Lipophilic M(α,α′-OC5H11)8phthalocyanines (M = H2 and Ni(II)): synthesis, electronic structure, and their utility for highly efficient carbonyl reductions
- Jiang, Yu, Li, Minzhi, Liang, Xu, Mack, John, Wildervanck, Martijn, Nyokong, Tebello, Qin, Mingfeng, Zhu, Weihua
- Authors: Jiang, Yu , Li, Minzhi , Liang, Xu , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Qin, Mingfeng , Zhu, Weihua
- Date: 2015-10-07
- Subjects: Dalton Transactions (2015), 44, 18237-18246, doi:10.1039/c5dt03256c
- Language: English
- Type: Article
- Identifier: vital:7282 , http://hdl.handle.net/10962/d1020322
- Description: A lipophilic and electron-rich phthalocyanine (α,α′-n-OC5H11)8-H2Pc and its nickel(II) complex (α,α′-n-OC5H11)8-Ni(II)Pc have been synthesized and characterized. Detailed analyses of the electronic structure were carried out by spectroscopy, electrochemistry, spectroelectrochemistry, and TD-DFT calculations. A series of experiments demonstrate that the (α,α′-n-OC5H11)8-Ni(II)Pc complex can be used as a catalyst for highly efficient carbonyl reductions. , Original publication is available at http://dx.doi.org/10.1039/C5DT03256C
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- Authors: Jiang, Yu , Li, Minzhi , Liang, Xu , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Qin, Mingfeng , Zhu, Weihua
- Date: 2015-10-07
- Subjects: Dalton Transactions (2015), 44, 18237-18246, doi:10.1039/c5dt03256c
- Language: English
- Type: Article
- Identifier: vital:7282 , http://hdl.handle.net/10962/d1020322
- Description: A lipophilic and electron-rich phthalocyanine (α,α′-n-OC5H11)8-H2Pc and its nickel(II) complex (α,α′-n-OC5H11)8-Ni(II)Pc have been synthesized and characterized. Detailed analyses of the electronic structure were carried out by spectroscopy, electrochemistry, spectroelectrochemistry, and TD-DFT calculations. A series of experiments demonstrate that the (α,α′-n-OC5H11)8-Ni(II)Pc complex can be used as a catalyst for highly efficient carbonyl reductions. , Original publication is available at http://dx.doi.org/10.1039/C5DT03256C
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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)
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- 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)
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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
- 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
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
- 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
Mercaptopyridine-substituted indium, zinc, and metal-free phthalocyanines: nonlinear optical studies in solution and on polymer matrices
- Bankole, Owolabi M, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7278 , http://hdl.handle.net/10962/d1020313
- Description: In this article, the nonlinear optical characterizations and optical limiting properties of metal-free (2), zinc (3), and indium (4) tetra 4-(2-mercaptopyridine) phthalocyanines are discussed. Nonlinear optical properties of the samples were evaluated using Z-scan at 532 nm and 10 ns pulse in CHCl3, and doped on poly(bisphenol A carbonate) (PBC) thin films. Thin films for 2, 3, and 4 are represented as 2-PBC, 3-PBC, and 4-PBC, respectively. We observed two-photon absorption (2PA) and strong reverse saturable absorption as the dominant mechanisms at nanosecond laser excitation in solution and thin films. By virtue of the magnitude of absorption coefficients and other nonlinear optical parameters estimated in this work, sample 4 was found to exhibit strongest nonlinear optical properties followed by 3, while 2 is the weakest nonlinear absorber of the studied samples. Large third-order susceptibility (1.46 × 10−9 esu and 7.74 × 10−10 esu) and hyperpolarizability (2.13 × 10−28 and 8.37 × 10−29 esu) were estimated for 4-PBC and 3-PBC, respectively. Our studies show that these molecules are suitable candidates for practical passive optical limiters. , Original publication is available at http://dx.doi.org/10.1080/00958972.2015.1077237
- Full Text: false
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7278 , http://hdl.handle.net/10962/d1020313
