prove useful in singlet oxygen applications such as photodynamic therapy (PDT). DFT and TD-DFT calculations were used to assess the impact of the positional isomerism of the 2-benzoyl-4-chlorophenoxy substituents on the electronic structures and optical spectroscopy.
- Full Text:
- Date Issued: 2014
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
Synthesis, Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems
- Okujima, Tetsuo, Mack, John, Nakamura, Jun, Kubheka, Gugu, Nyokong, Tebello, Zhu, Hua, Komobuchi, Naoki, Ono, Noboru, Yamada, Hiroko, Uno, Hidemitsu, Kobayashi, Nagao
- Authors: Okujima, Tetsuo , Mack, John , Nakamura, Jun , Kubheka, Gugu , Nyokong, Tebello , Zhu, Hua , Komobuchi, Naoki , Ono, Noboru , Yamada, Hiroko , Uno, Hidemitsu , Kobayashi, Nagao
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240360 , vital:50827 , xlink:href="https://doi.org/10.1002/chem.201602213"
- Description: A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels–Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π-molecular orbitals.
- Full Text:
- Date Issued: 2016
- Authors: Okujima, Tetsuo , Mack, John , Nakamura, Jun , Kubheka, Gugu , Nyokong, Tebello , Zhu, Hua , Komobuchi, Naoki , Ono, Noboru , Yamada, Hiroko , Uno, Hidemitsu , Kobayashi, Nagao
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240360 , vital:50827 , xlink:href="https://doi.org/10.1002/chem.201602213"
- Description: A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels–Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π-molecular orbitals.
- Full Text:
- Date Issued: 2016
Synthesis, characterization and photophysical properties of an acenaphthalene fused-ring-expanded NIR absorbing aza-BODIPY dye
- Majumdar, Poulomi, Mack, John, Nyokong, Tebello
- Authors: Majumdar, Poulomi , Mack, John , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189763 , vital:44929 , xlink:href="https://doi.org/10.1039/C5RA14916A"
- Description: The synthesis and characterization of an NIR absorbing acenaphthalene fused-ring-expanded aza-BODIPY dye are reported. In contrast with its naphtho-fused analogue, a stable complex is obtained when the corresponding phthalonitrile is used as the precursor. A comparison is made with the photophysical properties of 3,5-diphenyl-aza-dibenzoBODIPY.
- Full Text:
- Date Issued: 2015
- Authors: Majumdar, Poulomi , Mack, John , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189763 , vital:44929 , xlink:href="https://doi.org/10.1039/C5RA14916A"
- Description: The synthesis and characterization of an NIR absorbing acenaphthalene fused-ring-expanded aza-BODIPY dye are reported. In contrast with its naphtho-fused analogue, a stable complex is obtained when the corresponding phthalonitrile is used as the precursor. A comparison is made with the photophysical properties of 3,5-diphenyl-aza-dibenzoBODIPY.
