Electrode modification through click chemistry using Ni and Co alkyne phthalocyanines for electrocatalytic detection of hydrazine
- O'Donoghue, Charles S, Shumba, Munyaradzai, Nyokong, Tebello
- Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233032 , vital:50049 , xlink:href="https://doi.org/10.1002/elan.201700084"
- Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. 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, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
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- Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233032 , vital:50049 , xlink:href="https://doi.org/10.1002/elan.201700084"
- Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. 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, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
- Full Text:
Electrode modification through click chemistry using Ni and Co alkyne phthalocyanines for electrocatalytic detection of hydrazine
- O'Donoghue, Charles S, Shumba, Munyaradzai, Nyokong, Tebello
- Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242763 , vital:51076 , xlink:href="https://doi.org/10.1002/elan.201700084"
- Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. 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, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
- Full Text:
- Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242763 , vital:51076 , xlink:href="https://doi.org/10.1002/elan.201700084"
- Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. 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, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
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Electronic structure and NH-tautomerism of a novel metal-free phenanthroline-annelated phthalocyanine
- Martynov, Alexander G, Mack, John, Ngoy, Bokolombe P, Nyokong, Tebello, Gorbunova, Yulia G, Tsivadze, Aslan Yu
- Authors: Martynov, Alexander G , Mack, John , Ngoy, Bokolombe P , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239643 , vital:50751 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.072"
- Description: 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.
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- Authors: Martynov, Alexander G , Mack, John , Ngoy, Bokolombe P , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239643 , vital:50751 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.072"
- Description: 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.
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Enantioselective electrochemical carbon-chloride bond cleavage of hexachlorocyclohexanes (HCHs) catalyzed by Mn (III) Cl-phthalocyanine
- Wen, Junxia, Yu, Baoqui, Huang, Tingting, Mack, John, Wildervanck, Martijn, Nyokong, Tebello, Li, Minzhi, Zhu, Weihua, Liang, Xu
- Authors: Wen, Junxia , Yu, Baoqui , Huang, Tingting , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189252 , vital:44831 , xlink:href="https://doi.org/10.1016/j.jelechem.2017.09.020"
- Description: A lipophilic and electron-rich metallophthalocyanine Mn(III)Cl(α,α′-n-OC5H11)8Pc has been synthesized and characterized. A series of electrochemical experiments demonstrate that the Mn(III)Cl(α,α′-n-OC5H11)8Pc complex can be used as a catalyst for highly efficient carbon-chloride bond cleavage of environmental toxic hexachlorocyclohexanes (HCHs) through electrochemical catalysis, and that the increased catalytic efficiency is related to the enantiomeric carbon-chloride σ-bond of HCHs.
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- Authors: Wen, Junxia , Yu, Baoqui , Huang, Tingting , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189252 , vital:44831 , xlink:href="https://doi.org/10.1016/j.jelechem.2017.09.020"
- Description: A lipophilic and electron-rich metallophthalocyanine Mn(III)Cl(α,α′-n-OC5H11)8Pc has been synthesized and characterized. A series of electrochemical experiments demonstrate that the Mn(III)Cl(α,α′-n-OC5H11)8Pc complex can be used as a catalyst for highly efficient carbon-chloride bond cleavage of environmental toxic hexachlorocyclohexanes (HCHs) through electrochemical catalysis, and that the increased catalytic efficiency is related to the enantiomeric carbon-chloride σ-bond of HCHs.
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Exploiting Click Chemistry for the Covalent Immobilization of Tetra (4-Propargyloxyphenoxy) Metallophthalocyanines onto Phenylazide-Grafted Gold Surfaces
- Mwanza, Daniel, Mvango, Sindisiwe, Khene, Samson M, Nyokong, Tebello, Mashazi, Philani N
- Authors: Mwanza, Daniel , Mvango, Sindisiwe , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189177 , vital:44824 , xlink:href="https://doi.org/10.1016/j.electacta.2017.09.115"
- Description: In this study, tetra-(4-propargyloxy)phenoxy phthalocyanines (MTPrOPhOPc) were covalently immobilized as thin films onto gold surfaces via click reaction. The gold electrode surfaces were pre-functionalized with phenylazide (Au-PAz) thin film using in-situ diazonium generation followed by electrografting. Copper (I) catalyzed alkynyl-azide cycloaddition (CuCAAC) reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. Au-PAz-MTPrOPhOPc exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and spectroscopic surface characterization of the functionalized gold electrode surfaces confirmed the presence of the phenylazide and MTPrOPhOPc thin monolayer films. The excellent electroanalysis of hydrogen peroxide with the limit of detection (LoD) and limit of quantification (LoQ) in the μM range was obtained. The electrocatalytic reduction peaks for H2O2 were observed at −0.37 V for Au-PAz-Mn(OAc)TPrOPhOPc and −0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-Mn(OAc)TPrOPhOPc and Au-PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution.
