Graphene quantum dots functionalized with 4-amino-2, 2, 6, 6-tetramethylpiperidine-N-oxide as fluorescence “turn-on” nanosensors
- Achadu, Ojodomo J, Britton, Jonathan, Nyokong, Tebello
- Authors: Achadu, Ojodomo J , Britton, Jonathan , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239854 , vital:50773 , xlink:href="https://doi.org/10.1007/s10895-016-1916-y"
- Description: In this study, we report on the fabrication of simple and rapid graphene quantum dots (GQDs)-based fluorescence “turn-ON” nanoprobes for sensitive and selective detection of ascorbic acid (AA). Pristine GQDs and S and N co-doped-GQDs (SN-GQDs) were functionalized with 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4-amino-TEMPO, a nitroxide free radical). The nitroxide free radicals efficiently quenched the fluorescence of the GQDs and upon interaction of the nanoconjugates with ascorbic acid, the quenched fluorescence was restored. The linear ranges recorded were 0.5–5.7 μM and 0.1–5.5 μM for GQDs-4-amino-TEMPO and SN-GQDs-4amino-TEMPO nanoprobes, respectively. Limits of detection were found to be 60 nM and 84 nM for SN-GQDS-4-amino-TEMPO and GQDs-4-amino-TEMPO for AA detection, respectively. This novel fluorescence “turn-ON” technique showed to be highly rapid and selective towards AA detection.
- Full Text:
- Date Issued: 2016
- Authors: Achadu, Ojodomo J , Britton, Jonathan , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239854 , vital:50773 , xlink:href="https://doi.org/10.1007/s10895-016-1916-y"
- Description: In this study, we report on the fabrication of simple and rapid graphene quantum dots (GQDs)-based fluorescence “turn-ON” nanoprobes for sensitive and selective detection of ascorbic acid (AA). Pristine GQDs and S and N co-doped-GQDs (SN-GQDs) were functionalized with 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4-amino-TEMPO, a nitroxide free radical). The nitroxide free radicals efficiently quenched the fluorescence of the GQDs and upon interaction of the nanoconjugates with ascorbic acid, the quenched fluorescence was restored. The linear ranges recorded were 0.5–5.7 μM and 0.1–5.5 μM for GQDs-4-amino-TEMPO and SN-GQDs-4amino-TEMPO nanoprobes, respectively. Limits of detection were found to be 60 nM and 84 nM for SN-GQDS-4-amino-TEMPO and GQDs-4-amino-TEMPO for AA detection, respectively. This novel fluorescence “turn-ON” technique showed to be highly rapid and selective towards AA detection.
- Full Text:
- Date Issued: 2016
Interaction of graphene quantum dots with 4-acetamido-2, 2, 6, 6-tetramethylpiperidine-oxyl free radicals
- Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189031 , vital:44810 , xlink:href="https://doi.org/10.1007/s10895-015-1712-0"
- Description: We report on the interaction of graphene quantum dots (GQDs) with 4-acetamido-2,2,6,6-tetramethylpiperidineoxyl (4-acetamido-TEMPO) free radicals. The GQDs were N and S, N doped. The fluorescence quantum yields were higher for the doped GQDs compared to the undoped. The interaction is assessed by spectrofluorimetric, steady state/time resolved fluorescence and electron paramagnetic resonance (EPR) techniques. Fluorescence quenching was observed upon the addition of 4-acetamido-TEMPO to the GQDs. Photoinduced electron transfer (PET) mechanism was suggested as the plausible mechanism involved in the fluorescence quenching in which 4-acetamido-TEMPO acted as the electron acceptor.
- Full Text:
- Date Issued: 2016
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189031 , vital:44810 , xlink:href="https://doi.org/10.1007/s10895-015-1712-0"
- Description: We report on the interaction of graphene quantum dots (GQDs) with 4-acetamido-2,2,6,6-tetramethylpiperidineoxyl (4-acetamido-TEMPO) free radicals. The GQDs were N and S, N doped. The fluorescence quantum yields were higher for the doped GQDs compared to the undoped. The interaction is assessed by spectrofluorimetric, steady state/time resolved fluorescence and electron paramagnetic resonance (EPR) techniques. Fluorescence quenching was observed upon the addition of 4-acetamido-TEMPO to the GQDs. Photoinduced electron transfer (PET) mechanism was suggested as the plausible mechanism involved in the fluorescence quenching in which 4-acetamido-TEMPO acted as the electron acceptor.
- Full Text:
- Date Issued: 2016
The interaction between graphene quantum dots grafted with polyethyleneimine and Au@ Ag nanoparticles
- Achadu, Ojodomo John, Uddin, Imran, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Uddin, Imran , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188679 , vital:44775 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.03.016"
- Description: Graphene quantum dots grafted with polyethyleneimine (GQDs-PEI) and Au@Ag core-shell nanoparticles blend was demonstrated to be a novel biosensing nanoprobe for the rapid and highly sensitive detection of biothiols such as cysteine (Cys), homocysteine (Hcys) and glutathione (GSH). The fluorescence emission of GQDs-PEI was quenched efficiently upon interaction with Au@Ag core-shell nanoparticles. The quenched fluorescence emission of the GQDs-PEI was restored in the presence of the biothiols. The fluorimetric sensing is based on the strong affinity between the mercapto (SH) groups of the biothiols and the Au@Ag core-shell nanoparticles by which the interaction between GQDs-PEI and Au@Ag core-shell nanoparticles was disrupted with a consequent modulation (‘turn-on’) of the quenched GQDs-PEI emission. Thus, a new, simple, rapid and highly sensitive fluorescence nanoprobe for detecting biothiols has been developed in this work.
