Study of the photophysical behavior of tetrasulfonated metallophthalocyanines in the presence of CdTe quantum dots
- Idowu, Mopelola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264138 , vital:53701 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: Förster resonance energy transfer (FRET) studies were carried out with CdTe quantum dots (QDs) synthesized in aqueous phase and various tetrasulfonated metallophthalocyanines (MPcS4, M = aluminum ((OH)AlPcS4), zinc (ZnPcS4), silicon ((OH)2SiPcS4) and germanium ((OH)2GePcS4) in a H2O:MeOH (1:1) solvent mixture. The QDs studied were capped with thioglycolic acid (TGA) or mercaptopropionic acid (MPA) with sizes ranging from 2.3 to 3.7 nm. Non-radiative energy transfer from QDs emission to MPcS4 complexes was observed. Study of the photophysics of the MPcs in the presence of the QDs revealed high triplet state quantum yields (ΦT, ranging from 0.41 to 0.85 in the presence of QDs), with corresponding long triplet state lifetimes (τT, which ranged from 140 to 610 μs in the presence of QDs) to allow for photosensitized reactions to occur. The efficiency of energy transfer and the donor–acceptor distance between the MPcs and the QDs were also evaluated.
- Full Text:
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264138 , vital:53701 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
- Description: Förster resonance energy transfer (FRET) studies were carried out with CdTe quantum dots (QDs) synthesized in aqueous phase and various tetrasulfonated metallophthalocyanines (MPcS4, M = aluminum ((OH)AlPcS4), zinc (ZnPcS4), silicon ((OH)2SiPcS4) and germanium ((OH)2GePcS4) in a H2O:MeOH (1:1) solvent mixture. The QDs studied were capped with thioglycolic acid (TGA) or mercaptopropionic acid (MPA) with sizes ranging from 2.3 to 3.7 nm. Non-radiative energy transfer from QDs emission to MPcS4 complexes was observed. Study of the photophysics of the MPcs in the presence of the QDs revealed high triplet state quantum yields (ΦT, ranging from 0.41 to 0.85 in the presence of QDs), with corresponding long triplet state lifetimes (τT, which ranged from 140 to 610 μs in the presence of QDs) to allow for photosensitized reactions to occur. The efficiency of energy transfer and the donor–acceptor distance between the MPcs and the QDs were also evaluated.
- Full Text:
Study South Africa
- International Education Association of South Africa (IEASA), Jooste, Nico
- Authors: International Education Association of South Africa (IEASA) , Jooste, Nico
- Date: 2009
- Subjects: Education, Higher -- South Africa , Universities and colleges -- South Africa , Technical Institutes -- South Africa , Vocational guidance -- South Africa
- Language: English
- Type: text , book
- Identifier: http://hdl.handle.net/10962/64983 , vital:28642 , ISBN 9780620448161
- Description: [Extract from message from Minister of Higher Education and Training, Hon. Dr BE Nzimande]: It gives me pleasure to provide support to the International Education Association of South Africa’s (IEASA) 9th edition of the Study South Africa publication. The focus of this edition, which is Higher Education and Development in South Africa, is most appropriate today as South Africa continuously strives to ensure that higher education remains relevant and responsive to the developmental needs of the country. To this end, we always have to bear in mind that South Africa is a developing country, and as such still confronts challenges such as poverty and under-development. These challenges are characteristic of most developing countries, particularly in sub-Saharan Africa. Thus, our higher education sector, through its core functions of teaching, research, and community engagement, should seek to address these issues especially as they affect the poor and other vulnerable members of our society. Since we became a democratic state in 1994, South Africa has gone a long way to transform and restructure our higher education system to ensure amongst others equity with regard to the demographics of our staff and student population. The gender and racial profile of our students has improved significantly over the years to the extent that we now have black and female students constituting the majority at our institutions, especially at undergraduate level. It is also pleasing to note that our institutions enjoy good international standing. South African researchers and institutions continue to engage in research collaborations with their peers and counterparts around the world, and thus, are integral parts of research programmes and networks. With respect to student mobility, our higher education institutions continue to attract large numbers of international students, particularly from other parts of Africa. In 2007 the number of international students enrolled at our institutions was counted at 59 209, a significant increase from 44 439 in 2000. About 85% of these students originate from the African continent, more specifically the Southern African Development Community (SADC) region. Several factors account for the increase in the number of international students coming to South Africa. These include the country’s natural and ecological resources, rich and diverse cultural heritage, and the stable socio-political conditions. The consistent growth in the number of international students seeking to study in South Africa is a positive affirmation on the quality of the country’s institutions and the international reputation of their academics and qualifications. As a country, we see this growth as a positive development as it provides us with the opportunity not only to impart or relate our experiences, but also, to learn from others, and by so doing further enhance the international standing of our higher education system. , 9th Edition
- Full Text:
- Authors: International Education Association of South Africa (IEASA) , Jooste, Nico
- Date: 2009
- Subjects: Education, Higher -- South Africa , Universities and colleges -- South Africa , Technical Institutes -- South Africa , Vocational guidance -- South Africa
- Language: English
- Type: text , book
- Identifier: http://hdl.handle.net/10962/64983 , vital:28642 , ISBN 9780620448161
- Description: [Extract from message from Minister of Higher Education and Training, Hon. Dr BE Nzimande]: It gives me pleasure to provide support to the International Education Association of South Africa’s (IEASA) 9th edition of the Study South Africa publication. The focus of this edition, which is Higher Education and Development in South Africa, is most appropriate today as South Africa continuously strives to ensure that higher education remains relevant and responsive to the developmental needs of the country. To this end, we always have to bear in mind that South Africa is a developing country, and as such still confronts challenges such as poverty and under-development. These challenges are characteristic of most developing countries, particularly in sub-Saharan Africa. Thus, our higher education sector, through its core functions of teaching, research, and community engagement, should seek to address these issues especially as they affect the poor and other vulnerable members of our society. Since we became a democratic state in 1994, South Africa has gone a long way to transform and restructure our higher education system to ensure amongst others equity with regard to the demographics of our staff and student population. The gender and racial profile of our students has improved significantly over the years to the extent that we now have black and female students constituting the majority at our institutions, especially at undergraduate level. It is also pleasing to note that our institutions enjoy good international standing. South African researchers and institutions continue to engage in research collaborations with their peers and counterparts around the world, and thus, are integral parts of research programmes and networks. With respect to student mobility, our higher education institutions continue to attract large numbers of international students, particularly from other parts of Africa. In 2007 the number of international students enrolled at our institutions was counted at 59 209, a significant increase from 44 439 in 2000. About 85% of these students originate from the African continent, more specifically the Southern African Development Community (SADC) region. Several factors account for the increase in the number of international students coming to South Africa. These include the country’s natural and ecological resources, rich and diverse cultural heritage, and the stable socio-political conditions. The consistent growth in the number of international students seeking to study in South Africa is a positive affirmation on the quality of the country’s institutions and the international reputation of their academics and qualifications. As a country, we see this growth as a positive development as it provides us with the opportunity not only to impart or relate our experiences, but also, to learn from others, and by so doing further enhance the international standing of our higher education system. , 9th Edition
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Synthesis and characterization of electrocatalytic conjugates of tetraamino cobalt (II) phthalocyanine and single wall carbon nanotubes
- Mugadza, Tawanda, Nyokong, Tebello
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263341 , vital:53619 , xlink:href="https://doi.org/10.1016/j.electacta.2009.05.074"
- Description: In this paper we report on the synthesis and characterization of electrocatalytic conjugates of tetraamino cobalt (II) phthalocyanine and single walled carbon nanotubes (CoTAPc–SWCNT-linked) for use as electrode surface modifiers. FTIR, UV–vis and Raman spectroscopies were used to ascertain the chemical linkage between CoTAPc and SWCNT while cyclic voltammetry and rotating disk electrode voltammetry were used to assess the electrocatalytic efficiency of the linked product towards the oxidation of 2-mercaptoethanol. The CoTAPc–SWCNT-linked-GCE demonstrated very good catalytic efficiency relative to CoTAPc–SWCNT-mixed-GCE, CoTAPc-GCE and f-SWCNTs-GCE (functionalised SWCNT). CoTAPc–SWCNT-linked-GCE gave a sensitivity of 0.2 μA/μM and a limit of detection (LOD) of 1.2 × 10−7 M for 2-mercaptoethanol (2-ME) at pH 4.
- Full Text:
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263341 , vital:53619 , xlink:href="https://doi.org/10.1016/j.electacta.2009.05.074"
- Description: In this paper we report on the synthesis and characterization of electrocatalytic conjugates of tetraamino cobalt (II) phthalocyanine and single walled carbon nanotubes (CoTAPc–SWCNT-linked) for use as electrode surface modifiers. FTIR, UV–vis and Raman spectroscopies were used to ascertain the chemical linkage between CoTAPc and SWCNT while cyclic voltammetry and rotating disk electrode voltammetry were used to assess the electrocatalytic efficiency of the linked product towards the oxidation of 2-mercaptoethanol. The CoTAPc–SWCNT-linked-GCE demonstrated very good catalytic efficiency relative to CoTAPc–SWCNT-mixed-GCE, CoTAPc-GCE and f-SWCNTs-GCE (functionalised SWCNT). CoTAPc–SWCNT-linked-GCE gave a sensitivity of 0.2 μA/μM and a limit of detection (LOD) of 1.2 × 10−7 M for 2-mercaptoethanol (2-ME) at pH 4.
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Synthesis and electrochemistry of octapentylthio phthalocyanine complexes of manganese, titanium and vanadium
- Authors: Mbambisa, Gcineka
- Date: 2009
- Subjects: Electrochemistry , Phthalocyanines -- Synthesis , Manganese , Titanium , Vanadium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4368 , http://hdl.handle.net/10962/d1005033 , Electrochemistry , Phthalocyanines -- Synthesis , Manganese , Titanium , Vanadium
- Description: Synthesis of new thio derivatised Pcs with manganese, titanium and vanadium as a central metal is reported. The complexes synthesised were characterised using spectroscopic and electrochemical means. The complexes displayed interesting spectroscopic properties with absorption of the Q band being observed in the near infrared region. These complexes have unusual colours for MPc complexes, with purple or red colour being observed in solution. Interesting electrochemical properties were observed, with rare observation of the MnIV/MnIII redox couple. There was observation of oxidation peaks for the pentylthio derivatised Pc with titanium as the central metal; this is unusual since for reported thio derivatives based on TiPc, no oxidation was observed. The vanadium based Pc showed an interesting spectrum for the first ring based reduction. The absorption spectrum obtained for the 1st reduction of the vanadium complex using spectroelectrochemistry would normally indicate a metal based process but comparing with literature it was concluded that it is a ring based reduction process. Generally all the MPc complexes formed a well ordered stable monolayer on the gold electrode. Electrocatalytic studies using L-cysteine revealed that the SAM based on manganese (III) octapentylthio phthalocyanine (AcOMnOPTPc) was the most effective since it catalyses L-cysteine at much lower oxidation potentials and it is also much more stable.
- Full Text:
- Authors: Mbambisa, Gcineka
- Date: 2009
- Subjects: Electrochemistry , Phthalocyanines -- Synthesis , Manganese , Titanium , Vanadium
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4368 , http://hdl.handle.net/10962/d1005033 , Electrochemistry , Phthalocyanines -- Synthesis , Manganese , Titanium , Vanadium
- Description: Synthesis of new thio derivatised Pcs with manganese, titanium and vanadium as a central metal is reported. The complexes synthesised were characterised using spectroscopic and electrochemical means. The complexes displayed interesting spectroscopic properties with absorption of the Q band being observed in the near infrared region. These complexes have unusual colours for MPc complexes, with purple or red colour being observed in solution. Interesting electrochemical properties were observed, with rare observation of the MnIV/MnIII redox couple. There was observation of oxidation peaks for the pentylthio derivatised Pc with titanium as the central metal; this is unusual since for reported thio derivatives based on TiPc, no oxidation was observed. The vanadium based Pc showed an interesting spectrum for the first ring based reduction. The absorption spectrum obtained for the 1st reduction of the vanadium complex using spectroelectrochemistry would normally indicate a metal based process but comparing with literature it was concluded that it is a ring based reduction process. Generally all the MPc complexes formed a well ordered stable monolayer on the gold electrode. Electrocatalytic studies using L-cysteine revealed that the SAM based on manganese (III) octapentylthio phthalocyanine (AcOMnOPTPc) was the most effective since it catalyses L-cysteine at much lower oxidation potentials and it is also much more stable.
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Synthesis and Pd(II) binding studies of octasubstituted alkyl thio derivatised phthalocyanines
- Ogunbayo, T B, Nyokong, Tebello
- Authors: Ogunbayo, T B , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6587 , http://hdl.handle.net/10962/d1004170
- Description: Synthesis and characterization of non-peripherally (4,5) and peripherally (6,7) substituted metal free and Pd octapentylthiophthalocyanine and coordination of palladium ions to these Pcs are reported. The unmetalated complexes (4 and 6) show Pd coordination at the central metal and at the ring. The number of Pd ions bound to complex 4 were found to be five and to complex 6 were three. The equilibrium constant for the binding of Pd to complexes 4 was lower (K = 1.2 × 109 dm3 mol−1) than for complex 6 (K = 5.7 × 1010 dm3 mol−1).
- Full Text:
- Authors: Ogunbayo, T B , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6587 , http://hdl.handle.net/10962/d1004170
- Description: Synthesis and characterization of non-peripherally (4,5) and peripherally (6,7) substituted metal free and Pd octapentylthiophthalocyanine and coordination of palladium ions to these Pcs are reported. The unmetalated complexes (4 and 6) show Pd coordination at the central metal and at the ring. The number of Pd ions bound to complex 4 were found to be five and to complex 6 were three. The equilibrium constant for the binding of Pd to complexes 4 was lower (K = 1.2 × 109 dm3 mol−1) than for complex 6 (K = 5.7 × 1010 dm3 mol−1).
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Synthesis and photophysical behavior of axially substituted phthalocyanine, tetrabenzotriazaporphyrin, and triazatetrabenzcorrole phosphorous complexes
- Antunes, Edith M, Nyokong, Tebello
- Authors: Antunes, Edith M , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264518 , vital:53741 , xlink:href="https://doi.org/10.1142/S1088424609000048"
- Description: The synthesis of phosphorous phthalocyanines, triazatetrabenzcorroles, and tetrabenzotriazaporphyrins with a variety of axial ligands is reported. The new complexes are: phosphorous dihydroxy tetrabenzotriazaporphyrin (5, PV(OH)2TBTAP), diphenyl phosphorous phthalocyanine (6, [PV(Ph)2Pc](OH)), diphenyl phosphorous triazatetrabenzcorrole (7, PV(Ph)2TBC), and dioctyl phosphorous triazatetrabenzcorrole (8, PV(C8H17)2TBC). The complexes are not aggregated in dimethylsulfoxide (DMSO) and pyridine. Upon axial coordination of a phenyl or octyl group, the complexes are soluble (and not aggregated) in dichloromethane (DCM) and tetrahydrofuran (THF). The triplet lifetimes range from 395 to 546 μs (for complexes 5 to 8), with the P(Ph)2TBC (7) complex showing the longest triplet lifetime (546 μs), while the smallest triplet quantum yield (ΦT = 0.27) was obtained for the [P(Ph)2Pc](OH) (6) complex. [P(OH)2Pc](OH) (3) showed the shortest triplet lifetime (113 μs) and the largest triplet quantum yield (ΦT = 0.52).
- Full Text:
- Authors: Antunes, Edith M , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264518 , vital:53741 , xlink:href="https://doi.org/10.1142/S1088424609000048"
- Description: The synthesis of phosphorous phthalocyanines, triazatetrabenzcorroles, and tetrabenzotriazaporphyrins with a variety of axial ligands is reported. The new complexes are: phosphorous dihydroxy tetrabenzotriazaporphyrin (5, PV(OH)2TBTAP), diphenyl phosphorous phthalocyanine (6, [PV(Ph)2Pc](OH)), diphenyl phosphorous triazatetrabenzcorrole (7, PV(Ph)2TBC), and dioctyl phosphorous triazatetrabenzcorrole (8, PV(C8H17)2TBC). The complexes are not aggregated in dimethylsulfoxide (DMSO) and pyridine. Upon axial coordination of a phenyl or octyl group, the complexes are soluble (and not aggregated) in dichloromethane (DCM) and tetrahydrofuran (THF). The triplet lifetimes range from 395 to 546 μs (for complexes 5 to 8), with the P(Ph)2TBC (7) complex showing the longest triplet lifetime (546 μs), while the smallest triplet quantum yield (ΦT = 0.27) was obtained for the [P(Ph)2Pc](OH) (6) complex. [P(OH)2Pc](OH) (3) showed the shortest triplet lifetime (113 μs) and the largest triplet quantum yield (ΦT = 0.52).
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Synthesis and photophysical properties of antimony and lead phthalocyanines
- Modibane, Kwena Desmond, Guest
- Authors: Modibane, Kwena Desmond , Guest
- Date: 2009 , 2009-02-27
- Subjects: Phthalocyanines , Photochemistry , Antimony compounds , Lead compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4370 , http://hdl.handle.net/10962/d1005035 , Phthalocyanines , Photochemistry , Antimony compounds , Lead compounds
- Description: This work hereby presents the synthesis, spectroscopic and photophysical properties of newly synthesized lead (PbPc) and antimony (SbPc) phthalocyanines. The complexes are either unsubstituted or substituted at the peripheral and non-peripheral positions with phenoxy, 4-t-butylphenoxy and 4-benzyloxyphenoxy groups. The photophysical properties of these complexes were studied in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform as solvents. The fluorescence spectra for PbPc complexes were different to that of the excitation spectra due to demetallation upon excitation. On the other hand, the excitation spectra of oxidized antimony (Sb(V)Pc) derivatives were found to be similar to absorption spectra. High triplet quantum yields for PbPc and SbPc complexes ranging from 0.70 to 0.86, low triplet lifetimes (20–60 μs in DMSO, while they were <10 μs in the rest of the solvents) and low fluorescence quantum yields were observed and is attributed to the presence of heavy atoms (Pb and Sb ions). The nonlinear optical properties of PbPc complexes were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.8 W/cm2. The photodegradation studies of the PbPc and SbPc complexes synthesized showed that then are stable.
- Full Text:
- Authors: Modibane, Kwena Desmond , Guest
- Date: 2009 , 2009-02-27
- Subjects: Phthalocyanines , Photochemistry , Antimony compounds , Lead compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4370 , http://hdl.handle.net/10962/d1005035 , Phthalocyanines , Photochemistry , Antimony compounds , Lead compounds
- Description: This work hereby presents the synthesis, spectroscopic and photophysical properties of newly synthesized lead (PbPc) and antimony (SbPc) phthalocyanines. The complexes are either unsubstituted or substituted at the peripheral and non-peripheral positions with phenoxy, 4-t-butylphenoxy and 4-benzyloxyphenoxy groups. The photophysical properties of these complexes were studied in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform as solvents. The fluorescence spectra for PbPc complexes were different to that of the excitation spectra due to demetallation upon excitation. On the other hand, the excitation spectra of oxidized antimony (Sb(V)Pc) derivatives were found to be similar to absorption spectra. High triplet quantum yields for PbPc and SbPc complexes ranging from 0.70 to 0.86, low triplet lifetimes (20–60 μs in DMSO, while they were <10 μs in the rest of the solvents) and low fluorescence quantum yields were observed and is attributed to the presence of heavy atoms (Pb and Sb ions). The nonlinear optical properties of PbPc complexes were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.8 W/cm2. The photodegradation studies of the PbPc and SbPc complexes synthesized showed that then are stable.
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Synthesis of molecularly imprinted polymer for selective solid-phase extraction of Salbutamol from urine samples
- Mohammadi, Ali, Alizadeh, Taher, Dinarvand, Rassoul, Ganjali, Mohammed M, Walker, Roderick B
- Authors: Mohammadi, Ali , Alizadeh, Taher , Dinarvand, Rassoul , Ganjali, Mohammed M , Walker, Roderick B
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6410 , http://hdl.handle.net/10962/d1006496
- Description: A highly selective methacrylic based molecularly imprinted polymer (MIP) was synthesized and applied for the separation and the pre-concentration of salbutamol in urine samples. Spectrophotometric determination of salbutamol was achieved using 2,6-dichloroquinone chlorimide as colorimetric reagent. The detection limit of the method was ca. 13 ng/mL in urine after pre-concentration of the samples by MIP-SPE andanalysis with an optimized and sensitive spectrophotometric method. The linear dynamic range for salbutamol determination in urine was 0.04-0.75 μg mL-1. The recovery for the affinity based solid-phase extraction (SPE) with the MIP was more than 96 %.
- Full Text:
- Authors: Mohammadi, Ali , Alizadeh, Taher , Dinarvand, Rassoul , Ganjali, Mohammed M , Walker, Roderick B
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6410 , http://hdl.handle.net/10962/d1006496
- Description: A highly selective methacrylic based molecularly imprinted polymer (MIP) was synthesized and applied for the separation and the pre-concentration of salbutamol in urine samples. Spectrophotometric determination of salbutamol was achieved using 2,6-dichloroquinone chlorimide as colorimetric reagent. The detection limit of the method was ca. 13 ng/mL in urine after pre-concentration of the samples by MIP-SPE andanalysis with an optimized and sensitive spectrophotometric method. The linear dynamic range for salbutamol determination in urine was 0.04-0.75 μg mL-1. The recovery for the affinity based solid-phase extraction (SPE) with the MIP was more than 96 %.
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Synthesis, photophysical and nonlinear optical properties of microwave synthesized 4-tetra and octa-substituted lead phthalocyanines
- Modibane, Desmond K, Nyokong, Tebello
- Authors: Modibane, Desmond K , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263452 , vital:53629 , xlink:href="https://doi.org/10.1016/j.poly.2009.03.013"
- Description: This work presents the photophysical and nonlinear optical behaviour of newly synthesized complexes: 2,(3)-tetrakis(4-benzyloxyphenoxyphthalocyaninato) lead (5a) and 2,3-octakis(4-benzyloxyphenoxyphthalocyaninato) lead (6a). The nonlinear optical behaviour of complexes 5a and 6a are compared with those of 2,(3)-tetraphenoxyphthalocyaninato lead (5b), 2,(3)-tetrakis(4-t-butylphenoxyphthalocyaninato) lead (5c), 2,3-octaphenoxyphthalocyaninato lead (6b) and 2,3-octakis(4-t-butylphenoxyphthalocyaninato) lead (6c). The synthesis of 5a and 6a was performed using microwave irradiation. Photophysical properties were studied for these complexes in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform. The fluorescence spectra were different from excitation spectra due to demetallation upon excitation. High triplet quantum yields ranging from 0.80 to 0.86 (in DMSO, DMF and toluene) and low triplet lifetimes (20–50 μs in DMSO, and more than 10 μs in the rest of the solvents) were observed due to the presence of heavy atom. Nonlinear optical properties were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.6 W/cm2.
- Full Text:
- Authors: Modibane, Desmond K , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263452 , vital:53629 , xlink:href="https://doi.org/10.1016/j.poly.2009.03.013"
- Description: This work presents the photophysical and nonlinear optical behaviour of newly synthesized complexes: 2,(3)-tetrakis(4-benzyloxyphenoxyphthalocyaninato) lead (5a) and 2,3-octakis(4-benzyloxyphenoxyphthalocyaninato) lead (6a). The nonlinear optical behaviour of complexes 5a and 6a are compared with those of 2,(3)-tetraphenoxyphthalocyaninato lead (5b), 2,(3)-tetrakis(4-t-butylphenoxyphthalocyaninato) lead (5c), 2,3-octaphenoxyphthalocyaninato lead (6b) and 2,3-octakis(4-t-butylphenoxyphthalocyaninato) lead (6c). The synthesis of 5a and 6a was performed using microwave irradiation. Photophysical properties were studied for these complexes in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform. The fluorescence spectra were different from excitation spectra due to demetallation upon excitation. High triplet quantum yields ranging from 0.80 to 0.86 (in DMSO, DMF and toluene) and low triplet lifetimes (20–50 μs in DMSO, and more than 10 μs in the rest of the solvents) were observed due to the presence of heavy atom. Nonlinear optical properties were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.6 W/cm2.
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Synthesis, photophysical and photochemical properties of novel soluble tetra [4-(thiophen-3yl)-phenoxy] phthalocyaninato zinc (II) and Ti (IV) O complexes
- Erdoğmuş, Ali, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263318 , vital:53617 , xlink:href="https://doi.org/10.1016/j.ica.2009.07.015"
- Description: The synthesis, photophysical and photochemical properties of zinc and oxo-titanium phthalocyanine derivatives 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)zinc(II), (2); and 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)oxo-titanium(IV), (3), are described for the first time. These peripherally substituted complexes (2 and 3) have been synthesized and characterized by elemental analysis, IR, 1H NMR and electronic spectroscopy. The compounds (2 and 3) have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated within a wide concentration range. General trends are described for singlet oxygen, photodegradation, fluorescence quantum yields, triplet quantum yields and triplet life times of these complexes in DMSO, DMF and THF. Compound 2 has higher fluorescence quantum yields, triplet quantum yields and triplet life times than 3, however, the former has lower singlet oxygen quantum yields and photodegradation quantum yields than the latter.
- Full Text:
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263318 , vital:53617 , xlink:href="https://doi.org/10.1016/j.ica.2009.07.015"
- Description: The synthesis, photophysical and photochemical properties of zinc and oxo-titanium phthalocyanine derivatives 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)zinc(II), (2); and 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)oxo-titanium(IV), (3), are described for the first time. These peripherally substituted complexes (2 and 3) have been synthesized and characterized by elemental analysis, IR, 1H NMR and electronic spectroscopy. The compounds (2 and 3) have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated within a wide concentration range. General trends are described for singlet oxygen, photodegradation, fluorescence quantum yields, triplet quantum yields and triplet life times of these complexes in DMSO, DMF and THF. Compound 2 has higher fluorescence quantum yields, triplet quantum yields and triplet life times than 3, however, the former has lower singlet oxygen quantum yields and photodegradation quantum yields than the latter.
- Full Text:
Synthesis, photophysical and photochemical properties of octa-substituted antimony phthalocyanines
- Modibane, Desmond Kwena, Nyokong, Tebello
- Authors: Modibane, Desmond Kwena , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264226 , vital:53711 , xlink:href="https://doi.org/10.1016/j.poly.2008.11.052"
- Description: This work reports on the synthesis and photophysicochemical parameters of unsubstituted [SbIIIPc]+I3- and octa-phenoxy ([SbIIIOPPc]+I3-) and -4-t-butylphenoxy ([SbIIIOTBPPc]+I3-) substituted antimony phthalocyanines. Photophysical and photochemical properties were studied for these complexes in dimethylsulfoxide, dimethylformamide and toluene. The excitation spectra of oxidized antimony (Sb(V)Pc) derivates were similar to absorption spectra. Low fluorescence quantum yields, high triplet quantum yields and low triplet lifetimes were observed as the result of heavy atom (antimony ion).
- Full Text:
- Authors: Modibane, Desmond Kwena , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264226 , vital:53711 , xlink:href="https://doi.org/10.1016/j.poly.2008.11.052"
- Description: This work reports on the synthesis and photophysicochemical parameters of unsubstituted [SbIIIPc]+I3- and octa-phenoxy ([SbIIIOPPc]+I3-) and -4-t-butylphenoxy ([SbIIIOTBPPc]+I3-) substituted antimony phthalocyanines. Photophysical and photochemical properties were studied for these complexes in dimethylsulfoxide, dimethylformamide and toluene. The excitation spectra of oxidized antimony (Sb(V)Pc) derivates were similar to absorption spectra. Low fluorescence quantum yields, high triplet quantum yields and low triplet lifetimes were observed as the result of heavy atom (antimony ion).
- Full Text:
Synthesis, photophysical and photochemical studies of water soluble cationic zinc phthalocyanine derivatives
- Idowu, Mopelola, Nyokong, Tebello
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264245 , vital:53712 , xlink:href="https://doi.org/10.1016/j.poly.2008.11.021"
- Description: Peripherally and non-peripherally 2-diethylaminoethanethiol tetra-substituted zinc phthalocyanine (5a and 6a) and their quaternized derivatives (5b and 6b) have been synthesized and characterized. The quaternized derivatives (5b and 6b) show excellent solubility in aqueous medium. The photophysical and photochemical properties of the 2-diethylaminoethanethiol appended zinc phthalocyanine in dimethylsulfoxide (DMSO) for the non-ionic (5a and 6a) and in both DMSO and aqueous medium (phosphate buffered saline solution PBS, pH 7.4) (in the presence and absence of cremophore EL (CEL)) for the quaternized (5b and 6b) derivatives were studied and compared with that of the peripherally octa-substituted derivatives (7a and 7b). The complexes have intense absorption in the visible/near-IR region though the quaternized forms (5b, 6b and 7b) were slightly blue shifted and highly aggregate in aqueous solution. The triplet state quantum yields (ΦT) and the triplet lifetimes (τT) were found to be higher in DMSO (ΦT values ranged from 0.57 to 0.75 while τT values ranged from 190 to 220 μs in DMSO for all complexes) compared to aqueous medium (ΦT values ranged from 0.15 to 0.17 while τT values ranged from 20 to 70 μs in pH 7.4 buffer). Addition of cremophore EL in aqueous solution resulted in induced disaggregation leading to increased ΦT and τT.
- Full Text:
- Authors: Idowu, Mopelola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264245 , vital:53712 , xlink:href="https://doi.org/10.1016/j.poly.2008.11.021"
- Description: Peripherally and non-peripherally 2-diethylaminoethanethiol tetra-substituted zinc phthalocyanine (5a and 6a) and their quaternized derivatives (5b and 6b) have been synthesized and characterized. The quaternized derivatives (5b and 6b) show excellent solubility in aqueous medium. The photophysical and photochemical properties of the 2-diethylaminoethanethiol appended zinc phthalocyanine in dimethylsulfoxide (DMSO) for the non-ionic (5a and 6a) and in both DMSO and aqueous medium (phosphate buffered saline solution PBS, pH 7.4) (in the presence and absence of cremophore EL (CEL)) for the quaternized (5b and 6b) derivatives were studied and compared with that of the peripherally octa-substituted derivatives (7a and 7b). The complexes have intense absorption in the visible/near-IR region though the quaternized forms (5b, 6b and 7b) were slightly blue shifted and highly aggregate in aqueous solution. The triplet state quantum yields (ΦT) and the triplet lifetimes (τT) were found to be higher in DMSO (ΦT values ranged from 0.57 to 0.75 while τT values ranged from 190 to 220 μs in DMSO for all complexes) compared to aqueous medium (ΦT values ranged from 0.15 to 0.17 while τT values ranged from 20 to 70 μs in pH 7.4 buffer). Addition of cremophore EL in aqueous solution resulted in induced disaggregation leading to increased ΦT and τT.
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Synthesis, photophysics and photochemistry of novel tetra (quinoxalinyl) phthalocyaninato zinc (II) complexes
- Erdoğmuş, Ali, Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263441 , vital:53628 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.04.007"
- Description: The syntheses and spectral, photophysical and photochemical properties of some zinc phthalocyanine derivatives – {2, (3)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (β-ZnPc) and 1, (4)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (α-ZnPc)} – are presented. The β-substituted complex is more fluorescent and exhibits lower tendencies to undergo intersystem crossing than its α-substituted counterpart, as judged by the former's higher fluorescence quantum yield (ΦF) and lower triplet quantum yield (ΦT) than the latter's in three solvents (DMSO, DMF and toluene). Singlet oxygen quantum yield (ΦΔ) values show the same trends as ΦT values. The differences in the spectral and photophysical properties of α-ZnPc and β-ZnPc are partly attributed to greater molecular distortions in the former. Studies of the interaction of the triplet states of α-ZnPc and β-ZnPc with triplet oxygen showed that α-ZnPc is more vulnerable to oxygen quenching than β-ZnPc. Also, the smallest quenching rate constants were observed in DMSO, which is attributed to the higher viscosity of DMSO than DMF and toluene.
- Full Text:
- Authors: Erdoğmuş, Ali , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263441 , vital:53628 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.04.007"
- Description: The syntheses and spectral, photophysical and photochemical properties of some zinc phthalocyanine derivatives – {2, (3)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (β-ZnPc) and 1, (4)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (α-ZnPc)} – are presented. The β-substituted complex is more fluorescent and exhibits lower tendencies to undergo intersystem crossing than its α-substituted counterpart, as judged by the former's higher fluorescence quantum yield (ΦF) and lower triplet quantum yield (ΦT) than the latter's in three solvents (DMSO, DMF and toluene). Singlet oxygen quantum yield (ΦΔ) values show the same trends as ΦT values. The differences in the spectral and photophysical properties of α-ZnPc and β-ZnPc are partly attributed to greater molecular distortions in the former. Studies of the interaction of the triplet states of α-ZnPc and β-ZnPc with triplet oxygen showed that α-ZnPc is more vulnerable to oxygen quenching than β-ZnPc. Also, the smallest quenching rate constants were observed in DMSO, which is attributed to the higher viscosity of DMSO than DMF and toluene.
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Synthesis, spectroscopic and electrochemical properties of manganese, nickel and iron octakis-(2-diethylaminoethanethiol)-phthalocyanine
- Adebayo, A I, Nyokong, Tebello
- Authors: Adebayo, A I , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6563 , http://hdl.handle.net/10962/d1004122
- Description: The syntheses, spectroscopic and electrochemical properties of manganese (3), nickel (4) and iron (5) phthalocyanine complexes, octa-substituted at the peripheral positions with diethlyaminoethanethiol substituent, are reported. The electrochemistry of these complexes and the corresponding cobalt complex (6) are reported. Complex 3 showed two reversible reduction couples attributed to the MnIIIPc−2/MnIIPc−2 (E½ = −0.12 V versus Ag|AgCl) and MnIIPc−2/MnIIPc−3 (E½ = −0.82 V versus Ag|AgCl) species. Two ring-based reduction couples were also observed for complex 4. Two reduction couples, assigned to the FeIIPc−2/FeIPc−2 (E½ = −0.35 V versus Ag|AgCl) and FeIPc−2/FeIPc−3 (E½ = −0.96 V versus Ag|AgCl) species, and an oxidation couple, attributed to FeIIIPc−2/FeIIPc−2 (E½ = 0.26 V versus Ag|AgCl) species, were observed. For complex 6, two reductions and one oxidation were also observed with the potential range of 1.2 to −1.8 V versus Ag|AgCl Spectroelectrochemical studies were used to confirm some of the assigned processes.
- Full Text:
- Authors: Adebayo, A I , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6563 , http://hdl.handle.net/10962/d1004122
- Description: The syntheses, spectroscopic and electrochemical properties of manganese (3), nickel (4) and iron (5) phthalocyanine complexes, octa-substituted at the peripheral positions with diethlyaminoethanethiol substituent, are reported. The electrochemistry of these complexes and the corresponding cobalt complex (6) are reported. Complex 3 showed two reversible reduction couples attributed to the MnIIIPc−2/MnIIPc−2 (E½ = −0.12 V versus Ag|AgCl) and MnIIPc−2/MnIIPc−3 (E½ = −0.82 V versus Ag|AgCl) species. Two ring-based reduction couples were also observed for complex 4. Two reduction couples, assigned to the FeIIPc−2/FeIPc−2 (E½ = −0.35 V versus Ag|AgCl) and FeIPc−2/FeIPc−3 (E½ = −0.96 V versus Ag|AgCl) species, and an oxidation couple, attributed to FeIIIPc−2/FeIIPc−2 (E½ = 0.26 V versus Ag|AgCl) species, were observed. For complex 6, two reductions and one oxidation were also observed with the potential range of 1.2 to −1.8 V versus Ag|AgCl Spectroelectrochemical studies were used to confirm some of the assigned processes.
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Taking education and training to higher levels
- Authors: Phiri, Aretha
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:7203 , http://hdl.handle.net/10962/d1006400
- Description: Professor Tebello Nyokong of the Chemistry Department has won yet another prestigious award. She was voted "the most influential women in business and government" in the category of education and training, in an event sponsored by CEO Magazine.
- Full Text:
- Authors: Phiri, Aretha
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:7203 , http://hdl.handle.net/10962/d1006400
- Description: Professor Tebello Nyokong of the Chemistry Department has won yet another prestigious award. She was voted "the most influential women in business and government" in the category of education and training, in an event sponsored by CEO Magazine.
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The ambivalent engagement with Christianity in the writing of nineteenth- and early twentieth-century Africans in the Eastern Cape
- Authors: Nxasana, Thulani Litha
- Date: 2009
- Subjects: Authors, African -- South Africa -- Eastern Cape Authors, South African -- 19th century -- Criticism and interpretation Authors, South African -- 20th century -- Criticism and interpretation Soga, Tiyo, 1829-1871 -- Criticism and interpretation Mqhayi, S. E. K. -- Criticism and interpretation Mgqwetho, Nontsizi -- Criticism and interpretation South African literature -- 19th century -- History and criticism South African literature -- 20th century -- History and criticism Christianity and literature Ambivalence in literature
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2195 , http://hdl.handle.net/10962/d1002237
- Description: Until recently much of the literature recording the nineteenth and early twentieth centuries in the Eastern Cape focused purely on frontier conflict and missionary activity, ignoring the evolving culture of the colonized people. But as Somande Fikeni declares, “[i]t is important when celebrating the country’s heritage to look beyond battle sites, monuments and wars and to pay attention to South Africa’s intellectuals and knowledge producers” (quoted in Hollands 4). This is indeed the central purpose of my research. This thesis seeks to examine the influence of Christianity on early South African writing by Africans and the ambivalence with which Christianity is often treated in their work. In South Africa, as elsewhere in Africa, Christianity played a central role in the development of African literature through the influence of mission schools and printing presses. Thus from the outset the development of written literature was inseparable from the spread of Christianity. Nineteenth- and early twentieth-century writing by Africans reflects this: Christian idioms, biblical stories and images colour their work and yet are not employed unthinkingly. Each of the writers whom I will explore has a complex and at times ambivalent relationship with Christianity, and they use religious discourse for a variety of ends, some of them clearly at odds with their origins in the “civilizing mission” of Europe. According to Yunus Momoniat, “Their works . . . are the beginnings of an engagement not only with the world of words on a page, but also with the politics of literacy itself” (1). The subject of this research is three Xhosa writers from the Eastern Cape: the Reverend Tiyo Soga (1829-1871), the renowned novelist and “National Poet” S. E. K. Mqhayi (1875-1945), and the little-known poet Nontsizi Mgqwetho (Dates uknown, writings 1920-1929), who is described by Mbeki as “the most prolific woman Xhosa poet of the twentieth century” (6). The reason for focusing on the Eastern Cape is because the Xhosa “were the first Bantu people to be exposed to Christian proselytising and to receive a literate education” (Gerard 24). As a result much of the early literature in isiXhosa consisted of translations of the Bible and other Christian tracts, and such “improving” texts as Pilgrim’s Progress. In other words, it is in this work that the first roots of the influence of Christianity in southern Africa can be traced.
- Full Text:
- Authors: Nxasana, Thulani Litha
- Date: 2009
- Subjects: Authors, African -- South Africa -- Eastern Cape Authors, South African -- 19th century -- Criticism and interpretation Authors, South African -- 20th century -- Criticism and interpretation Soga, Tiyo, 1829-1871 -- Criticism and interpretation Mqhayi, S. E. K. -- Criticism and interpretation Mgqwetho, Nontsizi -- Criticism and interpretation South African literature -- 19th century -- History and criticism South African literature -- 20th century -- History and criticism Christianity and literature Ambivalence in literature
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2195 , http://hdl.handle.net/10962/d1002237
- Description: Until recently much of the literature recording the nineteenth and early twentieth centuries in the Eastern Cape focused purely on frontier conflict and missionary activity, ignoring the evolving culture of the colonized people. But as Somande Fikeni declares, “[i]t is important when celebrating the country’s heritage to look beyond battle sites, monuments and wars and to pay attention to South Africa’s intellectuals and knowledge producers” (quoted in Hollands 4). This is indeed the central purpose of my research. This thesis seeks to examine the influence of Christianity on early South African writing by Africans and the ambivalence with which Christianity is often treated in their work. In South Africa, as elsewhere in Africa, Christianity played a central role in the development of African literature through the influence of mission schools and printing presses. Thus from the outset the development of written literature was inseparable from the spread of Christianity. Nineteenth- and early twentieth-century writing by Africans reflects this: Christian idioms, biblical stories and images colour their work and yet are not employed unthinkingly. Each of the writers whom I will explore has a complex and at times ambivalent relationship with Christianity, and they use religious discourse for a variety of ends, some of them clearly at odds with their origins in the “civilizing mission” of Europe. According to Yunus Momoniat, “Their works . . . are the beginnings of an engagement not only with the world of words on a page, but also with the politics of literacy itself” (1). The subject of this research is three Xhosa writers from the Eastern Cape: the Reverend Tiyo Soga (1829-1871), the renowned novelist and “National Poet” S. E. K. Mqhayi (1875-1945), and the little-known poet Nontsizi Mgqwetho (Dates uknown, writings 1920-1929), who is described by Mbeki as “the most prolific woman Xhosa poet of the twentieth century” (6). The reason for focusing on the Eastern Cape is because the Xhosa “were the first Bantu people to be exposed to Christian proselytising and to receive a literate education” (Gerard 24). As a result much of the early literature in isiXhosa consisted of translations of the Bible and other Christian tracts, and such “improving” texts as Pilgrim’s Progress. In other words, it is in this work that the first roots of the influence of Christianity in southern Africa can be traced.
- Full Text:
The ataxia protein sacsin is a functional co-chaperone that protects against polyglutamine-expanded ataxin-1
- Parfitt, David A, Michael, Gregory J, Vermeulen, Esmeralda G M, Prodromou, Natalia V, Webb, Tom R, Gallo, Jean-Marc, Cheetham, Michael E, Nicoll, William S, Blatch, Gregory L, Chapple, J Paul
- Authors: Parfitt, David A , Michael, Gregory J , Vermeulen, Esmeralda G M , Prodromou, Natalia V , Webb, Tom R , Gallo, Jean-Marc , Cheetham, Michael E , Nicoll, William S , Blatch, Gregory L , Chapple, J Paul
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6485 , http://hdl.handle.net/10962/d1006262 , http://hmg.oxfordjournals.org/content/18/9/1556
- Description: An extensive protein–protein interaction network has been identified between proteins implicated in inherited ataxias. The protein sacsin, which is mutated in the early-onset neurodegenerative disease autosomal recessive spastic ataxia of Charlevoix-Saguenay, is a node in this interactome. Here, we have established the neuronal expression of sacsin and functionally characterized domains of the 4579 amino acid protein. Sacsin is most highly expressed in large neurons, particularly within brain motor systems, including cerebellar Purkinje cells. Its subcellular localization in SH-SY5Y neuroblastoma cells was predominantly cytoplasmic with a mitochondrial component. We identified a putative ubiquitin-like (UbL) domain at the N-terminus of sacsin and demonstrated an interaction with the proteasome. Furthermore, sacsin contains a predicted J-domain, the defining feature of DnaJ/Hsp40 proteins. Using a bacterial complementation assay, the sacsin J-domain was demonstrated to be functional. The presence of both UbL and J-domains in sacsin suggests that it may integrate the ubiquitin–proteasome system and Hsp70 function to a specific cellular role. The Hsp70 chaperone machinery is an important component of the cellular response towards aggregation prone mutant proteins that are associated with neurodegenerative diseases. We therefore investigated the effects of siRNA-mediated sacsin knockdown on polyglutamine-expanded ataxin-1. Importantly, SACS siRNA did not affect cell viability with GFP-ataxin-1[30Q], but enhanced the toxicity of GFP-ataxin- 1[82Q], suggesting that sacsin is protective against mutant ataxin-1. Thus, sacsin is an ataxia protein and a regulator of the Hsp70 chaperone machinery that is implicated in the processing of other ataxialinked proteins.
- Full Text:
- Authors: Parfitt, David A , Michael, Gregory J , Vermeulen, Esmeralda G M , Prodromou, Natalia V , Webb, Tom R , Gallo, Jean-Marc , Cheetham, Michael E , Nicoll, William S , Blatch, Gregory L , Chapple, J Paul
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6485 , http://hdl.handle.net/10962/d1006262 , http://hmg.oxfordjournals.org/content/18/9/1556
- Description: An extensive protein–protein interaction network has been identified between proteins implicated in inherited ataxias. The protein sacsin, which is mutated in the early-onset neurodegenerative disease autosomal recessive spastic ataxia of Charlevoix-Saguenay, is a node in this interactome. Here, we have established the neuronal expression of sacsin and functionally characterized domains of the 4579 amino acid protein. Sacsin is most highly expressed in large neurons, particularly within brain motor systems, including cerebellar Purkinje cells. Its subcellular localization in SH-SY5Y neuroblastoma cells was predominantly cytoplasmic with a mitochondrial component. We identified a putative ubiquitin-like (UbL) domain at the N-terminus of sacsin and demonstrated an interaction with the proteasome. Furthermore, sacsin contains a predicted J-domain, the defining feature of DnaJ/Hsp40 proteins. Using a bacterial complementation assay, the sacsin J-domain was demonstrated to be functional. The presence of both UbL and J-domains in sacsin suggests that it may integrate the ubiquitin–proteasome system and Hsp70 function to a specific cellular role. The Hsp70 chaperone machinery is an important component of the cellular response towards aggregation prone mutant proteins that are associated with neurodegenerative diseases. We therefore investigated the effects of siRNA-mediated sacsin knockdown on polyglutamine-expanded ataxin-1. Importantly, SACS siRNA did not affect cell viability with GFP-ataxin-1[30Q], but enhanced the toxicity of GFP-ataxin- 1[82Q], suggesting that sacsin is protective against mutant ataxin-1. Thus, sacsin is an ataxia protein and a regulator of the Hsp70 chaperone machinery that is implicated in the processing of other ataxialinked proteins.
- Full Text:
The binding roots of free speech
- Authors: Boughey, Thomas John George
- Date: 2009
- Subjects: Freedom of speech
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2849 , http://hdl.handle.net/10962/d1006255
- Description: This thesis argues that the modern notion of free-speech was born within the Westphalian nation-state. It suggests that the legal rights framework - particular to the Westphalian nationstate - not only legitimizes and legalizes the right to free-speech, but also enables us to invoke legally the necessary limitations that demand the limitation of free-speech in certain contexts. However, such a legal-rights framework is exclusive to the nation-state and cannot be enforced on an international level, outside of the nation-state boundary. With reference to examples on an international level, this thesis demonstrates that calls for the limitation of free-speech are indeed legitimate and necessary but cannot be enforced on an international level for the reasons just mentioned. In order to address this problem, this thesis proposes a framework - based on a Kantian model - that enables us to invoke the limitation of free-speech on an international level without appealing to a legal-rights discourse to do so.
- Full Text:
- Authors: Boughey, Thomas John George
- Date: 2009
- Subjects: Freedom of speech
- Language: English
- Type: Thesis , Masters , MA
- Identifier: vital:2849 , http://hdl.handle.net/10962/d1006255
- Description: This thesis argues that the modern notion of free-speech was born within the Westphalian nation-state. It suggests that the legal rights framework - particular to the Westphalian nationstate - not only legitimizes and legalizes the right to free-speech, but also enables us to invoke legally the necessary limitations that demand the limitation of free-speech in certain contexts. However, such a legal-rights framework is exclusive to the nation-state and cannot be enforced on an international level, outside of the nation-state boundary. With reference to examples on an international level, this thesis demonstrates that calls for the limitation of free-speech are indeed legitimate and necessary but cannot be enforced on an international level for the reasons just mentioned. In order to address this problem, this thesis proposes a framework - based on a Kantian model - that enables us to invoke the limitation of free-speech on an international level without appealing to a legal-rights discourse to do so.
- Full Text:
The both-and edition:
- Authors: Garman, Anthea
- Date: 2009
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/158817 , vital:40231 , https://hdl.handle.net/10520/EJC139955
- Description: I was driving down the N2 from Cape Town towards the airport recently and scanning the turn-offs for Vanguard Drive, when suddenly I noticed among the shacks that line the road some really interesting buildings. These were not the pale pink matchboxes that periodically spring up in rows alongside the derelict housing that millions of South Africans call home. They were multi-levelled, had large windows and looked like an architect might have had something to do with them. I was heartened at the sight of housing – at last – with humanity in mind. But as I reread the 2010 pieces in this edition, I’m reminded by Jane Duncan in particular (“Whose World Cup?” page 23) that prettifying the ghastly spaces in our world cup cities that will be visible to those international tourists is high on the agenda for our government. But then, I reason, at least someone will benefit from living along the noisy and congested airport route!.
- Full Text:
- Authors: Garman, Anthea
- Date: 2009
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/158817 , vital:40231 , https://hdl.handle.net/10520/EJC139955
- Description: I was driving down the N2 from Cape Town towards the airport recently and scanning the turn-offs for Vanguard Drive, when suddenly I noticed among the shacks that line the road some really interesting buildings. These were not the pale pink matchboxes that periodically spring up in rows alongside the derelict housing that millions of South Africans call home. They were multi-levelled, had large windows and looked like an architect might have had something to do with them. I was heartened at the sight of housing – at last – with humanity in mind. But as I reread the 2010 pieces in this edition, I’m reminded by Jane Duncan in particular (“Whose World Cup?” page 23) that prettifying the ghastly spaces in our world cup cities that will be visible to those international tourists is high on the agenda for our government. But then, I reason, at least someone will benefit from living along the noisy and congested airport route!.
- Full Text:
The challenges of education and development in twenty-first century South Africa
- Authors: Badat, Saleem
- Date: 2009
- Language: English
- Type: Conference paper , text
- Identifier: vital:7121 , http://hdl.handle.net/10962/d1006569
- Description: From the introduction: I have chosen to address the theme of The Challenges of Education and Development in the Twenty First Century. This is not only an extremely important theme but also one that is both complex and broad and can be approached in many different ways. With respect to complexity, the concepts of education and development, like the concepts of freedom and democracy, are defined in various ways and have a variety of meanings associated with them. Moreover, notions of education and development are not neutral in that they are embedded in different views of the world and society, including views on what constitutes a just and good society. Further, the choices, policies, actions and practices that are associated with particular conceptions of education and development are not benign in that they have real and differential effects on different social classes and groups in society. , Keynote Address at the 15th Annual Conference of the Headmasters of the Traditional State Boy’s Schools of South Africa’ Queens College, Queenstown, 26 August 2009.
- Full Text:
- Authors: Badat, Saleem
- Date: 2009
- Language: English
- Type: Conference paper , text
- Identifier: vital:7121 , http://hdl.handle.net/10962/d1006569
- Description: From the introduction: I have chosen to address the theme of The Challenges of Education and Development in the Twenty First Century. This is not only an extremely important theme but also one that is both complex and broad and can be approached in many different ways. With respect to complexity, the concepts of education and development, like the concepts of freedom and democracy, are defined in various ways and have a variety of meanings associated with them. Moreover, notions of education and development are not neutral in that they are embedded in different views of the world and society, including views on what constitutes a just and good society. Further, the choices, policies, actions and practices that are associated with particular conceptions of education and development are not benign in that they have real and differential effects on different social classes and groups in society. , Keynote Address at the 15th Annual Conference of the Headmasters of the Traditional State Boy’s Schools of South Africa’ Queens College, Queenstown, 26 August 2009.
- Full Text: