Assessing the electrocatalytic activity of a localized push-pull system in cobalt phthalocyanine/graphene quantum dot hybrids
- Nkhahle, Reitumetse, Nyokong, Tebello
- Authors: Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229909 , vital:49722 , xlink:href="https://doi.org/10.1016/j.matchemphys.2022.125842"
- Description: In this study, two cobalt phthalocyanines (asymmetric complex 1) and symmetric (complex 2) were synthesized and conjugated to nitrogen-doped graphene quantum dots (NGQDs) through covalent and non-covalent means to create Co phthalocyanine (CoPc)-NGQDs hybrid systems. The CoPcs and conjugates were applied as electrode modifiers on a glassy carbon electrode in the electrochemical sensing of nitrite. Of the CoPcs alone, complex 1 performed better than complex 2 regarding the limits of detection (LoD) recorded (5.74 μM for 1 and 15.1 μM for 2). Regarding the conjugates/nanocomposites, the π-π stacked conjugate derived from complex 2 (2πNGQDs) demonstrated highly favourable electrochemical potential with an LoD value of 0.70 μM. The nanocomposites fashioned from complex 1 were marred by a reduced loading which rendered the conjugates poor electrochemical sensors. These observations however do not disqualify GQDs as complementary nanomaterials to phthalocyanines but rather shed light on seeking alternative routes to increasing the Pc loading in conjugates (more so in π-π stacked conjugates).
- Full Text:
- Date Issued: 2022
- Authors: Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229909 , vital:49722 , xlink:href="https://doi.org/10.1016/j.matchemphys.2022.125842"
- Description: In this study, two cobalt phthalocyanines (asymmetric complex 1) and symmetric (complex 2) were synthesized and conjugated to nitrogen-doped graphene quantum dots (NGQDs) through covalent and non-covalent means to create Co phthalocyanine (CoPc)-NGQDs hybrid systems. The CoPcs and conjugates were applied as electrode modifiers on a glassy carbon electrode in the electrochemical sensing of nitrite. Of the CoPcs alone, complex 1 performed better than complex 2 regarding the limits of detection (LoD) recorded (5.74 μM for 1 and 15.1 μM for 2). Regarding the conjugates/nanocomposites, the π-π stacked conjugate derived from complex 2 (2πNGQDs) demonstrated highly favourable electrochemical potential with an LoD value of 0.70 μM. The nanocomposites fashioned from complex 1 were marred by a reduced loading which rendered the conjugates poor electrochemical sensors. These observations however do not disqualify GQDs as complementary nanomaterials to phthalocyanines but rather shed light on seeking alternative routes to increasing the Pc loading in conjugates (more so in π-π stacked conjugates).
- Full Text:
- Date Issued: 2022
The synergistic effects of coupling Au nanoparticles with an alkynyl Co (II) phthalocyanine on the detection of prostate specific antigen
- Nxele, Siphesihle Robin, Nkhahle, Reitumetse, Nyokong, Tebello
- Authors: Nxele, Siphesihle Robin , Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230232 , vital:49756 , xlink:href="https://doi.org/10.1016/j.talanta.2021.122948"
- Description: Prostate specific antigen (PSA) aptasensors are fabricated using a novel asymmetrically substituted Co phthalocyanine (CoPc), gold nanoparticles (AuNPs) and PSA-specific antigen. The fabricated aptasensors are: GCE-AuNPs-Aptamer, GCE@CoPc-Aptamer and GCE-AuNPs@CoPc-Aptamer (GCE = glassy carbon electrode). The fabricated sensors are characterized at each modification step to monitor the changes occurring at the sensor surface. Concentration studies were carried out using differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) to determine detection limits. All the fabricated aptasensors were found to be highly specific and selective but the GCE-AuNPs@CoPc-Aptamer nanoconjugate performed the best. The aptasensors were also tested in spiked serum samples and detection limits, as well as % recoveries were determined. The results obtained showed that the GCE-AuNPs@CoPc-Aptamer has the potential to be used for clinical studies as the results agree with those obtained for detection of PSA in buffer.
