(Ferrocenylpyrazolyl) zinc (II) benzoates as catalysts for the ring opening polymerization of ε-caprolactone
- Obuah, Collins, Lochee, Yemanlall, Jordaan, Johan H L, Otto, Daniel P, Nyokong, Tebello, Darkwa, James
- Authors: Obuah, Collins , Lochee, Yemanlall , Jordaan, Johan H L , Otto, Daniel P , Nyokong, Tebello , Darkwa, James
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189515 , vital:44853 , xlink:href="https://doi.org/10.1016/j.poly.2015.02.007"
- Description: The reaction of Zn(OAc)2 and C6H5COOH or 3,5-NO2-C6H3COOH with 3-ferrocenylpyrazolyl-methylenepyridine (L1), 3-ferrocenyl-5-methylpyrazolyl-methylenepyridine (L2), 3-ferrocenylpyrazolyl-ethylamine (L3) and 3-ferrocenyl-5-pyrazolyl-ethylamine (L4) afford the corresponding complexes [Zn(C6H5COO)2(L1)] (1), [Zn(C6H5COO)2(L2)] (2), [Zn(3,5-NO2-C6H3COO)2(L1)] (3), [Zn(3,5-NO2-C6H3 COO)2(L2)] (4), [Zn(C6H5COO)2(L3)] (5), [Zn(C6H5COO)2(L4)] (6), [Zn(3,5-NO2-C6H3COO)2(L3)] (7) and [Zn(3,5-NO2-C6H3COO)2(L4)] (8). These complexes behave as catalysts for the ring opening polymerization of e-caprolactone to produce polymers with molecular weight that range from 1480 to 7080 g mol1 and exhibited moderate to broad PDIs. Evidence of these complexes acting as catalysts was obtained from both the polymerization data and kinetic studies. The polymerization data show that variation of the [CL]/[C] from 100 to 800 produced PCL with relatively the same molecular weight indicative of a catalyst behavior. The appearance of induction period in kinetic plots strengthens the fact that these complexes are catalysts rather than initiators. MALDI-TOF MS and 1 H NMR data show di-hydroxy end groups, which support the coordination mechanism rather than insertion mechanism. To understand the broad PDIs obtained for some of the polymer, the electronic properties of the zinc complexes were investigated using cyclic voltammetry. The results show that the zinc complexes containing amine based ligands are highly electrophilic therefore making them unstable, hence the broad PDIs observed for zinc complexes containing amine based ligands. Among the eight complexes investigated, complex 7 is the most active catalyst with kp value of 1.18 107 h1 mol1 at 110 C.
- Full Text:
- Date Issued: 2015
- Authors: Obuah, Collins , Lochee, Yemanlall , Jordaan, Johan H L , Otto, Daniel P , Nyokong, Tebello , Darkwa, James
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189515 , vital:44853 , xlink:href="https://doi.org/10.1016/j.poly.2015.02.007"
- Description: The reaction of Zn(OAc)2 and C6H5COOH or 3,5-NO2-C6H3COOH with 3-ferrocenylpyrazolyl-methylenepyridine (L1), 3-ferrocenyl-5-methylpyrazolyl-methylenepyridine (L2), 3-ferrocenylpyrazolyl-ethylamine (L3) and 3-ferrocenyl-5-pyrazolyl-ethylamine (L4) afford the corresponding complexes [Zn(C6H5COO)2(L1)] (1), [Zn(C6H5COO)2(L2)] (2), [Zn(3,5-NO2-C6H3COO)2(L1)] (3), [Zn(3,5-NO2-C6H3 COO)2(L2)] (4), [Zn(C6H5COO)2(L3)] (5), [Zn(C6H5COO)2(L4)] (6), [Zn(3,5-NO2-C6H3COO)2(L3)] (7) and [Zn(3,5-NO2-C6H3COO)2(L4)] (8). These complexes behave as catalysts for the ring opening polymerization of e-caprolactone to produce polymers with molecular weight that range from 1480 to 7080 g mol1 and exhibited moderate to broad PDIs. Evidence of these complexes acting as catalysts was obtained from both the polymerization data and kinetic studies. The polymerization data show that variation of the [CL]/[C] from 100 to 800 produced PCL with relatively the same molecular weight indicative of a catalyst behavior. The appearance of induction period in kinetic plots strengthens the fact that these complexes are catalysts rather than initiators. MALDI-TOF MS and 1 H NMR data show di-hydroxy end groups, which support the coordination mechanism rather than insertion mechanism. To understand the broad PDIs obtained for some of the polymer, the electronic properties of the zinc complexes were investigated using cyclic voltammetry. The results show that the zinc complexes containing amine based ligands are highly electrophilic therefore making them unstable, hence the broad PDIs observed for zinc complexes containing amine based ligands. Among the eight complexes investigated, complex 7 is the most active catalyst with kp value of 1.18 107 h1 mol1 at 110 C.