- Full Text:
- Date Issued: 2016
- Authors: Achadu, Ojodomo John , Uddin, Imran , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188679 , vital:44775 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.03.016"
- Description: Graphene quantum dots grafted with polyethyleneimine (GQDs-PEI) and Au@Ag core-shell nanoparticles blend was demonstrated to be a novel biosensing nanoprobe for the rapid and highly sensitive detection of biothiols such as cysteine (Cys), homocysteine (Hcys) and glutathione (GSH). The fluorescence emission of GQDs-PEI was quenched efficiently upon interaction with Au@Ag core-shell nanoparticles. The quenched fluorescence emission of the GQDs-PEI was restored in the presence of the biothiols. The fluorimetric sensing is based on the strong affinity between the mercapto (SH) groups of the biothiols and the Au@Ag core-shell nanoparticles by which the interaction between GQDs-PEI and Au@Ag core-shell nanoparticles was disrupted with a consequent modulation (‘turn-on’) of the quenched GQDs-PEI emission. Thus, a new, simple, rapid and highly sensitive fluorescence nanoprobe for detecting biothiols has been developed in this work.
- Full Text:
- Date Issued: 2016
Fluorescence behavior of nanoconjugates of graphene quantum dots and zinc phthalocyanines
- Achadu, Ojodomo John, Uddin, Imran, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Uddin, Imran , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188777 , vital:44784 , xlink:href="https://doi.org/10.1016/j.jphotochem.2015.11.006"
- Description: Graphene quantum dots (GQDs) and zinc phthalocyanines interactions in different modes (covalent and non-covalent) are reported in this study. GQDs were covalently attached to the following complexes: zinc tetraamino phthalocyanine (ZnTAPc) via amide coupling, zinc tetracarboxyphenoxy Pc (ZnTCPPc) (π–π interaction) and cationic zinc tetrapyridiloxy Pc (ZnTmPyPc) (ionic interaction). GQDs fluorescence was quenched in the presence of the ZnPc derivatives. The nanoensembles of GQDs–ZnPcs showed stimulated emissions of the ZnPcs. The suggested quenching mechanism is through Förster resonance energy transfer (FRET). These novel nanoensembles hold promise for various optical and luminescence based applications.
- Full Text:
- Date Issued: 2016
- Authors: Achadu, Ojodomo John , Uddin, Imran , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188777 , vital:44784 , xlink:href="https://doi.org/10.1016/j.jphotochem.2015.11.006"
- Description: Graphene quantum dots (GQDs) and zinc phthalocyanines interactions in different modes (covalent and non-covalent) are reported in this study. GQDs were covalently attached to the following complexes: zinc tetraamino phthalocyanine (ZnTAPc) via amide coupling, zinc tetracarboxyphenoxy Pc (ZnTCPPc) (π–π interaction) and cationic zinc tetrapyridiloxy Pc (ZnTmPyPc) (ionic interaction). GQDs fluorescence was quenched in the presence of the ZnPc derivatives. The nanoensembles of GQDs–ZnPcs showed stimulated emissions of the ZnPcs. The suggested quenching mechanism is through Förster resonance energy transfer (FRET). These novel nanoensembles hold promise for various optical and luminescence based applications.
- Full Text:
- Date Issued: 2016
Fluorescence properties of alloyed ZnSeS quantum dots overcoated with ZnTe and ZnTe/ZnS shells
- Adegoke, Oluwasesan, Mashazi, Philani N, Nyokong, Tebello, Forbes, Patricia B C
- Authors: Adegoke, Oluwasesan , Mashazi, Philani N , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240754 , vital:50868 , xlink:href="https://doi.org/10.1016/j.optmat.2016.02.024"
- Description: Fluorescent alloyed ternary ZnSeS quantum dots (QDs) have been synthesized via the pyrolysis of organometallic precursors. The effects of passivation of ZnTe and ZnTe/ZnS shells on the optical properties of the ternary alloyed ZnSeS core have been studied. A ligand exchange reaction using L-cysteine as a capping ligand was used to obtain water-soluble nanocrystals. The nanocrystals were each characterized by UV/vis absorption and fluorescence spectroscopy, transmission electron microscopy, X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy (XPS). The photoluminescence (PL) quantum yield (QY) of alloyed ZnSeS QDs was 14% and this value increased to 27% when ZnTe was overcoated around the surface but further coating with a ZnS shell decreased the PL QY slightly to 24%. This implies that ZnTe shell suppressed non-radiative recombination exciton states in the alloyed core while further layering with a ZnS shell offered no further improvement in suppressing the defect states. XPS analysis confirmed the presence of the first shell layering but showed a weakened intensity signal of S (2p) and Se (3d) for the ZnSeS/ZnTe/ZnS QDs. Our work demonstrates for the first time that shell passivation of alloyed Zn-based QDs can offer improved optical properties. We hope the optical information presented in this work will be useful in the selection of alloyed Zn-based QDs appropriate for the intended application.
- Full Text:
- Date Issued: 2016
- Authors: Adegoke, Oluwasesan , Mashazi, Philani N , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240754 , vital:50868 , xlink:href="https://doi.org/10.1016/j.optmat.2016.02.024"
- Description: Fluorescent alloyed ternary ZnSeS quantum dots (QDs) have been synthesized via the pyrolysis of organometallic precursors. The effects of passivation of ZnTe and ZnTe/ZnS shells on the optical properties of the ternary alloyed ZnSeS core have been studied. A ligand exchange reaction using L-cysteine as a capping ligand was used to obtain water-soluble nanocrystals. The nanocrystals were each characterized by UV/vis absorption and fluorescence spectroscopy, transmission electron microscopy, X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy (XPS). The photoluminescence (PL) quantum yield (QY) of alloyed ZnSeS QDs was 14% and this value increased to 27% when ZnTe was overcoated around the surface but further coating with a ZnS shell decreased the PL QY slightly to 24%. This implies that ZnTe shell suppressed non-radiative recombination exciton states in the alloyed core while further layering with a ZnS shell offered no further improvement in suppressing the defect states. XPS analysis confirmed the presence of the first shell layering but showed a weakened intensity signal of S (2p) and Se (3d) for the ZnSeS/ZnTe/ZnS QDs. Our work demonstrates for the first time that shell passivation of alloyed Zn-based QDs can offer improved optical properties. We hope the optical information presented in this work will be useful in the selection of alloyed Zn-based QDs appropriate for the intended application.
