Characterization and Electrocatalytic Activity of Nanocomposites Consisting of Nanosized Cobalt Tetraaminophenoxy Phthalocyanine, Multi‐walled Carbon Nanotubes and Gold Nanoparticles
- Shumba, Munyaradzi, Nyokong, Tebello
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188659 , vital:44773 , xlink:href="https://doi.org/10.1002/elan.201501058"
- Description: Glassy carbon electrodes were modified with composites containing cobalt tetraaminophenoxy phthalocyanine nanoparticles (CoTAPhPcNP), multi-walled carbon nanotubes (MWCNT) and gold nanorods (AuNRs). The modified electrodes were studied for their electrocatalytic behavior towards the reduction of hydrogen peroxide. Phthalocyanine nanoparticles significantly improved electron transfer kinetics as compared to phthalocyanines which are not in the nanoparticle form when alone or in the presence of multiwalled carbon nanotubes (MWCNTs). CoTAPhPcNP-MWCNT-GCE proved to be suitable for hydrogen peroxide detection with a catalytic rate constant of 3.45×103 M−1 s−1 and a detection limit of 1.61×10−7 M. Adsorption Gibbs free energy ΔGo was found to be −19.22 kJ mol−1 for CoTAPhPcNP-MWCNT-GCE.
- Full Text:
- Date Issued: 2016
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188659 , vital:44773 , xlink:href="https://doi.org/10.1002/elan.201501058"
- Description: Glassy carbon electrodes were modified with composites containing cobalt tetraaminophenoxy phthalocyanine nanoparticles (CoTAPhPcNP), multi-walled carbon nanotubes (MWCNT) and gold nanorods (AuNRs). The modified electrodes were studied for their electrocatalytic behavior towards the reduction of hydrogen peroxide. Phthalocyanine nanoparticles significantly improved electron transfer kinetics as compared to phthalocyanines which are not in the nanoparticle form when alone or in the presence of multiwalled carbon nanotubes (MWCNTs). CoTAPhPcNP-MWCNT-GCE proved to be suitable for hydrogen peroxide detection with a catalytic rate constant of 3.45×103 M−1 s−1 and a detection limit of 1.61×10−7 M. Adsorption Gibbs free energy ΔGo was found to be −19.22 kJ mol−1 for CoTAPhPcNP-MWCNT-GCE.
- 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
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
Development of nanocomposites of phosphorus-nitrogen co-doped graphene oxide nanosheets and nanosized cobalt phthalocyanines for electrocatalysis
- Shumba, Munyaradzai, Nyokong, Tebello
- Authors: Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188574 , vital:44766 , xlink:href="https://doi.org/10.1016/j.electacta.2016.07.079"
- Description: Conjugates of reduced phosphorus-nitrogen co-doped graphene oxide nanosheets (rPNDGONS), reduced phosphorus doped graphene oxide nanosheets (rPDGONS), reduced nitrogen doped graphene oxide nanosheets (rNDGONS), reduced pyrolised graphene oxide nanosheets (rpyGONS) with nanosized cobalt (II) phthalocyanine (CoPcNP) or cobalt tetra amino phenoxy phthalocyanine (CoTAPhPcNP) were characterised and tested for their electrocatalytic behaviour towards the detection of hydrogen peroxide. Cyclic and linear scan voltammetries, and chronoamperometry were used to evaluate the electrocatalytic nature of the designed probes. For hydrogen peroxide detection, CoPcNP-rPNDGONS-GCE oxidation gave sensitivity of 12.00 mA/M, limit of detection of 4.48 nM, a rate constant of 2.66 × 105 M−1 s−1, adsorption equilibrium constant of 3.7 × 102 M−1 and Gibbs free energy −14.84 kJmol−1. The lowest detection limit was obtained for CoTAPhPcNP-rPNDGONS-GCE at 1.21 nM.
- Full Text:
- Date Issued: 2016
- Authors: Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188574 , vital:44766 , xlink:href="https://doi.org/10.1016/j.electacta.2016.07.079"
- Description: Conjugates of reduced phosphorus-nitrogen co-doped graphene oxide nanosheets (rPNDGONS), reduced phosphorus doped graphene oxide nanosheets (rPDGONS), reduced nitrogen doped graphene oxide nanosheets (rNDGONS), reduced pyrolised graphene oxide nanosheets (rpyGONS) with nanosized cobalt (II) phthalocyanine (CoPcNP) or cobalt tetra amino phenoxy phthalocyanine (CoTAPhPcNP) were characterised and tested for their electrocatalytic behaviour towards the detection of hydrogen peroxide. Cyclic and linear scan voltammetries, and chronoamperometry were used to evaluate the electrocatalytic nature of the designed probes. For hydrogen peroxide detection, CoPcNP-rPNDGONS-GCE oxidation gave sensitivity of 12.00 mA/M, limit of detection of 4.48 nM, a rate constant of 2.66 × 105 M−1 s−1, adsorption equilibrium constant of 3.7 × 102 M−1 and Gibbs free energy −14.84 kJmol−1. The lowest detection limit was obtained for CoTAPhPcNP-rPNDGONS-GCE at 1.21 nM.
- 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
Efficient energy transfer in ethynyl bridged corrole–BODIPY dyads
- Yan, Yu, Wu, Fan, Qin, Jiawei, Xu, Haijun, Shi, Maohu, Zhou, Jingfeng, Mack, John, Fomo, Gertrude, Nyokong, Tebello, Shen, Zhen
- Authors: Yan, Yu , Wu, Fan , Qin, Jiawei , Xu, Haijun , Shi, Maohu , Zhou, Jingfeng , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240899 , vital:50883 , xlink:href="https://doi.org/10.1039/C6RA12271J"
- Description: A series of new corrole–BODIPY dyads bridged by ethynyl linker moieties have been synthesized in high yields and fully characterized. The direction of energy transfer upon electronic excitation has been explored, and was found to be dependent on the number of corrole rings and their connection position on the BODIPY core. Intense bands in the absorption spectrum cover most of the visible region, which is potentially advantageous for capturing solar energy. Studies on the excitation spectra and lifetimes suggest that the energy transfer efficiency between the BODIPY and corrole moieties reaches almost 85%, which appears to be efficient in the context of energy transfer within the singlet manifold.
- Full Text:
- Date Issued: 2016
- Authors: Yan, Yu , Wu, Fan , Qin, Jiawei , Xu, Haijun , Shi, Maohu , Zhou, Jingfeng , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240899 , vital:50883 , xlink:href="https://doi.org/10.1039/C6RA12271J"
- Description: A series of new corrole–BODIPY dyads bridged by ethynyl linker moieties have been synthesized in high yields and fully characterized. The direction of energy transfer upon electronic excitation has been explored, and was found to be dependent on the number of corrole rings and their connection position on the BODIPY core. Intense bands in the absorption spectrum cover most of the visible region, which is potentially advantageous for capturing solar energy. Studies on the excitation spectra and lifetimes suggest that the energy transfer efficiency between the BODIPY and corrole moieties reaches almost 85%, which appears to be efficient in the context of energy transfer within the singlet manifold.