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- Authors: Mwanza, Daniel , Mvango, Sindisiwe , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189177 , vital:44824 , xlink:href="https://doi.org/10.1016/j.electacta.2017.09.115"
- Description: In this study, tetra-(4-propargyloxy)phenoxy phthalocyanines (MTPrOPhOPc) were covalently immobilized as thin films onto gold surfaces via click reaction. The gold electrode surfaces were pre-functionalized with phenylazide (Au-PAz) thin film using in-situ diazonium generation followed by electrografting. Copper (I) catalyzed alkynyl-azide cycloaddition (CuCAAC) reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. Au-PAz-MTPrOPhOPc exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and spectroscopic surface characterization of the functionalized gold electrode surfaces confirmed the presence of the phenylazide and MTPrOPhOPc thin monolayer films. The excellent electroanalysis of hydrogen peroxide with the limit of detection (LoD) and limit of quantification (LoQ) in the μM range was obtained. The electrocatalytic reduction peaks for H2O2 were observed at −0.37 V for Au-PAz-Mn(OAc)TPrOPhOPc and −0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-Mn(OAc)TPrOPhOPc and Au-PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution.
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First example of nonlinear optical materials based on nanoconjugates of sandwich phthalocyanines with quantum dots
- Oluwole, David O, Yagodin, Alexey V, Mkhize, Nhlakanipho C, Sekhosana, Kutloana E, Martynov, Alexander G, Gorbunova, Yulia G, Tsivadze, Aslan Yu, Nyokong, Tebello
- Authors: Oluwole, David O , Yagodin, Alexey V , Mkhize, Nhlakanipho C , Sekhosana, Kutloana E , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238014 , vital:50577 , xlink:href="https://doi.org/10.1002/chem.201604401"
- Description: We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double- and triple-decker europium(III) complexes 2 and 3 with the A3B-type phthalocyanine ligand (2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-n-butoxyphthalocyanine 1) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid-capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low-symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open-aperture Z-scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double- and triple-decker EuIII octa-n-butoxyphthalocyaninates 5 and 6 and their mixtures with trioctylphosphine oxide-capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π-electron system upon moving from double- to triple-decker complexes significantly improves the OL characteristics, making the low-symmetry triple-decker complex 3 the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm−2 input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double- and triple-decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.
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- Authors: Oluwole, David O , Yagodin, Alexey V , Mkhize, Nhlakanipho C , Sekhosana, Kutloana E , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238014 , vital:50577 , xlink:href="https://doi.org/10.1002/chem.201604401"
- Description: We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double- and triple-decker europium(III) complexes 2 and 3 with the A3B-type phthalocyanine ligand (2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-n-butoxyphthalocyanine 1) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid-capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low-symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open-aperture Z-scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double- and triple-decker EuIII octa-n-butoxyphthalocyaninates 5 and 6 and their mixtures with trioctylphosphine oxide-capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π-electron system upon moving from double- to triple-decker complexes significantly improves the OL characteristics, making the low-symmetry triple-decker complex 3 the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm−2 input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double- and triple-decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.
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Flexible Metal–Porphyrin Dimers (M= MnIIICl, CoII, NiII, CuII)
- Li, Minzhi, Zhang, Qian, Xu, Li, Zhu, Weihua, Mack, John, May, Aviwe K, Nyokong, Tebello, Kobayashi, Nagao, Liang, Xu
- Authors: Li, Minzhi , Zhang, Qian , Xu, Li , Zhu, Weihua , Mack, John , May, Aviwe K , Nyokong, Tebello , Kobayashi, Nagao , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239676 , vital:50754 , xlink:href="https://doi.org/10.1002/cplu.201600475"
- Description: Four metalloporphyrin dimers linked by bridging amide-bonded xanthene moieties and that contain either MnIII, CoII, NiII, or CuII metal centers were synthesized. Various spectroscopic, electrochemical, and spectroelectrochemical methods were used to study trends in their properties. Their electronic structure and optical properties were analyzed through a comparison of the electronic absorption and magnetic circular dichroism (MCD) spectral data with the results of time-dependent (TD)-DFT calculations.
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- Authors: Li, Minzhi , Zhang, Qian , Xu, Li , Zhu, Weihua , Mack, John , May, Aviwe K , Nyokong, Tebello , Kobayashi, Nagao , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239676 , vital:50754 , xlink:href="https://doi.org/10.1002/cplu.201600475"
- Description: Four metalloporphyrin dimers linked by bridging amide-bonded xanthene moieties and that contain either MnIII, CoII, NiII, or CuII metal centers were synthesized. Various spectroscopic, electrochemical, and spectroelectrochemical methods were used to study trends in their properties. Their electronic structure and optical properties were analyzed through a comparison of the electronic absorption and magnetic circular dichroism (MCD) spectral data with the results of time-dependent (TD)-DFT calculations.
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Fluorescence behaviour of supramolecular hybrids containing graphene quantum dots and pyrene-derivatized phthalocyanines and porphyrins
- Achadu, Ojodomo John, Managa, Muthumuni, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Managa, Muthumuni , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188953 , vital:44801 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.10.029"
- Description: Novel pyrene-derivatized zinc and cobalt phthalocyanines (Pcs) and porphyrins (Ps) were immobilized on graphene quantum dots (GQDs) to form GQDs-Pcs and GQDs-Ps supramolecular hybrids via the π–π stacking interaction method. Spectroscopic evidence shows that the resultant hybrids were stable owing to the strong π–π stacking interaction between the GQDs and the respective Pcs and Ps, thus leading to the fabrication of interesting and functional supramolecular hybrids by taking advantage of the delocalized π electron systems of GQDs and the macrocycles. The conjugates showed increased fluorescence quantum yields for the Pcs/Ps, but decreased values for the GQDs in the conjugates. These novel hybrid materials could potentially be deployed for studies in both fundamental and applied perspectives due to the synergistic contributions resulting from the combination of their excellent electronic and optical properties.
