Electrode modification through click chemistry using Ni and Co alkyne phthalocyanines for electrocatalytic detection of hydrazine
- O'Donoghue, Charles S, Shumba, Munyaradzai, Nyokong, Tebello
- Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242763 , vital:51076 , xlink:href="https://doi.org/10.1002/elan.201700084"
- Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1, 3-dipolar cycloaddition reaction, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
- Full Text:
- Date Issued: 2017
- Authors: O'Donoghue, Charles S , Shumba, Munyaradzai , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242763 , vital:51076 , xlink:href="https://doi.org/10.1002/elan.201700084"
- Description: This work reports on the development of sensors for the detection of hydrazine using glassy carbon electrodes (GCE) modified with phthalocyanines through click chemistry. Tetrakis(5-hexyn-oxy) cobalt(II) phthalocyanine (complex 2) and tetrakis(5-hexyn-oxy) nickel(II) phthalocyanine (complex 3) were employed as electrode modifiers for hydrazine detection. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1, 3-dipolar cycloaddition reaction, catalysed by a copper catalyst was utilised to “click” the phthalocyanines to the surface of the grafted GCE. The modified electrodes were characterized by scanning electrochemical microscopy, X-ray photoelectron spectroscopy and cyclic voltammetry. The electrografted CoP2-clicked-GCE and NiP3-clicked-GCE exhibited electrocatalytic activity towards the detection of hydrazine. The limit of detection (LoD) for the CoPc-GCE was 6.09 μM, while the NiPc-GCE had a LoD of 8.69 μM. The sensitivity was 51.32 μA mM−1 for the CoPc-GCE and 111.2 μA mM−1 for the NiPc-GCE.
- Full Text:
- Date Issued: 2017
First example of nonlinear optical materials based on nanoconjugates of sandwich phthalocyanines with quantum dots
- Oluwole, David O, Yagodin, Alexey V, Mkhize, Nhlakanipho C, Sekhosana, Kutloana E, Martynov, Alexander G, Gorbunova, Yulia G, Tsivadze, Aslan Yu, Nyokong, Tebello
- Authors: Oluwole, David O , Yagodin, Alexey V , Mkhize, Nhlakanipho C , Sekhosana, Kutloana E , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238014 , vital:50577 , xlink:href="https://doi.org/10.1002/chem.201604401"
- Description: We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double- and triple-decker europium(III) complexes 2 and 3 with the A3B-type phthalocyanine ligand (2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-n-butoxyphthalocyanine 1) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid-capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low-symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open-aperture Z-scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double- and triple-decker EuIII octa-n-butoxyphthalocyaninates 5 and 6 and their mixtures with trioctylphosphine oxide-capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π-electron system upon moving from double- to triple-decker complexes significantly improves the OL characteristics, making the low-symmetry triple-decker complex 3 the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm−2 input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double- and triple-decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.
- Full Text:
- Date Issued: 2017
- Authors: Oluwole, David O , Yagodin, Alexey V , Mkhize, Nhlakanipho C , Sekhosana, Kutloana E , Martynov, Alexander G , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238014 , vital:50577 , xlink:href="https://doi.org/10.1002/chem.201604401"
- Description: We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double- and triple-decker europium(III) complexes 2 and 3 with the A3B-type phthalocyanine ligand (2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-n-butoxyphthalocyanine 1) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid-capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low-symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open-aperture Z-scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double- and triple-decker EuIII octa-n-butoxyphthalocyaninates 5 and 6 and their mixtures with trioctylphosphine oxide-capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π-electron system upon moving from double- to triple-decker complexes significantly improves the OL characteristics, making the low-symmetry triple-decker complex 3 the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm−2 input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double- and triple-decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.
- Full Text:
- Date Issued: 2017
Flexible Metal–Porphyrin Dimers (M= MnIIICl, CoII, NiII, CuII)
- Li, Minzhi, Zhang, Qian, Xu, Li, Zhu, Weihua, Mack, John, May, Aviwe K, Nyokong, Tebello, Kobayashi, Nagao, Liang, Xu
- Authors: Li, Minzhi , Zhang, Qian , Xu, Li , Zhu, Weihua , Mack, John , May, Aviwe K , Nyokong, Tebello , Kobayashi, Nagao , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239676 , vital:50754 , xlink:href="https://doi.org/10.1002/cplu.201600475"
- Description: Four metalloporphyrin dimers linked by bridging amide-bonded xanthene moieties and that contain either MnIII, CoII, NiII, or CuII metal centers were synthesized. Various spectroscopic, electrochemical, and spectroelectrochemical methods were used to study trends in their properties. Their electronic structure and optical properties were analyzed through a comparison of the electronic absorption and magnetic circular dichroism (MCD) spectral data with the results of time-dependent (TD)-DFT calculations.
- Full Text:
- Date Issued: 2017
- Authors: Li, Minzhi , Zhang, Qian , Xu, Li , Zhu, Weihua , Mack, John , May, Aviwe K , Nyokong, Tebello , Kobayashi, Nagao , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239676 , vital:50754 , xlink:href="https://doi.org/10.1002/cplu.201600475"
- Description: Four metalloporphyrin dimers linked by bridging amide-bonded xanthene moieties and that contain either MnIII, CoII, NiII, or CuII metal centers were synthesized. Various spectroscopic, electrochemical, and spectroelectrochemical methods were used to study trends in their properties. Their electronic structure and optical properties were analyzed through a comparison of the electronic absorption and magnetic circular dichroism (MCD) spectral data with the results of time-dependent (TD)-DFT calculations.
