(Ferrocenylpyrazolyl) zinc (II) benzoates as catalysts for the ring opening polymerization of ε-caprolactone
- Obuah, Collins, Lochee, Yemanlall, Jordaan, Johan H L, Otto, Daniel P, Nyokong, Tebello, Darkwa, James
- Authors: Obuah, Collins , Lochee, Yemanlall , Jordaan, Johan H L , Otto, Daniel P , Nyokong, Tebello , Darkwa, James
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189515 , vital:44853 , xlink:href="https://doi.org/10.1016/j.poly.2015.02.007"
- Description: The reaction of Zn(OAc)2 and C6H5COOH or 3,5-NO2-C6H3COOH with 3-ferrocenylpyrazolyl-methylenepyridine (L1), 3-ferrocenyl-5-methylpyrazolyl-methylenepyridine (L2), 3-ferrocenylpyrazolyl-ethylamine (L3) and 3-ferrocenyl-5-pyrazolyl-ethylamine (L4) afford the corresponding complexes [Zn(C6H5COO)2(L1)] (1), [Zn(C6H5COO)2(L2)] (2), [Zn(3,5-NO2-C6H3COO)2(L1)] (3), [Zn(3,5-NO2-C6H3 COO)2(L2)] (4), [Zn(C6H5COO)2(L3)] (5), [Zn(C6H5COO)2(L4)] (6), [Zn(3,5-NO2-C6H3COO)2(L3)] (7) and [Zn(3,5-NO2-C6H3COO)2(L4)] (8). These complexes behave as catalysts for the ring opening polymerization of e-caprolactone to produce polymers with molecular weight that range from 1480 to 7080 g mol1 and exhibited moderate to broad PDIs. Evidence of these complexes acting as catalysts was obtained from both the polymerization data and kinetic studies. The polymerization data show that variation of the [CL]/[C] from 100 to 800 produced PCL with relatively the same molecular weight indicative of a catalyst behavior. The appearance of induction period in kinetic plots strengthens the fact that these complexes are catalysts rather than initiators. MALDI-TOF MS and 1 H NMR data show di-hydroxy end groups, which support the coordination mechanism rather than insertion mechanism. To understand the broad PDIs obtained for some of the polymer, the electronic properties of the zinc complexes were investigated using cyclic voltammetry. The results show that the zinc complexes containing amine based ligands are highly electrophilic therefore making them unstable, hence the broad PDIs observed for zinc complexes containing amine based ligands. Among the eight complexes investigated, complex 7 is the most active catalyst with kp value of 1.18 107 h1 mol1 at 110 C.
- Full Text:
- Date Issued: 2015
- Authors: Obuah, Collins , Lochee, Yemanlall , Jordaan, Johan H L , Otto, Daniel P , Nyokong, Tebello , Darkwa, James
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189515 , vital:44853 , xlink:href="https://doi.org/10.1016/j.poly.2015.02.007"
- Description: The reaction of Zn(OAc)2 and C6H5COOH or 3,5-NO2-C6H3COOH with 3-ferrocenylpyrazolyl-methylenepyridine (L1), 3-ferrocenyl-5-methylpyrazolyl-methylenepyridine (L2), 3-ferrocenylpyrazolyl-ethylamine (L3) and 3-ferrocenyl-5-pyrazolyl-ethylamine (L4) afford the corresponding complexes [Zn(C6H5COO)2(L1)] (1), [Zn(C6H5COO)2(L2)] (2), [Zn(3,5-NO2-C6H3COO)2(L1)] (3), [Zn(3,5-NO2-C6H3 COO)2(L2)] (4), [Zn(C6H5COO)2(L3)] (5), [Zn(C6H5COO)2(L4)] (6), [Zn(3,5-NO2-C6H3COO)2(L3)] (7) and [Zn(3,5-NO2-C6H3COO)2(L4)] (8). These complexes behave as catalysts for the ring opening polymerization of e-caprolactone to produce polymers with molecular weight that range from 1480 to 7080 g mol1 and exhibited moderate to broad PDIs. Evidence of these complexes acting as catalysts was obtained from both the polymerization data and kinetic studies. The polymerization data show that variation of the [CL]/[C] from 100 to 800 produced PCL with relatively the same molecular weight indicative of a catalyst behavior. The appearance of induction period in kinetic plots strengthens the fact that these complexes are catalysts rather than initiators. MALDI-TOF MS and 1 H NMR data show di-hydroxy end groups, which support the coordination mechanism rather than insertion mechanism. To understand the broad PDIs obtained for some of the polymer, the electronic properties of the zinc complexes were investigated using cyclic voltammetry. The results show that the zinc complexes containing amine based ligands are highly electrophilic therefore making them unstable, hence the broad PDIs observed for zinc complexes containing amine based ligands. Among the eight complexes investigated, complex 7 is the most active catalyst with kp value of 1.18 107 h1 mol1 at 110 C.
- Full Text:
- Date Issued: 2015
Characterization of some amino acid derivatives of benzoyl isothiocyanate: Crystal structures and theoretical prediction of their reactivity
- Odame, Felix, Hosten, Eric C, Betz, Richard, Lobb, Kevin A, Tshentu, Zenixole R
- Authors: Odame, Felix , Hosten, Eric C , Betz, Richard , Lobb, Kevin A , Tshentu, Zenixole R
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/447952 , vital:74686 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.05.053"
- Description: The reaction of benzoyl isothiocyanate with L-serine, L-proline, D-methionine and L-alanine gave 2-[(benzoylcarbamothioyl)amino]-3-hydroxypropanoic acid (I), 1-(benzoylcarbamothioyl)pyrrolidine-2-carboxylic acid (II), 2-[(benzoylcarbamothioyl)amino]-4-(methylsulfanyl)butanoic acid (III) and 2-[(benzoylcarbamothioyl)amino]propanoic acid (IV), respectively. The compounds have been characterized by IR, NMR, microanalyses and mass spectrometry. The crystal structures of all the compounds have also been discussed. Compound II showed rotamers in solution. DFT calculations of the frontier orbitals of the compounds have been carried out to ascertain the groups that contribute to the HOMO and LUMO, and to study their contribution to the reactivity of these compounds. The calculations indicated that the carboxylic acid group in these compounds is unreactive hence making the conversion to benzimidazoles via cyclization on the carboxylic acids impractical. This has been further confirmed by the reaction of compounds I–IV, respectively, with o-phenylene diamine which was unsuccessful but gave compound V.
- Full Text:
- Date Issued: 2015
- Authors: Odame, Felix , Hosten, Eric C , Betz, Richard , Lobb, Kevin A , Tshentu, Zenixole R
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/447952 , vital:74686 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.05.053"
- Description: The reaction of benzoyl isothiocyanate with L-serine, L-proline, D-methionine and L-alanine gave 2-[(benzoylcarbamothioyl)amino]-3-hydroxypropanoic acid (I), 1-(benzoylcarbamothioyl)pyrrolidine-2-carboxylic acid (II), 2-[(benzoylcarbamothioyl)amino]-4-(methylsulfanyl)butanoic acid (III) and 2-[(benzoylcarbamothioyl)amino]propanoic acid (IV), respectively. The compounds have been characterized by IR, NMR, microanalyses and mass spectrometry. The crystal structures of all the compounds have also been discussed. Compound II showed rotamers in solution. DFT calculations of the frontier orbitals of the compounds have been carried out to ascertain the groups that contribute to the HOMO and LUMO, and to study their contribution to the reactivity of these compounds. The calculations indicated that the carboxylic acid group in these compounds is unreactive hence making the conversion to benzimidazoles via cyclization on the carboxylic acids impractical. This has been further confirmed by the reaction of compounds I–IV, respectively, with o-phenylene diamine which was unsuccessful but gave compound V.
- Full Text:
- Date Issued: 2015
Electrocatalytic activity of bimetallic Au–Pd nanoparticles in the presence of cobalt tetraaminophthalocyanine
- Maringa, Audacity, Mashazi, Philani N, Nyokong, Tebello
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189719 , vital:44925 , xlink:href="https://doi.org/10.1016/j.jcis.2014.10.056"
- Description: Au and Pd nanoparticles were individually or together electrodeposited on top of polymerized cobalt tetraaminophthalocyanine (poly-CoTAPc). When Pd and Au nanoparticles are co-deposited together, the electrode is denoted as Au–Pd (co-deposited)/poly-CoTAPc-GCE. X-ray photoelectron spectroscopy (XPS) was used to show the successful deposition of AuNPs, PdNPs and Au–Pd (co-deposited). The scanning electrochemical microscopy showed that Au–Pd (co-deposited)/poly-CoTAPc-GCE (with current range of 9.5–13.5 lA) was more conducting than Au–Pd (co-deposited)-GCE (with current range of 8–12 lA). Electrochemical impedance spectroscopy (EIS) showed that there was less resistance to charge transfer for Au–Pd (co-deposited)/poly-CoTAPc-GCE compared to the rest of the electrodes. Au–Pd (co-deposited)/poly-CoTAPc-GCE showed the best activity for the electrooxidation of hydrazine in terms of limit of detection (0.5 lM), hence shows promise as an electrocatalyst for electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2015
- Authors: Maringa, Audacity , Mashazi, Philani N , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189719 , vital:44925 , xlink:href="https://doi.org/10.1016/j.jcis.2014.10.056"
- Description: Au and Pd nanoparticles were individually or together electrodeposited on top of polymerized cobalt tetraaminophthalocyanine (poly-CoTAPc). When Pd and Au nanoparticles are co-deposited together, the electrode is denoted as Au–Pd (co-deposited)/poly-CoTAPc-GCE. X-ray photoelectron spectroscopy (XPS) was used to show the successful deposition of AuNPs, PdNPs and Au–Pd (co-deposited). The scanning electrochemical microscopy showed that Au–Pd (co-deposited)/poly-CoTAPc-GCE (with current range of 9.5–13.5 lA) was more conducting than Au–Pd (co-deposited)-GCE (with current range of 8–12 lA). Electrochemical impedance spectroscopy (EIS) showed that there was less resistance to charge transfer for Au–Pd (co-deposited)/poly-CoTAPc-GCE compared to the rest of the electrodes. Au–Pd (co-deposited)/poly-CoTAPc-GCE showed the best activity for the electrooxidation of hydrazine in terms of limit of detection (0.5 lM), hence shows promise as an electrocatalyst for electrooxidation of hydrazine.
- Full Text:
- Date Issued: 2015
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
Facile synthesis, spectroscopic and electrochemical properties, and theoretical calculations of porphyrin dimers with a bridging amide-bonded xanthene moiety
- Liang, Xu, Xu, Li, Li, Minzhi, Mack, John, Stone, Justin, Nyokong, Tebello, Jiang, Yu, Kobayashi, Nagao, Zhu, Weihua
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241390 , vital:50935 , xlink:href="https://doi.org/10.1142/S1088424615500492"
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety.
- Full Text:
- Date Issued: 2015
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241390 , vital:50935 , xlink:href="https://doi.org/10.1142/S1088424615500492"
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety.
- Full Text:
- Date Issued: 2015
Isomerization of the 2-Norbornyl Carbocation
- Authors: Lobb, Kevin A
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/447992 , vital:74689 , xlink:href="https://doi.org/10.1002/ejoc.201500518"
- Description: In order to elucidate the mechanism for the isomerization of the 2-norbornyl carbocation into its most stable isomer, the 1,3-dimethylcyclopentenyl carbocation, an extensive set of the possible isomers of C7H11+ has been generated. Each one of these may undergo a number of transformations, and location of these transition states provides a searchable graph, from which pathways may be identified. This reveals that the preferred route for isomerization of the 2-norbornyl carbocation is not by ring opening of the non-classical center as has been reported in the literature (with an activation energy of 33.2 kcal/mol), but is initiated by cleavage of the C3–C4 bond (23.5 kcal/mol). Further, no single mechanism is sufficient to describe the full sequence of isomerizations of the 2-norbornyl carbocation to its most stable isomer, the 1,3-dimethylcylcopentenyl carbocation, but rather a collection (> 109) of pathways.
- Full Text:
- Date Issued: 2015
- Authors: Lobb, Kevin A
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/447992 , vital:74689 , xlink:href="https://doi.org/10.1002/ejoc.201500518"
- Description: In order to elucidate the mechanism for the isomerization of the 2-norbornyl carbocation into its most stable isomer, the 1,3-dimethylcyclopentenyl carbocation, an extensive set of the possible isomers of C7H11+ has been generated. Each one of these may undergo a number of transformations, and location of these transition states provides a searchable graph, from which pathways may be identified. This reveals that the preferred route for isomerization of the 2-norbornyl carbocation is not by ring opening of the non-classical center as has been reported in the literature (with an activation energy of 33.2 kcal/mol), but is initiated by cleavage of the C3–C4 bond (23.5 kcal/mol). Further, no single mechanism is sufficient to describe the full sequence of isomerizations of the 2-norbornyl carbocation to its most stable isomer, the 1,3-dimethylcylcopentenyl carbocation, but rather a collection (> 109) of pathways.
- Full Text:
- Date Issued: 2015
Multiple benefits and values of trees in urban landscapes in two towns in northern South Africa
- Shackleton, Sheona E, Chinyimba, Abby, Hebinck, Paul, Shackleton, Charlie M, Kaoma, Humphrey
- Authors: Shackleton, Sheona E , Chinyimba, Abby , Hebinck, Paul , Shackleton, Charlie M , Kaoma, Humphrey
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180874 , vital:43658 , xlink:href="https://doi.org/10.1016/j.landurbplan.2014.12.004"
- Description: Cities and towns can be conceptualised as complex social-ecological systems or landscapes that are composed of different spatial elements. Trees in urban landscapes provide a variety of tangible and intangible benefits (ecosystem services) that may be valued differently across diverse households and individuals. Here, we consider how the benefits and values of trees to urban residents vary across public and private spaces in three low income neighbourhoods in two medium-sized towns in northern South Africa. We find that the most asset poor residents in informal settlements derive significant benefits from the provisioning services offered by trees in natural green spaces on the ‘urban periphery’; in particular they value supplies of wood for energy, whilst also recognising the importance of regulating services such as shade. Trees in such spaces help these immigrants cope with a lack of infrastructure, services and disposable income after their move to the city. In new, low-cost housing neighbourhoods, the importance of trees in providing shade and shelter in gardens is emphasised due to the hot and dusty nature of these settlements, while residents in older township neighbourhoods make more mention of the aesthetic value of trees in private spaces as well as the fruits they provide. In all neighbourhoods, attitudes towards trees in public spaces were mixed because of their perceived association with crime, although low income households did make extensive use of tree products from natural areas. The relevance of the results for urban planning and greening in low income areas is discussed.
- Full Text:
- Date Issued: 2015
- Authors: Shackleton, Sheona E , Chinyimba, Abby , Hebinck, Paul , Shackleton, Charlie M , Kaoma, Humphrey
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/180874 , vital:43658 , xlink:href="https://doi.org/10.1016/j.landurbplan.2014.12.004"
- Description: Cities and towns can be conceptualised as complex social-ecological systems or landscapes that are composed of different spatial elements. Trees in urban landscapes provide a variety of tangible and intangible benefits (ecosystem services) that may be valued differently across diverse households and individuals. Here, we consider how the benefits and values of trees to urban residents vary across public and private spaces in three low income neighbourhoods in two medium-sized towns in northern South Africa. We find that the most asset poor residents in informal settlements derive significant benefits from the provisioning services offered by trees in natural green spaces on the ‘urban periphery’; in particular they value supplies of wood for energy, whilst also recognising the importance of regulating services such as shade. Trees in such spaces help these immigrants cope with a lack of infrastructure, services and disposable income after their move to the city. In new, low-cost housing neighbourhoods, the importance of trees in providing shade and shelter in gardens is emphasised due to the hot and dusty nature of these settlements, while residents in older township neighbourhoods make more mention of the aesthetic value of trees in private spaces as well as the fruits they provide. In all neighbourhoods, attitudes towards trees in public spaces were mixed because of their perceived association with crime, although low income households did make extensive use of tree products from natural areas. The relevance of the results for urban planning and greening in low income areas is discussed.
- Full Text:
- Date Issued: 2015
Photoinactivation of Candida albicans and Escherichia coli using aluminium phthalocyanine on gold nanoparticles
- Mthethwa, Thandekile, Nyokong, Tebello
- Authors: Mthethwa, Thandekile , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189854 , vital:44940 , xlink:href="https://doi.org/10.1039/C4PP00315B"
- Description: The conjugates of aluminium phthalocyanine (complex 1) with gold nanorods (complex 1–AuNRs) and bipyramids (complex 1–AuBPs) showed improved singlet oxygen quantum yields of 0.23 and 0.24, respectively, compared to that of complex 1 alone at 0.12. Complex 1 and its conjugates were used for the photoinactivation of fungi (C. albicans) and bacteria cells (E. coli). The Q band absorbances were the same for the Pc alone and when conjugated to AuNPs. The efficiency of these conjugates was evaluated by measuring the log reduction of the microorganisms (C. albicans and E. coli) after irradiation with visible light in the presence of photosensitizers. Aluminium phthalocyanine alone showed log 1.78 and log 2.51 reductions for C. albicans and E. coli respectively. However, the conjugates showed higher photosensitization with log 2.08 and log 3.34 for C. albicans and E. coli, respectively using 1–AuBPs. For complex 1–AuNRs log 2.53 and log 3.71 were achieved for C. albicans and E. coli respectively. The statistical analysis of the results showed that the enhanced photoinactivation observed in both microorganisms was irrespective of the shape of the nanoparticles conjugated. Photoinactivation of C. albicans was less than that of E. coli even though a higher concentration of complex 1 or its conjugates was used in C. albicans.
- Full Text:
- Date Issued: 2015
- Authors: Mthethwa, Thandekile , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189854 , vital:44940 , xlink:href="https://doi.org/10.1039/C4PP00315B"
- Description: The conjugates of aluminium phthalocyanine (complex 1) with gold nanorods (complex 1–AuNRs) and bipyramids (complex 1–AuBPs) showed improved singlet oxygen quantum yields of 0.23 and 0.24, respectively, compared to that of complex 1 alone at 0.12. Complex 1 and its conjugates were used for the photoinactivation of fungi (C. albicans) and bacteria cells (E. coli). The Q band absorbances were the same for the Pc alone and when conjugated to AuNPs. The efficiency of these conjugates was evaluated by measuring the log reduction of the microorganisms (C. albicans and E. coli) after irradiation with visible light in the presence of photosensitizers. Aluminium phthalocyanine alone showed log 1.78 and log 2.51 reductions for C. albicans and E. coli respectively. However, the conjugates showed higher photosensitization with log 2.08 and log 3.34 for C. albicans and E. coli, respectively using 1–AuBPs. For complex 1–AuNRs log 2.53 and log 3.71 were achieved for C. albicans and E. coli respectively. The statistical analysis of the results showed that the enhanced photoinactivation observed in both microorganisms was irrespective of the shape of the nanoparticles conjugated. Photoinactivation of C. albicans was less than that of E. coli even though a higher concentration of complex 1 or its conjugates was used in C. albicans.
- Full Text:
- Date Issued: 2015
Photophysical properties and photodynamic therapy effect of zinc phthalocyanine-spermine-single walled carbon nanotube conjugate on MCF-7 breast cancer cell line
- Ogbodu, Rachael O, Limson, Janice L, Prinsloo, Earl, Nyokong, Tebello
- Authors: Ogbodu, Rachael O , Limson, Janice L , Prinsloo, Earl , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189493 , vital:44851 , xlink:href="https://doi.org/10.1016/j.synthmet.2015.03.011"
- Description: The present study shows improved photodynamic therapy (PDT) effect of zinc mono carboxy phenoxy phthalocyanine (ZnMCPPc (1)) upon conjugation to spermine (via amide bond) as a targeting molecule on MCF-7 breast cancer cells. The ZnMCPPc-spermine (2) conjugate was adsorbed onto single walled carbon nanotubes (represented as ZnMCPPc-spermine-SWCNT (3)). There was no change in the fluorescence quantum yield of complex 1 following formation of 2 or 3. Complexes 2 and 3 showed improved photophysical properties; with over 50% increases in triplet and singlet oxygen quantum yields compared to 1. Complexes 1, 2 and 3 were relatively not toxic to MCF-7 cancer cells when incubated with 5–40 μM of each complex for 24 h in the dark. The PDT results showed that at 40 μM complex 1 resulted in only 64% decrease in cell viability, while 2 and 3 improved the PDT effect of 1 to 97% and 95% decrease in cell viability at 40 μM respectively.
- Full Text:
- Date Issued: 2015
- Authors: Ogbodu, Rachael O , Limson, Janice L , Prinsloo, Earl , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189493 , vital:44851 , xlink:href="https://doi.org/10.1016/j.synthmet.2015.03.011"
- Description: The present study shows improved photodynamic therapy (PDT) effect of zinc mono carboxy phenoxy phthalocyanine (ZnMCPPc (1)) upon conjugation to spermine (via amide bond) as a targeting molecule on MCF-7 breast cancer cells. The ZnMCPPc-spermine (2) conjugate was adsorbed onto single walled carbon nanotubes (represented as ZnMCPPc-spermine-SWCNT (3)). There was no change in the fluorescence quantum yield of complex 1 following formation of 2 or 3. Complexes 2 and 3 showed improved photophysical properties; with over 50% increases in triplet and singlet oxygen quantum yields compared to 1. Complexes 1, 2 and 3 were relatively not toxic to MCF-7 cancer cells when incubated with 5–40 μM of each complex for 24 h in the dark. The PDT results showed that at 40 μM complex 1 resulted in only 64% decrease in cell viability, while 2 and 3 improved the PDT effect of 1 to 97% and 95% decrease in cell viability at 40 μM respectively.
- Full Text:
- Date Issued: 2015
Conjugation of mono-substituted phthalocyanine derivatives to CdSe@ ZnS quantum dots and their applications as fluorescent-based sensors
- Adegoke, Oluwasesan, Nyokong, Tebello
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189842 , vital:44936 , xlink:href="https://doi.org/10.1016/j.synthmet.2013.11.016"
- Description: Unsymmetrically substituted derivatives of aluminium amino phthalocyanines were synthesized for the first time, fully characterized and conjugated to CdSe@ZnS quantum dots (QDs). The conjugates were employed as fluorescence-based sensors for anion sensing. Among the anions that enhanced the fluorescence of the probe, fluoride ion was chosen as the test ion to test the efficacy of the probe. Förster resonance energy transfer from the QDs to the phthalocyanine was observed as an indication for the fluorescence quenching of the QDs upon binding to the phthalocyanine. The fluorescence of the linked QDs was progressively enhanced, and linearly proportional to increasing concentrations of fluoride ion. The type of substituent attached to the phthalocyanine ring influenced the efficiency of fluorescence enhancement. The proposed nanoprobe has been employed to detect fluoride ion in cell culture medium and tap water.
- Full Text:
- Date Issued: 2014
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189842 , vital:44936 , xlink:href="https://doi.org/10.1016/j.synthmet.2013.11.016"
- Description: Unsymmetrically substituted derivatives of aluminium amino phthalocyanines were synthesized for the first time, fully characterized and conjugated to CdSe@ZnS quantum dots (QDs). The conjugates were employed as fluorescence-based sensors for anion sensing. Among the anions that enhanced the fluorescence of the probe, fluoride ion was chosen as the test ion to test the efficacy of the probe. Förster resonance energy transfer from the QDs to the phthalocyanine was observed as an indication for the fluorescence quenching of the QDs upon binding to the phthalocyanine. The fluorescence of the linked QDs was progressively enhanced, and linearly proportional to increasing concentrations of fluoride ion. The type of substituent attached to the phthalocyanine ring influenced the efficiency of fluorescence enhancement. The proposed nanoprobe has been employed to detect fluoride ion in cell culture medium and tap water.
- Full Text:
- Date Issued: 2014
Culture environment and hatchery of origin influence growth, condition and feeding organ morphology in the Pacific oyster Crassostrea gigas in South Africa
- Nel, A, Pitcher, G, Richoux, Nicole B, Jackson, S
- Authors: Nel, A , Pitcher, G , Richoux, Nicole B , Jackson, S
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/457215 , vital:75617 , xlink:href="https://doi.org/10.2989/1814232X.2014.982187"
- Description: South Africa lacks a commercial oyster hatchery. To inform the sourcing of seed for future hatchery establishments, we compared half-sib Pacific oyster Crassostrea gigas cohorts from hatcheries in Namibia and Chile. We measured oyster growth, mortality, condition and feeding organ morphology in Algoa Bay (AB, Eastern Cape) and Saldanha Bay (SB, Western Cape), South Africa, from July 2011 to June 2012. Within SB, 14.3% of mean daily sea temperatures exceeded this species’ thermal optimum of 19 °C, compared to 50.5% in AB. Food abundance (mean daily chlorophyll a concentration) in SB (7.8 mg m–3) was double that in AB (3.9 mg m–3) where, presumably to increase particle clearance rates in a relatively phytoplankton-poor environment, oysters had larger gill:palp surface area ratios. Plankton fatty acid profiles (indicators of food quality) differed between locations. In AB, instantaneous growth rates differed between cohorts, and trends varied seasonally. Within both locations, condition index was usually higher in Chilean oysters, whereas shell density was higher in Namibian oysters. In AB only, Chilean seed suffered substantially higher summer mortalities than Namibian seed, suggesting that the latter are more suited to temperatures in AB. AB should also be assessed for culture of the indigenous oyster species that occur there.