- Full Text:
- Date Issued: 2015
Synthesis, characterization and photophysical properties of an acenaphthalene fused-ring-expanded NIR absorbing aza-BODIPY dye
- Majumdar, Poulomi, Mack, John, Nyokong, Tebello
- Authors: Majumdar, Poulomi , Mack, John , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7283 , http://hdl.handle.net/10962/d1020328
- Description: The synthesis and characterization of an NIR absorbing acenaphthalene fused-ring-expanded aza-BODIPY dye are reported. In contrast with its naphtho-fused analogue, a stable complex is obtained when the corresponding phthalonitrile is used as the precursor. A comparison is made with the photophysical properties of 3,5-diphenyl-aza-dibenzoBODIPY. , Original publication is available at http://dx.doi.org/10.1039/C5RA14916A , Arbortext Advanced Print Publisher 9.1.510/W Unicode , Acrobat Distiller 8.1.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
- Full Text:
- Authors: Majumdar, Poulomi , Mack, John , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7283 , http://hdl.handle.net/10962/d1020328
- Description: The synthesis and characterization of an NIR absorbing acenaphthalene fused-ring-expanded aza-BODIPY dye are reported. In contrast with its naphtho-fused analogue, a stable complex is obtained when the corresponding phthalonitrile is used as the precursor. A comparison is made with the photophysical properties of 3,5-diphenyl-aza-dibenzoBODIPY. , Original publication is available at http://dx.doi.org/10.1039/C5RA14916A , Arbortext Advanced Print Publisher 9.1.510/W Unicode , Acrobat Distiller 8.1.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
- Full Text:
Synthesis, characterization and photodynamic therapy properties of an octa-4-tert-butylphenoxy-substituted phosphorus (V) triazatetrabenzcorrole
- Shi, Maohu, Tian, Jiangwei, Mkhize, Colin, Kubheka, Gugu, Zhou, Jinfeng, Mack, John, Nyokong, Tebello, Shen, Zhen
- Authors: Shi, Maohu , Tian, Jiangwei , Mkhize, Colin , Kubheka, Gugu , Zhou, Jinfeng , Mack, John , Nyokong, Tebello , Shen, Zhen
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241494 , vital:50944 , xlink:href="https://doi.org/10.1142/S1088424614500436"
- Description: A novel octa-4-tert-butylphenoxy-substituted phosphorus(V) triazatetrabenzcorrole (PVTBC), has been synthesized and characterized by MALDI-TOF MS and NMR, FT-IR and MCD spectroscopy. The fluorescence emission spectrum was used to determine the fluorescence quantum yield and the quantum yield for singlet oxygen generation was calculated by using 1,3-diphenylisobenzofuran as a scavenger. The photocytoxicity against U87MG cells was measured. The results indicated that PVTBC is potentially useful as an NIR region photosensitizer for photodynamic therapy (PDT).
- Full Text:
- Date Issued: 2014
- Authors: Shi, Maohu , Tian, Jiangwei , Mkhize, Colin , Kubheka, Gugu , Zhou, Jinfeng , Mack, John , Nyokong, Tebello , Shen, Zhen
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241494 , vital:50944 , xlink:href="https://doi.org/10.1142/S1088424614500436"
- Description: A novel octa-4-tert-butylphenoxy-substituted phosphorus(V) triazatetrabenzcorrole (PVTBC), has been synthesized and characterized by MALDI-TOF MS and NMR, FT-IR and MCD spectroscopy. The fluorescence emission spectrum was used to determine the fluorescence quantum yield and the quantum yield for singlet oxygen generation was calculated by using 1,3-diphenylisobenzofuran as a scavenger. The photocytoxicity against U87MG cells was measured. The results indicated that PVTBC is potentially useful as an NIR region photosensitizer for photodynamic therapy (PDT).
- Full Text:
- Date Issued: 2014
Synthesis, characterization and photodynamic activity of Sn (iv) triarylcorroles with red-shifted Q bands
- Babu, Balaji, Prinsloo, Earl, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187521 , vital:44668 , xlink:href="https://doi.org/10.1039/C9NJ03391B"
- Description: Two Sn(IV) triarylcorroles were synthesised and characterized. The absorption spectrum of a meso-thien-2-yl substituted tin(IV)corrole (1-Sn) is red shifted compared to its phenyl analogue (2-Sn) and shows no sign of aggregation in solution. 1-Sn and 2-Sn exhibited singlet oxygen quantum yields of 0.87 and 0.54 in DMF, and have a triplet lifetime of 31 and 50 μs, respectively. Time dependent cellular uptake in MCF-7 cells for 1-Sn reached a peak at 24 h, and 1-Sn was found to be more lipophilic than 2-Sn. 1-Sn showed good photo-cytotoxicity on exposure to a Thorlabs 625 nm LED with an IC50 value of 3.2 μM and remained inactive in the dark.