- Full Text:
- Date Issued: 2022
- Authors: Nxele, Siphesihle Robin , Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/230232 , vital:49756 , xlink:href="https://doi.org/10.1016/j.talanta.2021.122948"
- Description: Prostate specific antigen (PSA) aptasensors are fabricated using a novel asymmetrically substituted Co phthalocyanine (CoPc), gold nanoparticles (AuNPs) and PSA-specific antigen. The fabricated aptasensors are: GCE-AuNPs-Aptamer, GCE@CoPc-Aptamer and GCE-AuNPs@CoPc-Aptamer (GCE = glassy carbon electrode). The fabricated sensors are characterized at each modification step to monitor the changes occurring at the sensor surface. Concentration studies were carried out using differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) to determine detection limits. All the fabricated aptasensors were found to be highly specific and selective but the GCE-AuNPs@CoPc-Aptamer nanoconjugate performed the best. The aptasensors were also tested in spiked serum samples and detection limits, as well as % recoveries were determined. The results obtained showed that the GCE-AuNPs@CoPc-Aptamer has the potential to be used for clinical studies as the results agree with those obtained for detection of PSA in buffer.
- Full Text:
- Date Issued: 2022
Creating the Ideal Push-Pull System for Electrocatalysis A Comparative Study on Symmetrical and Asymmetrical Cardanol-based Cobalt Phthalocyanines
- Nkhahle, Reitumetse, Nyokong, Tebello
- Authors: Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/${Handle} , vital:44452 , xlink:href="https://doi.org/10.1002/elan.202060019"
- Description: A symmetrical cardanol-based cobalt phthalocyanine (Pc) along with its asymmetrical acid-based derivatives were synthesized and applied in the electrocatalysis of hydrazine. Despite the inhibition of electron movement by the bulky cardanol-based substituent throughout the series of molecules, an ideal combination of substituents was established in GCE-3 (2,9,16-tris(3- pentadecylphenoxy)-23-mono propionic acid phthalocyanato cobalt (II)) where a limit of detection (LoD) value of 5.10 μM (signal to noise ratio=5) was recorded for the detection of hydrazine. The results obtained serve as an illustration that the combination of electron-donating and electron-withdrawing substituents has a significant influence on the complete functioning of the phthalocyanine molecule(s) being investigated.
- Full Text:
- Date Issued: 2021
- Authors: Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/${Handle} , vital:44452 , xlink:href="https://doi.org/10.1002/elan.202060019"
- Description: A symmetrical cardanol-based cobalt phthalocyanine (Pc) along with its asymmetrical acid-based derivatives were synthesized and applied in the electrocatalysis of hydrazine. Despite the inhibition of electron movement by the bulky cardanol-based substituent throughout the series of molecules, an ideal combination of substituents was established in GCE-3 (2,9,16-tris(3- pentadecylphenoxy)-23-mono propionic acid phthalocyanato cobalt (II)) where a limit of detection (LoD) value of 5.10 μM (signal to noise ratio=5) was recorded for the detection of hydrazine. The results obtained serve as an illustration that the combination of electron-donating and electron-withdrawing substituents has a significant influence on the complete functioning of the phthalocyanine molecule(s) being investigated.
- Full Text:
- Date Issued: 2021
Electrochemical Detection of Nitrite on Electrodes Modified by Click Chemistry Using Asymmetrical Co (II) and Mn (III) Phthalocyanines Containing Push-Pull Substituents
- Nkhahle, Reitumetse, Nyokong, Tebello
- Authors: Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231425 , vital:49886 , xlink:href="https://doi.org/10.1149/1945-7111/ac377f"
- Description: The more conventional route to synthesizing asymmetric push-pull phthalocyanines (Pcs) involves pairing electron-donating substituents with electron-withdrawing groups in either an A3B or AB3 manner. In this work, a push-pull system fashioned from a substituent bearing different functional groups was created. Symmetric and asymmetric cobalt and manganese Pcs in which acetaminophen was the dominant substituent were synthesized where the asymmetric analogues bore an alkyne-terminated substituent. These complexes were applied as sensors towards the electro-oxidation of nitrite. In addition to comparing the asymmetric Pcs to the symmetric counterparts, an assessment on the different central metals as well as the method of electrode modification was made. From the studies performed, the results showed that the manganese complexes are generally better suited (more so when clicked on to the electrode) in the electrocatalysis of nitrite with a limit of detection and a catalytic rate values of 2.15 μM and 6.91 × 106 s−1 M−1 being recorded for the asymmetric MnPc.