- Full Text:
- Date Issued: 2014
- Authors: Nel, A , Pitcher, G , Richoux, Nicole B , Jackson, S
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/457215 , vital:75617 , xlink:href="https://doi.org/10.2989/1814232X.2014.982187"
- Description: South Africa lacks a commercial oyster hatchery. To inform the sourcing of seed for future hatchery establishments, we compared half-sib Pacific oyster Crassostrea gigas cohorts from hatcheries in Namibia and Chile. We measured oyster growth, mortality, condition and feeding organ morphology in Algoa Bay (AB, Eastern Cape) and Saldanha Bay (SB, Western Cape), South Africa, from July 2011 to June 2012. Within SB, 14.3% of mean daily sea temperatures exceeded this species’ thermal optimum of 19 °C, compared to 50.5% in AB. Food abundance (mean daily chlorophyll a concentration) in SB (7.8 mg m–3) was double that in AB (3.9 mg m–3) where, presumably to increase particle clearance rates in a relatively phytoplankton-poor environment, oysters had larger gill:palp surface area ratios. Plankton fatty acid profiles (indicators of food quality) differed between locations. In AB, instantaneous growth rates differed between cohorts, and trends varied seasonally. Within both locations, condition index was usually higher in Chilean oysters, whereas shell density was higher in Namibian oysters. In AB only, Chilean seed suffered substantially higher summer mortalities than Namibian seed, suggesting that the latter are more suited to temperatures in AB. AB should also be assessed for culture of the indigenous oyster species that occur there.
- Full Text:
- Date Issued: 2014
Enhanced optical limiting performance in phthalocyanine-quantum dot nanocomposites by free-carrier absorption mechanism
- Sanusi, Kayode, Khene, Samson M, Nyokong, Tebello
- Authors: Sanusi, Kayode , Khene, Samson M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193904 , vital:45404 , xlink:href="https://doi.org/10.1016/j.optmat.2014.07.024"
- Description: Enhanced nonlinear optical properties (in dimethyl sulphoxide) is observed for 2(3),9(10),16(17),23(24)-tetrakis-(4-aminophenoxy)phthalocyaninato indium(III) chloride (InPc) when covalently linked to CdSe/ZnS or CdSe quantum dots (QDs). The experimental nonlinear optical parameters were obtained from Z-Scan measurements. Contributions from two-photon absorption (2PA) due to the InPc, and free-carrier absorption (FCA) by QDS have been identified as the main factors responsible for the enhanced optical limiting. The effective nonlinear absorption coefficient for InPc-CdSe/ZnS was found to be 700.0 cm/GW. The FCA cross-sections for InPc-CdSe/ZnS and InPc-CdSe composites were found to be 1.52 × 10−19 and 6.00 × 10−20 cm2 respectively. A much lower limiting threshold of 92 mJ cm−2 was observed for InPc-CdSe/ZnS nanocomposite, hence, making it suitable for use as optical limiting material. Density Functional Theory (DFT) calculations on similar phthalocyanine-quantum dots system was modeled in order to explain the enhancement in the observed nonlinear optical properties of the Pc in the presence of the QDs. The experimentally determined nonlinear optical properties are well within the range of the DFT calculated properties.
- Full Text:
- Date Issued: 2014
- Authors: Sanusi, Kayode , Khene, Samson M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193904 , vital:45404 , xlink:href="https://doi.org/10.1016/j.optmat.2014.07.024"
- Description: Enhanced nonlinear optical properties (in dimethyl sulphoxide) is observed for 2(3),9(10),16(17),23(24)-tetrakis-(4-aminophenoxy)phthalocyaninato indium(III) chloride (InPc) when covalently linked to CdSe/ZnS or CdSe quantum dots (QDs). The experimental nonlinear optical parameters were obtained from Z-Scan measurements. Contributions from two-photon absorption (2PA) due to the InPc, and free-carrier absorption (FCA) by QDS have been identified as the main factors responsible for the enhanced optical limiting. The effective nonlinear absorption coefficient for InPc-CdSe/ZnS was found to be 700.0 cm/GW. The FCA cross-sections for InPc-CdSe/ZnS and InPc-CdSe composites were found to be 1.52 × 10−19 and 6.00 × 10−20 cm2 respectively. A much lower limiting threshold of 92 mJ cm−2 was observed for InPc-CdSe/ZnS nanocomposite, hence, making it suitable for use as optical limiting material. Density Functional Theory (DFT) calculations on similar phthalocyanine-quantum dots system was modeled in order to explain the enhancement in the observed nonlinear optical properties of the Pc in the presence of the QDs. The experimentally determined nonlinear optical properties are well within the range of the DFT calculated properties.
- Full Text:
- Date Issued: 2014
Higher education studies as a field of research
- Authors: McKenna, Sioux
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187405 , vital:44631 , xlink:href="https://hdl.handle.net/10520/EJC161436"
- Description: The field of Higher Education Studies is a rapidly growing one in South Africa and abroad but there has been little systematic review of the form this growth is taking. This article presents a case study of higher education research by considering a newly formed Higher Education Studies doctoral programme. The programme comprises 29 PhD scholars in 2014, all engaged in research on some aspect of higher education. The description of the PhD programme, the PhD scholars and what their research topics are, reveals a picture of the broad range of concerns within the field of Higher Education Studies and suggests that the field is a region, in Bernstein's terms. This means that it draws on multiple disciplines and looks both to the values and structures of those disciplines and to the professional world of work. It is argued that the strengthening of the epistemological base of Higher Education Studies is necessary for higher education research to move forwards with enhanced relational and positional autonomy.
- Full Text:
- Date Issued: 2014
- Authors: McKenna, Sioux
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187405 , vital:44631 , xlink:href="https://hdl.handle.net/10520/EJC161436"
- Description: The field of Higher Education Studies is a rapidly growing one in South Africa and abroad but there has been little systematic review of the form this growth is taking. This article presents a case study of higher education research by considering a newly formed Higher Education Studies doctoral programme. The programme comprises 29 PhD scholars in 2014, all engaged in research on some aspect of higher education. The description of the PhD programme, the PhD scholars and what their research topics are, reveals a picture of the broad range of concerns within the field of Higher Education Studies and suggests that the field is a region, in Bernstein's terms. This means that it draws on multiple disciplines and looks both to the values and structures of those disciplines and to the professional world of work. It is argued that the strengthening of the epistemological base of Higher Education Studies is necessary for higher education research to move forwards with enhanced relational and positional autonomy.
- Full Text:
- Date Issued: 2014
Photophysical properties of a new water soluble tetra thiamine substituted zinc phthalocyanine conjugated to gold nanorods of different aspect ratios
- Mthethwa, Thandekile, Antunes, Edith M, Nyokong, Tebello
- Authors: Mthethwa, Thandekile , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241583 , vital:50952 , xlink:href="https://doi.org/10.1039/C4DT00197D"
- Description: A water soluble zinc phthalocyanine substituted with thiamine is reported in this work. The aggregation of this compound in aqueous solutions causes quenching of the fluorescence quantum yields. Gold nanospheres and nanorods were linked to the phthalocyanine. X-ray photoelectron spectroscopy showed that both the amine and the sulphur groups on the thiamine substituent of the zinc phthalocyanine were involved in the linking to gold nanoparticles. The Pc showed an increase in the fluorescence quantum yields in the presence of the nanoparticles. The singlet oxygen quantum yield increased when the Pc was conjugated to the nanoparticles and even higher for larger aspect ratio gold nanorods.
- Full Text:
- Date Issued: 2014
- Authors: Mthethwa, Thandekile , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241583 , vital:50952 , xlink:href="https://doi.org/10.1039/C4DT00197D"
- Description: A water soluble zinc phthalocyanine substituted with thiamine is reported in this work. The aggregation of this compound in aqueous solutions causes quenching of the fluorescence quantum yields. Gold nanospheres and nanorods were linked to the phthalocyanine. X-ray photoelectron spectroscopy showed that both the amine and the sulphur groups on the thiamine substituent of the zinc phthalocyanine were involved in the linking to gold nanoparticles. The Pc showed an increase in the fluorescence quantum yields in the presence of the nanoparticles. The singlet oxygen quantum yield increased when the Pc was conjugated to the nanoparticles and even higher for larger aspect ratio gold nanorods.
- Full Text:
- Date Issued: 2014
Unsymmetrically substituted nickel triazatetra-benzcorrole and phthalocynanine complexes
- Adegoke, Oluwasesan, Nyokong, Tebello
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189818 , vital:44934 , xlink:href="https://doi.org/10.1007/s10895-013-1317-4"
- Description: We report on the design and application of fluorescent nanoprobes based on the covalent linking of L-glutathione-capped CdSe@ZnS quantum dots (QDs) to newly synthesized unsymmetrically substituted nickel mercaptosuccinic acid triazatetra-benzcorrole (3) and phthalocyanine (4) complexes. Fluorescence quenching of the QDs occurred on conjugation to complexes 3 or 4. The nanoprobes were selectively screened in the presence of different cations and Hg2+ showed excellent affinity in “turning ON” the fluorescence of the nanoprobes. Experimental results showed that the sensitivity of QDs-4 towards Hg2+ was much higher than that of QDs-3 nanoprobe. The mechanism of reaction has been elucidated based on the ability of Hg2+ to coordinate with the sulphur atom of the Ni complex ring and apparently “turn ON” the fluorescence of the linked QDs.
- Full Text:
- Date Issued: 2014
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189818 , vital:44934 , xlink:href="https://doi.org/10.1007/s10895-013-1317-4"
- Description: We report on the design and application of fluorescent nanoprobes based on the covalent linking of L-glutathione-capped CdSe@ZnS quantum dots (QDs) to newly synthesized unsymmetrically substituted nickel mercaptosuccinic acid triazatetra-benzcorrole (3) and phthalocyanine (4) complexes. Fluorescence quenching of the QDs occurred on conjugation to complexes 3 or 4. The nanoprobes were selectively screened in the presence of different cations and Hg2+ showed excellent affinity in “turning ON” the fluorescence of the nanoprobes. Experimental results showed that the sensitivity of QDs-4 towards Hg2+ was much higher than that of QDs-3 nanoprobe. The mechanism of reaction has been elucidated based on the ability of Hg2+ to coordinate with the sulphur atom of the Ni complex ring and apparently “turn ON” the fluorescence of the linked QDs.
- Full Text:
- Date Issued: 2014
Critical indirect effects of climate change on sub-A ntarctic ecosystem functioning
- Allan, E Louise, Froneman, P William, Durgadoo, Jonathan V, McQuaid, Christopher D, Ansorge, Isabelle J, Richoux, Nicole B
- Authors: Allan, E Louise , Froneman, P William , Durgadoo, Jonathan V , McQuaid, Christopher D , Ansorge, Isabelle J , Richoux, Nicole B
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/457934 , vital:75696 , xlink:href="https://doi.org/10.1002/ece3.678"
- Description: Sub‐Antarctic islands represent critical breeding habitats for land‐based top predators that dominate Southern Ocean food webs. Reproduction and molting incur high energetic demands that are sustained at the sub‐Antarctic Prince Edward Islands (PEIs) by both inshore (phytoplankton blooms; “island mass effect”; autochthonous) and offshore (allochthonous) productivity. As the relative contributions of these sustenance pathways are, in turn, affected by oceanographic conditions around the PEIs, we address the consequences of climatically driven changes in the physical environment on this island ecosystem. We show that there has been a measurable long‐term shift in the carbon isotope signatures of the benthos inhabiting the shallow shelf region of the PEIs, most likely reflecting a long‐term decline in enhanced phytoplankton productivity at the islands in response to a climate‐driven shift in the position of the sub‐Antarctic Front. Our results indicate that regional climate change has affected the balance between allochthonous and autochthonous productivity at the PEIs. Over the last three decades, inshore‐feeding top predators at the islands have shown a marked decrease in their population sizes. Conversely, population sizes of offshore‐feeding predators that forage over great distances from the islands have remained stable or increased, with one exception. Population decline of predators that rely heavily on organisms inhabiting the inshore region strongly suggest changes in prey availability, which are likely driven by factors such as fisheries impacts on some prey populations and shifts in competitive interactions among predators. In addition to these local factors, our analysis indicates that changes in prey availability may also result indirectly through regional climate change effects on the islands' marine ecosystem. Most importantly, our results indicate that a fundamental shift in the balance between allochthonous and autochthonous trophic pathways within this island ecosystem may be detected throughout the food web, demonstrating that the most powerful effects of climate change on marine systems may be indirect.
- Full Text:
- Date Issued: 2013
- Authors: Allan, E Louise , Froneman, P William , Durgadoo, Jonathan V , McQuaid, Christopher D , Ansorge, Isabelle J , Richoux, Nicole B
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/457934 , vital:75696 , xlink:href="https://doi.org/10.1002/ece3.678"
- Description: Sub‐Antarctic islands represent critical breeding habitats for land‐based top predators that dominate Southern Ocean food webs. Reproduction and molting incur high energetic demands that are sustained at the sub‐Antarctic Prince Edward Islands (PEIs) by both inshore (phytoplankton blooms; “island mass effect”; autochthonous) and offshore (allochthonous) productivity. As the relative contributions of these sustenance pathways are, in turn, affected by oceanographic conditions around the PEIs, we address the consequences of climatically driven changes in the physical environment on this island ecosystem. We show that there has been a measurable long‐term shift in the carbon isotope signatures of the benthos inhabiting the shallow shelf region of the PEIs, most likely reflecting a long‐term decline in enhanced phytoplankton productivity at the islands in response to a climate‐driven shift in the position of the sub‐Antarctic Front. Our results indicate that regional climate change has affected the balance between allochthonous and autochthonous productivity at the PEIs. Over the last three decades, inshore‐feeding top predators at the islands have shown a marked decrease in their population sizes. Conversely, population sizes of offshore‐feeding predators that forage over great distances from the islands have remained stable or increased, with one exception. Population decline of predators that rely heavily on organisms inhabiting the inshore region strongly suggest changes in prey availability, which are likely driven by factors such as fisheries impacts on some prey populations and shifts in competitive interactions among predators. In addition to these local factors, our analysis indicates that changes in prey availability may also result indirectly through regional climate change effects on the islands' marine ecosystem. Most importantly, our results indicate that a fundamental shift in the balance between allochthonous and autochthonous trophic pathways within this island ecosystem may be detected throughout the food web, demonstrating that the most powerful effects of climate change on marine systems may be indirect.
- Full Text:
- Date Issued: 2013
Optical limiting analysis of phthalocyanines in polymer thin films
- Britton, Jonathan, Litwinski, Christian, Antunes, Edith M, Durmus, Mahmut, Chaukea, Vongani, Nyokong, Tebello
- Authors: Britton, Jonathan , Litwinski, Christian , Antunes, Edith M , Durmus, Mahmut , Chaukea, Vongani , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232488 , vital:49996 , xlink:href="https://doi.org/10.1080/10601325.2013.736269"
- Description: This paper reports on the effect of embedding twelve phthalocyanines containing In, Ga, Zn and Al as central metals in polymer thin films on their optical limiting abilities. This paper also examines the effect of forming a covalent link between zinc tetraamino phthalocyanine (10) and poly (methyl acrylic acid) (PMAA), and Zn (11) or OHAl (12) octacarboxy phthalocyanines with polyethylenimine (PEI). The average film thickness (for phthalocyanines mixed or linked to polymers) of each Pc/Polymer films on glass was 95 μm. The hyperpolarizability of the twelve phthalocyanines was found to be in the range of 10−26 to 10−24 esu.L. This is significantly higher than the hyperpolarizabilities of these phthalocyanines in solution, which ranged from 10−30 to 10−26 esu.L. Degradation studies seem to indicate that placing a phthalocyanine within a polymer thin film may protect it slightly from photo- and thermal degradation.
- Full Text:
- Date Issued: 2013
- Authors: Britton, Jonathan , Litwinski, Christian , Antunes, Edith M , Durmus, Mahmut , Chaukea, Vongani , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232488 , vital:49996 , xlink:href="https://doi.org/10.1080/10601325.2013.736269"
- Description: This paper reports on the effect of embedding twelve phthalocyanines containing In, Ga, Zn and Al as central metals in polymer thin films on their optical limiting abilities. This paper also examines the effect of forming a covalent link between zinc tetraamino phthalocyanine (10) and poly (methyl acrylic acid) (PMAA), and Zn (11) or OHAl (12) octacarboxy phthalocyanines with polyethylenimine (PEI). The average film thickness (for phthalocyanines mixed or linked to polymers) of each Pc/Polymer films on glass was 95 μm. The hyperpolarizability of the twelve phthalocyanines was found to be in the range of 10−26 to 10−24 esu.L. This is significantly higher than the hyperpolarizabilities of these phthalocyanines in solution, which ranged from 10−30 to 10−26 esu.L. Degradation studies seem to indicate that placing a phthalocyanine within a polymer thin film may protect it slightly from photo- and thermal degradation.
- Full Text:
- Date Issued: 2013
The development of catalytic oxovanadium (IV)-containing microspheres for the oxidation of various organosulfur compounds
- Ogunlaja, Adeniyi S, Khene, Samson M, Antunes, Edith M, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- Authors: Ogunlaja, Adeniyi S , Khene, Samson M , Antunes, Edith M , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241783 , vital:50969 , xlink:href="https://doi.org/10.1016/j.apcata.2013.05.004"
- Description: The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting VIVOSO4 with poly[allylSB-co-EGDMA]. XPS and EPR were used to confirm the presence of vanadium (V4+) on the beads. The synthesized catalyst (poly[allylSB-co-EGDMA]-VO) was found to have a BET surface area of 22 m2 g−1 and porosity of 135 Å, with the atomic force microscopy (AFM) showing more insight on the porous nature of the beads. Oxidation of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using tert-butyl hydroperoxide (t-BuOOH) as oxidant. An overall conversion of 60%, 82%, 98% and 87% was achieved for thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6 dimethyldibenzothiophene (4,6-DMDBT) respectively at higher (t-BuOOH) to substrate ratio and at a temperature of 40 °C. The efficient oxidation of the various organosulfur compounds presents potential for the possible application of this catalyst in oxidative desulfurization (ODS) of crude oil.
- Full Text:
- Date Issued: 2013
- Authors: Ogunlaja, Adeniyi S , Khene, Samson M , Antunes, Edith M , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241783 , vital:50969 , xlink:href="https://doi.org/10.1016/j.apcata.2013.05.004"
- Description: The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting VIVOSO4 with poly[allylSB-co-EGDMA]. XPS and EPR were used to confirm the presence of vanadium (V4+) on the beads. The synthesized catalyst (poly[allylSB-co-EGDMA]-VO) was found to have a BET surface area of 22 m2 g−1 and porosity of 135 Å, with the atomic force microscopy (AFM) showing more insight on the porous nature of the beads. Oxidation of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using tert-butyl hydroperoxide (t-BuOOH) as oxidant. An overall conversion of 60%, 82%, 98% and 87% was achieved for thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6 dimethyldibenzothiophene (4,6-DMDBT) respectively at higher (t-BuOOH) to substrate ratio and at a temperature of 40 °C. The efficient oxidation of the various organosulfur compounds presents potential for the possible application of this catalyst in oxidative desulfurization (ODS) of crude oil.
- Full Text:
- Date Issued: 2013
The photophysical and photochemical behaviour of coumarin-derivatized zinc phthalocyanine when conjugated with gold nanoparticles and electrospun into polymer fibers
- Tombe, Sekai, Antunes, Edith M, Nyokong, Tebello
- Authors: Tombe, Sekai , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232534 , vital:50000 , xlink:href="https://doi.org/10.1039/C2NJ40984D"
- Description: Polymer composite fibers doped with phthalocyanines and phthalocyanine-functionalized gold nanoparticles were developed. The phthalocyanine and phthalocyanine-functionalized gold nanoparticles have been characterized using UV/Vis, fluorescence and X-ray photoelectron spectroscopy (XPS), time correlated single photon counting (TCSPC), time-resolved emission spectra (TRES) and transmission electron microscopy (TEM). The changes in photophysical and photochemical behavior of the phthalocyanines induced by their interaction with gold nanoparticles and polystyrene were also investigated. In the presence of gold nanoparticles, the fluorescence lifetimes and quantum yields of the phthalocyanine decreased, whereas the singlet oxygen quantum yield increased. This work shows that polymer composite fibers could be used as functional fibers for a variety of applications such as gas sensing when using the advantageous properties of phthalocyanines and gold nanoparticles.
- Full Text:
- Date Issued: 2013
- Authors: Tombe, Sekai , Antunes, Edith M , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232534 , vital:50000 , xlink:href="https://doi.org/10.1039/C2NJ40984D"
- Description: Polymer composite fibers doped with phthalocyanines and phthalocyanine-functionalized gold nanoparticles were developed. The phthalocyanine and phthalocyanine-functionalized gold nanoparticles have been characterized using UV/Vis, fluorescence and X-ray photoelectron spectroscopy (XPS), time correlated single photon counting (TCSPC), time-resolved emission spectra (TRES) and transmission electron microscopy (TEM). The changes in photophysical and photochemical behavior of the phthalocyanines induced by their interaction with gold nanoparticles and polystyrene were also investigated. In the presence of gold nanoparticles, the fluorescence lifetimes and quantum yields of the phthalocyanine decreased, whereas the singlet oxygen quantum yield increased. This work shows that polymer composite fibers could be used as functional fibers for a variety of applications such as gas sensing when using the advantageous properties of phthalocyanines and gold nanoparticles.
- Full Text:
- Date Issued: 2013
Oxovanadium (IV)-catalysed oxidation of dibenzothiophene and 4, 6-dimethyldibenzothiophene
- Ogunlaja, Adeniyi S, Chidawanyika, Wadzanai J U, Antunes, Edith M, Fernandes, Manuel A, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- Authors: Ogunlaja, Adeniyi S , Chidawanyika, Wadzanai J U , Antunes, Edith M , Fernandes, Manuel A , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246025 , vital:51429 , xlink:href="https://doi.org/10.1039/C2DT31433A"
- Description: The reaction between [VIVOSO4] and the tetradentate N2O2-donor Schiff base ligand, N,N-bis(o-hydroxybenzaldehyde)phenylenediamine (sal-HBPD), obtained by the condensation of salicylaldehyde and o-phenylenediamine in a molar ratio of 2 : 1 respectively, resulted in the formation of [VIVO(sal-HBPD)]. The molecular structure of [VIVO(sal-HBPD)] was determined by single crystal X-ray diffraction, and confirmed the distorted square pyramidal geometry of the complex with the N2O2 binding mode of the tetradentate ligand. The formation of the polymer-supported p[VIVO(sal-AHBPD)] proceeded via the nitrosation of sal-HBPD, followed by the reduction with hydrogen to form an amine group that was then linked to Merrifield beads followed by the reaction with [VIVOSO4]. XPS and EPR were used to confirm the presence of oxovanadium(IV) within the beads. The BET surface area and porosity of the heterogeneous catalyst p[VIVO(sal-AHBPD)] were found to be 6.9 m2 g−1 and 180.8 Å respectively. Microanalysis, TG, UV-Vis and FT-IR were used for further characterization of both [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)]. Oxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was investigated using [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)] as catalysts. Progress for oxidation of these model compounds was monitored with a gas chromatograph fitted with a flame ionization detector. The oxidation products were characterized using gas chromatography-mass spectrometry, microanalysis and NMR. Dibenzothiophene sulfone (DBTO2) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO2) were found to be the main products of oxidation. Oxovanadium(IV) Schiff base microspherical beads, p[VIVO(sal-AHBPD)], were able to catalyse the oxidation of sulfur in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) to a tune of 88.0% and 71.8% respectively after 3 h at 40 °C. These oxidation results show promise for potential application of this catalyst in the oxidative desulfurization of crude oils.
- Full Text:
- Date Issued: 2012
- Authors: Ogunlaja, Adeniyi S , Chidawanyika, Wadzanai J U , Antunes, Edith M , Fernandes, Manuel A , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/246025 , vital:51429 , xlink:href="https://doi.org/10.1039/C2DT31433A"
- Description: The reaction between [VIVOSO4] and the tetradentate N2O2-donor Schiff base ligand, N,N-bis(o-hydroxybenzaldehyde)phenylenediamine (sal-HBPD), obtained by the condensation of salicylaldehyde and o-phenylenediamine in a molar ratio of 2 : 1 respectively, resulted in the formation of [VIVO(sal-HBPD)]. The molecular structure of [VIVO(sal-HBPD)] was determined by single crystal X-ray diffraction, and confirmed the distorted square pyramidal geometry of the complex with the N2O2 binding mode of the tetradentate ligand. The formation of the polymer-supported p[VIVO(sal-AHBPD)] proceeded via the nitrosation of sal-HBPD, followed by the reduction with hydrogen to form an amine group that was then linked to Merrifield beads followed by the reaction with [VIVOSO4]. XPS and EPR were used to confirm the presence of oxovanadium(IV) within the beads. The BET surface area and porosity of the heterogeneous catalyst p[VIVO(sal-AHBPD)] were found to be 6.9 m2 g−1 and 180.8 Å respectively. Microanalysis, TG, UV-Vis and FT-IR were used for further characterization of both [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)]. Oxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was investigated using [VIVO(sal-HBPD)] and p[VIVO(sal-AHBPD)] as catalysts. Progress for oxidation of these model compounds was monitored with a gas chromatograph fitted with a flame ionization detector. The oxidation products were characterized using gas chromatography-mass spectrometry, microanalysis and NMR. Dibenzothiophene sulfone (DBTO2) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO2) were found to be the main products of oxidation. Oxovanadium(IV) Schiff base microspherical beads, p[VIVO(sal-AHBPD)], were able to catalyse the oxidation of sulfur in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) to a tune of 88.0% and 71.8% respectively after 3 h at 40 °C. These oxidation results show promise for potential application of this catalyst in the oxidative desulfurization of crude oils.
- Full Text:
- Date Issued: 2012