- Description: In this article, the nonlinear optical characterizations and optical limiting properties of metal-free (2), zinc (3), and indium (4) tetra 4-(2-mercaptopyridine) phthalocyanines are discussed. Nonlinear optical properties of the samples were evaluated using Z-scan at 532 nm and 10 ns pulse in CHCl3, and doped on poly(bisphenol A carbonate) (PBC) thin films. Thin films for 2, 3, and 4 are represented as 2-PBC, 3-PBC, and 4-PBC, respectively. We observed two-photon absorption (2PA) and strong reverse saturable absorption as the dominant mechanisms at nanosecond laser excitation in solution and thin films. By virtue of the magnitude of absorption coefficients and other nonlinear optical parameters estimated in this work, sample 4 was found to exhibit strongest nonlinear optical properties followed by 3, while 2 is the weakest nonlinear absorber of the studied samples. Large third-order susceptibility (1.46 × 10−9 esu and 7.74 × 10−10 esu) and hyperpolarizability (2.13 × 10−28 and 8.37 × 10−29 esu) were estimated for 4-PBC and 3-PBC, respectively. Our studies show that these molecules are suitable candidates for practical passive optical limiters. , Original publication is available at http://dx.doi.org/10.1080/00958972.2015.1077237
- Full Text: false
Nonlinear optical properties of natural laccaic acid dye studied using Z-scan technique
- Zongo, S, Sanusi, Kayode, Britton, Jonathan, Mthunzi, P, Nyokong, Tebello, Maaza, M, Sahraoui, B
- Authors: Zongo, S , Sanusi, Kayode , Britton, Jonathan , Mthunzi, P , Nyokong, Tebello , Maaza, M , Sahraoui, B
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7261 , http://hdl.handle.net/10962/d1020270
- Description: We have investigated the nonlinear optical properties, including the optical limiting behaviour for five different concentrations of laccaic acid dye in solution and a thin film obtained through doping in poly (methyl methacrylate) (PMMA) polymer. The experiments were performed by using single beam Z-scan technique at 532 nm with 10 ns, 10 Hz Nd:YAG laser pulses excitation. From the open-aperture Z-scan data, we derived that the laccaic dye samples exhibit strong two photon absorption (2PA). The nonlinear refractive index was determined through the closed aperture Z-scan data. The estimated absorption coefficient β2, nonlinear refractive index n2 and second order hyperpolarizability γ were found to be of the order of 10−10 m/W, 10−9 esu and 10−32 esu, respectively. The Z-scan study reveals that the natural laccaic acid dye emerges as a promising material for third order nonlinear optical devices application. , Original publication is available at http://dx.doi.org/10.1016/j.optmat.2015.04.031
- Full Text: false
- Authors: Zongo, S , Sanusi, Kayode , Britton, Jonathan , Mthunzi, P , Nyokong, Tebello , Maaza, M , Sahraoui, B
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7261 , http://hdl.handle.net/10962/d1020270
- Description: We have investigated the nonlinear optical properties, including the optical limiting behaviour for five different concentrations of laccaic acid dye in solution and a thin film obtained through doping in poly (methyl methacrylate) (PMMA) polymer. The experiments were performed by using single beam Z-scan technique at 532 nm with 10 ns, 10 Hz Nd:YAG laser pulses excitation. From the open-aperture Z-scan data, we derived that the laccaic dye samples exhibit strong two photon absorption (2PA). The nonlinear refractive index was determined through the closed aperture Z-scan data. The estimated absorption coefficient β2, nonlinear refractive index n2 and second order hyperpolarizability γ were found to be of the order of 10−10 m/W, 10−9 esu and 10−32 esu, respectively. The Z-scan study reveals that the natural laccaic acid dye emerges as a promising material for third order nonlinear optical devices application. , Original publication is available at http://dx.doi.org/10.1016/j.optmat.2015.04.031
- Full Text: false
Nonlinear optical response of tetra and mono substituted zinc phthalocyanine complexes
- Fashina, Adedayo, Nyokong, Tebello
- Authors: Fashina, Adedayo , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7281 , http://hdl.handle.net/10962/d1020318 , Original publication is available at http://dx.doi.org/10.1016/j.jlumin.2015.06.003
- Description: The nonlinear absorption properties of 6 mono-substituted and 3 symmetric zinc phthalocyanine complexes have been studied in dimethylsulfoxide (DMSO) using 10 ns pulses at 532 nm. The non linear absorption of the complexes has been studied using the Z-scan technique. The study showed that both the singlet and triplet excited states contribute to the non linear absorption behavior. The nonlinear third-order susceptibility and second-order hyperpolarizability values of the complexes are reported. It was observed that two of the symmetric phthalocyanine complexes (5-α substituted with aminophenoxy and 9-β substituted with carboxyphenoxy) showed better and promising optical nonlinearity when compared to the other complexes studied.
- Full Text: false
- Authors: Fashina, Adedayo , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7281 , http://hdl.handle.net/10962/d1020318 , Original publication is available at http://dx.doi.org/10.1016/j.jlumin.2015.06.003
- Description: The nonlinear absorption properties of 6 mono-substituted and 3 symmetric zinc phthalocyanine complexes have been studied in dimethylsulfoxide (DMSO) using 10 ns pulses at 532 nm. The non linear absorption of the complexes has been studied using the Z-scan technique. The study showed that both the singlet and triplet excited states contribute to the non linear absorption behavior. The nonlinear third-order susceptibility and second-order hyperpolarizability values of the complexes are reported. It was observed that two of the symmetric phthalocyanine complexes (5-α substituted with aminophenoxy and 9-β substituted with carboxyphenoxy) showed better and promising optical nonlinearity when compared to the other complexes studied.
- Full Text: false
Optical limiting and singlet oxygen generation properties of phosphorus triazatetrabenzcorroles
- Mkhize, Colin, Britton, Jonathan, Mack, John, Nyokong, Tebello
- Authors: Mkhize, Colin , Britton, Jonathan , Mack, John , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7257 , http://hdl.handle.net/10962/d1020266
- Description: Novel phosphorus triazatetrabenzcorrole (TBC) tetrasubstituted at the α- and β-positions of the peripheral fused benzene rings with t-butylphenoxy substituents have been prepared and characterized. The effect of the substituents on the electronic structures and optical properties is investigated with TD-DFT calculations and MCD spectroscopy. The optical limiting properties have been investigated to examine whether the lower symmetry that results from the direct pyrrole–pyrrole bond and hence the permanent dipole moment that is introduced result in higher safety thresholds, relative to the values that have been reported for phthalocyanines. The suitability of the compounds for singlet oxygen applications has also been examined. , Original publication is available at http://dx.doi.org/10.1142/S1088424614501065
- Full Text: false
- Authors: Mkhize, Colin , Britton, Jonathan , Mack, John , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7257 , http://hdl.handle.net/10962/d1020266
- Description: Novel phosphorus triazatetrabenzcorrole (TBC) tetrasubstituted at the α- and β-positions of the peripheral fused benzene rings with t-butylphenoxy substituents have been prepared and characterized. The effect of the substituents on the electronic structures and optical properties is investigated with TD-DFT calculations and MCD spectroscopy. The optical limiting properties have been investigated to examine whether the lower symmetry that results from the direct pyrrole–pyrrole bond and hence the permanent dipole moment that is introduced result in higher safety thresholds, relative to the values that have been reported for phthalocyanines. The suitability of the compounds for singlet oxygen applications has also been examined. , Original publication is available at http://dx.doi.org/10.1142/S1088424614501065
- Full Text: false
Optical properties of water-soluble l-cysteine-capped alloyed CdSeS quantum dot passivated with ZnSeTe and ZnSeTe/ZnS shells
- 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:7260 , http://hdl.handle.net/10962/d1020269
- Description: Alloyed quantum dots (QDs) passivated with shell materials have valuable optical characteristics suitable for a wide array of applications. In this work, alloyed ternary CdSeS QDs passivated with ZnSeTe and ZnSeTe/ZnS shells have been synthesized via a hot-injection method and a ligand exchange reaction employing l-cysteine as a thiol ligand has been used to obtain these water-soluble nanocrystals for the first time. The photoluminescence (PL) quantum yield (QY) of alloyed l-cysteine-capped CdSeS was 71.2% but decreased significantly to 5.2% upon passivation with a ZnSeTe shell. The red shift in PL emission of the CdSeS/ZnSeTe QDs was attributed to be strain-induced whilst a lattice-induced process likely created defect states in the core/shell interface hence contributing to the decline in the PL QY. Nonetheless, the fluorescence stability of CdSeS/ZnSeTe QDs in aqueous solution was unperturbed. Further passivation with a ZnS shell (CdSeS/ZnSeTe/ZnS) improved the PL QY to a value of 58.7% and thus indicates that the defect state in the QDs core/shell/shell structure was reduced. PL lifetime exciton measurements indicated that the rates of decay of the QDs influenced their photophysical properties. , Original publication is available at http://dx.doi.org/10.1016/j.optmat.2015.05.024
- Full Text: false
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7260 , http://hdl.handle.net/10962/d1020269