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- Authors: Achadu, Ojodomo John , Managa, Muthumuni , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188953 , vital:44801 , xlink:href="https://doi.org/10.1016/j.jphotochem.2016.10.029"
- Description: Novel pyrene-derivatized zinc and cobalt phthalocyanines (Pcs) and porphyrins (Ps) were immobilized on graphene quantum dots (GQDs) to form GQDs-Pcs and GQDs-Ps supramolecular hybrids via the π–π stacking interaction method. Spectroscopic evidence shows that the resultant hybrids were stable owing to the strong π–π stacking interaction between the GQDs and the respective Pcs and Ps, thus leading to the fabrication of interesting and functional supramolecular hybrids by taking advantage of the delocalized π electron systems of GQDs and the macrocycles. The conjugates showed increased fluorescence quantum yields for the Pcs/Ps, but decreased values for the GQDs in the conjugates. These novel hybrid materials could potentially be deployed for studies in both fundamental and applied perspectives due to the synergistic contributions resulting from the combination of their excellent electronic and optical properties.
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Graphene quantum dot-phthalocyanine polystyrene conjugate embedded in asymmetric polymer membranes for photocatalytic oxidation of 4-chlorophenol
- Mafukidze, Donovan M, Nyokong, Tebello
- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189189 , vital:44825 , xlink:href="https://doi.org/10.1080/00958972.2017.1400664"
- Description: The feasibility of using π–π stacking as a means of fixing unsubstituted Zn phthalocyanine (ZnPc) to a support prior to formation of photoactive polymer asymmetric membranes was explored. Stable ZnPc–graphene quantum dot-polystyrene conjugates (6.15 μmol/g ZnPc loading) were synthesized and embedded in polystyrene membranes which proved to be photoactive with a singlet oxygen quantum yield of 0.43 in ethanol and 0.37 in water. The membranes also proved to be active in the photocatalytic oxidation of 4-chlorophenol in water where the reaction followed second-order kinetics. At 3.24 × 10−4 mol L−1, the photo-oxidation of 4-chlorophenol was observed with a kobs of 35.9 L mol−1 min−1 and a half-life of 86 min.
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- Authors: Mafukidze, Donovan M , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189189 , vital:44825 , xlink:href="https://doi.org/10.1080/00958972.2017.1400664"
- Description: The feasibility of using π–π stacking as a means of fixing unsubstituted Zn phthalocyanine (ZnPc) to a support prior to formation of photoactive polymer asymmetric membranes was explored. Stable ZnPc–graphene quantum dot-polystyrene conjugates (6.15 μmol/g ZnPc loading) were synthesized and embedded in polystyrene membranes which proved to be photoactive with a singlet oxygen quantum yield of 0.43 in ethanol and 0.37 in water. The membranes also proved to be active in the photocatalytic oxidation of 4-chlorophenol in water where the reaction followed second-order kinetics. At 3.24 × 10−4 mol L−1, the photo-oxidation of 4-chlorophenol was observed with a kobs of 35.9 L mol−1 min−1 and a half-life of 86 min.
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Graphene quantum dots anchored onto mercaptopyridine-substituted zinc phthalocyanine-Au@ Ag nanoparticle hybrid: Application as fluorescence “off-on-off” sensor for Hg2+ and biothiols
- Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188194 , vital:44731 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.06.002"
- Description: Novel supramolecular hybrid containing polyethyleneimine-functionalized graphene quantum dots (PEI-GQDs) and mercaptopyridine-substituted zinc phthalocyanine (Pc)-Au@Ag nano-alloys is presented in this study. The designed hybrid was employed as a dual fluorescence nanoprobe for Hg2+ and biothiol detection in aqueous solution using PEI-GQDs as the fluorescence switching signal probe. The dual sensing platform for the analytes detection is firstly, based on the quenching (turn “OFF”) of the PEI-GQDs fluorescence upon π-π interaction or electrostatic attraction with Pc-Au@Ag conjugate. The quenched fluorescence can be switched back to the “ON” mode in the presence of Hg2+ and switched “OFF” again when biothiols are introduced to capture the Hg2+ ion via the formation of the strong metal-thiol bond (Hg-S). The “off-on-off” processes were modulated by different amounts of Hg2+ and biothiols. The nanoprobes were found to be highly stable and selective towards the target analytes in the presence of other amino acids and metal ions. Also, the probes were successfully deployed in the assay of the test analytes in spiked samples.
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- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188194 , vital:44731 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.06.002"
- Description: Novel supramolecular hybrid containing polyethyleneimine-functionalized graphene quantum dots (PEI-GQDs) and mercaptopyridine-substituted zinc phthalocyanine (Pc)-Au@Ag nano-alloys is presented in this study. The designed hybrid was employed as a dual fluorescence nanoprobe for Hg2+ and biothiol detection in aqueous solution using PEI-GQDs as the fluorescence switching signal probe. The dual sensing platform for the analytes detection is firstly, based on the quenching (turn “OFF”) of the PEI-GQDs fluorescence upon π-π interaction or electrostatic attraction with Pc-Au@Ag conjugate. The quenched fluorescence can be switched back to the “ON” mode in the presence of Hg2+ and switched “OFF” again when biothiols are introduced to capture the Hg2+ ion via the formation of the strong metal-thiol bond (Hg-S). The “off-on-off” processes were modulated by different amounts of Hg2+ and biothiols. The nanoprobes were found to be highly stable and selective towards the target analytes in the presence of other amino acids and metal ions. Also, the probes were successfully deployed in the assay of the test analytes in spiked samples.