- Full Text:
- Date Issued: 2021
- Authors: Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/231425 , vital:49886 , xlink:href="https://doi.org/10.1149/1945-7111/ac377f"
- Description: The more conventional route to synthesizing asymmetric push-pull phthalocyanines (Pcs) involves pairing electron-donating substituents with electron-withdrawing groups in either an A3B or AB3 manner. In this work, a push-pull system fashioned from a substituent bearing different functional groups was created. Symmetric and asymmetric cobalt and manganese Pcs in which acetaminophen was the dominant substituent were synthesized where the asymmetric analogues bore an alkyne-terminated substituent. These complexes were applied as sensors towards the electro-oxidation of nitrite. In addition to comparing the asymmetric Pcs to the symmetric counterparts, an assessment on the different central metals as well as the method of electrode modification was made. From the studies performed, the results showed that the manganese complexes are generally better suited (more so when clicked on to the electrode) in the electrocatalysis of nitrite with a limit of detection and a catalytic rate values of 2.15 μM and 6.91 × 106 s−1 M−1 being recorded for the asymmetric MnPc.
- Full Text:
- Date Issued: 2021
Analytical Detection and Electrocatalysis of Paracetamol in Aqueous Media Using Rare‐Earth Double‐Decker Phthalocyaninato Chelates as Electrochemically Active Materials
- Sekhosana, Kutloana E, Nkhahle, Reitumetse, Nyokong, Tebello
- Authors: Sekhosana, Kutloana E , Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190840 , vital:45033 , xlink:href="https://doi.org/10.1002/slct.202002268"
- Description: Paracetamol (PA), being an analgesic and antipyretic medicine, can cause fatal hepatotoxicity and nephrotoxicity when overdosed. It is therefore important to develop electrochemical sensors that can monitor and quantify it in aquatic environments. In this study, rare-earth sandwich-type phthalocyaninato chelates based on neodymium (1 a) and samarium (1 b) were employed as electrocatalysts to modify glassy carbon electrodes (GCE) for the first time. It was found that 1 a-modified GCE (herein referred to as 1 a-GCE) is less conductive than 1 b-modified counterpart (1 b-GCE). A larger rate constant was also obtained for 1 b-GCE. It was established that a faster oxidation rate efficiency was responsible for lower limit of detection value obtained for 1 b-GCE as compared to 1 a-GCE.
- Full Text:
- Date Issued: 2020
- Authors: Sekhosana, Kutloana E , Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190840 , vital:45033 , xlink:href="https://doi.org/10.1002/slct.202002268"
- Description: Paracetamol (PA), being an analgesic and antipyretic medicine, can cause fatal hepatotoxicity and nephrotoxicity when overdosed. It is therefore important to develop electrochemical sensors that can monitor and quantify it in aquatic environments. In this study, rare-earth sandwich-type phthalocyaninato chelates based on neodymium (1 a) and samarium (1 b) were employed as electrocatalysts to modify glassy carbon electrodes (GCE) for the first time. It was found that 1 a-modified GCE (herein referred to as 1 a-GCE) is less conductive than 1 b-modified counterpart (1 b-GCE). A larger rate constant was also obtained for 1 b-GCE. It was established that a faster oxidation rate efficiency was responsible for lower limit of detection value obtained for 1 b-GCE as compared to 1 a-GCE.
- Full Text:
- Date Issued: 2020
Electrocatalytic Activity of Asymmetrical Cobalt Phthalocyanines in the Presence of N Doped Graphene Quantum Dots: The Push-pull Effects of Substituents
- Nkhahle, Reitumetse, Sekhosana, Kutloano E, Centane, Sixolile, Nyokong, Tebello
- Authors: Nkhahle, Reitumetse , Sekhosana, Kutloano E , Centane, Sixolile , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186904 , vital:44546 , xlink:href="https://doi.org/10.1002/elan.201800837"
- Description: A series of Co phthalocyanine (CoPc) derivatives and their respective nitrogen doped graphene quantum dot conjugates were used as catalysts towards the electrooxidation of hydrazine. Using a glassy carbon electrode as a support for the electrocatalysts, through cyclic voltammetry and chronoamperometry, the effects of combining the CoPcs with the nitrogen doped graphene quantum dots (NGQDs) were studied. The general observations made were that the NGQDs improve the catalytic activity of the CoPcs in both the p-p stacked and covalently linked conjugates by increasing the sensitivities and lowering the limits of detection with values as low as 0.43 mM being recorded.
- Full Text:
- Date Issued: 2019
- Authors: Nkhahle, Reitumetse , Sekhosana, Kutloano E , Centane, Sixolile , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186904 , vital:44546 , xlink:href="https://doi.org/10.1002/elan.201800837"
- Description: A series of Co phthalocyanine (CoPc) derivatives and their respective nitrogen doped graphene quantum dot conjugates were used as catalysts towards the electrooxidation of hydrazine. Using a glassy carbon electrode as a support for the electrocatalysts, through cyclic voltammetry and chronoamperometry, the effects of combining the CoPcs with the nitrogen doped graphene quantum dots (NGQDs) were studied. The general observations made were that the NGQDs improve the catalytic activity of the CoPcs in both the p-p stacked and covalently linked conjugates by increasing the sensitivities and lowering the limits of detection with values as low as 0.43 mM being recorded.
- Full Text:
- Date Issued: 2019
Synthesis and photophysical properties of BODIPY-decorated graphene quantum dot–phthalocyanine conjugates
- Nwahara, Nnamdi, Nkhahle, Reitumetse, Ngoy, Bokolombe P, Mack, John, Nyokong, Tebello
- Authors: Nwahara, Nnamdi , Nkhahle, Reitumetse , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233409 , vital:50088 , xlink:href="https://doi.org/10.1039/C8NJ00758F"
- Description: This work reports on the synthesis and characterisation of novel supramolecular hybrids containing BODIPY-decorated graphene quantum dots (BODIPY@GQDs) and zinc phthalocyanine. Graphene quantum dots (GQDs) were functionalized with L-glutathione (GSH) in order to assist coupling to the BODIPY dye. {2,9(10)16(17)23(24)-Tetrakis-[3-(diethylamino)phenoxy]phthalocyaninato}zinc(II) (1) was immobilized via π–π stacking interaction on the BODIPY-decorated GQDs and pristine GQDs to form the supramolecular hybrids 1-BODIPY@GQDs and 1-GQDs, respectively. The photophysical and photochemical properties of these conjugates were investigated. Energy transfer occurred from the (i) GQDs to BODIPY, (ii) GQDs to 1, and (iii) BODIPY@GQDs to 1via fluorescence resonance energy transfer (FRET). The highest FRET efficiency was observed for the BODIPY@GQDs (0.93). The introduction of the BODIPY core to the GQD structure resulted in higher triplet, and singlet oxygen quantum yields for the resultant Pc/GQD hybrid (1-BODIPY@GQDs). The zeta potential values obtained imply a high colloidal stability for the supramolecular hybrids. The results suggest that such hybrids may be applied in fields such as photodynamic therapy (PDT), where a high singlet oxygen quantum yield is desired.
- Full Text:
- Date Issued: 2018
- Authors: Nwahara, Nnamdi , Nkhahle, Reitumetse , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233409 , vital:50088 , xlink:href="https://doi.org/10.1039/C8NJ00758F"
- Description: This work reports on the synthesis and characterisation of novel supramolecular hybrids containing BODIPY-decorated graphene quantum dots (BODIPY@GQDs) and zinc phthalocyanine. Graphene quantum dots (GQDs) were functionalized with L-glutathione (GSH) in order to assist coupling to the BODIPY dye. {2,9(10)16(17)23(24)-Tetrakis-[3-(diethylamino)phenoxy]phthalocyaninato}zinc(II) (1) was immobilized via π–π stacking interaction on the BODIPY-decorated GQDs and pristine GQDs to form the supramolecular hybrids 1-BODIPY@GQDs and 1-GQDs, respectively. The photophysical and photochemical properties of these conjugates were investigated. Energy transfer occurred from the (i) GQDs to BODIPY, (ii) GQDs to 1, and (iii) BODIPY@GQDs to 1via fluorescence resonance energy transfer (FRET). The highest FRET efficiency was observed for the BODIPY@GQDs (0.93). The introduction of the BODIPY core to the GQD structure resulted in higher triplet, and singlet oxygen quantum yields for the resultant Pc/GQD hybrid (1-BODIPY@GQDs). The zeta potential values obtained imply a high colloidal stability for the supramolecular hybrids. The results suggest that such hybrids may be applied in fields such as photodynamic therapy (PDT), where a high singlet oxygen quantum yield is desired.
- Full Text:
- Date Issued: 2018
The Primary Demonstration of Exciton Coupling Effects on Optical Limiting Properties of Blue Double-Decker Lanthanide Phthalocyanine Salts
- Sekhosana, Kutloano E, Nkhahle, Reitumetse, Nyokong, Tebello
- Authors: Sekhosana, Kutloano E , Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234614 , vital:50213 , xlink:href="https://doi.org/10.1002/slct.201800597"
- Description: In this manuscript, novel green and blue sandwich-type rare-earth phthalocyanines (LnPc2) are presented. This parent green LnPc2 complex is named bis-{2(3),9(10),16(17),23(24)-tetra(4-tert-buylphenoxy) phthalocyaninato} neodymium (III) (2) and modified into blue LnPc2 complexes (3), (4) and (5) based on hexadecyltrimethylammonium ion, mononeodymium(III) diacetate and monodysprosium(III) diacetate as counter ions, respectively. These stable blue lanthanide Pc salts are highly soluble in many organic and inorganic solvents. All complexes 2, 3, 4 and 5 were studied for optical limiting for the first time using Z-scan at nanosecond regime in the visible absorption spectral wavelength (532 nm). Our studies reveal the advantage of exciton coupling in blue sandwich-type rare-earth phthalocyanines over the π-radicals (characterized by blue valence at 485 nm) in the green counterpart which are in resonance with the 532 nm wavelength for optical limiting application. Large singlet ground state to excited state absorption cross section ratios were found, particularly for complex 5 in comparison to that of complex 2.
- Full Text:
- Date Issued: 2018
- Authors: Sekhosana, Kutloano E , Nkhahle, Reitumetse , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234614 , vital:50213 , xlink:href="https://doi.org/10.1002/slct.201800597"
- Description: In this manuscript, novel green and blue sandwich-type rare-earth phthalocyanines (LnPc2) are presented. This parent green LnPc2 complex is named bis-{2(3),9(10),16(17),23(24)-tetra(4-tert-buylphenoxy) phthalocyaninato} neodymium (III) (2) and modified into blue LnPc2 complexes (3), (4) and (5) based on hexadecyltrimethylammonium ion, mononeodymium(III) diacetate and monodysprosium(III) diacetate as counter ions, respectively. These stable blue lanthanide Pc salts are highly soluble in many organic and inorganic solvents. All complexes 2, 3, 4 and 5 were studied for optical limiting for the first time using Z-scan at nanosecond regime in the visible absorption spectral wavelength (532 nm). Our studies reveal the advantage of exciton coupling in blue sandwich-type rare-earth phthalocyanines over the π-radicals (characterized by blue valence at 485 nm) in the green counterpart which are in resonance with the 532 nm wavelength for optical limiting application. Large singlet ground state to excited state absorption cross section ratios were found, particularly for complex 5 in comparison to that of complex 2.
- Full Text:
- Date Issued: 2018
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