- Full Text:
- Date Issued: 2016
Electrocatalytic activity of nanocomposites of sulphur doped graphene oxide and nanosized cobalt phthalocyanines
- Shumba, Munyaradzi, Nyokong, Tebello
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188530 , vital:44762 , xlink:href="https://doi.org/10.1002/elan.201600226"
- Description: In this work we explore the electrocatalytic activity of nanocomposites of reduced sulphur doped graphene oxide nanosheets (rSDGONS) and cobalt phthalocyanine (CoPc) or cobalt tetra amino phthalocyanine (CoTAPc) towards hydrogen peroxide. Transmission electron microscopy, scanning electron microscopy, X-ray photon spectroscopy, X-ray diffraction, chronoamperometry, linear scan voltammetry and cyclic voltammetry were used to characterize the nanocomposites. Nanosized CoPc showed superior (in terms of currents) electrocatalytic oxidation and reduction of hydrogen peroxide compared to CoTAPc nanoparticles (CoTAPcNP). The lowest detection limit was obtained for hydrogen peroxide oxidation on electrodes modified with CoPcNP-rSDGONS at 1.49 µM. The same electrode gave a high adsorption equilibrium constant of 1.27×103 mol−1 and a Gibbs free energy of −17.71 kJ/mol, indicative of a spontaneous reaction on the electrode surface.
- Full Text:
- Date Issued: 2016
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188530 , vital:44762 , xlink:href="https://doi.org/10.1002/elan.201600226"
- Description: In this work we explore the electrocatalytic activity of nanocomposites of reduced sulphur doped graphene oxide nanosheets (rSDGONS) and cobalt phthalocyanine (CoPc) or cobalt tetra amino phthalocyanine (CoTAPc) towards hydrogen peroxide. Transmission electron microscopy, scanning electron microscopy, X-ray photon spectroscopy, X-ray diffraction, chronoamperometry, linear scan voltammetry and cyclic voltammetry were used to characterize the nanocomposites. Nanosized CoPc showed superior (in terms of currents) electrocatalytic oxidation and reduction of hydrogen peroxide compared to CoTAPc nanoparticles (CoTAPcNP). The lowest detection limit was obtained for hydrogen peroxide oxidation on electrodes modified with CoPcNP-rSDGONS at 1.49 µM. The same electrode gave a high adsorption equilibrium constant of 1.27×103 mol−1 and a Gibbs free energy of −17.71 kJ/mol, indicative of a spontaneous reaction on the electrode surface.
- Full Text:
- Date Issued: 2016
Electrode modification using alkyne manganese phthalocyanine and click chemistry for electrocatalysis
- O'Donoghue, Charles St John Nqwabuko, Fomo, Gertrude, Nyokong, Tebello
- Authors: O'Donoghue, Charles St John Nqwabuko , Fomo, Gertrude , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188541 , vital:44763 , xlink:href="https://doi.org/10.1002/elan.201600379"
- Description: In this work, azidobenzene diazonium salt is grafted onto a glassy carbon electrode (GCE) followed by clicking of manganese tetrahexynyl phthalocyanine for the electrocatalysis of hydrazine. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1,3-dipolar cycloaddition reaction, catalyzed by a copper catalyst was utilized to ‘click’ the manganese tetrahexynyl phthalocyanine to the surface of the grafted GCE. This new platform was then characterized using cyclic voltammetry (CV), scanning electrochemical microscopy (SECM) and X-ray photoelectron spectroscopy (XPS). Based on the cyclic voltammetry calibration curve of electrocatalysis for hydrazine, the clicked Mn phthalocyanine electrode proved to be an effective sensor with a sensitivity of 27.38 µA mM−1 and the limit of detection (LoD) of 15.4 pM which is a great improvement compared to other reported sensors for this analyte.
- Full Text:
- Date Issued: 2016
- Authors: O'Donoghue, Charles St John Nqwabuko , Fomo, Gertrude , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188541 , vital:44763 , xlink:href="https://doi.org/10.1002/elan.201600379"
- Description: In this work, azidobenzene diazonium salt is grafted onto a glassy carbon electrode (GCE) followed by clicking of manganese tetrahexynyl phthalocyanine for the electrocatalysis of hydrazine. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1,3-dipolar cycloaddition reaction, catalyzed by a copper catalyst was utilized to ‘click’ the manganese tetrahexynyl phthalocyanine to the surface of the grafted GCE. This new platform was then characterized using cyclic voltammetry (CV), scanning electrochemical microscopy (SECM) and X-ray photoelectron spectroscopy (XPS). Based on the cyclic voltammetry calibration curve of electrocatalysis for hydrazine, the clicked Mn phthalocyanine electrode proved to be an effective sensor with a sensitivity of 27.38 µA mM−1 and the limit of detection (LoD) of 15.4 pM which is a great improvement compared to other reported sensors for this analyte.
- Full Text:
- Date Issued: 2016
Electrode modification using nanocomposites of boron or nitrogen doped graphene oxide and cobalt (II) tetra aminophenoxy phthalocyanine nanoparticles
- Shumba, Munyaradzi, Nyokong, Tebello
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188699 , vital:44777 , xlink:href="https://doi.org/10.1016/j.electacta.2016.02.166"
- Description: Reduced graphene oxide nanosheets (rGONS), reduced boron doped graphene oxide nanosheets (rBDGONS) and reduced nitrogen doped graphene oxide nanosheets (rNDGONS) and their composites with cobalt tetra aminophenoxy phthalocyanine nanoparticles (CoTAPhPcNP) were employed towards the detection of hydrogen peroxide. The nanomaterials were characterized by absorption spectroscopy, transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, linear sweep voltammetry and cyclic voltammetry. rNDGONS showed excellent electrooxidation and electroreduction of hydrogen peroxide supported by superior surface coverage values. The inclusion of nanosized Pc significantly lowered the reduction overpotential. CoTAPhPcNP-rNDGONS-GCE gave a sensitivity of 39.30 mA/M, catalytic rate constant of 1 × 103 M−1 s−1 and a detection limit of 8.2 nM. An adsorption equilibrium constant and Gibbs free energy of 1.26 × 103 M−1 and −17.69 kJ mol−1 respectively were observed.
- Full Text:
- Date Issued: 2016
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188699 , vital:44777 , xlink:href="https://doi.org/10.1016/j.electacta.2016.02.166"
- Description: Reduced graphene oxide nanosheets (rGONS), reduced boron doped graphene oxide nanosheets (rBDGONS) and reduced nitrogen doped graphene oxide nanosheets (rNDGONS) and their composites with cobalt tetra aminophenoxy phthalocyanine nanoparticles (CoTAPhPcNP) were employed towards the detection of hydrogen peroxide. The nanomaterials were characterized by absorption spectroscopy, transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, linear sweep voltammetry and cyclic voltammetry. rNDGONS showed excellent electrooxidation and electroreduction of hydrogen peroxide supported by superior surface coverage values. The inclusion of nanosized Pc significantly lowered the reduction overpotential. CoTAPhPcNP-rNDGONS-GCE gave a sensitivity of 39.30 mA/M, catalytic rate constant of 1 × 103 M−1 s−1 and a detection limit of 8.2 nM. An adsorption equilibrium constant and Gibbs free energy of 1.26 × 103 M−1 and −17.69 kJ mol−1 respectively were observed.
- Full Text:
- Date Issued: 2016
Electrode modification using nanocomposites of electropolymerised cobalt phthalocyanines supported on multiwalled carbon nanotubes
- Nyoni, Stephen, Mashazi, Philani N, Nyokong, Tebello
- Authors: Nyoni, Stephen , Mashazi, Philani N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188730 , vital:44780 , xlink:href="https://doi.org/10.1007/s10008-015-2985-6"
- Description: A polymer of tetra(4)-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninatocobalt(II) (CoPyPc) has been deposited over a multiwalled carbon nanotube (MWCNT) platform and its electrocatalytic properties investigated side by side with polymerized cobalt tetraamino phthalocyanine (CoTAPc). X-ray photoelectron spectroscopy, scanning electron microscopy and cyclic voltammetry studies were used for characterization of the prepared polymers of cobalt phthalocyanine derivatives and their nanocomposites. L-Cysteine was used as a test analyte for the electrocatalytic activity of the nanocomposites of polymerized cobalt phthalocyanines and multiwalled carbon nanotubes. The electrocatalytic activity of both polymerized cobalt phthalocyanines was found to be superior when polymerization was done on top of MWCNTs compared to bare glassy carbon electrode. A higher sensitivity for L-cysteine detection was obtained on CoTAPc compared to CoPyPc.