- Full Text:
- Date Issued: 2017
Forest degradation and invasive species synergistically impact Mimusops andongensis (Sapotaceae) in Lama Forest Reserve, Benin
- Sinasson, Gisèle K, Shackleton, Charlie M, Glèlè Kakaï, Romain L, Sinsin, Brice
- Authors: Sinasson, Gisèle K , Shackleton, Charlie M , Glèlè Kakaï, Romain L , Sinsin, Brice
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182038 , vital:43792 , xlink:href="https://doi.org/10.1111/btp.12370"
- Description: Harvesting of Non-Timber Forest Products (NTFPs) can threaten target species, especially those with limited distribution and density. Exploited species also face threats from habitat fragmentation, fire, and invasive species. We assessed the impact of human disturbances and invasive species on the population of a key multipurpose NTFP species, Mimusops andongensis, in Lama Forest reserve (Benin). The densities of adult trees and regenerative stems decreased with increasing degradation. Mimusops andongensis contributed less to total tree density with increasing human disturbance. There were significantly fewer M. andongensis recruits with increasing cover of invasive Chromolaena odorata. Smaller diameter individuals predominated in non-degraded and moderately degraded sites while in degraded sites, the structure showed a negative exponential trend with the density of small diameter individuals being less than two trees/ha. Larger individuals were also rare in degraded sites. The low density of both mature trees and seedlings in degraded sites may undermine the long-term viability of M. andongensis, despite existing protection against NTFP harvesting and other anthropogenic pressures. Management should emphasize facilitating recruitment subsidies and limiting the presence of C. odorata.
- Full Text:
- Date Issued: 2017
- Authors: Sinasson, Gisèle K , Shackleton, Charlie M , Glèlè Kakaï, Romain L , Sinsin, Brice
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/182038 , vital:43792 , xlink:href="https://doi.org/10.1111/btp.12370"
- Description: Harvesting of Non-Timber Forest Products (NTFPs) can threaten target species, especially those with limited distribution and density. Exploited species also face threats from habitat fragmentation, fire, and invasive species. We assessed the impact of human disturbances and invasive species on the population of a key multipurpose NTFP species, Mimusops andongensis, in Lama Forest reserve (Benin). The densities of adult trees and regenerative stems decreased with increasing degradation. Mimusops andongensis contributed less to total tree density with increasing human disturbance. There were significantly fewer M. andongensis recruits with increasing cover of invasive Chromolaena odorata. Smaller diameter individuals predominated in non-degraded and moderately degraded sites while in degraded sites, the structure showed a negative exponential trend with the density of small diameter individuals being less than two trees/ha. Larger individuals were also rare in degraded sites. The low density of both mature trees and seedlings in degraded sites may undermine the long-term viability of M. andongensis, despite existing protection against NTFP harvesting and other anthropogenic pressures. Management should emphasize facilitating recruitment subsidies and limiting the presence of C. odorata.
- Full Text:
- Date Issued: 2017
Optical Limiting Properties of 3, 5-Dithienylenevinylene BODIPY Dyes at 532 nm
- Harris, Jessica, Gai, Lizhi, Kubheka, Gugu, Mack, John, Nyokong, Tebello, Shen, Zhen
- Authors: Harris, Jessica , Gai, Lizhi , Kubheka, Gugu , Mack, John , Nyokong, Tebello , Shen, Zhen
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189274 , vital:44833 , xlink:href="https://doi.org/10.1002/chem.201702503"
- Description: The optical limiting properties of a series of near infrared absorbing 3,5-dithienylenevinylene BODIPY (borondipyrromethene) dyes (1–3) that contain donor and acceptor moieties in their p-conjugation systems were studied by using the z-scan technique at 532 nm in the nanosecond pulse range. A strong reverse saturable absorption response was observed when the compounds are embedded into poly(bisphenol carbonate A) polymer thin films, which demonstrates that BODIPY dyes with this type of structure are suitable for use in optical limiting applications.
- Full Text:
- Date Issued: 2017
- Authors: Harris, Jessica , Gai, Lizhi , Kubheka, Gugu , Mack, John , Nyokong, Tebello , Shen, Zhen
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189274 , vital:44833 , xlink:href="https://doi.org/10.1002/chem.201702503"
- Description: The optical limiting properties of a series of near infrared absorbing 3,5-dithienylenevinylene BODIPY (borondipyrromethene) dyes (1–3) that contain donor and acceptor moieties in their p-conjugation systems were studied by using the z-scan technique at 532 nm in the nanosecond pulse range. A strong reverse saturable absorption response was observed when the compounds are embedded into poly(bisphenol carbonate A) polymer thin films, which demonstrates that BODIPY dyes with this type of structure are suitable for use in optical limiting applications.