- Description: Alloyed quantum dots (QDs) passivated with shell materials have valuable optical characteristics suitable for a wide array of applications. In this work, alloyed ternary CdSeS QDs passivated with ZnSeTe and ZnSeTe/ZnS shells have been synthesized via a hot-injection method and a ligand exchange reaction employing l-cysteine as a thiol ligand has been used to obtain these water-soluble nanocrystals for the first time. The photoluminescence (PL) quantum yield (QY) of alloyed l-cysteine-capped CdSeS was 71.2% but decreased significantly to 5.2% upon passivation with a ZnSeTe shell. The red shift in PL emission of the CdSeS/ZnSeTe QDs was attributed to be strain-induced whilst a lattice-induced process likely created defect states in the core/shell interface hence contributing to the decline in the PL QY. Nonetheless, the fluorescence stability of CdSeS/ZnSeTe QDs in aqueous solution was unperturbed. Further passivation with a ZnS shell (CdSeS/ZnSeTe/ZnS) improved the PL QY to a value of 58.7% and thus indicates that the defect state in the QDs core/shell/shell structure was reduced. PL lifetime exciton measurements indicated that the rates of decay of the QDs influenced their photophysical properties. , Original publication is available at http://dx.doi.org/10.1016/j.optmat.2015.05.024
- Full Text: false
Photodynamic antimicrobial chemotherapy activity of (5,10,15,20-tetrakis(4-(4-carboxyphenycarbonoimidoyl)phenyl)porphyrinato) chloro gallium(III)
- Managa, Muthumuni, Amuhaya, Edith K, Nyokong, Tebello
- Authors: Managa, Muthumuni , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7296 , http://hdl.handle.net/10962/d1020359
- Description: (5,10,15,20-Tetrakis(4-(4-carboxyphenycarbonoimidoyl)phenyl)porphyrinato) chloro gallium(III) (complex 1) was conjugated to platinum nanoparticles (PtNPs) (represented as 1-PtNPs). The resulting conjugate showed 18 nm red shift in the Soret band when compared to 1 alone. Complex 1 and 1-PtNPs showed promising photodynamic antimicrobial chemotherapy (PACT) activity against Staphylococcus aureus, Escherichia coli and Candida albicans in solution where the log reductions obtained were 4.92, 3.76, and 3.95, respectively for 1-PtNPs. The singlet oxygen quantum yields obtained were higher at 0.56 for 1-PtNPs in DMF while that of 1 was 0.52 in the same solvent. This resulted in improved PACT activity for 1-PtNPs compared to 1 alone. , Original publication is available at http://dx.doi.org/10.1016/j.saa.2015.06.088
- Full Text: false
- Authors: Managa, Muthumuni , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7296 , http://hdl.handle.net/10962/d1020359
- Description: (5,10,15,20-Tetrakis(4-(4-carboxyphenycarbonoimidoyl)phenyl)porphyrinato) chloro gallium(III) (complex 1) was conjugated to platinum nanoparticles (PtNPs) (represented as 1-PtNPs). The resulting conjugate showed 18 nm red shift in the Soret band when compared to 1 alone. Complex 1 and 1-PtNPs showed promising photodynamic antimicrobial chemotherapy (PACT) activity against Staphylococcus aureus, Escherichia coli and Candida albicans in solution where the log reductions obtained were 4.92, 3.76, and 3.95, respectively for 1-PtNPs. The singlet oxygen quantum yields obtained were higher at 0.56 for 1-PtNPs in DMF while that of 1 was 0.52 in the same solvent. This resulted in improved PACT activity for 1-PtNPs compared to 1 alone. , Original publication is available at http://dx.doi.org/10.1016/j.saa.2015.06.088
- Full Text: false
Photophysical studies of newly derivatized mono substituted phthalocyanines grafted onto silica nanoparticles via click chemistry
- Fashina, Adedayo, Amuhaya, Edith K, Nyokong, Tebello
- Authors: Fashina, Adedayo , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7272 , http://hdl.handle.net/10962/d1020287 , Original publication is available at http://dx.doi.org/10.1016/j.saa.2014.12.070
- Description: This work reports on the synthesis, characterization and photophysical studies of newly derived phthalocyanine complexes and the phthalocyanine–silica nanoparticles conjugates. The derived phthalocyanine complexes have one terminal alkyne group. The derived phthalocyanine complexes showed improved photophysical properties (ФF, ФT, ΦΔ and τT) compared to the respective phthalocyanine complexes from which they were derived. The derived phthalocyanine complexes were conjugated to the surface of an azide functionalized silica nanoparticles via copper (1) catalyzed cyclo-addition reaction. All the conjugates showed lower triplet quantum yields ranging from 0.37 to 0.44 compared to the free phthalocyanine complexes. The triplet lifetimes ranged from 352 to 484 μs for the conjugates and from 341 to 366 μs for the free phthalocyanine complexes.
- Full Text: false
- Authors: Fashina, Adedayo , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7272 , http://hdl.handle.net/10962/d1020287 , Original publication is available at http://dx.doi.org/10.1016/j.saa.2014.12.070
- Description: This work reports on the synthesis, characterization and photophysical studies of newly derived phthalocyanine complexes and the phthalocyanine–silica nanoparticles conjugates. The derived phthalocyanine complexes have one terminal alkyne group. The derived phthalocyanine complexes showed improved photophysical properties (ФF, ФT, ΦΔ and τT) compared to the respective phthalocyanine complexes from which they were derived. The derived phthalocyanine complexes were conjugated to the surface of an azide functionalized silica nanoparticles via copper (1) catalyzed cyclo-addition reaction. All the conjugates showed lower triplet quantum yields ranging from 0.37 to 0.44 compared to the free phthalocyanine complexes. The triplet lifetimes ranged from 352 to 484 μs for the conjugates and from 341 to 366 μs for the free phthalocyanine complexes.
- Full Text: false
Physicochemical and photodynamic antimicrobial chemotherapy studies of mono- and tetra-pyridyloxy substituted indium(III) phthalocyanines
- Osifeko, Olawale L, Durmuş, Mahmut, Nyokong, Tebello
- Authors: Osifeko, Olawale L , Durmuş, Mahmut , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: text , Article
- Identifier: vital:7255 , http://hdl.handle.net/10962/d1020264 , http://dx.doi.org/10.1016/j.jphotochem.2014.12.011
- Description: The synthesis and photophysicochemical properties of mono- and tetra-pyridyloxy substituted indium(III) phthalocyanines (InPcs) are presented in this study. General trends are described for quantum yields of fluorescence, triplet, singlet oxygen and photodegradation as well as lifetimes of fluorescence and triplet state of these compounds. The complexes exhibited high singlet oxygen quantum yields (ФΔ) ranging from 0.44 to 0.66 in DMF, and from 0.44 to 0.69 in DMSO and ФΔ = 0.31 for the quartenized tetra substituted InPc which is soluble in water. The triplet quantum yields (ФT) ranged from 0.77 to 0.95 in DMF and from 0.77 to 0.94) in DMSO. The tetra substituted photosensitizers do not differ in their inactivation of bacteria with over 8 log reduction of viable bacteria when compared with the mono substituted photosensitizer which could only manage a 1 log reduction. , Original publication is available at http://dx.doi.org/10.1016/j.jphotochem.2014.12.011
- Full Text: false
- Authors: Osifeko, Olawale L , Durmuş, Mahmut , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: text , Article
- Identifier: vital:7255 , http://hdl.handle.net/10962/d1020264 , http://dx.doi.org/10.1016/j.jphotochem.2014.12.011
- Description: The synthesis and photophysicochemical properties of mono- and tetra-pyridyloxy substituted indium(III) phthalocyanines (InPcs) are presented in this study. General trends are described for quantum yields of fluorescence, triplet, singlet oxygen and photodegradation as well as lifetimes of fluorescence and triplet state of these compounds. The complexes exhibited high singlet oxygen quantum yields (ФΔ) ranging from 0.44 to 0.66 in DMF, and from 0.44 to 0.69 in DMSO and ФΔ = 0.31 for the quartenized tetra substituted InPc which is soluble in water. The triplet quantum yields (ФT) ranged from 0.77 to 0.95 in DMF and from 0.77 to 0.94) in DMSO. The tetra substituted photosensitizers do not differ in their inactivation of bacteria with over 8 log reduction of viable bacteria when compared with the mono substituted photosensitizer which could only manage a 1 log reduction. , Original publication is available at http://dx.doi.org/10.1016/j.jphotochem.2014.12.011
- Full Text: false
Physicochemical behavior of nanohybrids of mono and tetra substituted carboxyphenoxy phthalocyanine covalently linked to GSH–CdTe/CdS/ZnS quantum dots
- Oluwole, David O, Nyokong, Tebello
- Authors: Oluwole, David O , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: text , Article
- Identifier: vital:7266 , http://hdl.handle.net/10962/d1020275 , http://dx.doi.org/10.1016/j.poly.2014.10.024