- Full Text:
Graphene quantum dots coordinated to mercaptopyridine-substituted phthalocyanines: Characterization and application as fluorescence “turn ON” nanoprobes
- Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188293 , vital:44742 , xlink:href="https://doi.org/10.1016/j.saa.2016.11.043"
- Description: This study reports on the design of novel nanoconjugates of graphene quantum dots (GQDs) and tetra or octa-mercaptopyridine-substituted zinc and aluminium phthalocyanines (Pcs) deployed as fluorescence “turn ON” nanoprobes. The phthalocyanines were separately adsorbed onto the planar structure of graphene quantum dots (GQDs) via π-π stacking interaction to form GQDs-mercaptopyridine Pcs nanoconjugates. The quaternized Pc complexes could also interact with the GQDs through electrostatic attraction due to the positive charges on the Pcs ring substituents and the negative charges on the surface of GQDs. The fluorescence emission of the GQDs was quenched upon coordination to the respective Pcs. However, the fluorescence emission was “turned ON” in the presence of Hg2 + employed as a test analyte. The mechanism of the “turn ON” of the GQDs emission in the nanoconjugates is ascribed to the strong affinity of Hg2 + to bind with the bridging sulfur on the Pcs periphery thereby disrupting the π-π stacking interaction between the GQDs and the Pcs with a consequent “turn ON” of the coordinated GQDs' fluorescence.
- Full Text:
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188293 , vital:44742 , xlink:href="https://doi.org/10.1016/j.saa.2016.11.043"
- Description: This study reports on the design of novel nanoconjugates of graphene quantum dots (GQDs) and tetra or octa-mercaptopyridine-substituted zinc and aluminium phthalocyanines (Pcs) deployed as fluorescence “turn ON” nanoprobes. The phthalocyanines were separately adsorbed onto the planar structure of graphene quantum dots (GQDs) via π-π stacking interaction to form GQDs-mercaptopyridine Pcs nanoconjugates. The quaternized Pc complexes could also interact with the GQDs through electrostatic attraction due to the positive charges on the Pcs ring substituents and the negative charges on the surface of GQDs. The fluorescence emission of the GQDs was quenched upon coordination to the respective Pcs. However, the fluorescence emission was “turned ON” in the presence of Hg2 + employed as a test analyte. The mechanism of the “turn ON” of the GQDs emission in the nanoconjugates is ascribed to the strong affinity of Hg2 + to bind with the bridging sulfur on the Pcs periphery thereby disrupting the π-π stacking interaction between the GQDs and the Pcs with a consequent “turn ON” of the coordinated GQDs' fluorescence.
- Full Text:
Graphene quantum dots decorated with maleimide and zinc tetramaleimido-phthalocyanine: Application in the design of “OFF-ON” fluorescence sensors for biothiols
- Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188282 , vital:44741 , xlink:href="https://doi.org/10.1016/j.talanta.2017.01.031"
- Description: The fabrication of maleimide-derivatized graphene quantum dots (M-GQDs) and zinc phthalocyanine (2) as novel sensor probes for the selective detection of biothiols (cysteine, homocysteine or glutathione) through the rapid and specific Michael addition reaction between biothiols and the maleimide-derivatized probes is presented in this study. GQDs directly functionalized with maleimide units (M-GQDs) were synthesized and deployed for biothiols recognition following the principle of Michael addition. M-GQDs probe was found to be highly sensitive and selective towards biothiols detection in the nanomolar range in aqueous solution and at physiological pH (7.0). On the other hand, non-covalent interaction between pristine GQDs and novel zinc tetramaleimido-derivatized phthalocyanine resulted in the quenching of the pristine GQDs fluorescence emission which was switched back to the “ON” mode by Michael addition mechanism in the presence of biothiols. Tested relevant biomolecules did not interfere in the quantitative recognition of the biothiols. The probes showed to be highly sensitive, specific and selective for biothiols sensing in simulated real samples.
- Full Text:
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188282 , vital:44741 , xlink:href="https://doi.org/10.1016/j.talanta.2017.01.031"
- Description: The fabrication of maleimide-derivatized graphene quantum dots (M-GQDs) and zinc phthalocyanine (2) as novel sensor probes for the selective detection of biothiols (cysteine, homocysteine or glutathione) through the rapid and specific Michael addition reaction between biothiols and the maleimide-derivatized probes is presented in this study. GQDs directly functionalized with maleimide units (M-GQDs) were synthesized and deployed for biothiols recognition following the principle of Michael addition. M-GQDs probe was found to be highly sensitive and selective towards biothiols detection in the nanomolar range in aqueous solution and at physiological pH (7.0). On the other hand, non-covalent interaction between pristine GQDs and novel zinc tetramaleimido-derivatized phthalocyanine resulted in the quenching of the pristine GQDs fluorescence emission which was switched back to the “ON” mode by Michael addition mechanism in the presence of biothiols. Tested relevant biomolecules did not interfere in the quantitative recognition of the biothiols. The probes showed to be highly sensitive, specific and selective for biothiols sensing in simulated real samples.