- Full Text:
- Date Issued: 2015
(Ferrocenylpyrazolyl)zinc(II) benzoates as catalysts for the ring opening polymerization of ε-caprolactone
- Obuah, Collins, Lochee, Yemanlall, Jordaan, Johan H.L., Otto, Daniel P., Nyokong, Tebello, Darkwa, James
- Authors: Obuah, Collins , Lochee, Yemanlall , Jordaan, Johan H.L. , Otto, Daniel P. , Nyokong, Tebello , Darkwa, James
- Language: English
- Type: Article
- Identifier: vital:7264 , http://hdl.handle.net/10962/d1020273
- Description: The reaction of Zn(OAc)2 and C6H5COOH or 3,5-NO2-C6H3COOH with 3-ferrocenylpyrazolyl-methylenepyridine (L1), 3-ferrocenyl-5-methylpyrazolyl-methylenepyridine (L2), 3-ferrocenylpyrazolyl-ethylamine (L3) and 3-ferrocenyl-5-pyrazolyl-ethylamine (L4) afford the corresponding complexes [Zn(C6H5COO)2(L1)] (1), [Zn(C6H5COO)2(L2)] (2), [Zn(3,5-NO2-C6H3COO)2(L1)] (3), [Zn(3,5-NO2-C6H3COO)2(L2)] (4), [Zn(C6H5COO)2(L3)] (5), [Zn(C6H5COO)2(L4)] (6), [Zn(3,5-NO2-C6H3COO)2(L3)] (7) and [Zn(3,5-NO2-C6H3COO)2(L4)] (8). These complexes behave as catalysts for the ring opening polymerization of ɛ-caprolactone to produce polymers with molecular weight that range from 1480 to 7080 g mol−1 and exhibited moderate to broad PDIs. Evidence of these complexes acting as catalysts was obtained from both the polymerization data and kinetic studies. The polymerization data show that variation of the [CL]/[C] from 100 to 800 produced PCL with relatively the same molecular weight indicative of a catalyst behavior. The appearance of induction period in kinetic plots strengthens the fact that these complexes are catalysts rather than initiators. MALDI-TOF MS and 1H NMR data show di-hydroxy end groups, which support the coordination mechanism rather than insertion mechanism. To understand the broad PDIs obtained for some of the polymer, the electronic properties of the zinc complexes were investigated using cyclic voltammetry. The results show that the zinc complexes containing amine based ligands are highly electrophilic therefore making them unstable, hence the broad PDIs observed for zinc complexes containing amine based ligands. Among the eight complexes investigated, complex 7 is the most active catalyst with kp value of 1.18 × 10−7 h−1 mol−1 at 110 °C. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2015.02.007
- Full Text: false
- Authors: Obuah, Collins , Lochee, Yemanlall , Jordaan, Johan H.L. , Otto, Daniel P. , Nyokong, Tebello , Darkwa, James
- Language: English
- Type: Article
- Identifier: vital:7264 , http://hdl.handle.net/10962/d1020273
- Description: The reaction of Zn(OAc)2 and C6H5COOH or 3,5-NO2-C6H3COOH with 3-ferrocenylpyrazolyl-methylenepyridine (L1), 3-ferrocenyl-5-methylpyrazolyl-methylenepyridine (L2), 3-ferrocenylpyrazolyl-ethylamine (L3) and 3-ferrocenyl-5-pyrazolyl-ethylamine (L4) afford the corresponding complexes [Zn(C6H5COO)2(L1)] (1), [Zn(C6H5COO)2(L2)] (2), [Zn(3,5-NO2-C6H3COO)2(L1)] (3), [Zn(3,5-NO2-C6H3COO)2(L2)] (4), [Zn(C6H5COO)2(L3)] (5), [Zn(C6H5COO)2(L4)] (6), [Zn(3,5-NO2-C6H3COO)2(L3)] (7) and [Zn(3,5-NO2-C6H3COO)2(L4)] (8). These complexes behave as catalysts for the ring opening polymerization of ɛ-caprolactone to produce polymers with molecular weight that range from 1480 to 7080 g mol−1 and exhibited moderate to broad PDIs. Evidence of these complexes acting as catalysts was obtained from both the polymerization data and kinetic studies. The polymerization data show that variation of the [CL]/[C] from 100 to 800 produced PCL with relatively the same molecular weight indicative of a catalyst behavior. The appearance of induction period in kinetic plots strengthens the fact that these complexes are catalysts rather than initiators. MALDI-TOF MS and 1H NMR data show di-hydroxy end groups, which support the coordination mechanism rather than insertion mechanism. To understand the broad PDIs obtained for some of the polymer, the electronic properties of the zinc complexes were investigated using cyclic voltammetry. The results show that the zinc complexes containing amine based ligands are highly electrophilic therefore making them unstable, hence the broad PDIs observed for zinc complexes containing amine based ligands. Among the eight complexes investigated, complex 7 is the most active catalyst with kp value of 1.18 × 10−7 h−1 mol−1 at 110 °C. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2015.02.007
- Full Text: false
A comparative photophysicochemical study of phthalocyanines encapsulated in core–shell silica nanoparticles
- Fashina, Adedayo, Amuhaya, Edith, Nyokong, Tebello
- Authors: Fashina, Adedayo , Amuhaya, Edith , Nyokong, Tebello
- Language: English
- Type: text
- Identifier: vital:7271 , http://hdl.handle.net/10962/d1020286 , Original publication is available at http://dx.doi.org/10.1016/j.saa.2014.08.062
- Full Text: false
- Authors: Fashina, Adedayo , Amuhaya, Edith , Nyokong, Tebello
- Language: English
- Type: text
- Identifier: vital:7271 , http://hdl.handle.net/10962/d1020286 , Original publication is available at http://dx.doi.org/10.1016/j.saa.2014.08.062
- Full Text: false
A comparative photophysicochemical study of phthalocyanines encapsulated in core–shell silica nanoparticles
- Fashina, Adedayo, Amuhaya, Edith, Nyokong, Tebello
- Authors: Fashina, Adedayo , Amuhaya, Edith , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189708 , vital:44924 , xlink:href="https://doi.org/10.1016/j.saa.2014.08.062"
- Description: This work presents the synthesis and characterization of a new zinc phthalocyanine complex tetrasubstituted with 3-carboxyphenoxy in the peripheral position. The photophysical properties of the new complex are compared with those of phthalocyanines tetra substituted with 3-carboxyphenoxy or 4- carboxyphenoxy at non-peripheral positions. Three phthalocyanine complexes were encapsulated within silica matrix to form a core shell and the hybrid nanoparticles particles obtained were spherical and mono dispersed. When encapsulated within the silica shell nanoparticles, phthalocyanines showed improved triplet quantum yields and singlet oxygen quantum yields than surface grafted derivatives. The improvements observed could be attributed to the protection provided for the phthalocyanine complexes by the silica matrix.
- Full Text:
- Date Issued: 2015
- Authors: Fashina, Adedayo , Amuhaya, Edith , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189708 , vital:44924 , xlink:href="https://doi.org/10.1016/j.saa.2014.08.062"
- Description: This work presents the synthesis and characterization of a new zinc phthalocyanine complex tetrasubstituted with 3-carboxyphenoxy in the peripheral position. The photophysical properties of the new complex are compared with those of phthalocyanines tetra substituted with 3-carboxyphenoxy or 4- carboxyphenoxy at non-peripheral positions. Three phthalocyanine complexes were encapsulated within silica matrix to form a core shell and the hybrid nanoparticles particles obtained were spherical and mono dispersed. When encapsulated within the silica shell nanoparticles, phthalocyanines showed improved triplet quantum yields and singlet oxygen quantum yields than surface grafted derivatives. The improvements observed could be attributed to the protection provided for the phthalocyanine complexes by the silica matrix.