- Full Text:
- Date Issued: 2016
- Authors: Nyoni, Stephen , Mashazi, Philani N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188730 , vital:44780 , xlink:href="https://doi.org/10.1007/s10008-015-2985-6"
- Description: A polymer of tetra(4)-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninatocobalt(II) (CoPyPc) has been deposited over a multiwalled carbon nanotube (MWCNT) platform and its electrocatalytic properties investigated side by side with polymerized cobalt tetraamino phthalocyanine (CoTAPc). X-ray photoelectron spectroscopy, scanning electron microscopy and cyclic voltammetry studies were used for characterization of the prepared polymers of cobalt phthalocyanine derivatives and their nanocomposites. L-Cysteine was used as a test analyte for the electrocatalytic activity of the nanocomposites of polymerized cobalt phthalocyanines and multiwalled carbon nanotubes. The electrocatalytic activity of both polymerized cobalt phthalocyanines was found to be superior when polymerization was done on top of MWCNTs compared to bare glassy carbon electrode. A higher sensitivity for L-cysteine detection was obtained on CoTAPc compared to CoPyPc.
- 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 L, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Osifeko, Olawale L , 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 L , 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
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
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
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
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
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
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
Nonlinear optical behavior of neodymium mono-and bi-nuclear phthalocyanines linked to zinc oxide nanoparticles and incorporated into poly acrylic acid
- Sekhosana, Kutloana E, Amuhaya, Edith K, Nyokong, Tebello
- Authors: Sekhosana, Kutloana E , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188766 , vital:44783 , xlink:href="https://doi.org/10.1016/j.poly.2015.12.045"
- Description: Syntheses of bis{23-(3,4-di-yloxybenzoic acid)-(2(3), 9(10), 16(17), 23(24))-(hexakis-pyridin-3-yloxy phthalocyaninato)} dineodymium (III) acetate (3) and 2(3), 9(10), 16(17), 23(24)-(tetrapyridin-3-yloxy phthalocyaninato) neodymium (III) acetate (4) as well as their conjugates with ZnO nanoparticles (conjugates 6, 7 and 8) are presented. Thin films of conjugate 6 (where complex 3 is linked to ZnO nanoparticles via an amide bond) gave the best third-order susceptibility (5.89 × 10−8 esu), second-order hyperpolarizability (2.53 × 10−25 esu) and the lowest limiting threshold values (0.12 J cm−2). The nonlinear behavior is enhanced in solid state when compared to solution.
- Full Text:
- Date Issued: 2016
- Authors: Sekhosana, Kutloana E , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188766 , vital:44783 , xlink:href="https://doi.org/10.1016/j.poly.2015.12.045"
- Description: Syntheses of bis{23-(3,4-di-yloxybenzoic acid)-(2(3), 9(10), 16(17), 23(24))-(hexakis-pyridin-3-yloxy phthalocyaninato)} dineodymium (III) acetate (3) and 2(3), 9(10), 16(17), 23(24)-(tetrapyridin-3-yloxy phthalocyaninato) neodymium (III) acetate (4) as well as their conjugates with ZnO nanoparticles (conjugates 6, 7 and 8) are presented. Thin films of conjugate 6 (where complex 3 is linked to ZnO nanoparticles via an amide bond) gave the best third-order susceptibility (5.89 × 10−8 esu), second-order hyperpolarizability (2.53 × 10−25 esu) and the lowest limiting threshold values (0.12 J cm−2). The nonlinear behavior is enhanced in solid state when compared to solution.
- 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