- Full Text:
Halogen substituted A2B type Co (III) triarylcorroles
- Niu, Yingjie, Li, Minzhi, Zhang, Qianchong, Zhu, Weihua, Mack, John, Fomo, Gertrude, Nyokong, Tebello, Liang, Xu
- Authors: Niu, Yingjie , Li, Minzhi , Zhang, Qianchong , Zhu, Weihua , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233048 , vital:50051 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.02.049"
- Description: Seven low symmetry A2B type Co(III)triarylcorroles with electron withdrawing meso-aryl substituents have been synthesized and characterized. A detailed analysis of the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry and spectroelectrochemistry to trends predicted in a series of DFT and TD-DFT calculations. The results demonstrate that Co(III)corroles are highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, there is a marked enhancement in their homogenous catalytic ability when halogen atoms are introduced at the B position, which demonstrates that facile modifying the meso-aryl rings is a effective strategy for developing new HER catalysts. The electrochemical results demonstrate that an unusual two step modulation of HER reactions can be achieved by using singly and doubly electrochemical reduced cobalt triarylcorroles anions.
- Full Text:
- Authors: Niu, Yingjie , Li, Minzhi , Zhang, Qianchong , Zhu, Weihua , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233048 , vital:50051 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.02.049"
- Description: Seven low symmetry A2B type Co(III)triarylcorroles with electron withdrawing meso-aryl substituents have been synthesized and characterized. A detailed analysis of the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry and spectroelectrochemistry to trends predicted in a series of DFT and TD-DFT calculations. The results demonstrate that Co(III)corroles are highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, there is a marked enhancement in their homogenous catalytic ability when halogen atoms are introduced at the B position, which demonstrates that facile modifying the meso-aryl rings is a effective strategy for developing new HER catalysts. The electrochemical results demonstrate that an unusual two step modulation of HER reactions can be achieved by using singly and doubly electrochemical reduced cobalt triarylcorroles anions.
- Full Text:
Highly efficient CCl bond cleavage and unprecedented CC bond cleavage of environmentally toxic DDT through molecular electrochemical catalysis
- Liang, Xu, Huang, Tingting, Li, Minzhi, Mack, John, Wildervanck, Martijn, Nyokong, Tebello, Zhu, Weihua
- Authors: Liang, Xu , Huang, Tingting , Li, Minzhi , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Zhu, Weihua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188921 , vital:44798 , xlink:href="https://doi.org/10.1016/j.apcata.2017.07.026"
- Description: The electrocatalytic properties of a Co(II)octaalkoxyphthalocyanine complex (Co(II)Pc) with eight strongly electron-donating substituents provide the first example of the complete dechlorination of DDT through molecular electrocatalysis, rather than the use of metal electrodes which had been achieved previously. Interaction with a highly nucleophilic [Co(I)Pc]2− species results in rapid cleavage of the C(sp3) Cl, C(sp2) Cl and aromatic C(sp2) Cl bonds. Bis(p-chlorophenyl)methanone (BPCl2) is detected in high yield along with its full dechlorination product, diphenylmethanone (BP) and the conventional C Cl bond cleavage products, due to an unprecedented C C bond cleavage reaction that is followed by the formation of a C−O bond. Theoretical calculations are used to analyze trends in the electronic structure of the Co(II)octaalkoxyphthalocyanine complex that account for the efficiency of the C Cl bond cleavage reactions, and the reaction process and mechanism are analyzed in depth.
- Full Text:
- Authors: Liang, Xu , Huang, Tingting , Li, Minzhi , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Zhu, Weihua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188921 , vital:44798 , xlink:href="https://doi.org/10.1016/j.apcata.2017.07.026"
- Description: The electrocatalytic properties of a Co(II)octaalkoxyphthalocyanine complex (Co(II)Pc) with eight strongly electron-donating substituents provide the first example of the complete dechlorination of DDT through molecular electrocatalysis, rather than the use of metal electrodes which had been achieved previously. Interaction with a highly nucleophilic [Co(I)Pc]2− species results in rapid cleavage of the C(sp3) Cl, C(sp2) Cl and aromatic C(sp2) Cl bonds. Bis(p-chlorophenyl)methanone (BPCl2) is detected in high yield along with its full dechlorination product, diphenylmethanone (BP) and the conventional C Cl bond cleavage products, due to an unprecedented C C bond cleavage reaction that is followed by the formation of a C−O bond. Theoretical calculations are used to analyze trends in the electronic structure of the Co(II)octaalkoxyphthalocyanine complex that account for the efficiency of the C Cl bond cleavage reactions, and the reaction process and mechanism are analyzed in depth.
- Full Text:
Improved nonlinear optical behaviour of ball type indium (III) phthalocyanine linked to glutathione capped nanoparticles
- Nwaji, Njemuwa, Oluwole, David O, Mack, John, Louzada, Marcel, Khene, Samson M, Britton, Jonathan, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Oluwole, David O , Mack, John , Louzada, Marcel , Khene, Samson M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239654 , vital:50752 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.066"
- Description: The synthesis of ball–type indium phthalocyanine (complex 4) and its covalent attachment to glutathione (GSH–) capped (Ag, Au, CdTeSe, CdTeSe/ZnO) nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical behaviour were investigated. We observed a decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield of the nanoconjugates in comparison to complex 4 alone. The reverse saturable absorption was found to be dependent on excited state absorption. The optical limiting threshold ranges from 0.40–0.78 (J/cm2). The nanoconjugate of the complex 4 with GSH–CdTeSe/ZnO (QD1) accounted for the most improved triplet state parameters and nonlinear optical behaviour in comparison to complex 4 and the other nanoconjugates studied in this work.