- Full Text:
- Date Issued: 2015
Characterization of porphyrin nanorods on fluorine doped tin oxide glass sheet
- George, Reama C, Falgenhauer, Jane, Geis, Clemens, Nyokong, Tebello, Schlettwein, Derck
- Authors: George, Reama C , Falgenhauer, Jane , Geis, Clemens , Nyokong, Tebello , Schlettwein, Derck
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193542 , vital:45344 , xlink:href="https://doi.org/10.1142/S1088424615500923"
- Description: Porphyrin nanorods (PNR) have been fabricated by electrostatic self-assembly of two oppositely charged porphyrin molecules. The free base meso-tetra-(4-phenylsulphonate) porphyrin (TPPS4)4) served as negatively charged counterpart for the positively charged metallo meso-tetra(4-NN-methylpyridyl) porphyrins (MTM’PyP) with either Sn, Co, Mn or In as central metal M. Films of PNR were prepared on fluorine doped tin oxide glass sheets (FTO) by using a drop-dry method. The electronic spectra revealed J-aggregation of the charged molecules for the colloid PNR as well as for the films. Transmission electron microscopy confirmed the formation of porphyrin nanorods. The laser microscope and scanning electron microscope (SEM) images of the PNR/FTO films showed the formation of three kinds of structures in the films which consist of differently branched or linear needles with their main axis grown in the direction of the solvent flow during preparation. During cyclic voltammetry either applying negative potentials from 0.0 V to -1.0 V or positive potentials from 0.0 V to ++2.2 V irreversible reduction or oxidation reactions were detected for the films. Consistently, SEM images taken following cyclic voltammetry showed the disintegration of the PNR on the films into smaller subunits. Spectroelectrochemical measurements showed the formation of porphyrin anionic radicals during oxidation by a decrease in the absorption intensities and broadening of spectra with an additional band appearing around 900 nm. A similar trend was observed when negative potentials were applied but in this case the cationic radical was produced. In both cases the decrease of the intensity of the J-aggregate confirms a loss of intermolecular coupling, again consistent with the smaller subunits observed in SEM analysis.
- Full Text:
- Date Issued: 2015
- Authors: George, Reama C , Falgenhauer, Jane , Geis, Clemens , Nyokong, Tebello , Schlettwein, Derck
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193542 , vital:45344 , xlink:href="https://doi.org/10.1142/S1088424615500923"
- Description: Porphyrin nanorods (PNR) have been fabricated by electrostatic self-assembly of two oppositely charged porphyrin molecules. The free base meso-tetra-(4-phenylsulphonate) porphyrin (TPPS4)4) served as negatively charged counterpart for the positively charged metallo meso-tetra(4-NN-methylpyridyl) porphyrins (MTM’PyP) with either Sn, Co, Mn or In as central metal M. Films of PNR were prepared on fluorine doped tin oxide glass sheets (FTO) by using a drop-dry method. The electronic spectra revealed J-aggregation of the charged molecules for the colloid PNR as well as for the films. Transmission electron microscopy confirmed the formation of porphyrin nanorods. The laser microscope and scanning electron microscope (SEM) images of the PNR/FTO films showed the formation of three kinds of structures in the films which consist of differently branched or linear needles with their main axis grown in the direction of the solvent flow during preparation. During cyclic voltammetry either applying negative potentials from 0.0 V to -1.0 V or positive potentials from 0.0 V to ++2.2 V irreversible reduction or oxidation reactions were detected for the films. Consistently, SEM images taken following cyclic voltammetry showed the disintegration of the PNR on the films into smaller subunits. Spectroelectrochemical measurements showed the formation of porphyrin anionic radicals during oxidation by a decrease in the absorption intensities and broadening of spectra with an additional band appearing around 900 nm. A similar trend was observed when negative potentials were applied but in this case the cationic radical was produced. In both cases the decrease of the intensity of the J-aggregate confirms a loss of intermolecular coupling, again consistent with the smaller subunits observed in SEM analysis.
- Full Text:
- Date Issued: 2015
Comparative electrocatalytic studies of nanocomposites of mixed and covalently linked multiwalled carbon nanotubes and 4-(4, 6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt (II)
- Nyoni, Stephen, Nyokong, Tebello
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189285 , vital:44834 , xlink:href="https://doi.org/10.1016/j.poly.2015.05.038"
- Description: Electrocatalytic behavior of 4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt(II) (CoPyPc) when mixed or covalently mixed to multiwalled carbon nanotubes (MWCNTs) is reported. Infra-red spectroscopy was used to confirm amide linkage of the covalently linked nanocomposite. Rotating disk electrode (RDE) and cyclic (CV) voltammetry studies were used for the electrochemical characterization of the prepared phthalocyanine and MWCNT nanocomposite. The electrocatalytic effects of the nanocomposites of the cobalt phthalocyanine derivative were then investigated towards L-cysteine oxidation using both RDE and CV experiments, and the electrocatalytic performance of the covalently linked cobalt phthalocyanine-MWCNT was found to be superior over the mixed nanocomposite.
- Full Text:
- Date Issued: 2015
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189285 , vital:44834 , xlink:href="https://doi.org/10.1016/j.poly.2015.05.038"
- Description: Electrocatalytic behavior of 4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt(II) (CoPyPc) when mixed or covalently mixed to multiwalled carbon nanotubes (MWCNTs) is reported. Infra-red spectroscopy was used to confirm amide linkage of the covalently linked nanocomposite. Rotating disk electrode (RDE) and cyclic (CV) voltammetry studies were used for the electrochemical characterization of the prepared phthalocyanine and MWCNT nanocomposite. The electrocatalytic effects of the nanocomposites of the cobalt phthalocyanine derivative were then investigated towards L-cysteine oxidation using both RDE and CV experiments, and the electrocatalytic performance of the covalently linked cobalt phthalocyanine-MWCNT was found to be superior over the mixed nanocomposite.