- Full Text:
- Date Issued: 2016
Nonlinear optical response of a low symmetry phthalocyanine in the presence of gold nanoparticles when in solution or embedded in poly acrylic acid polymer thin films
- Bankole, Owolabi M, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188719 , vital:44779 , xlink:href="https://doi.org/10.1016/j.jphotochem.2015.12.014"
- Description: In this article, we explored the photophysical and nonlinear optical (NLO) characterizations of low symmetry phthalocyanine (ZnPc-NH2) covalently linked to MPA-capped AuNPs (ZnPc-NH2-AuNPs) and poly acrylic acid (ZnPc-NH2-PAA). Nonlinear optical (NLO) properties of the samples were evaluated using Z-scan technique at 532 nm and 10 ns pulsed duration. We observed enhanced photophysical and nonlinear optical behaviour for the ZnPc-NH2 in presence of AuNPs. By virtue of the magnitude of absorption coefficients and other NLO optical parameters estimated in this work, ZnPc-NH2-AuNPs was found to exhibit improved nonlinear optical response compared to the ZnPc-NH2 and ZnPc-NH2-PAA. Both ZnPc-NH2-AuNPs and ZnPc-NH2 doped in PAA possess strong nonlinear absorption coefficients and very low limiting thresholds than when measured in solution.
- Full Text:
- Date Issued: 2016
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188719 , vital:44779 , xlink:href="https://doi.org/10.1016/j.jphotochem.2015.12.014"
- Description: In this article, we explored the photophysical and nonlinear optical (NLO) characterizations of low symmetry phthalocyanine (ZnPc-NH2) covalently linked to MPA-capped AuNPs (ZnPc-NH2-AuNPs) and poly acrylic acid (ZnPc-NH2-PAA). Nonlinear optical (NLO) properties of the samples were evaluated using Z-scan technique at 532 nm and 10 ns pulsed duration. We observed enhanced photophysical and nonlinear optical behaviour for the ZnPc-NH2 in presence of AuNPs. By virtue of the magnitude of absorption coefficients and other NLO optical parameters estimated in this work, ZnPc-NH2-AuNPs was found to exhibit improved nonlinear optical response compared to the ZnPc-NH2 and ZnPc-NH2-PAA. Both ZnPc-NH2-AuNPs and ZnPc-NH2 doped in PAA possess strong nonlinear absorption coefficients and very low limiting thresholds than when measured in solution.
- Full Text:
- Date Issued: 2016
Comparative studies on photophysical and optical limiting characterizations of low symmetry phthalocyanine linked to Fe 3 O 4–Ag core–shell or hybrid nanoparticles
- Bankole, Owolabi M, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188788 , vital:44785 , xlink:href="https://doi.org/10.1039/C6NJ01511E"
- Description: Photophysical and nonlinear optical (NLO) behaviours of low symmetry zinc phthalocyanine (1) linked to Fe3O4/Ag core–shell (represented as Fe/Ag) or Fe3O4–Ag hybrid (represented as FeAg) nanoparticles were investigated in DMSO. Triplet quantum yields and NLO parameters of phthalocyanine improved due to the combined effects of magnetic–metallic nanoparticles. A direct relationship between the increased triplet excited state absorptions by already excited molecules and reverse saturable absorption (RSA) was established as the predominant mechanism responsible for nonlinearity of the samples. Our findings show that, at the same approximate concentrations and conditions, 1-FeAg enhanced the OL potentials of 1 more than 1-Fe/Ag.
- Full Text:
- Date Issued: 2016
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188788 , vital:44785 , xlink:href="https://doi.org/10.1039/C6NJ01511E"
- Description: Photophysical and nonlinear optical (NLO) behaviours of low symmetry zinc phthalocyanine (1) linked to Fe3O4/Ag core–shell (represented as Fe/Ag) or Fe3O4–Ag hybrid (represented as FeAg) nanoparticles were investigated in DMSO. Triplet quantum yields and NLO parameters of phthalocyanine improved due to the combined effects of magnetic–metallic nanoparticles. A direct relationship between the increased triplet excited state absorptions by already excited molecules and reverse saturable absorption (RSA) was established as the predominant mechanism responsible for nonlinearity of the samples. Our findings show that, at the same approximate concentrations and conditions, 1-FeAg enhanced the OL potentials of 1 more than 1-Fe/Ag.
- Full Text:
- Date Issued: 2016
Nonlinear optical behavior of alkyne terminated phthalocyanines in solution and when embedded in polysulfone as thin films: effects of aggregation
- Bankole, Owolabi M, Yilmaz, Yusuf, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Yilmaz, Yusuf , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189110 , vital:44817 , xlink:href="https://doi.org/10.1016/j.optmat.2015.11.041"
- Description: We report here for the first time, on the comparative studies of the photophysical and optical limiting behavior of our two novel phthalocyanines namely 2(3), 9(10), 16(17), 23(24)-tetrakis-(4-(5-methylhex-1-yn-3-yloxy)) phthalocyanines 2, and 2(3), 9(10), 16(17), 23(24)-tetrakis-(4-(5-methylhex-1-yn-3-yloxy)) phthalocyaninato zinc (II) (3) in solution and thin films. Nonlinear optical (NLO) properties of the samples in solution and contained in polysulfone (PSU) thin films were evaluated using Z-scan technique at 532 nm and 10 ns pulsed duration. Effects of aggregation and disaggregation on the NLO performance of metal-free phthalocyanine are reported in detail. Our findings showed that the prepared Pcs show larger nonlinear absorption coefficient and lower limiting thresholds when embedded in polysulfone films compared to in solutions. The values of nonlinear susceptibility and hyperpolarizability recorded for 3-PSU in this work are respectively, ∼2.09 × 10−8 esu and ∼1.02 × 10−26 esu. These values are among the largest values reported for phthalocyanines and other macrocycles doped on polymer matrices.
- Full Text:
- Date Issued: 2016
- Authors: Bankole, Owolabi M , Yilmaz, Yusuf , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189110 , vital:44817 , xlink:href="https://doi.org/10.1016/j.optmat.2015.11.041"
- Description: We report here for the first time, on the comparative studies of the photophysical and optical limiting behavior of our two novel phthalocyanines namely 2(3), 9(10), 16(17), 23(24)-tetrakis-(4-(5-methylhex-1-yn-3-yloxy)) phthalocyanines 2, and 2(3), 9(10), 16(17), 23(24)-tetrakis-(4-(5-methylhex-1-yn-3-yloxy)) phthalocyaninato zinc (II) (3) in solution and thin films. Nonlinear optical (NLO) properties of the samples in solution and contained in polysulfone (PSU) thin films were evaluated using Z-scan technique at 532 nm and 10 ns pulsed duration. Effects of aggregation and disaggregation on the NLO performance of metal-free phthalocyanine are reported in detail. Our findings showed that the prepared Pcs show larger nonlinear absorption coefficient and lower limiting thresholds when embedded in polysulfone films compared to in solutions. The values of nonlinear susceptibility and hyperpolarizability recorded for 3-PSU in this work are respectively, ∼2.09 × 10−8 esu and ∼1.02 × 10−26 esu. These values are among the largest values reported for phthalocyanines and other macrocycles doped on polymer matrices.
- Full Text:
- Date Issued: 2016
Enhanced nonlinear optical responses of zinc diaminopyrimidin-2-ylthio phthalocyanine conjugated to AgxAuy alloy nanoparticles
- Bankole, Owolabi M, Osifeko, Olawale, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Osifeko, Olawale , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240382 , vital:50829 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.06.025"
- Description: In this article, the photophysical and nonlinear optical (NLO) characterizations of diaminopyrimidin-2-ylthio phthalocyaninatozinc (II) (2) before and after conjugation to AgxAuy nano-alloys are discussed. Phthalocyanines-AgxAuy (2-AgxAuy) composites showed enhanced triplet state and nonlinear optical behaviour when compared to free phthalocyanine. Optical limiting (OL) responses of the samples were evaluated using Z-scan technique at 532 nm and 10 ns in dimethyl sulfoxide. Reverse saturable absorption (RSA), which is a direct consequence of triplet absorption of already excited molecules was observed as the dominant mechanism responsible for nonlinearity of the samples. By virtue of the magnitude of absorption coefficients and other NLO optical parameters estimated in this work, 2-AgxAuy composites were found to exhibit stronger optical limiting responses than unconjugated phthalocyanine. The large third-order susceptibilities of the composites make them suitable materials for attenuating modern laser radiations, and also found useful in various optical applications.
- Full Text:
- Date Issued: 2016
- Authors: Bankole, Owolabi M , Osifeko, Olawale , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240382 , vital:50829 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.06.025"
- Description: In this article, the photophysical and nonlinear optical (NLO) characterizations of diaminopyrimidin-2-ylthio phthalocyaninatozinc (II) (2) before and after conjugation to AgxAuy nano-alloys are discussed. Phthalocyanines-AgxAuy (2-AgxAuy) composites showed enhanced triplet state and nonlinear optical behaviour when compared to free phthalocyanine. Optical limiting (OL) responses of the samples were evaluated using Z-scan technique at 532 nm and 10 ns in dimethyl sulfoxide. Reverse saturable absorption (RSA), which is a direct consequence of triplet absorption of already excited molecules was observed as the dominant mechanism responsible for nonlinearity of the samples. By virtue of the magnitude of absorption coefficients and other NLO optical parameters estimated in this work, 2-AgxAuy composites were found to exhibit stronger optical limiting responses than unconjugated phthalocyanine. The large third-order susceptibilities of the composites make them suitable materials for attenuating modern laser radiations, and also found useful in various optical applications.
- Full Text:
- Date Issued: 2016
Improvement of nonlinear optical properties of phthalocyanine bearing diethyleneglycole chains
- Britton, Jonathan, Martynov, Alexander G, Oluwole, David O, Gorbunova, Yulia G, Tsivadze, Yulia G, Nyokong, Tebello
- Authors: Britton, Jonathan , Martynov, Alexander G , Oluwole, David O , Gorbunova, Yulia G , Tsivadze, Yulia G , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239812 , vital:50769 , xlink:href="https://doi.org/10.1142/S1088424616501042"
- Description: This paper reports the successful synthesis of the low symmetry phthalocyanines: metal-free 2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-nn-butoxyphthalocyanine 1H22 and its zinc complex 1Zn along with their nonlinear optical (NLO) behavior in solution and in thin films. 1H NMR investigations evidenced of higher dissymmetry of electronic density in 1H22 in comparison with 1Zn. This dissymmetry is responsible for unusually higher values of Im[χ(3)χ(3)]/αα, βeffβeff, and γγ for 1H22in contrast to 1Zn, where the notable effect of heavy-metal enhancement of ISC was expected. Both compounds showed Im[χ(3)χ(3)]/αα values of the order of 10−11−11 in chloroform which are higher in comparison to the symmetrical octabutoxyphthalocyanine H2[(BuO)8Pc]. NLO properties of 1H22 were improved via its incorporation into polycarbonate polymeric matrix together with CdSe@CdS-TOPO quantum dots. In such composite the value of Im[χ(3)χ(3)]/αα was almost three times higher in comparison with 1H22 solution in chloroform. The obtained composites are expected to be perspective components of optical materials, capable of protection against strong light irradiation
- Full Text:
- Date Issued: 2016
- Authors: Britton, Jonathan , Martynov, Alexander G , Oluwole, David O , Gorbunova, Yulia G , Tsivadze, Yulia G , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239812 , vital:50769 , xlink:href="https://doi.org/10.1142/S1088424616501042"
- Description: This paper reports the successful synthesis of the low symmetry phthalocyanines: metal-free 2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-nn-butoxyphthalocyanine 1H22 and its zinc complex 1Zn along with their nonlinear optical (NLO) behavior in solution and in thin films. 1H NMR investigations evidenced of higher dissymmetry of electronic density in 1H22 in comparison with 1Zn. This dissymmetry is responsible for unusually higher values of Im[χ(3)χ(3)]/αα, βeffβeff, and γγ for 1H22in contrast to 1Zn, where the notable effect of heavy-metal enhancement of ISC was expected. Both compounds showed Im[χ(3)χ(3)]/αα values of the order of 10−11−11 in chloroform which are higher in comparison to the symmetrical octabutoxyphthalocyanine H2[(BuO)8Pc]. NLO properties of 1H22 were improved via its incorporation into polycarbonate polymeric matrix together with CdSe@CdS-TOPO quantum dots. In such composite the value of Im[χ(3)χ(3)]/αα was almost three times higher in comparison with 1H22 solution in chloroform. The obtained composites are expected to be perspective components of optical materials, capable of protection against strong light irradiation
- Full Text:
- Date Issued: 2016
The photobleaching of the free and encapsulated metallic phthalocyanine and its effect on the photooxidation of simple molecules
- Fanchiotti, Brenda Gomes, Machado, Marcella Piffer Zamprogno, de Paula, Letícia Camilato, Durmuş, Mahmut, Nyokong, Tebello, da Silva, Gonçalves, da Silva, André Romero
- Authors: Fanchiotti, Brenda Gomes , Machado, Marcella Piffer Zamprogno , de Paula, Letícia Camilato , Durmuş, Mahmut , Nyokong, Tebello , da Silva, Gonçalves , da Silva, André Romero
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239687 , vital:50755 , xlink:href="https://doi.org/10.1016/j.jphotobiol.2016.10.007"
- Description: The photobleaching of an unsubstituted phthalocyanine (gallium(III) phthalocyanine chloride (GaPc)) and a substituted phthalocyanine (1,4-(tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato) indium(III) chloride (InTBPPc)) was monitored for the free photosensitizers and for the phthalocyanines encapsulated into nanoparticles of PEGylated poly(D,L-lactide-co-glycolide) (PLGA-PEG). Phosphate-buffered solutions (PBS) and organic solutions of the free GaPc or the free InTBPPc, and suspensions of each encapsulated photosensitizer (2–15 μmol/L) were irradiated using a laser diode of 665 nm with a power of 1–104 mW and a light dose of 7.5 J/cm2. The relative absorbance (RA) of the free GaPc dissolved in 1-methyl-2-pyrrolidone (MP) decreased 8.4 times when the laser power increased from 1 mW to 104 mW. However, the free or encapsulated GaPc did not suffer the photobleaching in PBS solution. The RA values decreased 2.4 times and 22.2 times for the free InTBPPc dissolved in PBS solution and in dimethylformamide (DMF), respectively, but the encapsulated InTBPPc was only photobleached when the laser power was 104 mW at 8 μmol/L. The increase of the free GaPc concentration favored the photobleaching in MP until 8 μmol/L while the increase from 2 μmol/L to 5 μmol/L reduced the photodegradation in PBS solution. However, the photobleaching of the free InTBPPc in DMF or in PBS solution, and of each encapsulated photosensitizer was not influenced by increasing the concentration. The influence of the photobleaching on the capability of the free and encapsulated GaPc and InTBPPc to photooxidate the simple molecules was investigated monitoring the fluorescence of dimethylanthracene (DMA) and the tryptophan (Trp). Free InTBPPc was 2.0 and 1.8 times faster to photooxidate the DMA and Trp than it was the free GaPc, but the encapsulated GaPc was 3.4 times more efficient to photooxidize the Trp than it was the encapsulated InTBPPc due to the photodegradation suffered by the encapsulated InTBPPc. The participation of the singlet oxygen was confirmed with the sodium azide in the photobleaching of all free and encapsulated photosensitizer, and in the photooxidation of the DMA and Trp. The asymmetry of InTBPPc increased the solubility of the free compound, decreasing the aggregation state of the photosensitizer and favoring the photobleaching process. The encapsulation shows capability in decreasing the photobleaching of both photosensitizers but the confocal micrographs showed that the increase of the solubility favored the InTBPPc photobleaching during the acquisition of optical cross section. A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2016
- Authors: Fanchiotti, Brenda Gomes , Machado, Marcella Piffer Zamprogno , de Paula, Letícia Camilato , Durmuş, Mahmut , Nyokong, Tebello , da Silva, Gonçalves , da Silva, André Romero
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239687 , vital:50755 , xlink:href="https://doi.org/10.1016/j.jphotobiol.2016.10.007"
- Description: The photobleaching of an unsubstituted phthalocyanine (gallium(III) phthalocyanine chloride (GaPc)) and a substituted phthalocyanine (1,4-(tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato) indium(III) chloride (InTBPPc)) was monitored for the free photosensitizers and for the phthalocyanines encapsulated into nanoparticles of PEGylated poly(D,L-lactide-co-glycolide) (PLGA-PEG). Phosphate-buffered solutions (PBS) and organic solutions of the free GaPc or the free InTBPPc, and suspensions of each encapsulated photosensitizer (2–15 μmol/L) were irradiated using a laser diode of 665 nm with a power of 1–104 mW and a light dose of 7.5 J/cm2. The relative absorbance (RA) of the free GaPc dissolved in 1-methyl-2-pyrrolidone (MP) decreased 8.4 times when the laser power increased from 1 mW to 104 mW. However, the free or encapsulated GaPc did not suffer the photobleaching in PBS solution. The RA values decreased 2.4 times and 22.2 times for the free InTBPPc dissolved in PBS solution and in dimethylformamide (DMF), respectively, but the encapsulated InTBPPc was only photobleached when the laser power was 104 mW at 8 μmol/L. The increase of the free GaPc concentration favored the photobleaching in MP until 8 μmol/L while the increase from 2 μmol/L to 5 μmol/L reduced the photodegradation in PBS solution. However, the photobleaching of the free InTBPPc in DMF or in PBS solution, and of each encapsulated photosensitizer was not influenced by increasing the concentration. The influence of the photobleaching on the capability of the free and encapsulated GaPc and InTBPPc to photooxidate the simple molecules was investigated monitoring the fluorescence of dimethylanthracene (DMA) and the tryptophan (Trp). Free InTBPPc was 2.0 and 1.8 times faster to photooxidate the DMA and Trp than it was the free GaPc, but the encapsulated GaPc was 3.4 times more efficient to photooxidize the Trp than it was the encapsulated InTBPPc due to the photodegradation suffered by the encapsulated InTBPPc. The participation of the singlet oxygen was confirmed with the sodium azide in the photobleaching of all free and encapsulated photosensitizer, and in the photooxidation of the DMA and Trp. The asymmetry of InTBPPc increased the solubility of the free compound, decreasing the aggregation state of the photosensitizer and favoring the photobleaching process. The encapsulation shows capability in decreasing the photobleaching of both photosensitizers but the confocal micrographs showed that the increase of the solubility favored the InTBPPc photobleaching during the acquisition of optical cross section. A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2016
Aggregation control of robust water-soluble zinc (II) phthalocyanine-based photosensitizers
- Ikeuchi, Takuro, Mack, John, Nyokong, Tebello, Kobayashi, Nagao, Kimura, Mutsumi
- Authors: Ikeuchi, Takuro , Mack, John , Nyokong, Tebello , Kobayashi, Nagao , Kimura, Mutsumi
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239709 , vital:50757 , xlink:href="https://doi.org/10.1021/acs.langmuir.6b03552"
- Description: A water-soluble zinc phthalocyanine (ZnPc) complex with four negatively charged electron-withdrawing sulfonic acid substituents at the nonperipheral positions (α-ZnTSPc) is found to have a high singlet oxygen (1O2) quantum yield and exhibits high photostability. The formation of aggregates is hindered and the highest occupied molecular orbital is significantly stabilized, making α-ZnTSPc potentially suitable for its use as a photosensitizer for photodynamic therapy and photoimmunotherapy. Atomic force microscopy (AFM) reveals that mixtures of the negatively charged α-ZnTSPc complex with a similar positively charged ZnPc were found to result in the self-assembly of one-dimensional accordion-like fibers. Supramolecular fibers can be formed in aqueous solutions through intermolecular electrostatic and donor–acceptor interactions between the two water-soluble ZnPcs.
- Full Text:
- Date Issued: 2016
- Authors: Ikeuchi, Takuro , Mack, John , Nyokong, Tebello , Kobayashi, Nagao , Kimura, Mutsumi
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239709 , vital:50757 , xlink:href="https://doi.org/10.1021/acs.langmuir.6b03552"
- Description: A water-soluble zinc phthalocyanine (ZnPc) complex with four negatively charged electron-withdrawing sulfonic acid substituents at the nonperipheral positions (α-ZnTSPc) is found to have a high singlet oxygen (1O2) quantum yield and exhibits high photostability. The formation of aggregates is hindered and the highest occupied molecular orbital is significantly stabilized, making α-ZnTSPc potentially suitable for its use as a photosensitizer for photodynamic therapy and photoimmunotherapy. Atomic force microscopy (AFM) reveals that mixtures of the negatively charged α-ZnTSPc complex with a similar positively charged ZnPc were found to result in the self-assembly of one-dimensional accordion-like fibers. Supramolecular fibers can be formed in aqueous solutions through intermolecular electrostatic and donor–acceptor interactions between the two water-soluble ZnPcs.
- Full Text:
- Date Issued: 2016
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
Optically active BODIPYs
- Lu, Hua, Mack, John, Nyokong, Tebello, Kobayashi, Nagao, Shen, Zhen
- Authors: Lu, Hua , Mack, John , Nyokong, Tebello , Kobayashi, Nagao , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240421 , vital:50833 , xlink:href="https://doi.org/10.1016/j.ccr.2016.03.015"
- Description: This review highlights and summarizes various optically active BODIPY molecules and describes the analysis of their circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy, to provide a platform for the rational design of novel optically active BODIPY structures and the development of new chiroptical applications. Possible future research directions are also discussed.
- Full Text:
- Date Issued: 2016
- Authors: Lu, Hua , Mack, John , Nyokong, Tebello , Kobayashi, Nagao , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240421 , vital:50833 , xlink:href="https://doi.org/10.1016/j.ccr.2016.03.015"
- Description: This review highlights and summarizes various optically active BODIPY molecules and describes the analysis of their circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy, to provide a platform for the rational design of novel optically active BODIPY structures and the development of new chiroptical applications. Possible future research directions are also discussed.
- Full Text:
- Date Issued: 2016
MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine
- Mack, John, Mkhize, Scebi, Safonoya, Evgeniya A, Gorbunova, Yulia G, Tsivadze, Aslan Yu, Nyokong, Tebello
- Authors: Mack, John , Mkhize, Scebi , Safonoya, Evgeniya A , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240743 , vital:50867 , xlink:href="https://doi.org/10.1142/S1088424616500322"
- Description: An analysis of the MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine is reported. This study provides a reassessment of an earlier study on the nature of the bands in UV-visible absorption spectra of magnesium and zinc tetra-(15-crown-5-oxanthreno)-phthalocyanine that was based on an analysis of TD-DFT calculations for a series of model complexes with the B3LYP functional. A detailed analysis of MCD spectral data and TD-DFT calculations with the CAM-B3LYP functional for the complete Mg(II) complex provides an additional insight into the optical properties and electronic structures of tetra-(15-crown-5-oxanthreno)-phthalocyanines. Thus, the bands in the Q-band region are reassigned as being due exclusively to the Q transition of Gouterman’s 4-orbital model, since intense pseudo-A1𝒜1 terms are observed in the MCD spectrum in a spectral region that had previously been assigned as charge transfer bands.
- Full Text:
- Date Issued: 2016
- Authors: Mack, John , Mkhize, Scebi , Safonoya, Evgeniya A , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240743 , vital:50867 , xlink:href="https://doi.org/10.1142/S1088424616500322"
- Description: An analysis of the MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine is reported. This study provides a reassessment of an earlier study on the nature of the bands in UV-visible absorption spectra of magnesium and zinc tetra-(15-crown-5-oxanthreno)-phthalocyanine that was based on an analysis of TD-DFT calculations for a series of model complexes with the B3LYP functional. A detailed analysis of MCD spectral data and TD-DFT calculations with the CAM-B3LYP functional for the complete Mg(II) complex provides an additional insight into the optical properties and electronic structures of tetra-(15-crown-5-oxanthreno)-phthalocyanines. Thus, the bands in the Q-band region are reassigned as being due exclusively to the Q transition of Gouterman’s 4-orbital model, since intense pseudo-A1𝒜1 terms are observed in the MCD spectrum in a spectral region that had previously been assigned as charge transfer bands.
- Full Text:
- Date Issued: 2016
Synthesis and singlet oxygen production by a phthalocyanine when embedded in asymmetric polymer membranes
- Mafukidze, Donovan M, Mashazi, Philani N, Nyokong, Tebello
- Authors: Mafukidze, Donovan M , Mashazi, Philani N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188563 , vital:44765 , xlink:href="https://doi.org/10.1016/j.polymer.2016.10.032"
- Description: 2(3), 9(10), 16(17), 23(24)-Tetrakis-(4-aminophenoxy) phthalocyaninato indium (III) chloride (ClInTAPPc, 3) was first conjugated to two different polymers: polystyrene (PS) and polyacrylonitrile (PAN) to form 3-PS and 3-PAN. The conjugates were cast into the corresponding polymers to form membranes represented as 3-PS-membrane and 3-PAN-membrane, respectively. The prepared membranes were characterized using various techniques including scanning electron microscopy and solid state UV/Vis spectroscopy. Singlet oxygen quantum yields were higher for the 3-PS-membrane at 0.51 compared to 3-PAN-membrane at 0.35. The larger singlet oxygen also applies to 3-PS (0.63) compared to 3-PAN (0.38) when in solution.
- Full Text:
- Date Issued: 2016
- Authors: Mafukidze, Donovan M , Mashazi, Philani N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188563 , vital:44765 , xlink:href="https://doi.org/10.1016/j.polymer.2016.10.032"
- Description: 2(3), 9(10), 16(17), 23(24)-Tetrakis-(4-aminophenoxy) phthalocyaninato indium (III) chloride (ClInTAPPc, 3) was first conjugated to two different polymers: polystyrene (PS) and polyacrylonitrile (PAN) to form 3-PS and 3-PAN. The conjugates were cast into the corresponding polymers to form membranes represented as 3-PS-membrane and 3-PAN-membrane, respectively. The prepared membranes were characterized using various techniques including scanning electron microscopy and solid state UV/Vis spectroscopy. Singlet oxygen quantum yields were higher for the 3-PS-membrane at 0.51 compared to 3-PAN-membrane at 0.35. The larger singlet oxygen also applies to 3-PS (0.63) compared to 3-PAN (0.38) when in solution.
- Full Text:
- Date Issued: 2016
Photophysical properties of tetraphenylporphyrinsubphthalocyanine conjugates
- Managa, Muthumuni, Mack, John, Remiro-Buenamañana, Sonia, Tshangana, Charmaine, Cammidge, Andrew N, Nyokong, Tebello
- Authors: Managa, Muthumuni , Mack, John , Remiro-Buenamañana, Sonia , Tshangana, Charmaine , Cammidge, Andrew N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240766 , vital:50869 , xlink:href="https://doi.org/10.1142/S1088424615500959"
- Description: Novel tetraphenylporphyrin-subphthalocyanine conjugates have been prepared and characterized. An analysis of their optical spectroscopy and electronic structures using fluorescence emission and magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations, demonstrates that the two chromophores do not interact to any significant extent.
- Full Text:
- Date Issued: 2016
- Authors: Managa, Muthumuni , Mack, John , Remiro-Buenamañana, Sonia , Tshangana, Charmaine , Cammidge, Andrew N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240766 , vital:50869 , xlink:href="https://doi.org/10.1142/S1088424615500959"
- Description: Novel tetraphenylporphyrin-subphthalocyanine conjugates have been prepared and characterized. An analysis of their optical spectroscopy and electronic structures using fluorescence emission and magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations, demonstrates that the two chromophores do not interact to any significant extent.
- Full Text:
- Date Issued: 2016
Effects of pluronic silica nanoparticles on the photophysical and photodynamic therapy behavior of triphenyl-p-phenoxy benzoic acid metalloporphyrins
- Managa, Muthumuni, Britton, Jonathan, Prinsloo, Earl, Nyokong, Tebello
- Authors: Managa, Muthumuni , Britton, Jonathan , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239698 , vital:50756 , xlink:href="https://doi.org/10.1080/00958972.2016.1236372"
- Description: 5, 10, 15, Triphenyl-20-p-phenoxy benzoic acid porphyrins (P) containing Zn (ZnP), Ga (GaP), and Si (SiP) were synthesized and conjugated to pluronic-silica (PluS) nanoparticles (NPs) where the fluorescence and singlet oxygen generating behavior of the porphyrins were investigated. The highest singlet oxygen quantum yield (ΦΔ) was obtained for ZnP. When the porphyrins were conjugated to the PluS NPs, the ΦΔ was quenched and fluorescence was enhanced. The pore size of the NPs upon conjugation decreased from 18.9 nm for PluS NPs to 2.4 nm (for ZnP as an example) as determined by applying the Brunauer–Emmett–Teller method. The porphyrin complexes and their conjugates were tested for their photodynamic therapy (PDT) activity on MCF-7 breast cancer cells. It was found that ZnP and its conjugate showed the highest PDT activity. The p > 0.05 indicated that ZnP is significantly different than GaP and SiP.
- Full Text:
- Date Issued: 2016
- Authors: Managa, Muthumuni , Britton, Jonathan , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239698 , vital:50756 , xlink:href="https://doi.org/10.1080/00958972.2016.1236372"
- Description: 5, 10, 15, Triphenyl-20-p-phenoxy benzoic acid porphyrins (P) containing Zn (ZnP), Ga (GaP), and Si (SiP) were synthesized and conjugated to pluronic-silica (PluS) nanoparticles (NPs) where the fluorescence and singlet oxygen generating behavior of the porphyrins were investigated. The highest singlet oxygen quantum yield (ΦΔ) was obtained for ZnP. When the porphyrins were conjugated to the PluS NPs, the ΦΔ was quenched and fluorescence was enhanced. The pore size of the NPs upon conjugation decreased from 18.9 nm for PluS NPs to 2.4 nm (for ZnP as an example) as determined by applying the Brunauer–Emmett–Teller method. The porphyrin complexes and their conjugates were tested for their photodynamic therapy (PDT) activity on MCF-7 breast cancer cells. It was found that ZnP and its conjugate showed the highest PDT activity. The p > 0.05 indicated that ZnP is significantly different than GaP and SiP.
- Full Text:
- Date Issued: 2016
Synthesis and dark toxicity of 5-(4-carboxyphenyl)-10, 15, 20-tris (phenyl)-porphyrinato chlorido gallium (III) when conjugated to δ-aminolevulinic acid
- Managa, Muthumuni, Mkhize, Scebi, Britton, Jonathan, Prinsloo, Earl, Nyokong, Tebello
- Authors: Managa, Muthumuni , Mkhize, Scebi , Britton, Jonathan , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240014 , vital:50789 , xlink:href="https://doi.org/10.1080/00958972.2016.1223292"
- Description: 5-(4-Carboxyphenyl)-10,15,20-tris(phenyl)-porphyrinato chlorido gallium(III) (2) was synthesized and then linked to ethyl ester δ-aminolevulinic acid to form 3. There was no shift in Soret band following conjugation. The fluorescence and singlet oxygen generating behavior of the porphyrins were also investigated. The highest singlet oxygen quantum yield (ΦΔ) obtained was that of 3. Complexes 2 and 3 as well as metal free 5-(4-carboxyphenyl)-10,15,20-tris(phenyl)-porphyrinato showed no dark toxicity on MCF-7 breast cancer cells.
- Full Text:
- Date Issued: 2016
- Authors: Managa, Muthumuni , Mkhize, Scebi , Britton, Jonathan , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240014 , vital:50789 , xlink:href="https://doi.org/10.1080/00958972.2016.1223292"
- Description: 5-(4-Carboxyphenyl)-10,15,20-tris(phenyl)-porphyrinato chlorido gallium(III) (2) was synthesized and then linked to ethyl ester δ-aminolevulinic acid to form 3. There was no shift in Soret band following conjugation. The fluorescence and singlet oxygen generating behavior of the porphyrins were also investigated. The highest singlet oxygen quantum yield (ΦΔ) obtained was that of 3. Complexes 2 and 3 as well as metal free 5-(4-carboxyphenyl)-10,15,20-tris(phenyl)-porphyrinato showed no dark toxicity on MCF-7 breast cancer cells.
- Full Text:
- Date Issued: 2016
Conjugation of azide-functionalised CdSe/ZnS quantum dots with tetrakis (5-hexyn-oxy) Fe (II) phthalocyanine via click chemistry for electrocatalysis
- Nxele, Siphesihle R, Nyokong, Tebello
- Authors: Nxele, Siphesihle R , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188755 , vital:44782 , xlink:href="https://doi.org/10.1016/j.electacta.2016.01.234"
- Description: In this work, azide-funtionalised CdSe/ZnS QDs are conjugated with tetrakis(5-hexyn-oxy) Fe(II) phthalocyanine for the electrocatalytic detection of paraquat. The conjugate was fully characterised using various techniques to confirm the success of the reaction. They also showed good electrocatalytic ability towards the electroreduction of paraquat with limits of detection (LoD) of 5.9 × 10−9 μM which is a great improvement compared to other reported sensors for this analyte.
- Full Text:
- Date Issued: 2016
- Authors: Nxele, Siphesihle R , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188755 , vital:44782 , xlink:href="https://doi.org/10.1016/j.electacta.2016.01.234"
- Description: In this work, azide-funtionalised CdSe/ZnS QDs are conjugated with tetrakis(5-hexyn-oxy) Fe(II) phthalocyanine for the electrocatalytic detection of paraquat. The conjugate was fully characterised using various techniques to confirm the success of the reaction. They also showed good electrocatalytic ability towards the electroreduction of paraquat with limits of detection (LoD) of 5.9 × 10−9 μM which is a great improvement compared to other reported sensors for this analyte.
- Full Text:
- Date Issued: 2016