- Full Text:
- Date Issued: 2019
- Authors: Babu, Balaji , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187521 , vital:44668 , xlink:href="https://doi.org/10.1039/C9NJ03391B"
- Description: Two Sn(IV) triarylcorroles were synthesised and characterized. The absorption spectrum of a meso-thien-2-yl substituted tin(IV)corrole (1-Sn) is red shifted compared to its phenyl analogue (2-Sn) and shows no sign of aggregation in solution. 1-Sn and 2-Sn exhibited singlet oxygen quantum yields of 0.87 and 0.54 in DMF, and have a triplet lifetime of 31 and 50 μs, respectively. Time dependent cellular uptake in MCF-7 cells for 1-Sn reached a peak at 24 h, and 1-Sn was found to be more lipophilic than 2-Sn. 1-Sn showed good photo-cytotoxicity on exposure to a Thorlabs 625 nm LED with an IC50 value of 3.2 μM and remained inactive in the dark.
- Full Text:
- Date Issued: 2019
Synthesis, characterization and electrochemistry of rhodium (iii) complexes of meso-substituted [14] tribenzotriphyrin (2.1. 1)
- Xue, Zhaoli, Wang, Yemei, Mack, John, Mkhize, Scebi, Nyokong, Tebello, Fang, Yuanyuan, Ou, Zhongping, Kadish, Karl M
- Authors: Xue, Zhaoli , Wang, Yemei , Mack, John , Mkhize, Scebi , Nyokong, Tebello , Fang, Yuanyuan , Ou, Zhongping , Kadish, Karl M
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241043 , vital:50899 , xlink:href="https://doi.org/10.1039/C6RA03028A"
- Description: A thermal reaction using a series of [14]tribenzotriphyrins(2.1.1) (TriPs, 1a–d) with Rh2(C8H12)Cl2 provides RhIII–TriP complexes (2a–d) in 40−52% yields. The complexes were characterized by mass spectrometry, UV-visible absorption and 1H NMR spectroscopy. Single crystal X-ray analysis reveals that 2b adopts a dome-shaped conformation. The rhodium(III) ion is coordinated by the three pyrrole nitrogen atoms, two chloride ions and the nitrogen atom of an acetonitrile (CH3CN) solvent molecule. The optical spectra can be assigned using Michl's perimeter model. The L and B bands of the 2a–d complexes lie at ca. 600 and 500 nm, respectively, and are markedly red shifted relative to those of 1a–d. A reversible one-electron oxidation and two reversible one-electron reductions are observed in the cyclic voltammograms of 2a–d in CH2Cl2. The redox potentials are consistent with the optical data and the relatively narrow HOMO–LUMO gaps that are predicted in DFT calculations. TD-DFT calculations have been used to assign a third intense spectral band at 375 nm to a higher energy π → π* transition of the [14]tribenzotriphyrin(2.1.1) π-system.
- Full Text:
- Date Issued: 2016
- Authors: Xue, Zhaoli , Wang, Yemei , Mack, John , Mkhize, Scebi , Nyokong, Tebello , Fang, Yuanyuan , Ou, Zhongping , Kadish, Karl M
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241043 , vital:50899 , xlink:href="https://doi.org/10.1039/C6RA03028A"
- Description: A thermal reaction using a series of [14]tribenzotriphyrins(2.1.1) (TriPs, 1a–d) with Rh2(C8H12)Cl2 provides RhIII–TriP complexes (2a–d) in 40−52% yields. The complexes were characterized by mass spectrometry, UV-visible absorption and 1H NMR spectroscopy. Single crystal X-ray analysis reveals that 2b adopts a dome-shaped conformation. The rhodium(III) ion is coordinated by the three pyrrole nitrogen atoms, two chloride ions and the nitrogen atom of an acetonitrile (CH3CN) solvent molecule. The optical spectra can be assigned using Michl's perimeter model. The L and B bands of the 2a–d complexes lie at ca. 600 and 500 nm, respectively, and are markedly red shifted relative to those of 1a–d. A reversible one-electron oxidation and two reversible one-electron reductions are observed in the cyclic voltammograms of 2a–d in CH2Cl2. The redox potentials are consistent with the optical data and the relatively narrow HOMO–LUMO gaps that are predicted in DFT calculations. TD-DFT calculations have been used to assign a third intense spectral band at 375 nm to a higher energy π → π* transition of the [14]tribenzotriphyrin(2.1.1) π-system.