- Full Text:
- Date Issued: 2015
Comparative electrocatalytic studies of nanocomposites of mixed and covalently linked multiwalled carbon nanotubes and 4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt(II)
- Nyoni, Stephen, Nyokong, Tebello
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7285 , http://hdl.handle.net/10962/d1020332
- Description: Electrocatalytic behavior of 4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt(II) (CoPyPc) when mixed or covalently mixed to multiwalled carbon nanotubes (MWCNTs) is reported. Infra-red spectroscopy was used to confirm amide linkage of the covalently linked nanocomposite. Rotating disk electrode (RDE) and cyclic (CV) voltammetry studies were used for the electrochemical characterization of the prepared phthalocyanine and MWCNT nanocomposite. The electrocatalytic effects of the nanocomposites of the cobalt phthalocyanine derivative were then investigated towards l-cysteine oxidation using both RDE and CV experiments, and the electrocatalytic performance of the covalently linked cobalt phthalocyanine-MWCNT was found to be superior over the mixed nanocomposite. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2015.05.038
- Full Text: false
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7285 , http://hdl.handle.net/10962/d1020332
- Description: Electrocatalytic behavior of 4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninato cobalt(II) (CoPyPc) when mixed or covalently mixed to multiwalled carbon nanotubes (MWCNTs) is reported. Infra-red spectroscopy was used to confirm amide linkage of the covalently linked nanocomposite. Rotating disk electrode (RDE) and cyclic (CV) voltammetry studies were used for the electrochemical characterization of the prepared phthalocyanine and MWCNT nanocomposite. The electrocatalytic effects of the nanocomposites of the cobalt phthalocyanine derivative were then investigated towards l-cysteine oxidation using both RDE and CV experiments, and the electrocatalytic performance of the covalently linked cobalt phthalocyanine-MWCNT was found to be superior over the mixed nanocomposite. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2015.05.038
- Full Text: false
Comparative photophysicochemical behavior of nanoconjugates of indium tetracarboxyphenoxy phthalocyanines covalently linked to CdTe/ZnSe/ZnO quantum dots
- Oluwole, David O, Nyokong, Tebello
- Authors: Oluwole, David O , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: text , Article
- Identifier: vital:7294 , http://hdl.handle.net/10962/d1020357 , http://dx.doi.org/10.1016/j.jphotochem.2015.07.009
- Description: This work reports on the photophysicochemical behavior of different nanoconjugates of core/shell/shell (GSH-CdTe/ZnSe/ZnO), core/shell (GSH-CdTe/ZnSe) and core (GSH-CdTe) (quantum dots QDs) with indium tetracarboxyphenoxy phthalocyanines ((OH)InTCPPc) in dimethylsulfoxide. The fluorescence quantum yields (Φf) and lifetimes (τf, in brackets) of QDs ranged from 0.20 (13.9 ns) to 0.42 (25.6 ns). The highest Φf value was obtained for GSH-CdTe/ZnSe/ZnO (4.5) while the least was observed in GSH-CdTe/ZnSe/ZnO (7.6), the numbers in brackets refer to the sizes. For (OH)InTCPPc alone a Φf and τf values of 0.02 and 2.43 ns, respectively were obtained. In the nanoconjugates, pivotal decrease in the Φf and τf of the QDs were observed with increase in the triplet and singlet oxygen quantum yields of (OH)InTCPPc. , Original publication is available at http://dx.doi.org/10.1016/j.jphotochem.2015.07.009
- Full Text: false
- Date Issued: 2015
- Authors: Oluwole, David O , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: text , Article
- Identifier: vital:7294 , http://hdl.handle.net/10962/d1020357 , http://dx.doi.org/10.1016/j.jphotochem.2015.07.009
- Description: This work reports on the photophysicochemical behavior of different nanoconjugates of core/shell/shell (GSH-CdTe/ZnSe/ZnO), core/shell (GSH-CdTe/ZnSe) and core (GSH-CdTe) (quantum dots QDs) with indium tetracarboxyphenoxy phthalocyanines ((OH)InTCPPc) in dimethylsulfoxide. The fluorescence quantum yields (Φf) and lifetimes (τf, in brackets) of QDs ranged from 0.20 (13.9 ns) to 0.42 (25.6 ns). The highest Φf value was obtained for GSH-CdTe/ZnSe/ZnO (4.5) while the least was observed in GSH-CdTe/ZnSe/ZnO (7.6), the numbers in brackets refer to the sizes. For (OH)InTCPPc alone a Φf and τf values of 0.02 and 2.43 ns, respectively were obtained. In the nanoconjugates, pivotal decrease in the Φf and τf of the QDs were observed with increase in the triplet and singlet oxygen quantum yields of (OH)InTCPPc. , Original publication is available at http://dx.doi.org/10.1016/j.jphotochem.2015.07.009
- Full Text: false
- Date Issued: 2015
Corrole–BODIPY conjugates: enhancing the fluorescence and phosphorescence of the corrole complex via efficient through bond energy transfer
- Chen, Wei, Zhang, Jianfeng, Mack, John, Kubheka, Gugu Patience, Nyokong, Tebello, Shen, Zhen, Wei Chen
- Authors: Chen, Wei , Zhang, Jianfeng , Mack, John , Kubheka, Gugu Patience , Nyokong, Tebello , Shen, Zhen , Wei Chen
- Date: 2015-06-08
- Subjects: RSC Advances (2015), 5, 50962-50967, doi:10.1039/C5RA07250F
- Language: English
- Type: Article
- Identifier: vital:7268 , http://hdl.handle.net/10962/d1020277
- Description: New corrole–BODIPY conjugates have been synthesized in high yield under mild conditions. Upon excitation at the absorption maximum of the BODIPY antenna chromophore, the fluorescence intensity of the free base corrole–BODIPY conjugate increases by ca. 300%, and significant phosphorescence intensity is observed for the iridium(III) complex of the conjugate, while almost no phosphorescence is observed for the parent iridium(III) corrole, due to through-bond energy transfer from the BODIPY antenna-chromophore to the corrole core. , Original publication is available at http://dx.doi.org/10.1039/c5ra07250f , Arbortext Advanced Print Publisher 9.1.510/W Unicode , Acrobat Distiller 8.1.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
- Full Text:
- Authors: Chen, Wei , Zhang, Jianfeng , Mack, John , Kubheka, Gugu Patience , Nyokong, Tebello , Shen, Zhen , Wei Chen
- Date: 2015-06-08
- Subjects: RSC Advances (2015), 5, 50962-50967, doi:10.1039/C5RA07250F
- Language: English
- Type: Article
- Identifier: vital:7268 , http://hdl.handle.net/10962/d1020277
- Description: New corrole–BODIPY conjugates have been synthesized in high yield under mild conditions. Upon excitation at the absorption maximum of the BODIPY antenna chromophore, the fluorescence intensity of the free base corrole–BODIPY conjugate increases by ca. 300%, and significant phosphorescence intensity is observed for the iridium(III) complex of the conjugate, while almost no phosphorescence is observed for the parent iridium(III) corrole, due to through-bond energy transfer from the BODIPY antenna-chromophore to the corrole core. , Original publication is available at http://dx.doi.org/10.1039/c5ra07250f , Arbortext Advanced Print Publisher 9.1.510/W Unicode , Acrobat Distiller 8.1.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
- Full Text:
Deposition of CdS, CdS/ZnSe and CdS/ZnSe/ZnS shells around CdSeTe alloyed core quantum dots: effects on optical properties
- Adegoke, Oluwasesan, Nyokong, Tebello, Forbes, Patricia B C
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7289 , http://hdl.handle.net/10962/d1020342
- Description: In this work, we synthesized water-soluble L-cysteine-capped alloyed CdSeTe core quantum dots (QDs) and investigated the structural and optical properties of deposition of each of CdS, CdS/ZnSe and CdS/ZnSe/ZnS shell layers. Photophysical results showed that the overcoating of a CdS shell around the alloyed CdSeTe core [quantum yield (QY) = 8.4%] resulted in effective confinement of the radiative exciton with an improved QY value of 93.5%. Subsequent deposition of a ZnSe shell around the CdSeTe/CdS surface decreased the QY value to 24.7%, but an increase in the QY value of up to 49.5% was observed when a ZnS shell was overcoated around the CdSeTe/CdS/ZnSe surface. QDs with shell layers showed improved stability relative to the core. Data obtained from time-resolved fluorescence measurements provided useful insight into variations in the photophysical properties of the QDs upon the formation of each shell layer. Our study suggests that the formation of CdSeTe/CdS core/shell QDs meets the requirements of quality QDs in terms of high photoluminescence QY and stability, hence further deposition of additional shells are not necessary in improving the optical properties of the core/shell QDs. Copyright © 2015 John Wiley & Sons, Ltd. , Original publication is available at http://dx.doi.org/10.1002/bio.3013
- Full Text: false
- Date Issued: 2015
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7289 , http://hdl.handle.net/10962/d1020342
- Description: In this work, we synthesized water-soluble L-cysteine-capped alloyed CdSeTe core quantum dots (QDs) and investigated the structural and optical properties of deposition of each of CdS, CdS/ZnSe and CdS/ZnSe/ZnS shell layers. Photophysical results showed that the overcoating of a CdS shell around the alloyed CdSeTe core [quantum yield (QY) = 8.4%] resulted in effective confinement of the radiative exciton with an improved QY value of 93.5%. Subsequent deposition of a ZnSe shell around the CdSeTe/CdS surface decreased the QY value to 24.7%, but an increase in the QY value of up to 49.5% was observed when a ZnS shell was overcoated around the CdSeTe/CdS/ZnSe surface. QDs with shell layers showed improved stability relative to the core. Data obtained from time-resolved fluorescence measurements provided useful insight into variations in the photophysical properties of the QDs upon the formation of each shell layer. Our study suggests that the formation of CdSeTe/CdS core/shell QDs meets the requirements of quality QDs in terms of high photoluminescence QY and stability, hence further deposition of additional shells are not necessary in improving the optical properties of the core/shell QDs. Copyright © 2015 John Wiley & Sons, Ltd. , Original publication is available at http://dx.doi.org/10.1002/bio.3013
- Full Text: false
- Date Issued: 2015
Effects of differently shaped silver nanoparticles on the photophysics of pyridylsulfanyl-substituted phthalocyanines
- D'Souza, Sarah, Mashazi, Philani N, Britton, Jonathan, Nyokong, Tebello
- Authors: D'Souza, Sarah , Mashazi, Philani N , Britton, Jonathan , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193564 , vital:45348 , xlink:href="https://doi.org/10.1016/j.poly.2015.06.038"
- Description: This paper reports on the photophysical behavior of (2-pyridylsulfanyl)phthalocyaninato zinc(II) and 2,9(10),16(17),23(24)-tetra-(2-pyridylsulfanyl)phthalocyaninato zinc(II) in the presence of differently shaped silver nanoparticles (nanospheres, nanotriangles and nanoflowers). The presence of shaped nanoparticles increased both triplet quantum yields and lifetimes of the tetra-substituted mercaptopyridine zinc phthalocyanine in DMSO. It is apparent from this work that the shape of the silver nanoparticle used is of little consequence in influencing photophysical behavior of the phthalocyanines.
- Full Text:
- Date Issued: 2015
- Authors: D'Souza, Sarah , Mashazi, Philani N , Britton, Jonathan , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193564 , vital:45348 , xlink:href="https://doi.org/10.1016/j.poly.2015.06.038"
- Description: This paper reports on the photophysical behavior of (2-pyridylsulfanyl)phthalocyaninato zinc(II) and 2,9(10),16(17),23(24)-tetra-(2-pyridylsulfanyl)phthalocyaninato zinc(II) in the presence of differently shaped silver nanoparticles (nanospheres, nanotriangles and nanoflowers). The presence of shaped nanoparticles increased both triplet quantum yields and lifetimes of the tetra-substituted mercaptopyridine zinc phthalocyanine in DMSO. It is apparent from this work that the shape of the silver nanoparticle used is of little consequence in influencing photophysical behavior of the phthalocyanines.