- Description: Zinc monocarboxyphenoxy and tetracarboxyphenoxy phthalocyanines were covalently linked with three different sizes of glutathione capped core/shell/shell {CdTe/CdS/ZnS(4.2), CdTe/CdS/ZnS(5.1) and CdTe/CdS/ZnS(6.7)}; a core shell {CdTe/CdS(3.1)} and core {CdTe(2.4)} quantum dots. The physicochemical behavior and Förster resonance energy transfer (FRET) processes of the nanohybrids were investigated. The highest FRET efficiency was observed with CdTe/CdS/ZnS(6.7) nanohybrids with 98% and the least efficiency was observed with CdTe(2.4) nanohybrids with 85%. The CdTe/CdS/ZnS(6.7) also showed the best physicochemical behavior. These good physicochemical properties make the synthesized nanohybrids viable photosensitizers. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.10.024
- Full Text: false
- Authors: Oluwole, David O , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: text , Article
- Identifier: vital:7266 , http://hdl.handle.net/10962/d1020275 , http://dx.doi.org/10.1016/j.poly.2014.10.024
- Description: Zinc monocarboxyphenoxy and tetracarboxyphenoxy phthalocyanines were covalently linked with three different sizes of glutathione capped core/shell/shell {CdTe/CdS/ZnS(4.2), CdTe/CdS/ZnS(5.1) and CdTe/CdS/ZnS(6.7)}; a core shell {CdTe/CdS(3.1)} and core {CdTe(2.4)} quantum dots. The physicochemical behavior and Förster resonance energy transfer (FRET) processes of the nanohybrids were investigated. The highest FRET efficiency was observed with CdTe/CdS/ZnS(6.7) nanohybrids with 98% and the least efficiency was observed with CdTe(2.4) nanohybrids with 85%. The CdTe/CdS/ZnS(6.7) also showed the best physicochemical behavior. These good physicochemical properties make the synthesized nanohybrids viable photosensitizers. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.10.024
- Full Text: false
Structural and optical properties of alloyed quaternary CdSeTeS core and CdSeTeS/ZnS core–shell quantum dots
- 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:7244 , http://hdl.handle.net/10962/d1020248
- Description: Synthesis of fluorescent alloyed quantum dots (QDs) with unique optical properties suitable for a wide array of chemical, physical and biological applications is of research interest. In this work, highly luminescent and photostable alloyed quaternary CdSeTeS core QDs of two different sizes were fabricated via the organometallic hot-injection synthetic route. Characterization of the nanocrystals were performed using TEM, XRD, UV/vis and fluorescence spectrophotometric techniques. We have demonstrated in this work that the well fabricated alloyed quaternary CdSeTeS core QDs possess unique optical properties that are advantageous over conventional core/shell systems. Formation of the CdSeTeS/ZnS core/shell with the desired optical properties comes with a number of challenges, hence the advantages of the quaternary alloyed core over the core/shell QDs are (i) avoidance of the challenging process of determining the proper shell thickness which can provide the desired optical properties in the core/shell system and (ii) avoidance of the lattice-induced mismatch between the core and the shell material which can either lead to incomplete exciton confinement or dislocation at the core/shell interface. , Original publication is available at http://dx.doi.org/10.1016/j.jallcom.2015.05.083
- Full Text: false
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7244 , http://hdl.handle.net/10962/d1020248
- Description: Synthesis of fluorescent alloyed quantum dots (QDs) with unique optical properties suitable for a wide array of chemical, physical and biological applications is of research interest. In this work, highly luminescent and photostable alloyed quaternary CdSeTeS core QDs of two different sizes were fabricated via the organometallic hot-injection synthetic route. Characterization of the nanocrystals were performed using TEM, XRD, UV/vis and fluorescence spectrophotometric techniques. We have demonstrated in this work that the well fabricated alloyed quaternary CdSeTeS core QDs possess unique optical properties that are advantageous over conventional core/shell systems. Formation of the CdSeTeS/ZnS core/shell with the desired optical properties comes with a number of challenges, hence the advantages of the quaternary alloyed core over the core/shell QDs are (i) avoidance of the challenging process of determining the proper shell thickness which can provide the desired optical properties in the core/shell system and (ii) avoidance of the lattice-induced mismatch between the core and the shell material which can either lead to incomplete exciton confinement or dislocation at the core/shell interface. , Original publication is available at http://dx.doi.org/10.1016/j.jallcom.2015.05.083
- Full Text: false
The development of Palladium(II)-specific amine-functionalized silica-based microparticles : adsorption and column separation studies
- Fayemi, Omolola E, Ogunlaja, Adeniyi S, Antunes, Edith M, Nyokong, Tebello, Tshentu, Zenixole R
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7270 , http://hdl.handle.net/10962/d1020285
- Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species ([PtCl6]2− and [PdCl4]2−) on silica-based microparticles functionalized with ammonium centers based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) were investigated. The functionalized sorbent materials were characterized using SEM, XPS, BET, and FTIR. The sorbents were used in the batch and column study for adsorption and selective separation of [PtCl62− and PdCl4]2−. The adsorption model for both [PtCl6]2− and [PdCl4]2− on the different sorbent materials fitted the Freundlich isotherm with R2 values > 0.99. The S-TETA sorbent material was palladium(II) specific. Pd(II) loaded on the silica column was recovered using 3% m/v thiourea solution as the eluting agent. Separation of platinum and palladium was achieved by selective stripping of [PtCl6]2− with 0.5 M of NaClO4 in 1.0 M HCl while Pd(II) was eluted with 0.5 M thiourea in 1.0 M HCl. The separation of palladium (Pd) from a mixture containing platinum (Pt), iridium (Ir), and rhodium (Rh) was successful on silica functionalized with triethylenetriamine (TETA) showing specificity for palladium(II) and a loading capacity of 0.27 mg/g. S-TETA showed potential for use in the recovery of palladium from platinum group metals such as from solutions of worn out automobile emission control catalytic convertors and other secondary sources. , Original publication is available at http://dx.doi.org/10.1080/01496395.2014.978017
- Full Text: false
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7270 , http://hdl.handle.net/10962/d1020285
- Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species ([PtCl6]2− and [PdCl4]2−) on silica-based microparticles functionalized with ammonium centers based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) were investigated. The functionalized sorbent materials were characterized using SEM, XPS, BET, and FTIR. The sorbents were used in the batch and column study for adsorption and selective separation of [PtCl62− and PdCl4]2−. The adsorption model for both [PtCl6]2− and [PdCl4]2− on the different sorbent materials fitted the Freundlich isotherm with R2 values > 0.99. The S-TETA sorbent material was palladium(II) specific. Pd(II) loaded on the silica column was recovered using 3% m/v thiourea solution as the eluting agent. Separation of platinum and palladium was achieved by selective stripping of [PtCl6]2− with 0.5 M of NaClO4 in 1.0 M HCl while Pd(II) was eluted with 0.5 M thiourea in 1.0 M HCl. The separation of palladium (Pd) from a mixture containing platinum (Pt), iridium (Ir), and rhodium (Rh) was successful on silica functionalized with triethylenetriamine (TETA) showing specificity for palladium(II) and a loading capacity of 0.27 mg/g. S-TETA showed potential for use in the recovery of palladium from platinum group metals such as from solutions of worn out automobile emission control catalytic convertors and other secondary sources. , Original publication is available at http://dx.doi.org/10.1080/01496395.2014.978017
- Full Text: false
The Development of Palladium(II)-Specific Amine-Functionalized Silica-Based Microparticles: Adsorption and Column Separation Studies
- Fayemi, Omolola E, Ogunlaja, Adeniyi S, Antunes, Edith M, Nyokong, Tebello, Tshentu, Zenixole R
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7269 , http://hdl.handle.net/10962/d1020278
- Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species ([PtCl6]2− and [PdCl4]2−) on silica-based microparticles functionalized with ammonium centers based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) were investigated. The functionalized sorbent materials were characterized using SEM, XPS, BET, and FTIR. The sorbents were used in the batch and column study for adsorption and selective separation of [PtCl62− and PdCl4]2−. The adsorption model for both [PtCl6]2− and [PdCl4]2− on the different sorbent materials fitted the Freundlich isotherm with R2 values > 0.99. The S-TETA sorbent material was palladium(II) specific. Pd(II) loaded on the silica column was recovered using 3% m/v thiourea solution as the eluting agent. Separation of platinum and palladium was achieved by selective stripping of [PtCl6]2− with 0.5 M of NaClO4 in 1.0 M HCl while Pd(II) was eluted with 0.5 M thiourea in 1.0 M HCl. The separation of palladium (Pd) from a mixture containing platinum (Pt), iridium (Ir), and rhodium (Rh) was successful on silica functionalized with triethylenetriamine (TETA) showing specificity for palladium(II) and a loading capacity of 0.27 mg/g. S-TETA showed potential for use in the recovery of palladium from platinum group metals such as from solutions of worn out automobile emission control catalytic convertors and other secondary sources. , Original publication is available at http://dx.doi.org/10.1080/01496395.2014.978017
- Full Text: false
- Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7269 , http://hdl.handle.net/10962/d1020278
- Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species ([PtCl6]2− and [PdCl4]2−) on silica-based microparticles functionalized with ammonium centers based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) were investigated. The functionalized sorbent materials were characterized using SEM, XPS, BET, and FTIR. The sorbents were used in the batch and column study for adsorption and selective separation of [PtCl62− and PdCl4]2−. The adsorption model for both [PtCl6]2− and [PdCl4]2− on the different sorbent materials fitted the Freundlich isotherm with R2 values > 0.99. The S-TETA sorbent material was palladium(II) specific. Pd(II) loaded on the silica column was recovered using 3% m/v thiourea solution as the eluting agent. Separation of platinum and palladium was achieved by selective stripping of [PtCl6]2− with 0.5 M of NaClO4 in 1.0 M HCl while Pd(II) was eluted with 0.5 M thiourea in 1.0 M HCl. The separation of palladium (Pd) from a mixture containing platinum (Pt), iridium (Ir), and rhodium (Rh) was successful on silica functionalized with triethylenetriamine (TETA) showing specificity for palladium(II) and a loading capacity of 0.27 mg/g. S-TETA showed potential for use in the recovery of palladium from platinum group metals such as from solutions of worn out automobile emission control catalytic convertors and other secondary sources. , Original publication is available at http://dx.doi.org/10.1080/01496395.2014.978017
- Full Text: false
Visible light transformation of Rhodamine 6G using tetracarbazole zinc phthalocyanine when embedded in electrospun fibers and in the presence of ZnO and Ag particles
- Khoza, Phindile, Nyokong, Tebello
- Authors: Khoza, Phindile , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7246 , http://hdl.handle.net/10962/d1020251
- Description: Herein, we report the photocatalytic transformation of Rhodamine 6G (Rh 6G) using tetracarbazole zinc phthalocyanine (TCbZnPc) when alone or when conjugated with ZnO macroparticles (ZnOMPs) and silver nanoparticles (AgNPs), represented as TCbZnPc–ZnOMPs and TCbZnPc–AgNPs, respectively. The photocatalysts were supported onto electrospun polystyrene fibers. The efficiency of TCbZnPc was improved by the presence of both ZnOMPs and AgNPs. HPLC equipped with UV–vis was used to study phototransformation products. The mechanism of transformation was via the N-de-ethylation of Rh 6G. , Original publication is available at http://dx.doi.org/10.1080/00958972.2015.1013944
- Full Text: false
- Authors: Khoza, Phindile , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7246 , http://hdl.handle.net/10962/d1020251
- Description: Herein, we report the photocatalytic transformation of Rhodamine 6G (Rh 6G) using tetracarbazole zinc phthalocyanine (TCbZnPc) when alone or when conjugated with ZnO macroparticles (ZnOMPs) and silver nanoparticles (AgNPs), represented as TCbZnPc–ZnOMPs and TCbZnPc–AgNPs, respectively. The photocatalysts were supported onto electrospun polystyrene fibers. The efficiency of TCbZnPc was improved by the presence of both ZnOMPs and AgNPs. HPLC equipped with UV–vis was used to study phototransformation products. The mechanism of transformation was via the N-de-ethylation of Rh 6G. , Original publication is available at http://dx.doi.org/10.1080/00958972.2015.1013944
- Full Text: false
(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
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
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