- Full Text:
- Date Issued: 2016
Synthesis and properties of chiral amide-bonded porphyrin dimers with various functional bridging blocks
- Zhu, Weihua, Haider, Syed Najeeb-uz-Zaman, Zhang, Honglin, Attatsi, Isaac K, Mack, John, Dingiswayo, Somila, Nyokong, Tebello, Song, Yuting, Xu, Haijun, Liang, Xu
- Authors: Zhu, Weihua , Haider, Syed Najeeb-uz-Zaman , Zhang, Honglin , Attatsi, Isaac K , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Song, Yuting , Xu, Haijun , Liang, Xu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186791 , vital:44534 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107740"
- Description: Eight porphyrin dimers with various functional bridging blocks and chiral amide-bonds were synthesized and characterized. An analysis of the spectroscopy and electrochemistry has been carried out to demonstrate that the chiral properties can be modified by changing the interchromophoric through-space coupling distance between the two porphyrin chromophores by introducing various bonding and bridging blocks.
- Full Text:
- Date Issued: 2019
- Authors: Zhu, Weihua , Haider, Syed Najeeb-uz-Zaman , Zhang, Honglin , Attatsi, Isaac K , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Song, Yuting , Xu, Haijun , Liang, Xu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186791 , vital:44534 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107740"
- Description: Eight porphyrin dimers with various functional bridging blocks and chiral amide-bonds were synthesized and characterized. An analysis of the spectroscopy and electrochemistry has been carried out to demonstrate that the chiral properties can be modified by changing the interchromophoric through-space coupling distance between the two porphyrin chromophores by introducing various bonding and bridging blocks.
- Full Text:
- Date Issued: 2019
Synthesis and photophysicochemical properties of BODIPY dye functionalized gold nanorods for use in antimicrobial photodynamic therapy
- Kubheka, Gugu, Uddin, Imran, Amuhaya, Edith, Mack, John, Nyokong, Tebello
- Authors: Kubheka, Gugu , Uddin, Imran , Amuhaya, Edith , Mack, John , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239897 , vital:50778 , xlink:href="https://doi.org/10.1142/S108842461650070X"
- Description: A series of boron dipyrromethene (BODIPY) dyes with properties that are ideal for a good photosensitizer have been prepared. Functionalization with bromine atoms and attachment to gold nanoparticles through a meso-aniline group results in high singlet oxygen quantum yields and low fluorescent quantum yields. Molecular modelling was used to analyze trends in the MO energies of various brominated aniline BODIPY dyes.
- Full Text:
- Date Issued: 2016
- Authors: Kubheka, Gugu , Uddin, Imran , Amuhaya, Edith , Mack, John , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239897 , vital:50778 , xlink:href="https://doi.org/10.1142/S108842461650070X"
- Description: A series of boron dipyrromethene (BODIPY) dyes with properties that are ideal for a good photosensitizer have been prepared. Functionalization with bromine atoms and attachment to gold nanoparticles through a meso-aniline group results in high singlet oxygen quantum yields and low fluorescent quantum yields. Molecular modelling was used to analyze trends in the MO energies of various brominated aniline BODIPY dyes.
- Full Text:
- Date Issued: 2016
Synthesis and photophysical properties of covalent conjugates of aqua platinum (II) and octacarboxy-substituted zinc phthalocyanine
- Bulgakov, Roman A, Kuznetsova, Nina A, Dolotova, Olga V, Solovieva, Ludmila I, Mack, John, Chidawanyika, Wadzanai J U, Kaliya, Oleg L, Nyokong, Tebello
- Authors: Bulgakov, Roman A , Kuznetsova, Nina A , Dolotova, Olga V , Solovieva, Ludmila I , Mack, John , Chidawanyika, Wadzanai J U , Kaliya, Oleg L , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242726 , vital:51073 , xlink:href="https://doi.org/10.1142/S1088424612501209"
- Description: New covalent conjugates of aqua platinum(II) and octacarboxy-substituted zinc phthalocyanine, bearing one, two, three and four aqua platinum moieties on the periphery of the Pc ligand have been synthesized and characterized. The effect of the stepwise introduction of the aqua platinums on the photophysical and photochemical properties of these compounds has been investigated in dimethylsulfoxide solution. It has been found that aqua platinum moieties have only a limited effect on the dynamics of the singlet and triplet excited states, on the ability to sensitize singlet oxygen formation and on the photostability. Each conjugate has a high singlet oxygen quantum yield (ΦΔ 0.51–0.62) and thus retains potential for use as a dual action anticancer drugs by acting as a sensitizer for PDT in addition to the likely chemotherapeutic effects of the Pt(II) complexes.
- Full Text:
- Date Issued: 2012
- Authors: Bulgakov, Roman A , Kuznetsova, Nina A , Dolotova, Olga V , Solovieva, Ludmila I , Mack, John , Chidawanyika, Wadzanai J U , Kaliya, Oleg L , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242726 , vital:51073 , xlink:href="https://doi.org/10.1142/S1088424612501209"
- Description: New covalent conjugates of aqua platinum(II) and octacarboxy-substituted zinc phthalocyanine, bearing one, two, three and four aqua platinum moieties on the periphery of the Pc ligand have been synthesized and characterized. The effect of the stepwise introduction of the aqua platinums on the photophysical and photochemical properties of these compounds has been investigated in dimethylsulfoxide solution. It has been found that aqua platinum moieties have only a limited effect on the dynamics of the singlet and triplet excited states, on the ability to sensitize singlet oxygen formation and on the photostability. Each conjugate has a high singlet oxygen quantum yield (ΦΔ 0.51–0.62) and thus retains potential for use as a dual action anticancer drugs by acting as a sensitizer for PDT in addition to the likely chemotherapeutic effects of the Pt(II) complexes.
- Full Text:
- Date Issued: 2012
Synthesis and photophysical properties of BODIPY-decorated graphene quantum dot–phthalocyanine conjugates
- Nwahara, Nnamdi, Nkhahle, Reitumetse, Ngoy, Bokolombe P, Mack, John, Nyokong, Tebello
- Authors: Nwahara, Nnamdi , Nkhahle, Reitumetse , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233409 , vital:50088 , xlink:href="https://doi.org/10.1039/C8NJ00758F"
- Description: This work reports on the synthesis and characterisation of novel supramolecular hybrids containing BODIPY-decorated graphene quantum dots (BODIPY@GQDs) and zinc phthalocyanine. Graphene quantum dots (GQDs) were functionalized with L-glutathione (GSH) in order to assist coupling to the BODIPY dye. {2,9(10)16(17)23(24)-Tetrakis-[3-(diethylamino)phenoxy]phthalocyaninato}zinc(II) (1) was immobilized via π–π stacking interaction on the BODIPY-decorated GQDs and pristine GQDs to form the supramolecular hybrids 1-BODIPY@GQDs and 1-GQDs, respectively. The photophysical and photochemical properties of these conjugates were investigated. Energy transfer occurred from the (i) GQDs to BODIPY, (ii) GQDs to 1, and (iii) BODIPY@GQDs to 1via fluorescence resonance energy transfer (FRET). The highest FRET efficiency was observed for the BODIPY@GQDs (0.93). The introduction of the BODIPY core to the GQD structure resulted in higher triplet, and singlet oxygen quantum yields for the resultant Pc/GQD hybrid (1-BODIPY@GQDs). The zeta potential values obtained imply a high colloidal stability for the supramolecular hybrids. The results suggest that such hybrids may be applied in fields such as photodynamic therapy (PDT), where a high singlet oxygen quantum yield is desired.