- Full Text:
- Date Issued: 2015
Effects of Redox Mediators on the Catalytic Activity of Iron Porphyrins towards Oxygen Reduction in Acidic Media
- He, Qinggang, Wu, Gang, Liu, Ke, Khene, M Samson, Li, Qing, Mugadza, Tawanda, Deunf, Elise, Nyokong, Tebello, Chen, Shaowei W
- Authors: He, Qinggang , Wu, Gang , Liu, Ke , Khene, M Samson , Li, Qing , Mugadza, Tawanda , Deunf, Elise , Nyokong, Tebello , Chen, Shaowei W
- Language: English
- Type: Article
- Identifier: vital:7291 , http://hdl.handle.net/10962/d1020354
- Description: The effects of different redox mediators on the oxygen reduction reaction (ORR) catalyzed by an iron porphyrin complex, iron(III) meso-tetra(N-methyl-4-pyridyl)porphine chloride [FeIIITMPyP], in 0.1 M triflic acid were investigated by cyclic voltammetry (CV) and spectroelectrochemistry in conjunction with density functional theory (DFT) calculations. The formal potentials of the FeIIITMPyP catalyst and the redox mediators, as well as the half-wave potentials for the ORR, were determined by CV in the absence and presence of oxygen in acidic solutions. UV/Vis spectroscopic and spectroelectrochemical studies confirmed that only the 2,2′-azino-bis(3-ethylbenzothiazioline-6-sulfonic acid)diammonium salt (C18H24N6O6S4) showed effective interactions with FeIIITMPyP during the ORR. DFT calculations suggested strong interaction between FeIIITMPyP and the C18H24N6O6S4 redox mediator. The redox mediator caused lengthening of the dioxygen iron bond, which thus suggested easier dioxygen reduction. Consistent results were observed in electrochemical impedance spectroscopic measurements for which the electron-transfer kinetics were also evaluated. , Original publication is available at http://dx.doi.org/10.1002/celc.201402054
- Full Text: false
- Authors: He, Qinggang , Wu, Gang , Liu, Ke , Khene, M Samson , Li, Qing , Mugadza, Tawanda , Deunf, Elise , Nyokong, Tebello , Chen, Shaowei W
- Language: English
- Type: Article
- Identifier: vital:7291 , http://hdl.handle.net/10962/d1020354
- Description: The effects of different redox mediators on the oxygen reduction reaction (ORR) catalyzed by an iron porphyrin complex, iron(III) meso-tetra(N-methyl-4-pyridyl)porphine chloride [FeIIITMPyP], in 0.1 M triflic acid were investigated by cyclic voltammetry (CV) and spectroelectrochemistry in conjunction with density functional theory (DFT) calculations. The formal potentials of the FeIIITMPyP catalyst and the redox mediators, as well as the half-wave potentials for the ORR, were determined by CV in the absence and presence of oxygen in acidic solutions. UV/Vis spectroscopic and spectroelectrochemical studies confirmed that only the 2,2′-azino-bis(3-ethylbenzothiazioline-6-sulfonic acid)diammonium salt (C18H24N6O6S4) showed effective interactions with FeIIITMPyP during the ORR. DFT calculations suggested strong interaction between FeIIITMPyP and the C18H24N6O6S4 redox mediator. The redox mediator caused lengthening of the dioxygen iron bond, which thus suggested easier dioxygen reduction. Consistent results were observed in electrochemical impedance spectroscopic measurements for which the electron-transfer kinetics were also evaluated. , Original publication is available at http://dx.doi.org/10.1002/celc.201402054
- Full Text: false
Effects of ZnO nanohexagons and nanorods on the fluorescence behavior of metallophthalocyanines
- D’Souza, Sarah, Moeno, Sharon, Nyokong, Tebello
- Authors: D’Souza, Sarah , Moeno, Sharon , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7263 , http://hdl.handle.net/10962/d1020272
- Description: This paper looks at the fluorescence behavior of zinc phthalocyanines: 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptoacetic acid phthalocyaninato) zinc(II) (ZnTMAAPc), 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptopropanoic acid phthalocyaninato) zinc(II) (ZnTMPAPc) and (OH)AlPcSmix (the latter contains a mixture of the di-, tri- and tetra-sulfonated derivatives with an average of three sulfonated groups per molecule) in the presence of ZnO nanoparticles. Fluorescence lifetimes of Pc complexes generally decreased in the presence of ZnO nanoparticles, with generally longer lifetimes for ZnO nanohexagons compared to ZnO nanorods. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.09.012
- Full Text: false
- Authors: D’Souza, Sarah , Moeno, Sharon , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7263 , http://hdl.handle.net/10962/d1020272
- Description: This paper looks at the fluorescence behavior of zinc phthalocyanines: 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptoacetic acid phthalocyaninato) zinc(II) (ZnTMAAPc), 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptopropanoic acid phthalocyaninato) zinc(II) (ZnTMPAPc) and (OH)AlPcSmix (the latter contains a mixture of the di-, tri- and tetra-sulfonated derivatives with an average of three sulfonated groups per molecule) in the presence of ZnO nanoparticles. Fluorescence lifetimes of Pc complexes generally decreased in the presence of ZnO nanoparticles, with generally longer lifetimes for ZnO nanohexagons compared to ZnO nanorods. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.09.012
- Full Text: false
Effects of ZnO nanohexagons and nanorods on the fluorescence behavior of metallophthalocyanines
- D'Souza, Sarah, Moeno, Sharon, Nyokong, Tebello
- Authors: D'Souza, Sarah , Moeno, Sharon , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189741 , vital:44927 , xlink:href="https://doi.org/10.1016/j.poly.2014.09.012"
- Description: This paper looks at the fluorescence behavior of zinc phthalocyanines: 2,(3),9(10),16(17),23(24)-tetrakis- (mercaptoacetic acid phthalocyaninato) zinc(II) (ZnTMAAPc), 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptopropanoic acid phthalocyaninato) zinc(II) (ZnTMPAPc) and (OH)AlPcSmix (the latter contains a mixture of the di-, tri- and tetra-sulfonated derivatives with an average of three sulfonated groups per molecule) in the presence of ZnO nanoparticles. Fluorescence lifetimes of Pc complexes generally decreased in the presence of ZnO nanoparticles, with generally longer lifetimes for ZnO nanohexagons compared to ZnO nanorods.
- Full Text:
- Date Issued: 2015
- Authors: D'Souza, Sarah , Moeno, Sharon , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189741 , vital:44927 , xlink:href="https://doi.org/10.1016/j.poly.2014.09.012"
- Description: This paper looks at the fluorescence behavior of zinc phthalocyanines: 2,(3),9(10),16(17),23(24)-tetrakis- (mercaptoacetic acid phthalocyaninato) zinc(II) (ZnTMAAPc), 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptopropanoic acid phthalocyaninato) zinc(II) (ZnTMPAPc) and (OH)AlPcSmix (the latter contains a mixture of the di-, tri- and tetra-sulfonated derivatives with an average of three sulfonated groups per molecule) in the presence of ZnO nanoparticles. Fluorescence lifetimes of Pc complexes generally decreased in the presence of ZnO nanoparticles, with generally longer lifetimes for ZnO nanohexagons compared to ZnO nanorods.
- Full Text:
- Date Issued: 2015
Electrocatalytic activity of bimetallic Au–Pd nanoparticles in the presence of cobalt tetraaminophthalocyanine
- Maringa, Audacity, Mashazi, Philani N, Nyokong, Tebello
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189719 , vital:44925 , xlink:href="https://doi.org/10.1016/j.jcis.2014.10.056"
- Description: Au and Pd nanoparticles were individually or together electrodeposited on top of polymerized cobalt tetraaminophthalocyanine (poly-CoTAPc). When Pd and Au nanoparticles are co-deposited together, the electrode is denoted as Au–Pd (co-deposited)/poly-CoTAPc-GCE. X-ray photoelectron spectroscopy (XPS) was used to show the successful deposition of AuNPs, PdNPs and Au–Pd (co-deposited). The scanning electrochemical microscopy showed that Au–Pd (co-deposited)/poly-CoTAPc-GCE (with current range of 9.5–13.5 lA) was more conducting than Au–Pd (co-deposited)-GCE (with current range of 8–12 lA). Electrochemical impedance spectroscopy (EIS) showed that there was less resistance to charge transfer for Au–Pd (co-deposited)/poly-CoTAPc-GCE compared to the rest of the electrodes. Au–Pd (co-deposited)/poly-CoTAPc-GCE showed the best activity for the electrooxidation of hydrazine in terms of limit of detection (0.5 lM), hence shows promise as an electrocatalyst for electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2015
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189719 , vital:44925 , xlink:href="https://doi.org/10.1016/j.jcis.2014.10.056"
- Description: Au and Pd nanoparticles were individually or together electrodeposited on top of polymerized cobalt tetraaminophthalocyanine (poly-CoTAPc). When Pd and Au nanoparticles are co-deposited together, the electrode is denoted as Au–Pd (co-deposited)/poly-CoTAPc-GCE. X-ray photoelectron spectroscopy (XPS) was used to show the successful deposition of AuNPs, PdNPs and Au–Pd (co-deposited). The scanning electrochemical microscopy showed that Au–Pd (co-deposited)/poly-CoTAPc-GCE (with current range of 9.5–13.5 lA) was more conducting than Au–Pd (co-deposited)-GCE (with current range of 8–12 lA). Electrochemical impedance spectroscopy (EIS) showed that there was less resistance to charge transfer for Au–Pd (co-deposited)/poly-CoTAPc-GCE compared to the rest of the electrodes. Au–Pd (co-deposited)/poly-CoTAPc-GCE showed the best activity for the electrooxidation of hydrazine in terms of limit of detection (0.5 lM), hence shows promise as an electrocatalyst for electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2015
Electrocatalytic activity of bimetallic Au–Pd nanoparticles in the presence of cobalt tetraaminophthalocyanine
- Maringa, Audacity, Mashazi, Philani N, Nyokong, Tebello
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7245 , http://hdl.handle.net/10962/d1020250
- Description: Au and Pd nanoparticles were individually or together electrodeposited on top of polymerized cobalt tetraaminophthalocyanine (poly-CoTAPc). When Pd and Au nanoparticles are co-deposited together, the electrode is denoted as Au–Pd (co-deposited)/poly-CoTAPc-GCE. X-ray photoelectron spectroscopy (XPS) was used to show the successful deposition of AuNPs, PdNPs and Au–Pd (co-deposited). The scanning electrochemical microscopy showed that Au–Pd (co-deposited)/poly-CoTAPc-GCE (with current range of 9.5–13.5 μA) was more conducting than Au–Pd (co-deposited)-GCE (with current range of 8–12 μA). Electrochemical impedance spectroscopy (EIS) showed that there was less resistance to charge transfer for Au–Pd (co-deposited)/poly-CoTAPc-GCE compared to the rest of the electrodes. Au–Pd (co-deposited)/poly-CoTAPc-GCE showed the best activity for the electrooxidation of hydrazine in terms of limit of detection (0.5 μM), hence shows promise as an electrocatalyst for electrooxidation of hydrazine. , Original publication is available at http://dx.doi.org/10.1016/j.jcis.2014.10.056
- Full Text: false
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7245 , http://hdl.handle.net/10962/d1020250
- Description: Au and Pd nanoparticles were individually or together electrodeposited on top of polymerized cobalt tetraaminophthalocyanine (poly-CoTAPc). When Pd and Au nanoparticles are co-deposited together, the electrode is denoted as Au–Pd (co-deposited)/poly-CoTAPc-GCE. X-ray photoelectron spectroscopy (XPS) was used to show the successful deposition of AuNPs, PdNPs and Au–Pd (co-deposited). The scanning electrochemical microscopy showed that Au–Pd (co-deposited)/poly-CoTAPc-GCE (with current range of 9.5–13.5 μA) was more conducting than Au–Pd (co-deposited)-GCE (with current range of 8–12 μA). Electrochemical impedance spectroscopy (EIS) showed that there was less resistance to charge transfer for Au–Pd (co-deposited)/poly-CoTAPc-GCE compared to the rest of the electrodes. Au–Pd (co-deposited)/poly-CoTAPc-GCE showed the best activity for the electrooxidation of hydrazine in terms of limit of detection (0.5 μM), hence shows promise as an electrocatalyst for electrooxidation of hydrazine. , Original publication is available at http://dx.doi.org/10.1016/j.jcis.2014.10.056
- Full Text: false
Electrocatalytic studies of covalently immobilized metal tetra-amino phthalocyanines onto derivatized screen-printed gold electrodes
- Mashazi, Philani N, Nyokong, Tebello
- Authors: Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249059 , vital:51774 , xlink:href="https://doi.org/10.1007/s00604-010-0438-6"
- Description: Metal tetra-amino phthalocyanine complexes (MTAPc; where M is Co or Mn) were immobilized on screen-printed gold electrodes pre-modified with monolayers of benzylamino groups. The functionalized electrodes were then activated using benzene-1,4-dicarbaldehyde as a linker before MTAPc complexes were immobilized. The surface coverages for the modified electrodes confirmed the perpendicular orientation of the MTAPcs. The apparent electron transfer constant (kapp) for the electrodes is 2.2 × 10−5 cm.s−1 for both CoTAPc and MnTAPc modified electrodes as calculated with data from impedance measurements. The kapp values for the bare and benzylamino modified electrodes were found to be 1.2 × 10−4 cm.s−1 and 4.9 × 10−6 cm.s−1, respectively. The electrocatalysis of the modified electrodes towards detection of H2O2 gave significant peak current densities and electrocatalytic potentials at −0.28 V and −0.31 V for the MnTAPc and CoTAPc modified electrodes, respectively.