- Full Text:
- Date Issued: 2017
Synthesis of silver nanoparticles from a Desmodium adscendens extract and its antibacterial evaluation on wound dressing material
- Lakkakula, Jaya R, Ndinteh, Derek T, van Vuuren, Sandy F, Olivier, Denise K, Krause, Rui W M
- Authors: Lakkakula, Jaya R , Ndinteh, Derek T , van Vuuren, Sandy F , Olivier, Denise K , Krause, Rui W M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/195025 , vital:45520 , xlink:href="https://doi.org/10.1049/iet-nbt.2017.0084"
- Description: The one-pot synthesis of silver nanoparticles (AgNPs) using the medium-polar extract of Desmodium adscendens (Sw.) DC. is presented here as an alternative synthesis of metal NPs. Characterisation of the formed NPs showed polydispersed AgNPs ranging from 15 to 100 nm where the concentration of metal ions was found to play a role in the size and shape of the prepared NPs. It could be established that the flavonoids, saponins, and alkaloids present in the extract acted as both reducing and stabilising agents during the formation of the capped metal NPs. This means of NP synthesis was also employed during the in situ immobilisation of AgNPs on gauze and plaster. An evaluation of the antibacterial activity of the medium-polar D. adscendens extract, AgNPs suspended in solution, and the immobilised AgNPs against Staphylococcus aureus (ATCC 25923), Bacillus cereus (ATCC 11778), and Escherichia coli (ATCC 25922) showed high efficacy against the latter in particular. This suggests that gauze, dilute silver nitrate solutions, and D. adscendens extract could be used successfully in the simple in situ preparation of effective antibacterial wound dressings.
- Full Text:
- Date Issued: 2017
- Authors: Lakkakula, Jaya R , Ndinteh, Derek T , van Vuuren, Sandy F , Olivier, Denise K , Krause, Rui W M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/195025 , vital:45520 , xlink:href="https://doi.org/10.1049/iet-nbt.2017.0084"
- Description: The one-pot synthesis of silver nanoparticles (AgNPs) using the medium-polar extract of Desmodium adscendens (Sw.) DC. is presented here as an alternative synthesis of metal NPs. Characterisation of the formed NPs showed polydispersed AgNPs ranging from 15 to 100 nm where the concentration of metal ions was found to play a role in the size and shape of the prepared NPs. It could be established that the flavonoids, saponins, and alkaloids present in the extract acted as both reducing and stabilising agents during the formation of the capped metal NPs. This means of NP synthesis was also employed during the in situ immobilisation of AgNPs on gauze and plaster. An evaluation of the antibacterial activity of the medium-polar D. adscendens extract, AgNPs suspended in solution, and the immobilised AgNPs against Staphylococcus aureus (ATCC 25923), Bacillus cereus (ATCC 11778), and Escherichia coli (ATCC 25922) showed high efficacy against the latter in particular. This suggests that gauze, dilute silver nitrate solutions, and D. adscendens extract could be used successfully in the simple in situ preparation of effective antibacterial wound dressings.
- Full Text:
- Date Issued: 2017
The effects of expansive shrubs on plant species richness and soils in semi-arid communal lands, South Africa
- Sholto-Douglas, Craig, Shackleton, Charlie M, Ruwanza, Sheunesu, Dold, Tony
- Authors: Sholto-Douglas, Craig , Shackleton, Charlie M , Ruwanza, Sheunesu , Dold, Tony
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/398394 , vital:69408 , xlink:href="https://doi.org/10.1002/ldr.2745"
- Description: Expansion by expansive species can have severe ecological, social and economic impacts through the reduction of ecosystem goods and services and species richness. However, expansion by expansive species may also offer benefits to ecosystems and humans, through the supply of ecosystem goods and services (such as firewood, fodder and fruits), as well as potentially offering refugia in heavily used landscapes. Here, we examine the effects of four expansive dwarf shrub species (Aspalathus subtingens, Dicerothamnus rhinocerotis, Pteronia incana and Oedera genistifolia) on plant species richness (at the point scale), vegetation cover, soil properties and whether the expansive species offer refugia to other species. Plant species richness, cover and soil properties were recorded in 1-m2 quadrats located within a mosaic of expanded and non-expanded patches for the four expansive shrub species. Plant species richness was significantly higher in the non-expanded areas compared to the expanded ones for all four expansive species. Some of the expansive shrubs provided refugia to certain plant species and limited the frequency of other species. With regard to species composition, there was little separation of expanded and non-expanded samples within sites, indicating that the site factors were stronger determinants of plant species richness and composition than expansion. Therefore, it is more likely that the reduction in species richness in expanded sites is caused by multiple drivers, including vegetation attributes cover, litter cover and soil nutrients (organic C, Zn and P) and soil compaction.
- Full Text:
- Date Issued: 2017
- Authors: Sholto-Douglas, Craig , Shackleton, Charlie M , Ruwanza, Sheunesu , Dold, Tony
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/398394 , vital:69408 , xlink:href="https://doi.org/10.1002/ldr.2745"
- Description: Expansion by expansive species can have severe ecological, social and economic impacts through the reduction of ecosystem goods and services and species richness. However, expansion by expansive species may also offer benefits to ecosystems and humans, through the supply of ecosystem goods and services (such as firewood, fodder and fruits), as well as potentially offering refugia in heavily used landscapes. Here, we examine the effects of four expansive dwarf shrub species (Aspalathus subtingens, Dicerothamnus rhinocerotis, Pteronia incana and Oedera genistifolia) on plant species richness (at the point scale), vegetation cover, soil properties and whether the expansive species offer refugia to other species. Plant species richness, cover and soil properties were recorded in 1-m2 quadrats located within a mosaic of expanded and non-expanded patches for the four expansive shrub species. Plant species richness was significantly higher in the non-expanded areas compared to the expanded ones for all four expansive species. Some of the expansive shrubs provided refugia to certain plant species and limited the frequency of other species. With regard to species composition, there was little separation of expanded and non-expanded samples within sites, indicating that the site factors were stronger determinants of plant species richness and composition than expansion. Therefore, it is more likely that the reduction in species richness in expanded sites is caused by multiple drivers, including vegetation attributes cover, litter cover and soil nutrients (organic C, Zn and P) and soil compaction.
- Full Text:
- Date Issued: 2017
A chiral hemiporphyrazine derivative
- Wu, Yanping, Gai, Lizhi, Xiao, Xuqiong, Lu, Hua, Li, Zhifang, Mack, John, Harris, Jessica, Nyokong, Tebello, Shen, Zhen
- Authors: Wu, Yanping , Gai, Lizhi , Xiao, Xuqiong , Lu, Hua , Li, Zhifang , Mack, John , Harris, Jessica , Nyokong, Tebello , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240404 , vital:50831 , xlink:href="https://doi.org/10.1002/asia.201600754"
- Description: The synthesis of an optically active hemiporphyrazine with chiral binaphthyl substituents (1) is reported, providing the first example of the incorporation of an intrinsically chiral moiety into the macrocyclic core of a hemiporphyrazine analogue. A negative circular dichroism (CD) signal is observed in the 325–450 nm region of the CD spectrum of (S,S)-1, while mainly positive bands are observed in the 220–325 nm region. Mirror symmetry is observed across the entire wavelength range of the CD spectra of (R,R)-1 and (S,S)-1. An irreversible one-electron oxidation wave with an onset potential at 1.07 V is observed by cyclic voltammetry, along with a reversible one-electron reduction wave at −0.85 V. Density functional calculations reproduce the experimentally observed data and trends, and provide further insight into the nature of the electronic transitions.
- Full Text:
- Date Issued: 2016
- Authors: Wu, Yanping , Gai, Lizhi , Xiao, Xuqiong , Lu, Hua , Li, Zhifang , Mack, John , Harris, Jessica , Nyokong, Tebello , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240404 , vital:50831 , xlink:href="https://doi.org/10.1002/asia.201600754"
- Description: The synthesis of an optically active hemiporphyrazine with chiral binaphthyl substituents (1) is reported, providing the first example of the incorporation of an intrinsically chiral moiety into the macrocyclic core of a hemiporphyrazine analogue. A negative circular dichroism (CD) signal is observed in the 325–450 nm region of the CD spectrum of (S,S)-1, while mainly positive bands are observed in the 220–325 nm region. Mirror symmetry is observed across the entire wavelength range of the CD spectra of (R,R)-1 and (S,S)-1. An irreversible one-electron oxidation wave with an onset potential at 1.07 V is observed by cyclic voltammetry, along with a reversible one-electron reduction wave at −0.85 V. Density functional calculations reproduce the experimentally observed data and trends, and provide further insight into the nature of the electronic transitions.
- Full Text:
- Date Issued: 2016
Characterization and Electrocatalytic Activity of Nanocomposites Consisting of Nanosized Cobalt Tetraaminophenoxy Phthalocyanine, Multi‐walled Carbon Nanotubes and Gold Nanoparticles
- Shumba, Munyaradzi, Nyokong, Tebello
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188659 , vital:44773 , xlink:href="https://doi.org/10.1002/elan.201501058"
- Description: Glassy carbon electrodes were modified with composites containing cobalt tetraaminophenoxy phthalocyanine nanoparticles (CoTAPhPcNP), multi-walled carbon nanotubes (MWCNT) and gold nanorods (AuNRs). The modified electrodes were studied for their electrocatalytic behavior towards the reduction of hydrogen peroxide. Phthalocyanine nanoparticles significantly improved electron transfer kinetics as compared to phthalocyanines which are not in the nanoparticle form when alone or in the presence of multiwalled carbon nanotubes (MWCNTs). CoTAPhPcNP-MWCNT-GCE proved to be suitable for hydrogen peroxide detection with a catalytic rate constant of 3.45×103 M−1 s−1 and a detection limit of 1.61×10−7 M. Adsorption Gibbs free energy ΔGo was found to be −19.22 kJ mol−1 for CoTAPhPcNP-MWCNT-GCE.
- Full Text:
- Date Issued: 2016
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188659 , vital:44773 , xlink:href="https://doi.org/10.1002/elan.201501058"
- Description: Glassy carbon electrodes were modified with composites containing cobalt tetraaminophenoxy phthalocyanine nanoparticles (CoTAPhPcNP), multi-walled carbon nanotubes (MWCNT) and gold nanorods (AuNRs). The modified electrodes were studied for their electrocatalytic behavior towards the reduction of hydrogen peroxide. Phthalocyanine nanoparticles significantly improved electron transfer kinetics as compared to phthalocyanines which are not in the nanoparticle form when alone or in the presence of multiwalled carbon nanotubes (MWCNTs). CoTAPhPcNP-MWCNT-GCE proved to be suitable for hydrogen peroxide detection with a catalytic rate constant of 3.45×103 M−1 s−1 and a detection limit of 1.61×10−7 M. Adsorption Gibbs free energy ΔGo was found to be −19.22 kJ mol−1 for CoTAPhPcNP-MWCNT-GCE.
- Full Text:
- Date Issued: 2016
Effects of the invasive shrub, Lantana camara, on soil properties in the Eastern Cape, South Africa
- Ruwanza, Sheunesu, Shackleton, Charlie M
- Authors: Ruwanza, Sheunesu , Shackleton, Charlie M
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180459 , vital:43391 , xlink:href="https://doi.org/10.1111/wbm.12094"
- Description: Lantana camara L. is an invasive alien shrub of worldwide significance due to its impacts on biodiversity. It can alter the soil properties of invaded ecosystems and, as a result, affect management outcomes. However, knowledge on the impacts of L. camara on soil properties is scanty, especially in South Africa, despite the pervasive presence of the plant in the country. In this comparative study, the soils underneath L. camara were assessed in order to determine if they had different properties (soil physico-chemical properties, penetration resistance, infiltration, hydraulic conductivity and water repellency) in comparison to the soils in adjacent natural sites in the Eastern Cape, South Africa. Soil samples were collected from the top soil beneath the canopy of both L. camara-invaded and adjacent natural sites in five different locations over three summer months. The soils that were collected from underneath L. camara had a significantly higher total C, total P, gravimetric soil moisture (in November and December) and were repellent, compared to the soils in the adjacent natural sites. Soil penetration resistance was significantly higher in the natural sites than in the L. camara-invaded sites. The soil hydraulic conductivity, soil infiltration rate, soil pH, exchangeable cations and total N showed no significant difference between the invaded and the natural sites. It appears that the soils underneath L. camara have a high total C and total P, soil moisture and are repellent, thus influencing nutrient cycling, potentially making the soil properties underneath it ideal for its own growth. This could contribute to the success of L. camara as an invasive species.
- Full Text:
- Date Issued: 2016
- Authors: Ruwanza, Sheunesu , Shackleton, Charlie M
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180459 , vital:43391 , xlink:href="https://doi.org/10.1111/wbm.12094"
- Description: Lantana camara L. is an invasive alien shrub of worldwide significance due to its impacts on biodiversity. It can alter the soil properties of invaded ecosystems and, as a result, affect management outcomes. However, knowledge on the impacts of L. camara on soil properties is scanty, especially in South Africa, despite the pervasive presence of the plant in the country. In this comparative study, the soils underneath L. camara were assessed in order to determine if they had different properties (soil physico-chemical properties, penetration resistance, infiltration, hydraulic conductivity and water repellency) in comparison to the soils in adjacent natural sites in the Eastern Cape, South Africa. Soil samples were collected from the top soil beneath the canopy of both L. camara-invaded and adjacent natural sites in five different locations over three summer months. The soils that were collected from underneath L. camara had a significantly higher total C, total P, gravimetric soil moisture (in November and December) and were repellent, compared to the soils in the adjacent natural sites. Soil penetration resistance was significantly higher in the natural sites than in the L. camara-invaded sites. The soil hydraulic conductivity, soil infiltration rate, soil pH, exchangeable cations and total N showed no significant difference between the invaded and the natural sites. It appears that the soils underneath L. camara have a high total C and total P, soil moisture and are repellent, thus influencing nutrient cycling, potentially making the soil properties underneath it ideal for its own growth. This could contribute to the success of L. camara as an invasive species.
- Full Text:
- Date Issued: 2016
Electrocatalytic activity of nanocomposites of sulphur doped graphene oxide and nanosized cobalt phthalocyanines
- Shumba, Munyaradzi, Nyokong, Tebello
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188530 , vital:44762 , xlink:href="https://doi.org/10.1002/elan.201600226"
- Description: In this work we explore the electrocatalytic activity of nanocomposites of reduced sulphur doped graphene oxide nanosheets (rSDGONS) and cobalt phthalocyanine (CoPc) or cobalt tetra amino phthalocyanine (CoTAPc) towards hydrogen peroxide. Transmission electron microscopy, scanning electron microscopy, X-ray photon spectroscopy, X-ray diffraction, chronoamperometry, linear scan voltammetry and cyclic voltammetry were used to characterize the nanocomposites. Nanosized CoPc showed superior (in terms of currents) electrocatalytic oxidation and reduction of hydrogen peroxide compared to CoTAPc nanoparticles (CoTAPcNP). The lowest detection limit was obtained for hydrogen peroxide oxidation on electrodes modified with CoPcNP-rSDGONS at 1.49 µM. The same electrode gave a high adsorption equilibrium constant of 1.27×103 mol−1 and a Gibbs free energy of −17.71 kJ/mol, indicative of a spontaneous reaction on the electrode surface.
- Full Text:
- Date Issued: 2016
- Authors: Shumba, Munyaradzi , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188530 , vital:44762 , xlink:href="https://doi.org/10.1002/elan.201600226"
- Description: In this work we explore the electrocatalytic activity of nanocomposites of reduced sulphur doped graphene oxide nanosheets (rSDGONS) and cobalt phthalocyanine (CoPc) or cobalt tetra amino phthalocyanine (CoTAPc) towards hydrogen peroxide. Transmission electron microscopy, scanning electron microscopy, X-ray photon spectroscopy, X-ray diffraction, chronoamperometry, linear scan voltammetry and cyclic voltammetry were used to characterize the nanocomposites. Nanosized CoPc showed superior (in terms of currents) electrocatalytic oxidation and reduction of hydrogen peroxide compared to CoTAPc nanoparticles (CoTAPcNP). The lowest detection limit was obtained for hydrogen peroxide oxidation on electrodes modified with CoPcNP-rSDGONS at 1.49 µM. The same electrode gave a high adsorption equilibrium constant of 1.27×103 mol−1 and a Gibbs free energy of −17.71 kJ/mol, indicative of a spontaneous reaction on the electrode surface.
- Full Text:
- Date Issued: 2016
Electrode modification using alkyne manganese phthalocyanine and click chemistry for electrocatalysis
- O'Donoghue, Charles St John Nqwabuko, Fomo, Gertrude, Nyokong, Tebello
- Authors: O'Donoghue, Charles St John Nqwabuko , Fomo, Gertrude , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188541 , vital:44763 , xlink:href="https://doi.org/10.1002/elan.201600379"
- Description: In this work, azidobenzene diazonium salt is grafted onto a glassy carbon electrode (GCE) followed by clicking of manganese tetrahexynyl phthalocyanine for the electrocatalysis of hydrazine. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1,3-dipolar cycloaddition reaction, catalyzed by a copper catalyst was utilized to ‘click’ the manganese tetrahexynyl phthalocyanine to the surface of the grafted GCE. This new platform was then characterized using cyclic voltammetry (CV), scanning electrochemical microscopy (SECM) and X-ray photoelectron spectroscopy (XPS). Based on the cyclic voltammetry calibration curve of electrocatalysis for hydrazine, the clicked Mn phthalocyanine electrode proved to be an effective sensor with a sensitivity of 27.38 µA mM−1 and the limit of detection (LoD) of 15.4 pM which is a great improvement compared to other reported sensors for this analyte.
- Full Text:
- Date Issued: 2016
- Authors: O'Donoghue, Charles St John Nqwabuko , Fomo, Gertrude , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188541 , vital:44763 , xlink:href="https://doi.org/10.1002/elan.201600379"
- Description: In this work, azidobenzene diazonium salt is grafted onto a glassy carbon electrode (GCE) followed by clicking of manganese tetrahexynyl phthalocyanine for the electrocatalysis of hydrazine. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1,3-dipolar cycloaddition reaction, catalyzed by a copper catalyst was utilized to ‘click’ the manganese tetrahexynyl phthalocyanine to the surface of the grafted GCE. This new platform was then characterized using cyclic voltammetry (CV), scanning electrochemical microscopy (SECM) and X-ray photoelectron spectroscopy (XPS). Based on the cyclic voltammetry calibration curve of electrocatalysis for hydrazine, the clicked Mn phthalocyanine electrode proved to be an effective sensor with a sensitivity of 27.38 µA mM−1 and the limit of detection (LoD) of 15.4 pM which is a great improvement compared to other reported sensors for this analyte.
- Full Text:
- Date Issued: 2016
Synthesis, Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems
- Okujima, Tetsuo, Mack, John, Nakamura, Jun, Kubheka, Gugu, Nyokong, Tebello, Zhu, Hua, Komobuchi, Naoki, Ono, Noboru, Yamada, Hiroko, Uno, Hidemitsu, Kobayashi, Nagao
- Authors: Okujima, Tetsuo , Mack, John , Nakamura, Jun , Kubheka, Gugu , Nyokong, Tebello , Zhu, Hua , Komobuchi, Naoki , Ono, Noboru , Yamada, Hiroko , Uno, Hidemitsu , Kobayashi, Nagao
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240360 , vital:50827 , xlink:href="https://doi.org/10.1002/chem.201602213"
- Description: A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels–Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π-molecular orbitals.
- Full Text:
- Date Issued: 2016
- Authors: Okujima, Tetsuo , Mack, John , Nakamura, Jun , Kubheka, Gugu , Nyokong, Tebello , Zhu, Hua , Komobuchi, Naoki , Ono, Noboru , Yamada, Hiroko , Uno, Hidemitsu , Kobayashi, Nagao
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240360 , vital:50827 , xlink:href="https://doi.org/10.1002/chem.201602213"
- Description: A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels–Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π-molecular orbitals.
- Full Text:
- Date Issued: 2016
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
Synthesis and Photophysical Investigation of Tetraazaporphyrin Substituted with Aggregation‐Induced Emission (AIE) Active Moieties
- Tasso, Thiago T, Furuyama, Taniyuki, Mack, John, Nyokong, Tebello, Kobayashi, Nagao
- Authors: Tasso, Thiago T , Furuyama, Taniyuki , Mack, John , Nyokong, Tebello , Kobayashi, Nagao
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193553 , vital:45346 , xlink:href="https://doi.org/10.1002/ejic.201500726"
- Description: The synthesis and characterization of free-base and ZnII tetraazaporphyrins with tetraphenylethylene (TPE) or diphenylphenanthrene (DPP) moieties that are known to be aggregation-induced emission (AIE) active is reported. The optical spectra contain the characteristic Q and B absorption bands of Gouterman's four-orbital model and a broad envelope of weaker charge-transfer bands in the 450–600 nm region. The observed fluorescence emission lies beyond 670 nm and originates exclusively from the decay of the S1 state of the macrocycle, regardless of the excitation wavelength used. Theoretical calculations provide further evidence of strong electronic communication between the peripheral TPE or DPP moieties and the central ring. The ZnII complexes were found to have relatively high singlet-oxygen quantum yields.
- Full Text:
- Date Issued: 2015
- Authors: Tasso, Thiago T , Furuyama, Taniyuki , Mack, John , Nyokong, Tebello , Kobayashi, Nagao
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193553 , vital:45346 , xlink:href="https://doi.org/10.1002/ejic.201500726"
- Description: The synthesis and characterization of free-base and ZnII tetraazaporphyrins with tetraphenylethylene (TPE) or diphenylphenanthrene (DPP) moieties that are known to be aggregation-induced emission (AIE) active is reported. The optical spectra contain the characteristic Q and B absorption bands of Gouterman's four-orbital model and a broad envelope of weaker charge-transfer bands in the 450–600 nm region. The observed fluorescence emission lies beyond 670 nm and originates exclusively from the decay of the S1 state of the macrocycle, regardless of the excitation wavelength used. Theoretical calculations provide further evidence of strong electronic communication between the peripheral TPE or DPP moieties and the central ring. The ZnII complexes were found to have relatively high singlet-oxygen quantum yields.