- Full Text:
- Authors: Nwaji, Njemuwa , Oluwole, David O , Mack, John , Louzada, Marcel , Khene, Samson M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239654 , vital:50752 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.066"
- Description: The synthesis of ball–type indium phthalocyanine (complex 4) and its covalent attachment to glutathione (GSH–) capped (Ag, Au, CdTeSe, CdTeSe/ZnO) nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical behaviour were investigated. We observed a decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield of the nanoconjugates in comparison to complex 4 alone. The reverse saturable absorption was found to be dependent on excited state absorption. The optical limiting threshold ranges from 0.40–0.78 (J/cm2). The nanoconjugate of the complex 4 with GSH–CdTeSe/ZnO (QD1) accounted for the most improved triplet state parameters and nonlinear optical behaviour in comparison to complex 4 and the other nanoconjugates studied in this work.
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Improved photocatalytic degradation of Orange G using hybrid nanofibers
- Ledwaba, Mpho, Masilela, Nkosiphile, Nyokong, Tebello, Antunes, Edith M
- Authors: Ledwaba, Mpho , Masilela, Nkosiphile , Nyokong, Tebello , Antunes, Edith M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239632 , vital:50750 , xlink:href="https://doi.org/10.1007/s11051-017-3853-3"
- Description: Functionalised electrospun polyamide-6 (PA-6) nanofibres incorporating gadolinium oxide nanoparticles conjugated to zinc tetracarboxyphenoxy phthalocyanine (ZnTCPPc) as the sensitizer were prepared for the photocatalytic degradation of Orange G. Fibres incorporating the phthalocyanine alone or a mixture of the nanoparticles and phthalocyanine were also generated. The singlet oxygen-generating ability of the sensitizer was shown to be maintained within the fibre mat, with the singlet oxygen quantum yields increasing upon incorporation of the magnetic nanoparticles. Consequently, the rate of the photodegradation of Orange G was observed to increase with an increase in singlet oxygen quantum yield. A reduction in the half-lives for the functionalised nanofibres was recorded in the presence of the magnetic nanoparticles, indicating an improvement in the efficiency of the degradation process.
- Full Text:
- Authors: Ledwaba, Mpho , Masilela, Nkosiphile , Nyokong, Tebello , Antunes, Edith M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239632 , vital:50750 , xlink:href="https://doi.org/10.1007/s11051-017-3853-3"
- Description: Functionalised electrospun polyamide-6 (PA-6) nanofibres incorporating gadolinium oxide nanoparticles conjugated to zinc tetracarboxyphenoxy phthalocyanine (ZnTCPPc) as the sensitizer were prepared for the photocatalytic degradation of Orange G. Fibres incorporating the phthalocyanine alone or a mixture of the nanoparticles and phthalocyanine were also generated. The singlet oxygen-generating ability of the sensitizer was shown to be maintained within the fibre mat, with the singlet oxygen quantum yields increasing upon incorporation of the magnetic nanoparticles. Consequently, the rate of the photodegradation of Orange G was observed to increase with an increase in singlet oxygen quantum yield. A reduction in the half-lives for the functionalised nanofibres was recorded in the presence of the magnetic nanoparticles, indicating an improvement in the efficiency of the degradation process.
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Improving singlet oxygen generating abilities of phthalocyanines
- Nwahara, Nnamdi, Britton, Jonathan, Nyokong, Tebello
- Authors: Nwahara, Nnamdi , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188943 , vital:44800 , xlink:href="https://doi.org/10.1080/00958972.2017.1313975"
- Description: Glutathione-capped graphene quantum dots (GQDs@GSH) were covalently linked to folic acid (FA). Aluminum tetrasulfonated phthalocyanine (ClAlTSPc) was then adsorbed on the GQDs@GSH-FA conjugate to form GQDs@GSH-FA/ClAlTSPc or on GQDs@GSH and pristine GQDs alone to form GQDs@GSH/ClAlTSPc and GQDs/ClAlTSPc, respectively. We report for the first time on the photophysicochemical behavior of the resulting nanoconjugates. The fluorescence quantum yields of pristine GQDs, GQDS@GSH, or GQDs@GSH-FA conjugate were quenched upon non-covalent interaction (π–π) with ClAlTSPc. There was an increase in triplet quantum yields from 0.38 for ClAlTSPc alone to 0.60, 0.75, and 0.73 when ClAlTSPc was linked to pristine GQDs, GQDs@GSH, and GQDs@GSH-FA, respectively. The singlet oxygen quantum yields also increased from 0.37 for ClAlTSPc alone to 0.42 (for ClALTSPc with pristine GQDs), 0.52 (for ClAlTSPc with GQDs@GSH), and 0.54 (for ClAlTSPc with GQDs@GSH-FA). Thus, the present work may lead to a new generation of carbon-based nanomaterial photodynamic therapy agents with overall performance superior to conventional agents in terms of singlet oxygen generation, water dispersibility, and biocompatibility.
- Full Text:
- Authors: Nwahara, Nnamdi , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188943 , vital:44800 , xlink:href="https://doi.org/10.1080/00958972.2017.1313975"
- Description: Glutathione-capped graphene quantum dots (GQDs@GSH) were covalently linked to folic acid (FA). Aluminum tetrasulfonated phthalocyanine (ClAlTSPc) was then adsorbed on the GQDs@GSH-FA conjugate to form GQDs@GSH-FA/ClAlTSPc or on GQDs@GSH and pristine GQDs alone to form GQDs@GSH/ClAlTSPc and GQDs/ClAlTSPc, respectively. We report for the first time on the photophysicochemical behavior of the resulting nanoconjugates. The fluorescence quantum yields of pristine GQDs, GQDS@GSH, or GQDs@GSH-FA conjugate were quenched upon non-covalent interaction (π–π) with ClAlTSPc. There was an increase in triplet quantum yields from 0.38 for ClAlTSPc alone to 0.60, 0.75, and 0.73 when ClAlTSPc was linked to pristine GQDs, GQDs@GSH, and GQDs@GSH-FA, respectively. The singlet oxygen quantum yields also increased from 0.37 for ClAlTSPc alone to 0.42 (for ClALTSPc with pristine GQDs), 0.52 (for ClAlTSPc with GQDs@GSH), and 0.54 (for ClAlTSPc with GQDs@GSH-FA). Thus, the present work may lead to a new generation of carbon-based nanomaterial photodynamic therapy agents with overall performance superior to conventional agents in terms of singlet oxygen generation, water dispersibility, and biocompatibility.
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Investigation of photophysicochemical properties of zinc phthalocyanines conjugated to metallic nanoparticles
- Dube, Edith, Nwaji, Njemuwa, Oluwole, David O, Mack, John, Nyokong, Tebello
- Authors: Dube, Edith , Nwaji, Njemuwa , Oluwole, David O , Mack, John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233425 , vital:50089 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.09.020"
- Description: The syntheses of zinc(II) tetra–[3–(4–phenoxy) (propanoic acid) phthalocyanine] (2) and zinc(II) mono–[3–(4–phenoxy) (propanoic acid) phthalocyanine (3) are reported in this work. Compounds 2 and 3 were covalently linked to glutathione capped silver (AgNPs–GSH), gold (AuNPs–GSH) and silver-gold alloy (Ag3Au1NPs–GSH) nanoparticles (NPs) via an amide bond formation to afford the conjugates: 2–AgNPs–GSH, 3–AgNPs–GSH, 2–AuNPs–GSH, 3–AuNPs–GSH, 2-Ag3Au1NPs–GSH and 3-Ag3Au1NPs–GSH. The photophysicochemical behaviours of the compounds and their conjugates with NPs were assessed in solution. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet quantum yields in comparison to the compounds. Accordingly, the AgNPs and AuNPs conjugates with the compounds afforded high singlet quantum yields. On the contrary, the conjugates of the alloy afforded decreased singlet quantum yields probably due to the screening effect. The compounds and their conjugates with NPs could serve as a viable and efficacious photosensitizer for photodynamic therapy.
- Full Text:
- Authors: Dube, Edith , Nwaji, Njemuwa , Oluwole, David O , Mack, John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233425 , vital:50089 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.09.020"
- Description: The syntheses of zinc(II) tetra–[3–(4–phenoxy) (propanoic acid) phthalocyanine] (2) and zinc(II) mono–[3–(4–phenoxy) (propanoic acid) phthalocyanine (3) are reported in this work. Compounds 2 and 3 were covalently linked to glutathione capped silver (AgNPs–GSH), gold (AuNPs–GSH) and silver-gold alloy (Ag3Au1NPs–GSH) nanoparticles (NPs) via an amide bond formation to afford the conjugates: 2–AgNPs–GSH, 3–AgNPs–GSH, 2–AuNPs–GSH, 3–AuNPs–GSH, 2-Ag3Au1NPs–GSH and 3-Ag3Au1NPs–GSH. The photophysicochemical behaviours of the compounds and their conjugates with NPs were assessed in solution. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet quantum yields in comparison to the compounds. Accordingly, the AgNPs and AuNPs conjugates with the compounds afforded high singlet quantum yields. On the contrary, the conjugates of the alloy afforded decreased singlet quantum yields probably due to the screening effect. The compounds and their conjugates with NPs could serve as a viable and efficacious photosensitizer for photodynamic therapy.
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Laser induced photodegradation of Orange G using phthalocyanine–cobalt ferrite magnetic nanoparticle conjugates electrospun in polystyrene nanofibers
- Mapukata, Sivuyisiwe, Chindeka, Francis, Sekhosana, Kutloano E, Nyokong, Tebello
- Authors: Mapukata, Sivuyisiwe , Chindeka, Francis , Sekhosana, Kutloano E , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188617 , vital:44769 , xlink:href="https://doi.org/10.1016/j.mcat.2017.06.028"
- Description: Conjugates of zinc tetracarboxyphenoxy phthalocyanine (ZnTCPPc) and zinc tetraaminophenoxy phthalocyanine (ZnTAPPc) with amine and carboxyl functionalised cobalt ferrite magnetic nanoparticles (CoFe2O4 MNPs), respectively were electrospun into polystyrene (PS) fibers. The resulting composites; ZnTCPPc-CoFe2O4/PS and ZnTAPPc-CoFe2O4/PS were compared based on their photophysical properties and photocatalytic efficiencies in degrading Orange G (OG) using laser as the photoexcitation source. The photocatalytic efficiencies of ZnTCPPc-CoFe2O4/PS and ZnTAPPc-CoFe2O4/PS were compared based on them having different lengths in the linkage chains between the Pcs and CoFe2O4 MNPs and different sizes. Covalent linkage of the Pcs to the CoFe2O4 MNPs enhanced the singlet oxygen and reactive oxygen species (ROS) production of the Pcs and CoFe2O4, respectively hence ZnTCPPc-CoFe2O4/PS and ZnTAPPc-CoFe2O4/PS were found to be more effective photocatalysts than their respective Pcs and CoFe2O4 MNPs. Moreover, the kinetic analyses of the photodecomposition of OG showed that the degradation was in agreement with both pseudo-first order kinetics and followed the Langmuir–Hinshelwood model.