- Full Text:
- Date Issued: 2018
- Authors: Nwahara, Nnamdi , Nkhahle, Reitumetse , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233409 , vital:50088 , xlink:href="https://doi.org/10.1039/C8NJ00758F"
- Description: This work reports on the synthesis and characterisation of novel supramolecular hybrids containing BODIPY-decorated graphene quantum dots (BODIPY@GQDs) and zinc phthalocyanine. Graphene quantum dots (GQDs) were functionalized with L-glutathione (GSH) in order to assist coupling to the BODIPY dye. {2,9(10)16(17)23(24)-Tetrakis-[3-(diethylamino)phenoxy]phthalocyaninato}zinc(II) (1) was immobilized via π–π stacking interaction on the BODIPY-decorated GQDs and pristine GQDs to form the supramolecular hybrids 1-BODIPY@GQDs and 1-GQDs, respectively. The photophysical and photochemical properties of these conjugates were investigated. Energy transfer occurred from the (i) GQDs to BODIPY, (ii) GQDs to 1, and (iii) BODIPY@GQDs to 1via fluorescence resonance energy transfer (FRET). The highest FRET efficiency was observed for the BODIPY@GQDs (0.93). The introduction of the BODIPY core to the GQD structure resulted in higher triplet, and singlet oxygen quantum yields for the resultant Pc/GQD hybrid (1-BODIPY@GQDs). The zeta potential values obtained imply a high colloidal stability for the supramolecular hybrids. The results suggest that such hybrids may be applied in fields such as photodynamic therapy (PDT), where a high singlet oxygen quantum yield is desired.
- Full Text:
- Date Issued: 2018
Synthesis and Photophysical Investigation of Tetraazaporphyrin Substituted with Aggregation‐Induced Emission (AIE) Active Moieties
- Tasso, Thiago T, Furuyama, Taniyuki, Mack, John, Nyokong, Tebello, Kobayashi, Nagao
- Authors: Tasso, Thiago T , Furuyama, Taniyuki , Mack, John , Nyokong, Tebello , Kobayashi, Nagao
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193553 , vital:45346 , xlink:href="https://doi.org/10.1002/ejic.201500726"
- Description: The synthesis and characterization of free-base and ZnII tetraazaporphyrins with tetraphenylethylene (TPE) or diphenylphenanthrene (DPP) moieties that are known to be aggregation-induced emission (AIE) active is reported. The optical spectra contain the characteristic Q and B absorption bands of Gouterman's four-orbital model and a broad envelope of weaker charge-transfer bands in the 450–600 nm region. The observed fluorescence emission lies beyond 670 nm and originates exclusively from the decay of the S1 state of the macrocycle, regardless of the excitation wavelength used. Theoretical calculations provide further evidence of strong electronic communication between the peripheral TPE or DPP moieties and the central ring. The ZnII complexes were found to have relatively high singlet-oxygen quantum yields.
- Full Text:
- Date Issued: 2015
- Authors: Tasso, Thiago T , Furuyama, Taniyuki , Mack, John , Nyokong, Tebello , Kobayashi, Nagao
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193553 , vital:45346 , xlink:href="https://doi.org/10.1002/ejic.201500726"
- Description: The synthesis and characterization of free-base and ZnII tetraazaporphyrins with tetraphenylethylene (TPE) or diphenylphenanthrene (DPP) moieties that are known to be aggregation-induced emission (AIE) active is reported. The optical spectra contain the characteristic Q and B absorption bands of Gouterman's four-orbital model and a broad envelope of weaker charge-transfer bands in the 450–600 nm region. The observed fluorescence emission lies beyond 670 nm and originates exclusively from the decay of the S1 state of the macrocycle, regardless of the excitation wavelength used. Theoretical calculations provide further evidence of strong electronic communication between the peripheral TPE or DPP moieties and the central ring. The ZnII complexes were found to have relatively high singlet-oxygen quantum yields.
- Full Text:
- Date Issued: 2015