- Full Text:
- Date Issued: 2015
Behavior of palladium nanoparticles in the absence or presence of cobalt tetraaminophthalocyanine for the electrooxidation of hydrazine
- Maringa, Audacity, Nyokong, Tebello
- Authors: Maringa, Audacity , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189796 , vital:44932 , xlink:href="https://doi.org/10.1002/elan.201400028"
- Description: We report on the electrodeposition of palladium nanoparticles (PdNPs) on a glassy carbon electrode (GCE) and onto a poly-CoTAPc-GCE (CoTAPc=cobalt tetraamino phthalocyanine) surface. The electrodes are denoted as PdNPs-GCE and PdNPs/poly-CoTAPc-GCE, respectively. PdNPs/poly-CoTAPc-GCE showed the best activity for the oxidation of hydrazine at the lowest potential of −0.28 V and with the highest currents. The results were further supported by electrochemical impedance spectroscopy (EIS) which showed that there was less resistance to charge transfer for PdNPs/poly-CoTAPc-GCE compared to PdNPs-GCE. The catalytic rate constant for hydrazine oxidation was 6.12×108 cm3 mol−1 s−1 using PdNPs/poly-CoTAPc-GCE.
- Full Text:
- Date Issued: 2014
- Authors: Maringa, Audacity , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189796 , vital:44932 , xlink:href="https://doi.org/10.1002/elan.201400028"
- Description: We report on the electrodeposition of palladium nanoparticles (PdNPs) on a glassy carbon electrode (GCE) and onto a poly-CoTAPc-GCE (CoTAPc=cobalt tetraamino phthalocyanine) surface. The electrodes are denoted as PdNPs-GCE and PdNPs/poly-CoTAPc-GCE, respectively. PdNPs/poly-CoTAPc-GCE showed the best activity for the oxidation of hydrazine at the lowest potential of −0.28 V and with the highest currents. The results were further supported by electrochemical impedance spectroscopy (EIS) which showed that there was less resistance to charge transfer for PdNPs/poly-CoTAPc-GCE compared to PdNPs-GCE. The catalytic rate constant for hydrazine oxidation was 6.12×108 cm3 mol−1 s−1 using PdNPs/poly-CoTAPc-GCE.
- Full Text:
- Date Issued: 2014
Contrasting architecture of key African and Australian savanna tree taxa drives intercontinental structural divergence
- Moncrieff, Glenn R, Lehmann, Caroline E, Schnitzler, Jan, Gambiza, James, Hiernaux, Pierre, Ryan, Casey M, Shackleton, Charlie M, Williams, Richard J, Higgins, Steven I
- Authors: Moncrieff, Glenn R , Lehmann, Caroline E , Schnitzler, Jan , Gambiza, James , Hiernaux, Pierre , Ryan, Casey M , Shackleton, Charlie M , Williams, Richard J , Higgins, Steven I
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180919 , vital:43670 , xlink:href="https://doi.org/10.1111/geb.12205"
- Description: We examined differences in the architecture of African and Australian savanna trees. We sought to attribute variation in tree architecture to current environments, wood density and phylogeny, and thereby elucidate the relative importance of biogeographic idiosyncrasies versus current factors in underpinning architectural differences.
- Full Text:
- Date Issued: 2014
- Authors: Moncrieff, Glenn R , Lehmann, Caroline E , Schnitzler, Jan , Gambiza, James , Hiernaux, Pierre , Ryan, Casey M , Shackleton, Charlie M , Williams, Richard J , Higgins, Steven I
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180919 , vital:43670 , xlink:href="https://doi.org/10.1111/geb.12205"
- Description: We examined differences in the architecture of African and Australian savanna trees. We sought to attribute variation in tree architecture to current environments, wood density and phylogeny, and thereby elucidate the relative importance of biogeographic idiosyncrasies versus current factors in underpinning architectural differences.
- Full Text:
- Date Issued: 2014
Development of Graphene/CdSe Quantum Dots‐Co Phthalocyanine Nanocomposite for Oxygen Reduction Reaction
- Nyoni, Stephen, Nyokong, Tebello
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189944 , vital:44950 , xlink:href="https://doi.org/10.1002/elan.201400372"
- Description: Nanocomposites containing CdSe quantum dots, tetra(4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninatocobalt(II)) (CoPyPc) and reduced graphene nanosheets (rGNS) were devoloped and used for the modification of a glassy carbon electrode. Characterization of the nanocomposites was done by transmission electron microscopy (TEM) and X-ray diffraction (XRD) analyses. Cyclic voltammetry (CV) was used for electrochemical characterization of the prepared nanocomposite for oxygen reduction reaction. The oxygen reduction activity for rGNS/CdSe-CoPyPc nanocomposite was found to be superior over the individual nanomaterials in this study. The activity of the nanocomposite towards oxygen reduction was also tested for tolerance to methanol crossover effect using chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) studies.
- Full Text:
- Date Issued: 2014
- Authors: Nyoni, Stephen , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189944 , vital:44950 , xlink:href="https://doi.org/10.1002/elan.201400372"
- Description: Nanocomposites containing CdSe quantum dots, tetra(4-(4,6-diaminopyrimidin-2-ylthio) phthalocyaninatocobalt(II)) (CoPyPc) and reduced graphene nanosheets (rGNS) were devoloped and used for the modification of a glassy carbon electrode. Characterization of the nanocomposites was done by transmission electron microscopy (TEM) and X-ray diffraction (XRD) analyses. Cyclic voltammetry (CV) was used for electrochemical characterization of the prepared nanocomposite for oxygen reduction reaction. The oxygen reduction activity for rGNS/CdSe-CoPyPc nanocomposite was found to be superior over the individual nanomaterials in this study. The activity of the nanocomposite towards oxygen reduction was also tested for tolerance to methanol crossover effect using chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) studies.
- Full Text:
- Date Issued: 2014
Effects of redox mediators on the catalytic activity of iron porphyrins towards oxygen reduction in acidic media
- He, Qinggang, Wu, Gang, Liu, Ke, Khene, Samson M, Li, Qing, Mugadza, Tawanda, Deunf, Elise, Nyokong, Tebello, Chen, Shaowei W
- Authors: He, Qinggang , Wu, Gang , Liu, Ke , Khene, Samson M , Li, Qing , Mugadza, Tawanda , Deunf, Elise , Nyokong, Tebello , Chen, Shaowei W
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241472 , vital:50942 , xlink:href="https://doi.org/10.1002/celc.201402054"
- 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.
- Full Text:
- Date Issued: 2014
- Authors: He, Qinggang , Wu, Gang , Liu, Ke , Khene, Samson M , Li, Qing , Mugadza, Tawanda , Deunf, Elise , Nyokong, Tebello , Chen, Shaowei W
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241472 , vital:50942 , xlink:href="https://doi.org/10.1002/celc.201402054"
- 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.
- Full Text:
- Date Issued: 2014
Electro‐oxidation of acetaminophen on nickel/poly (o‐aminophenol)/multi‐walled carbon nanotube nanocomposite modified graphite electrode.
- Naeemy, Ali, Mohammadi, Ali, Bakhtiari, Hediech, Ashouri, Nasim, Walker, Roderick B
- Authors: Naeemy, Ali , Mohammadi, Ali , Bakhtiari, Hediech , Ashouri, Nasim , Walker, Roderick B
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184107 , vital:44173 , xlink:href="https://ietresearch.onlinelibrary.wiley.com/doi/pdf/10.1049/mnl.2014.0197"
- Description: Poly(o-aminophenol) (POAP)/multi-walled carbon nanotube (MWCNT) nanocomposite and POAP in the absence of the MWCNT were fabricated by consecutive cyclic voltammetry (CV) on a graphite (G) electrode. The dispersion of nickel (II) ions was accomplished and incorporated into the polymeric electrodes (G/POAP and G/POAP-MWCNT) by immersing them into a 0.1 M nickel (II) solution. Following preparation of G/POAP/Ni and G/POAP-MWCNT/Ni, the electrochemical behaviour was examined using CV. Scanning electron microscopy was used for characterisation of the nanocomposite. The prepared electrodes showed enhanced electrocatalytic activity for the oxidation of acetaminophen and facilitated the detection of acetaminophen in a 0.1 M NaOH solution. Compared with the G/POAP/Ni electrode, the G/POAP-MWCNT/Ni electrode had a significant current response of acetaminophen oxidation because of the synergistic effects of POAP and the MWCNT. By CV, the calibration plot was linear in the range of 1–13 mM with standard deviation between 0.3 and 6.54% for acetaminophen. The G/POAP-MWCNT/Ni was successfully applied for acetaminophen determination in tablets and the results showed sufficient precision and achieved a mean recovery of 96.8% (R.S.D. = 4.9%).
- Full Text:
- Date Issued: 2014
- Authors: Naeemy, Ali , Mohammadi, Ali , Bakhtiari, Hediech , Ashouri, Nasim , Walker, Roderick B
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/184107 , vital:44173 , xlink:href="https://ietresearch.onlinelibrary.wiley.com/doi/pdf/10.1049/mnl.2014.0197"
- Description: Poly(o-aminophenol) (POAP)/multi-walled carbon nanotube (MWCNT) nanocomposite and POAP in the absence of the MWCNT were fabricated by consecutive cyclic voltammetry (CV) on a graphite (G) electrode. The dispersion of nickel (II) ions was accomplished and incorporated into the polymeric electrodes (G/POAP and G/POAP-MWCNT) by immersing them into a 0.1 M nickel (II) solution. Following preparation of G/POAP/Ni and G/POAP-MWCNT/Ni, the electrochemical behaviour was examined using CV. Scanning electron microscopy was used for characterisation of the nanocomposite. The prepared electrodes showed enhanced electrocatalytic activity for the oxidation of acetaminophen and facilitated the detection of acetaminophen in a 0.1 M NaOH solution. Compared with the G/POAP/Ni electrode, the G/POAP-MWCNT/Ni electrode had a significant current response of acetaminophen oxidation because of the synergistic effects of POAP and the MWCNT. By CV, the calibration plot was linear in the range of 1–13 mM with standard deviation between 0.3 and 6.54% for acetaminophen. The G/POAP-MWCNT/Ni was successfully applied for acetaminophen determination in tablets and the results showed sufficient precision and achieved a mean recovery of 96.8% (R.S.D. = 4.9%).
- Full Text:
- Date Issued: 2014