- Full Text:
- Date Issued: 2015
- Authors: Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249059 , vital:51774 , xlink:href="https://doi.org/10.1007/s00604-010-0438-6"
- Description: Metal tetra-amino phthalocyanine complexes (MTAPc; where M is Co or Mn) were immobilized on screen-printed gold electrodes pre-modified with monolayers of benzylamino groups. The functionalized electrodes were then activated using benzene-1,4-dicarbaldehyde as a linker before MTAPc complexes were immobilized. The surface coverages for the modified electrodes confirmed the perpendicular orientation of the MTAPcs. The apparent electron transfer constant (kapp) for the electrodes is 2.2 × 10−5 cm.s−1 for both CoTAPc and MnTAPc modified electrodes as calculated with data from impedance measurements. The kapp values for the bare and benzylamino modified electrodes were found to be 1.2 × 10−4 cm.s−1 and 4.9 × 10−6 cm.s−1, respectively. The electrocatalysis of the modified electrodes towards detection of H2O2 gave significant peak current densities and electrocatalytic potentials at −0.28 V and −0.31 V for the MnTAPc and CoTAPc modified electrodes, respectively.
- Full Text:
- Date Issued: 2015
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
Electrode modification using alkynyl substituted Fe (II) phthalocyanine via electrografting and click chemistry for electrocatalysis
- Nxele, Siphesihle R, Mashazi, Philani N, Nyokong, Tebello
- Authors: Nxele, Siphesihle R , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189296 , vital:44835 , xlink:href="https://doi.org/10.1002/elan.201500212"
- Description: In this work, tetrakis(5-hexyn-oxy)Fe(II) phthalocyanine was synthesised in order to perform a click reaction between the terminal alkyne groups and an azide group on a glassy carbon electrode (GCE) surface. An azide group was formed on the electrode surface following electrografting using 4-azidobenzene diazonium tetrafluoroborate by electrochemical reduction. The Cu(I) catalyzed alkyne-azide Huisgen cycloaddition reaction was then employed in order to react the terminal alkyne groups on the phthalocyanine with the azide groups on the GCE surface. The modified electrode was employed to catalyse the oxidation of hydrazine. The electrode showed good electrocatalytic ability towards the detection of hydrazine with a sensitivity of 15.38 µA mM−1 and a limit of detection of 1.09 µM.
- Full Text:
- Date Issued: 2015
- Authors: Nxele, Siphesihle R , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189296 , vital:44835 , xlink:href="https://doi.org/10.1002/elan.201500212"
- Description: In this work, tetrakis(5-hexyn-oxy)Fe(II) phthalocyanine was synthesised in order to perform a click reaction between the terminal alkyne groups and an azide group on a glassy carbon electrode (GCE) surface. An azide group was formed on the electrode surface following electrografting using 4-azidobenzene diazonium tetrafluoroborate by electrochemical reduction. The Cu(I) catalyzed alkyne-azide Huisgen cycloaddition reaction was then employed in order to react the terminal alkyne groups on the phthalocyanine with the azide groups on the GCE surface. The modified electrode was employed to catalyse the oxidation of hydrazine. The electrode showed good electrocatalytic ability towards the detection of hydrazine with a sensitivity of 15.38 µA mM−1 and a limit of detection of 1.09 µM.
- Full Text:
- Date Issued: 2015
Electrode Modification Using Alkynyl Substituted Fe(II) Phthalocyanine via Electrografting and Click Chemistry for Electrocatalysis
- Nxele, Siphesihle R, Mashazi, Philani N, Nyokong, Tebello
- Authors: Nxele, Siphesihle R , Mashazi, Philani N , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7284 , http://hdl.handle.net/10962/d1020329
- Description: In this work, tetrakis(5-hexyn-oxy)Fe(II) phthalocyanine was synthesised in order to perform a click reaction between the terminal alkyne groups and an azide group on a glassy carbon electrode (GCE) surface. An azide group was formed on the electrode surface following electrografting using 4-azidobenzene diazonium tetrafluoroborate by electrochemical reduction. The Cu(I) catalyzed alkyne-azide Huisgen cycloaddition reaction was then employed in order to react the terminal alkyne groups on the phthalocyanine with the azide groups on the GCE surface. The modified electrode was employed to catalyse the oxidation of hydrazine. The electrode showed good electrocatalytic ability towards the detection of hydrazine with a sensitivity of 15.38 µA mM−1 and a limit of detection of 1.09 µM. , Original publication is available at http://dx.doi.org/10.1002/elan.201500212
- Full Text: false
- Authors: Nxele, Siphesihle R , Mashazi, Philani N , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7284 , http://hdl.handle.net/10962/d1020329
- Description: In this work, tetrakis(5-hexyn-oxy)Fe(II) phthalocyanine was synthesised in order to perform a click reaction between the terminal alkyne groups and an azide group on a glassy carbon electrode (GCE) surface. An azide group was formed on the electrode surface following electrografting using 4-azidobenzene diazonium tetrafluoroborate by electrochemical reduction. The Cu(I) catalyzed alkyne-azide Huisgen cycloaddition reaction was then employed in order to react the terminal alkyne groups on the phthalocyanine with the azide groups on the GCE surface. The modified electrode was employed to catalyse the oxidation of hydrazine. The electrode showed good electrocatalytic ability towards the detection of hydrazine with a sensitivity of 15.38 µA mM−1 and a limit of detection of 1.09 µM. , Original publication is available at http://dx.doi.org/10.1002/elan.201500212
- Full Text: false