- Full Text:
- Authors: Mapukata, Sivuyisiwe , Chindeka, Francis , Sekhosana, Kutloano E , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188617 , vital:44769 , xlink:href="https://doi.org/10.1016/j.mcat.2017.06.028"
- Description: Conjugates of zinc tetracarboxyphenoxy phthalocyanine (ZnTCPPc) and zinc tetraaminophenoxy phthalocyanine (ZnTAPPc) with amine and carboxyl functionalised cobalt ferrite magnetic nanoparticles (CoFe2O4 MNPs), respectively were electrospun into polystyrene (PS) fibers. The resulting composites; ZnTCPPc-CoFe2O4/PS and ZnTAPPc-CoFe2O4/PS were compared based on their photophysical properties and photocatalytic efficiencies in degrading Orange G (OG) using laser as the photoexcitation source. The photocatalytic efficiencies of ZnTCPPc-CoFe2O4/PS and ZnTAPPc-CoFe2O4/PS were compared based on them having different lengths in the linkage chains between the Pcs and CoFe2O4 MNPs and different sizes. Covalent linkage of the Pcs to the CoFe2O4 MNPs enhanced the singlet oxygen and reactive oxygen species (ROS) production of the Pcs and CoFe2O4, respectively hence ZnTCPPc-CoFe2O4/PS and ZnTAPPc-CoFe2O4/PS were found to be more effective photocatalysts than their respective Pcs and CoFe2O4 MNPs. Moreover, the kinetic analyses of the photodecomposition of OG showed that the degradation was in agreement with both pseudo-first order kinetics and followed the Langmuir–Hinshelwood model.
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Nanocomposites of sulphur-nitrogen co-doped graphene oxide nanosheets and cobalt mono carboxyphenoxy phthalocyanines for facile electrocatalysis
- Shumba, Munyaradzi, Centane, Sixolile, Chindeka, Francis, Nyokong, Tebello
- Authors: Shumba, Munyaradzi , Centane, Sixolile , Chindeka, Francis , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239665 , vital:50753 , xlink:href="https://doi.org/10.1016/j.jelechem.2017.03.006"
- Description: Nanocomposites consisting of cobalt mono carboxyphenoxy phthalocyanine (CoMCPhPc) either covalently linked to graphene oxide nanosheets (GONS), sulphur doped graphene oxide nanosheets (SDGONS), nitrogen doped graphene oxide nanosheets (NDGONS) or sulphur/nitrogen co-doped graphene oxide nanosheets (SNDGONS) or sequentially added were used to modify glassy carbon electrode. The modified electrodes were characterised using several techniques: voltammetry, X-ray photon spectroscopy and scanning electron spectroscopy before testing their activity on the detection of hydrogen peroxide at pH 7. The presence of SNDGONS had a significant improvement on the currents as compared to CoMCPhPc modification alone in both sequentially added or covalently linked to MPcs. CoMCPhPc-SNDGONS(seq)-GCE and CoMCPhPc-SDGONS(linked)-GCE resulted in impressive limits of detection and catalytic rate constant values of 1.58 nM and 5.44 nM, 3.07 × 105 M−1 s−1 and 3.01 × 103 M−1 s−1 respectively. Gibbs energy value was determined to be −21.22 kJ mol−1 for CoMCPhPc-SNDGONS(linked)-GCE indicative of a facile spontaneous electroreduction reaction on the surface of this electrode.
- Full Text:
- Authors: Shumba, Munyaradzi , Centane, Sixolile , Chindeka, Francis , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239665 , vital:50753 , xlink:href="https://doi.org/10.1016/j.jelechem.2017.03.006"
- Description: Nanocomposites consisting of cobalt mono carboxyphenoxy phthalocyanine (CoMCPhPc) either covalently linked to graphene oxide nanosheets (GONS), sulphur doped graphene oxide nanosheets (SDGONS), nitrogen doped graphene oxide nanosheets (NDGONS) or sulphur/nitrogen co-doped graphene oxide nanosheets (SNDGONS) or sequentially added were used to modify glassy carbon electrode. The modified electrodes were characterised using several techniques: voltammetry, X-ray photon spectroscopy and scanning electron spectroscopy before testing their activity on the detection of hydrogen peroxide at pH 7. The presence of SNDGONS had a significant improvement on the currents as compared to CoMCPhPc modification alone in both sequentially added or covalently linked to MPcs. CoMCPhPc-SNDGONS(seq)-GCE and CoMCPhPc-SDGONS(linked)-GCE resulted in impressive limits of detection and catalytic rate constant values of 1.58 nM and 5.44 nM, 3.07 × 105 M−1 s−1 and 3.01 × 103 M−1 s−1 respectively. Gibbs energy value was determined to be −21.22 kJ mol−1 for CoMCPhPc-SNDGONS(linked)-GCE indicative of a facile spontaneous electroreduction reaction on the surface of this electrode.
- Full Text: