Novel gallium (III) phthalocyanine derivatives–Synthesis, photophysics and photochemistry
- Authors: Chauke, Vongani , Ogunsipe, Abimbola , Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283118 , vital:55912 , xlink:href="https://doi.org/10.1016/j.poly.2007.01.016"
- Description: The syntheses of gallium(III) chloride phthalocyanine {(Cl)GaPc}, octaphenoxyphthalocyaninato gallium(III) chloride {(Cl)GaOPPc} and octakis(4-tert-butylphenoxy)phthalocyaninato gallium(III) chloride {(Cl)GaOTBPPc}; as well as their photophysical and photochemical parameters are hereby presented. Fluorescence quantum yields do not vary much among the three metallophthalocyanines (MPcs); therefore it was concluded that the effect of the substituents is not significant amongst (Cl)GaPc, (Cl)GaOPPc and (Cl)GaOTBPPc. Solvents effects, however, had an effect on the results. Triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. We have also reported photodegradation and singlet oxygen quantum yields. There was no clear correlation between the later parameters. It was, however, established that the three MPcs were stable.
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- Date Issued: 2007
Comparative electrooxidation of sulphite by self-assembled monolayers (SAMs) of Co (II), Fe (II), Ni (II) and Mn (III) tetrakis benzylmercapto and dodecylmercapto metallophthalocyanines complexes on gold electrodes
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281223 , vital:55703 , xlink:href="https://doi.org/10.1016/j.talanta.2006.11.042"
- Description: This work reports on the use of Co(II), Fe(II), Mn(III) and Ni(II) tetrakis benzylmercapto and dodecylmercapto phthalocyanine complexes for gold electrode modification for electrooxidation of sulphite ions. The complexes were successfully used to modify gold electrodes by self-assembled monolayer (SAM) technique. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, underpotential deposition (UPD) of copper and solution redox chemistry of [Fe(H2O)63+]/[Fe(H2O)62+]. All the modified electrodes showed improved catalytic activities than the unmodified gold electrode towards sulphite ion electrooxidation with all the modified electrodes exhibiting high resistance to electrode surface passivation. Better catalytic performance were obtained for the CoPcs, FePcs and MnPcs which have metal based redox processes within the range of the sulphite electrooxidation peak, while the NiPcs which did not show metal based redox reaction performed less. The catalytic current was found to be linear with sulphite ion concentration in the concentration range employed in this work (0.1–1 mM) and sensitivities ranging from 1.68 to 2.96 μA/mM were observed for all the modified electrodes. Mechanisms of the catalytic oxidation of sulphite ions are proposed.
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- Date Issued: 2007
Photocatalysis of 4-nitrophenol using zinc phthalocyanine complexes
- Authors: Marais, Eloïse , Klein, Rosalyn , Antunes, Edith M , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281286 , vital:55709 , xlink:href="https://doi.org/10.1016/j.molcata.2006.07.055"
- Description: Photodegradation of 4-nitrophenol (4-Np) in the presence of zinc tetrasulfophthalocyanine (ZnPcS4), zinc octacarboxyphthalocyanine (ZnPc(COOH)8) and a sulfonated ZnPc containing a mixture of differently sulfonated derivatives (ZnPcSmix), as photocatalysts is reported. ZnPcSmix is the most effective catalyst in terms of a high quantum yield for 4-Np degradation and the stability of the catalyst. However ZnPc(COOH)8 degrades readily during the catalysis, but it has a higher quantum yield (Φ4-Np) for 4-Np degradation than the rest of the complexes. The Φ4-Np values were closely related to the singlet oxygen quantum yields ΦΔ and hence aggregation. The rate constants for the reaction with 4-Np were kr = 0.67 × 106 mol−1 dm3 s−1 for ZnPcSmix and 2.8 × 108 mol−1 dm3 s−1 for ZnPc(COOH)8.
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- Date Issued: 2007
South African marxist state theory: a critical overview
- Authors: Helliker, Kirk D
- Date: 2007
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/144778 , vital:38378 , DOI: 10.1080/02589348808704885
- Description: The article provides a critical analysis of Marxist work on the South African state. It first examines the early Poulantzian‐State Derivationist debate on the relation between state and society, and then discusses the ‘new directions’ which focus on the state itself. The sensitivity of the ‘new directions’ to the traditional Weberian concern about state bureaucracy is important for enriching Marxist theory. But the article concludes by suggesting that a comprehensive dialectical Marxist approach to the South African state still awaits development.
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- Date Issued: 2007
Light on a hill: building the Constitutional Court of South Africa, Bronwyn Law-Viljoen (Ed.): book review
- Authors: Simbao, Ruth K
- Date: 2007
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/147324 , vital:38626 , https://0-hdl.handle.net.wam.seals.ac.za/10520/EJC31011
- Description: Light on a hill : Building the Constitutional Court of South Africa is a visually elegant book that claims to 'reflect the spirit of the Court and be a beautiful object in its own right' (p. 8). Certainly this book is striking, with its rich photographs by Angela Buckland, its fresh, breathable design by Adele Prins, and its broad format with lavish centerfolds. Reading the text is in many ways an enlightening process of understanding the conceptual underpinnings of the buildings that make up the Constitutional Court complex, but this process of reading takes a few twists and turns along the way.
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- Date Issued: 2007
Synthesis, Photophysical and Photochemical Properties of Poly (oxyethylene)‐Substituted Phthalocyaninato Oxotitanium (IV) Complexes
- Authors: Atilla, Devrim , Durmus, Mahmut , Yılmaz, Özgür , Gürek, Ayşe Gül , Ahsen, Vefa , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271263 , vital:54526 , xlink:href="https://doi.org/10.1002/ejic.200700057"
- Description: The synthesis, photophysical and photochemical properties of tetra- and chlorotetrapoly(oxyethylene)-substituted oxotitanium(IV) phthalocyanines are reported for the first time. The new compounds were characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy, electronic spectroscopy and mass spectra. These complexes showed monomeric behaviour in solution. General trends are described for photodegredation, singlet oxygen, triplet state and fluorescence quantum yields, and triplet and fluorescence lifetimes of these compounds in dimethyl sulfoxide (DMSO). Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications. The complexes showed high triplet quantum yields and triplet lifetimes in DMSO. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism), were 0.72 and 0.78 for 3a and 5a, respectively. Thus, these complexes show potential as Type II photosensitizers. These complexes were also quenched by benzoquinone for fluorescence quenching studies.
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- Date Issued: 2007
Synthesis and electrochemical properties of benzyl-mercapto and dodecyl-mercapto tetrasubstituted manganese phthalocyanine complexes
- Authors: Agboola, Bolade , Ozoemena, Kenneth I , Westbroek, Philippe , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281321 , vital:55713 , xlink:href="https://doi.org/10.1016/j.electacta.2006.09.002"
- Description: Manganese tetrakis (benzyl-mercapto) phthalocyanine (MnTBMPc) and manganese tetrakis (dodecyl-mercapto) phthalocyanine (MnTDMPc) complexes were synthesized and their spectral and electrochemical properties are reported. Cyclic voltammetric data showed three reversible to quasi-reversible and two irreversible redox processes for both complexes. Ring substituents influenced the positions of both oxidation and reduction redox couples. Spectroelectrochemistry confirmed the first two reductions to be due to MnIIIPc2−/MnIIPc2− and MnIIPc3−/MnIIPc2− processes. The first example of a formation of self-assembled monolayers (SAMs) using thiol substituted MnPc complexes is presented, the SAMs were found to show blocking characteristics towards some faradaic reactions.
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- Date Issued: 2007
Electroanalysis of thiocyanate using a novel glassy carbon electrode modified by aryl radicals and cobalt tetracarboxyphthalocyanine
- Authors: Matemadombo, Fungisai , Westbroek, Philippe , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268750 , vital:54228 , xlink:href="https://doi.org/10.1016/j.electacta.2007.06.064"
- Description: Electrochemical grafting of 4-nitrobenzenediazonium tetrafluoroborate onto a glassy carbon electrode (GCE) results in the formation of a nitrophenyl radical, which reacts with the surface to form a covalent bond (grafting) and results in a nitrophenyl modified electrode. The nitro group is electrochemically reduced to a NH2 group. Cobalt tetracarboxyphthalocyanine (CoTCPc) complex is then attached to the NH2 group using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) and N-hydroxysuccinimide (NHS) as coupling agents. The new CoTCPc modified electrode was characterized using cyclic voltammetry and then employed for the catalytic oxidation of thiocyanate.
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- Date Issued: 2007
The humanities, vocationalism and the public good: exploring 'the Hamlet factor'
- Authors: Wright, Laurence
- Date: 2007
- Language: English
- Type: text , article
- Identifier: vital:7028 , http://hdl.handle.net/10962/d1007214 , https://doi.org/10.1080/17535360712331393503
- Description: preprint , This paper argues that the social mission of the humanities is no longer well understood by the public, sometimes not even by the very institutions seeking to attract students to these disciplines, the universities. It becomes difficult to argue for the cogency of research in the humanities, let alone for a specific national research agenda, when the general relation between the humanities and society is widely mistaken. To address such misapprehensions, the discussion outlines as clearly as possible the characteristic procedures of the humanities, the manner in which they inform individual and social transformation, and the contemporary predicament which makes them more rather than less needed in society’s repertoire of educational resources. With this understanding in place, the paper then puts forward suggestions for strengthening research in the humanities as part of a broader programme to renovate the humanities in the South African education system.
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- Date Issued: 2007
Figuring maternity: Christine Dixie's Parturient Prospects
- Authors: Schmahmann, Brenda
- Date: 2017
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/147748 , vital:38667 , https://doi.org/10.1080/00043389.2007.11877068
- Description: The Interior, Birthing Tray and Parturition are three sub-sections of a project entitled Parturient Prospects that artist Christine Dixie began in 2005, when she was pregnant with her second child, and completed by the end of 2006. In Parturient Prospects, the author reveals, Dixie situates her experiences against Western discourses, especially images from early modern Europe. Focusing on the ways in which visual representations construct woman as ‘other’, Dixie invokes reference to not only representations of birth and maternity but also religious, medical and geographical images.
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- Date Issued: 2017
Antjie Krog and the accumulation of ‘media meta‐capital’:
- Authors: Garman, Anthea
- Date: 2007
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/159713 , vital:40336 , DOI: 10.1080/1013929X.2007.9678272
- Description: While Krog's significant body of work in poetry, prose and journalism is undoubtedly central in her trajectory towards international renown, in this essay I explore the dynamics of her “meteoric rise in status”. The news media's role in mediating Krog to the world for nearly 40 years becomes crucial to this investigation. I use a mix of media theory and field theory to illuminate the multi‐faceted and complex relationship Krog has had with the news media and I argue that her acquisition of ‘media meta‐capital’ has played a significant role in her attainment of a unique voice and speaking platform in a postapartheid, public domain in which few white voices, and especially Afrikaner ones, are being heard.
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- Date Issued: 2007
Synthesis and photodynamic potential of tetra-and octa-triethyleneoxysulfonyl substituted zinc phthalocyanines
- Authors: Atilla, Devrim , Savdan, Nil , Durmus, Mahmut , Gürek, Ayşe Gül , Khan, Tania , Rück, Angelika , Walt, Heinrich , Nyokong, Tebello , Ahsen, Vefa
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281342 , vital:55715 , xlink:href="https://doi.org/10.1016/j.jphotochem.2006.08.022"
- Description: Synthesis of the water soluble zinc phthalocyanines (3, 4) obtained from the phthalonitriles substituted with oligo(ethyleneoxy)thia groups are described. The new compounds have been characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy, including HSQC, HMBC and COSY bidimensional correlation techniques, electronic spectroscopy and mass spectra. The aggregation behaviour of the phthalocyanine compounds (3, 4) was investigated using UV–vis spectroscopy in dimethylsulphoxide. Photochemical and photophysical measurements were conducted on oligo(ethyleneoxy)thia appended zinc phthalocyanines. General trends are described for quantum yields of photodegredation, fluorescence yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds. The phototoxicity against cancer cells of the new compounds was investigated during several in vitro experiments. The dye-sensitized photooxidation of 1,3-diphenylisobenzofurane via 1O2 was studied in dimethylsulphoxide.
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- Date Issued: 2007
Patriotic history and the politicisation of memory: manipulation of popular music to re-invent the liberation struggle in Zimbabwe
- Authors: Thram, Diane Janell
- Date: 2007
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/147836 , vital:38677 , https://0-doi.org.wam.seals.ac.za/10.1080/02560040608540456
- Description: This paper investigates how the music nationalism promulgated by the ZANU-PF regime's former Minister of Information and Publicity, Jonathan Moyo, appropriated history and culture in its relentless effort to convince the citizenry that the on-going crisis in Zimbabwe is a continuation of the liberation struggle. It documents how Moyo's propagandised ‘patriotic history’ was written into song lyrics and used in frequently televised propaganda videos and CD/cassette releases to create a music nationalism that appropriated the music of the 1970s Second Chimurenga struggle, then performed to resist colonial oppression, and used it as propaganda intended to maintain the current oppressive regime's grip on political power. It argues that the appropriation of indigenous song/dance forms and the ‘chimurenga music’ of the liberation war has failed to achieve unification of the nation; and that rather, the propaganda's manipulation of memory has offended the Shona cultural aesthetic that requires songwriters to speak the truth of their experience in their music.
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- Date Issued: 2007
Immobilization of tetra-amine substituted metallophthalocyanines at gold surfaces modified with mercaptopropionic acid or DTSP-SAMs
- Authors: Matemadombo, Fungisai , Westbroek, Philippe , Nyokong, Tebello , Ozoemena, Kenneth , De Clerck, Karen , Kiekens, Paul
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283924 , vital:56003 , xlink:href="https://doi.org/10.1016/j.electacta.2006.08.027"
- Description: This paper shows that amine substituted cobalt phthalocyanine (CoTAPc) can be deposited on gold surfaces by using an interconnecting layer of a self-assembled monolayer (SAM) of mercaptopropionic acid or Lomant's reagent (dithiobis(N-succinimidyl propionate) (DTSP)). In both cases the new bond formed is obtained by the creation of an amide. The layers were characterized by electrochemistry and showed high coverage fractions (near 100%). Reductive and oxidative desorption of the SAMs limit the useful potential window from −0.6 to +0.5 V versus Ag|AgCl. The SAM-CoTAPc layers show electrocatalytic activities towards oxygen reduction through the Co(I) central metal ion. The amount of CoTAPc molecules deposited (obtained from the Co central metal ion activity in nitrogen purged solutions) revealed that the CoTAPc molecules are bonded in a perpendicular manner at the surface. Taking into account a surface of 200 Å2 for a flatly bonded MPc, this should result in a four times less amount of deposited CoTAPc compared to the experimental value obtained. Both methods showed good results and promising long-term stability and will be interesting tools for further research in surface modification and sensor development.
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- Date Issued: 2007
The synthesis, fluorescence behaviour and singlet oxygen studies of new water-soluble cationic gallium (III) phthalocyanines
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/280207 , vital:55586 , xlink:href="https://doi.org/10.1016/j.inoche.2006.11.012"
- Description: The preparation of cationic water-soluble gallium phthalocyanine derivatives are described for the first time. Peripheral and non-peripheral 3-hydroxypyridine tetrasubstituted gallium(III)phthalocyanines (5a, 6a) and their quaternarized derivatives (5b and 6b) have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternarized compounds (5b and 6b) are soluble in water and not aggregated (in water and in organic solvents) within a wide concentration range. General trends are described for singlet oxygen quantum yields, fluorescence quantum yields and fluorescence lifetimes of these compounds. These complexes showed better singlet oxygen quantum yields in water than the related quarternarized porphyrazine complexes.
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- Date Issued: 2007
Photochemistry, photophysics and nonlinear optical parameters of phenoxy and tert-butylphenoxy substituted indium (III) phthalocyanines
- Authors: Chauke, Vongani , Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268823 , vital:54235 , xlink:href="https://doi.org/10.1016/j.jphotochem.2007.05.022"
- Description: This work hereby presents the syntheses, photochemistry and photophysics of octaphenoxy ((Cl)InOPPc) and octakis(4-tert-butylphenoxy)chloroindium ((Cl)InOTBPPc) phthalocyanines. Calculated nonlinear parameters of these complexes are compared with those of the corresponding GaPc derivatives and tetrasubstituted GaPc and InPc complexes. Fluorescence quantum yields do not vary much between (Cl)InOPPc and (Cl)InOTBPPc complexes in different solvents. High quantum yields of triplet state (ΦT ranging from 0.70 to 0.91 in dimethysulphoxide, DMSO) and singlet oxygen generation (ΦΔ, ranging from 0.61 to 0.79 in DMSO) were obtained. Short triplet lifetimes 50–60 μs were obtained in DMSO). The optical limiting threshold intensity (Ilim) for the InPc derivatives were calculated and compared with those of corresponding tetrasubstituted InPc and GaPc complexes. The latter were found to be better optical limiters.
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- Date Issued: 2007
Synthesis and solvent effects on the electronic absorption and fluorescence spectral properties of substituted zinc phthalocyanines
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283140 , vital:55914 , xlink:href="https://doi.org/10.1016/j.poly.2007.01.018"
- Description: The synthesis and spectroscopic properties of the following tetra- and octa-substituted aryloxy zinc(II) phthalocyanines are reported for the first time: 1,(4)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (7); 2,(3)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (8); 2,3-(octabenzyloxyphenoxyphthalocyaninato) zinc(II) (9). The new compounds have been characterized by elemental analysis, IR, 1H NMR spectroscopy and electronic spectroscopy. Spectroscopic properties of these compounds were investigated in different solvents. Protonation of non-peripherally substituted complex 7 resulted in the splitting and red-shifting of the Q-band. The peripherally substituted derivatives 8 and 9, did not show the split in the Q-band. Fluorescence spectra of the derivatives show Stokes shifts typical of MPc complexes.
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- Date Issued: 2007
JM Coetzee and the ethics of reading:
- Authors: Marais, Mike
- Date: 2007
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/144253 , vital:38325 , https://www.jstor.org/stable/pdf/26286886.pdf
- Description: One of Derek Attridge's principal concerns in J. M. Coetzee and the Ethics of Reading is the relationship that is established with alterity in the writing and reading of literary works. As is evident from the fact that some of the chapters in the book date back more than a decade, this is an abiding concern. Indeed, The Singularity of Literature, which also appeared in 2004, theorizes this relationship at great length. In it, Attridge describes the literary text as the emanation of an act of creation, that is, that mysterious experience in which the writer, who is located in culture's familiar modes of understanding, encounters something strange (in that it does not yet exist within the horizon that culture provides for thinking and feeling) and is required to resist the mind's tendency to reduce novelty by understanding it in terms of the familiar.
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- Date Issued: 2007
Synthesis, photophysical and photochemical properties of aryloxy tetra-substituted gallium and indium phthalocyanine derivatives
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281431 , vital:55724 , xlink:href="https://doi.org/10.1016/j.tet.2006.11.089"
- Description: The synthesis, photophysical and photochemical properties of the tetra-substituted aryloxy gallium(III) and indium(III) phthalocyanines are reported for the first time. General trends are described for photodegradation, singlet oxygen, fluorescence, and triplet quantum yields and triplet lifetimes of these compounds. The introduction of phenoxy and tert-butylphenoxy substituents on the ring resulted in lowering of fluorescence quantum yields and lifetimes, and triplet quantum yields, and an increase of kIC, kISC, and kF. Photoreduction of the complexes was observed during laser flash photolysis. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) ranged from 0.41 to 0.91. Thus, these complexes show potential as Type II photosensitizers.
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- Date Issued: 2007
Electrocatalytic oxidation of chlorophenols by electropolymerised nickel (II) tetrakis benzylmercapto and dodecylmercapto metallophthalocyanines complexes on gold electrodes
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281247 , vital:55705 , xlink:href="https://doi.org/10.1016/j.electacta.2007.02.017"
- Description: This work reports on the use of nickel(II) tetrakis benzylmercapto (NiTBMPc) and dodecylmercapto (NiTDMPc) metallophthalocyanine complexes films on gold electrodes for the electrochemical oxidation of 4-chlorophenol (4-CP) and 2,4,5-trichlorophenol (TCP). Both NiTBMPc and NiTDMPc complexes were successfully deposited on gold electrodes by electropolymerisation. The films were electro-transformed in aqueous 0.1 M NaOH solution to the ‘O–Ni–O oxo’ bridged form. For both complexes, films with different thickness were prepared and characterised by electrochemical impedance and UV–vis (on indium tin oxide) spectroscopies and the results showed typical behaviour for modified electrodes with increasing charge transfer resistance values (Rp) with polymer thickness. The poly-Ni(OH)NiPcs showed better catalytic activity than their poly-NiPcs counterparts.
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- Date Issued: 2007